Polyurethane

Edited by Fahmina Zafar and Eram Sharmin

 POLYURETHANE
Edited by Fahmina Zafar and Eram Sharmin
Polyurethane
[Link]
Edited by Fahmina Zafar and Eram Sharmin

Contributors
Vickie Shim, Iain Anderson, Joerg Bohme, Christoph Josten, Maria Butnaru, M. S. El-Shahawi, Ahmadreza
Gharehbaghi, Žiga Voršič, Khairiah Haji Badri, Jan Bodi, Petr Martinec, Zoltan Bodi, Jiri Scucka, Suzana M Cakic, Ivan S
Ristić, Olivera Ristic, Yerkesh Batyrbekov, Rinat M Iskakov, Ahmed Tawfik, Ilsiya Mullayanovna Davletbaeva, Valentina
Cauda, Valfredo Lemos, Rafael Oliveira, Devendra Deo Pathak, Mariana Paulino, Filipe Teixeira-Dias, Issam A.M.,
Rashidah Mohamed Hamidi, Nataly Kozak, Eugenia Lobko, Anastasiya Hubina, Fahmina Zafar, Eram Sharmin

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Polyurethane
Edited by Fahmina Zafar and Eram Sharmin
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ISBN 978-953-51-0726-2
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 Meet the editors

Dr Fahmina Zafar is Senior Research Associate/Scientist

Pool [Under Scientists’ Pool Scheme, Council of Sci-
entific and Industrial Research (C.S.I.R.), India] at the
Department of Chemistry, Jamia Millia Islamia (J.M.I.)
(A Central University), New Delhi, India. Dr Zafar has
received her Ph.D in Chemistry from the same Univer-
sity in 2006. She was a Research Associate and Senior
Research Fellow (C.S.I.R., India) at J.M.I. She holds [Link]. in Organic
Chemistry from J.M.I. in 1999 and [Link]. in Chemistry and Textile Cloth-
ing from Mahila Vidyalaya Degree College, Lucknow University, Uttar
Pradesh in 1995. She has more than 80 publications in conference Proceed-
ings, refereed journals and Books. Her pioneer work is in the development
of bio-based Polymers, metallopolymers, organic-inorganic hybrid and
nanocomposites for Green Environment in different fields of applications.
Dr Zafar is expert in synthesis and characterization of seed oil derived
polymers such as polyurethanes, polyesteramides, polyurethaneamides
for antimicrobial and corrosion protective applications.

Dr Eram Sharmin, Senior Research Associate [Under Sci-

entists’ Pool Scheme, Council of Scientific and Industrial
Research (CSIR), India] at the Department of Chemistry,
Jamia Millia Islamia (JMI) (A Central University), New
Delhi, India, has persued her PhD (JMI, 2007), MSc
(Aligarh Muslim University-AMU, Aligarh, UP, India
2000) and BSc (AMU, 1998) degree in Chemistry. Hav-
ing previously worked as Senior Research Fellow and Research Associate
(CSIR, India) at JMI, she has about 65 publications in conference proceed-
ings, refereed journals and books. Her research interests include green
organic-inorganic hybrid and composite materials from bio-based epoxies,
polyols, polyurethanes as antimicrobial and corrosion resistant coatings.
Contents

Preface XIII

Section 1 Introduction 1

Chapter 1 Polyurethane: An Introduction 3

Eram Sharmin and Fahmina Zafar

Section 2 Synthesis and Properties 17

Chapter 2 New Liquid Crystalline Polyurethane

Elastomers Containing Thiazolo [5,4d]
Thiazole Moiety: Synthesis and Properties 19
Ahmed Issam Mohammed and Mohamed Rashidah Hamidi

Chapter 3 The Modification of Polyurethanes by Highly

Ordered Coordination Compounds of Transition Metals 33
Ruslan Davletbaev, Ilsiya Davletbaeva and Olesya Gumerova

Chapter 4 Bottom-Up Nanostructured Segmented

Polyurethanes with Immobilized in situ Transition
and Rare-Earth Metal Chelate Compounds – Polymer
Topology – Structure and Properties Relationship 51
Nataly Kozak and Eugenia Lobko

Chapter 5 Thermal Analysis of Polyurethane

Dispersions Based on Different Polyols 79
Suzana M. Cakić, Ivan S. Ristić and Olivera Z. Ristić

Chapter 6 Polyurethane Flexible Foam Fire Behavior 101

Ahmadreza Gharehbagh and Zahed Ahmadi

Section 3 Applications 121

Chapter 7 Polyurethane in Urological Practice 123

Valentina Cauda and Furio Cauda
X Contents

Chapter 8 Polyurethane as Carriers of Antituberculosis Drugs 147

Yerkesh Batyrbekov and Rinat Iskakov

Chapter 9 Use of Polyurethane Foam in Orthopaedic

Biomechanical Experimentation and Simulation 171
V. Shim, J. Boheme, C. Josten and I. Anderson

Chapter 10 Biocompatibility and Biological

Performance of the Improved Polyurethane
Membranes for Medical Applications 201
Maria Butnaru, Ovidiu Bredetean, Doina Macocinschi,
Cristina Daniela Dimitriu, Laura Knieling and Valeria Harabagiu

Chapter 11 HTPB-Polyurethane: A Versatile

Fuel Binder for Composite Solid Propellant 229
Abhay K. Mahanta and Devendra D. Pathak

Chapter 12 Synthesis of a New Sorbent Based on

Grafted PUF for the Application in the Solid
Phase Extraction of Cadmium and Lead 263
Rafael Vasconcelos Oliveira and Valfredo Azevedo Lemos

Chapter 13 Fast, Selective Removal and

Determination of Total Bismuth (III) and
(V) in Water by Procaine Hydrochloride Immobilized
Polyurethane Foam Packed Column Prior to Inductively
Coupled Plasma – Optical Emission Spectrometry 281
M.S. El-Shahawi, A.A. Al-Sibaai, H.M. Al-Saidi and E.A. Assirey

Chapter 14 Polyurethane Grouting Technologies 307

Jan Bodi, Zoltan Bodi, Jiri Scucka and Petr Martinec

Chapter 15 On the Use of Polyurethane Foam

Paddings to Improve Passive Safety
in Crashworthiness Applications 337
Mariana Paulino and Filipe Teixeira-Dias

Chapter 16 Polyurethane Trickling Filter in

Combination with Anaerobic Hybrid Reactor
for Treatment of Tomato Industry Wastewater 355
Ahmed Tawfik

Chapter 17 Polyurethane as an Isolation for Covered Conductors 381

Žiga Voršič

Section 4 Bio-Based Polyurethanes 407

Chapter 18 Seed Oil Based Polyurethanes: An Insight 409

Eram Sharmin, Fahmina Zafar and Sharif Ahmad
 Contents XI

Chapter 19 Polyglucanurethanes: Cross-Linked Polyurethanes

Based on Microbial Exopolysaccharide Xanthan 431
Nataly Kozak and Anastasyia Hubina

Chapter 20 Biobased Polyurethane from

Palm Kernel Oil-Based Polyol 447
Khairiah Haji Badri
Preface

Polyurethane [PU] is a class of polymers built up of carabamate linkages, which

provide special characteristics to the material. It is the outcome of pioneering research
work of Otto Bayer and his coworkers in 1937 at I.G. Farben laboratories, in
Leverkusen, Germany. Initial PU consisted of foams and fibres, while today,
innovations and researches in the past decades have brought colossal changes in the
world of PU. Attention is focussed on green PU such as from non-isocyanate
technologies, from biobased polyols and isocyanates, PU hybrids, PU composites and
so on. PU find versatile applications as foams, adhesive, surface coatings, and sealants,
to name a few. The enchanting and worthy world of PU beckoned us to bring forth the
book titled “Polyurethane”. The book is divided into three sections: structures,
properties and characterization of PU, applications of PU and a separate section on
Biobased PU, covering the research and development in these areas. Each contributed
chapter handles new and interesting topics introducing the reader to the wider known
and unknown applications of PU such as PU for medical, urological stenting practice,
carriers of antituberculosis drugs, orthopaedic, fuel binder, extraction of metals,
grouting technologies, crashworthiness, isolation for covered conductor, treatment of
industry wastewater, cast elastomers, alkanolamide PU coatings and foams, and
others. The book aims to cater a larger audience comprising of readers from polymer
chemistry, materials chemistry, and industrial chemistry.

It is an immense pleasure to see the book “Polyurethane” in its final shape; the credit
goes together to the authors, contributors, and the technical staff of InTech Open
Access Publisher, particularly, to Mrs. Marija Radja and Mr. Vedran Greblo, Editor
Relations Consultants, the funding agency Council of Scientific and Industrial
Research, New Delhi, India for Senior Research Associateship (Under Scientists’ Pool
Scheme, CSIR). Without their help and dedication, it would be impossible to have this
book published so efficiently. Time has come to thank them all.

Eram Sharmin and Fahmina Zafar, Ph.D.

Senior Research Associates, Department of Chemistry,
Jamia Millia Islamia, A Central University, New Delhi,
India
 Section 1

Introduction
 Chapter 1

Polyurethane: An Introduction

Eram Sharmin and Fahmina Zafar

Additional information is available at the end of the chapter

[Link]

1. Introduction
1.1. History of polyurethane
The discovery of polyurethane [PU] dates back to the year 1937 by Otto Bayer and his
coworkers at the laboratories of I.G. Farben in Leverkusen, Germany. The initial works
focussed on PU products obtained from aliphatic diisocyanate and diamine forming
polyurea, till the interesting properties of PU obtained from an aliphatic diisocyanate and
glycol, were realized. Polyisocyanates became commercially available in the year 1952, soon
after the commercial scale production of PU was witnessed (after World War II) from
toluene diisocyanate (TDI) and polyester polyols. In the years that followed (1952-1954),
different polyester-polyisocyanate systems were developed by Bayer.

Polyester polyols were gradually replaced by polyether polyols owing to their several
advantages such as low cost, ease of handling, and improved hydrolytic stability over the
former. Poly(tetramethylene ether) glycol (PTMG), was introduced by DuPont in 1956 by
polymerizing tetrahydrofuran, as the first commercially available polyether polyol. Later,
in 1957, BASF and Dow Chemical produced polyalkylene glycols. Based on PTMG and
4,4’-diphenylmethane diisocyanate (MDI), and ethylene diamine, a Spandex fibre called
Lycra was produced by Dupont. With the decades, PU graduated from flexible PU foams
(1960) to rigid PU foams (polyisocyanurate foams-1967) as several blowing agents,
polyether polyols, and polymeric isocyanate such as poly methylene diphenyl
diisocyanate (PMDI) became available. These PMDI based PU foams showed good
thermal resistance and flame retardance.

In 1969, PU Reaction Injection Moulding [PU RIM] technology was introduced which
further advanced into Reinforced Reaction Injection Moulding [RRIM] producing high
performance PU material that in 1983 yielded the first plastic-body automobile in the
United States. In 1990s, due to the rising awareness towards the hazards of using chloro-

©©2012
2012Sharmin
Sharminand
andZafar,
Zafar,licensee InTech.
licensee ThisThis
InTech. is aispaper distributed
an open under the
access chapter terms of the
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License Attribution License ([Link]
([Link] which
which permits unrestricted use, permits
unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.
distribution, and reproduction in any medium, provided the original work is properly cited.
4 Polyurethane

alkanes as blowing agents (Montreal protocol, 1987), several other blowing agents
outpoured in the market (e.g., carbon dioxide, pentane, 1,1,1,2-tetrafluoroethane, 1,1,1,3,3-
pentafluoropropane). At the same time, two-pack PU, PU- polyurea spray coating
technology came into foreplay, which bore significant advantages of being moisture
insensitive with fast reactivity. Then blossomed the strategy of the utilization of vegetable
oil based polyols for the development of PU. Today, the world of PU has come a long way
from PU hybrids, PU composites, non-isocyanate PU, with versatile applications in
several diverse fields. Interests in PU arose due to their simple synthesis and application
protocol, simple (few) basic reactants and superior properties of the final product. The
proceeding sections provide a brief description of raw materials required in PU synthesis
as well as the general chemistry involved in the production of PU.

2. Raw materials
PU are formed by chemical reaction between a di/poly isocyanate and a diol or polyol,
forming repeating urethane groups, generally, in presence of a chain extender, catalyst,
and/or other additives. Often, ester, ether, urea and aromatic rings are also present along
with urethane linkages in PU backbone.

2.1. Isocyanates
Isocyanates are essential components required for PU synthesis. These are di-or
polyfunctional isocyanates containg two or more than two –NCO groups per molecule.
These can be aliphatic, cycloaliphatic, polycyclic or aromatic in nature such as TDI, MDI,
xylene diisocyanate (XDI), meta-tetramethylxylylene diisocyanate (TMXDI),
hydrogenated xylene diisocyanate (HXDI), naphthalene 1,5-diisocyanate (NDI), p-
phenylene diisocyanate (PPDI), 3,3’-dimethyldiphenyl-4, 4’-diisocyanate (DDDI), 1,6
hexamethylene diisocyanate (HDI), 2,2,4-trimethylhexamethylene diisocyanate (TMDI),
isophorone diisocyanate (IPDI), 4,4’-dicyclohexylmethane diisocyanate (H12MDI),
norbornane diisocyanate (NDI), 4,4’-dibenzyl diisocyanate (DBDI). Figure 1 shows
examples of some common isocyanates.

The isocyanate group bears cumulated double bond sequence as R-N=C=O, wherein
the reactivity of isocyanate is governed by the positive character of the carbon atom
(Scheme 1), which is susceptible to attack by nucleophiles, and oxygen and nitrogen by
electrophiles.

If R is an aromatic group, the negative charge gets delocalized into R (Scheme 2), thus, the
aromatic isocyanates are more reactive than aliphatic or cycloaliphatic isocyanates. In case of
aromatic isocyanates, the nature of the substituent also determines the reactivity, i.e.,
electron attracting substituents in ortho or para position increase the reactivity and electron
donating substituents lower the reactivity of isocyanate group. In diisocyanates, the
presence of the electron attracting second isocyanate increases the reactivity of the first
 Polyurethane: An Introduction 5

isocyanate; para substituted aromatic diisocyanates are more reactive that their ortho
analogs primarily attributed to the steric hindrance conferred by the second –NCO
functionality. The reactivities of the two-NCO groups in isocyanates also differ with respect
to each other, based on the position of –NCO groups. For example, the two-NCO groups in
IPDI differ in their reactivity due to the difference in the point of location of –NCO groups.
TMXDI serves as an aliphatic isocyanate since the two isocyanate groups are not in
conjugation with the aromatic ring. Another isocyanate of increasing interests is vinyl
terminated isocyanate since along with the –NCO group, the extra vinyl group provides
sites for crosslinking (Figure 2).

OCN NCO CH3 NCO

OCN NCO

H3C

2,4-TDI 2,6-TDI NDI

NCO

NCO
OCN
OCN NCO

4, 4'-MDI HDI

OCN NCO
OCN NCO

IPDI H12MDI

Figure 1. Common isocyanates

R N C O R N C O

or

R N C O R N C O

Scheme 1. Resonance in isocyanate

6 Polyurethane

N C O N C O

N C O

Scheme 2. Resonance in aromatic isocyanate

NCO
NCO

OCN

TMXDI Vinyl terminated isocyanate

Figure 2. Other isocyanates

Polyisocyanates such as triisocyanates derived as TDI, HDI, IPDI adducts with

trimethylolpropane (TMP), dimerized isocyanates termed as uretdiones, polymeric MDI,
blocked isocyanates (where alcohols, phenols, oximes, lactams, hydroxylamines are blocking
agents) are also used in PU production. Lately, fatty acid derived isocyanates are also
prepared via Curtius rearrangement with view to produce entirely biobased PU. The choice
of the isocyanate for PU production is governed by the properties required for end-use
applications. To prepare rigid PU, aromatic isocyanates are chosen, however, PU derived
from these isocyanates show lower oxidative and ultraviolet stabilities.

2.2. Polyols
Substances bearing plurality of hydroxyl groups are termed as spolyols. They may also
contain ester, ether, amide, acrylic, metal, metalloid and other functionalities, along with
hydroxyl groups. Polyester polyols (PEP) consist of ester and hydroxylic groups in one
backbone. They are generally prepared by the condensation reaction between glycols, i.e.,
ethylene glycol, 1,4-butane diol, 1,6-hexane diol and a dicarboxylic acid/anhydride (aliphatic
 Polyurethane: An Introduction 7

or aromatic). The properties of PU also depend upon the degree of cross-linking as well as
molecular weight of the starting PEP. While highly branched PEP result in rigid PU with
good heat and chemical resistance, less branched PEP give PU with good flexibility (at low
temperature) and low chemical resistance. Similarly, low molecular weight polyols produce
rigid PU while high molecular weight long chain polyols yield flexible PU. An excellent
example of naturally occurring PEP is Castor oil. Other vegetable oils (VO) by chemical
transformations also result in PEP. PEP are susceptible to hydrolysis due to the presence of
ester groups, and this also leads to the deterioration of their mechanical properties. This
problem can be overcome by the addition of little amount of carbodiimides. Polyether
polyols (PETP) are less expensive than PEP. They are produced by addition reaction of
ethylene or propylene oxide with alcohol or amine starters or initiators in presence of an
acid or base catalyst. PU developed from PETP show high moisture permeability and low
Tg, which limits their extensive use in coatings and paints. Another example of polyols is
acrylated polyol (ACP) made by free radical polymerization of hydroxyl ethyl
acrylate/methacrylate with other acrylics. ACP produce PU with improved thermal stability
and also impart typical characteristics of acrylics to resultant PU. These PU find applications
as coating materials. Polyols are further modified with metal salts (e.g., metal acetates,
carboxylates, chlorides) forming metal containing polyols or hybrid polyols (MHP). PU
obtained from MHP show good thermal stability, gloss and anti-microbial behavior.
Literature reports several examples of VO based PEP, PETP, ACP, MHP used as PU coating
materials. Another example is VO derived fatty amide diols and polyols (described in detail
in chapter 20 Seed oil based polyurethanes: an insight), which have served as excellent
starting materials for the development of PU. These PU have shown good thermal stability
and hydrolytic resistance due to the presence of amide group in the diol or polyol backbone.

2.3. Additives
Along with a polyol and an isocyanate, some additives may also be required during PU
production, primarily to control the reaction, modify the reaction conditions, and also to
finish or modify the final product. These include catalysts, chain extenders, crosslinkers,
fillers, moisture scavengers, colourants and others. In PU production, catalysts are added to
promote the reaction to occur at enhanced reaction rates, at lower temperatures, for
deblocking the blocked isocyanates, for decreasing the deblocking and curing temperatures
and times. A number of aliphatic and aromatic amines (e.g., diaminobicyclooctane-
DABCO), organometallic compounds (e.g., dibutyltin dilaurate, dibutyltin diacetate), alkali
metal salts of carboxylic acids and phenols (calcium, magnesium, strontium, barium, salts of
hexanoic, octanoic, naphthenic, linolenic acid) are used as catalysts. In case of tertiary
amines, their catalytic activity is determined by their structure as well as their basicity;
catalytic activity increases with increased basicity and decreases with the steric hindrance on
the nitrogen atom of amine. They promote their catalytic action by complex formation
between amine and isocyanate, by donating the electrons on nitrogen atom of tertiary amine
to the positively charged carbon atom of the isocyanate. Metal catalysts bear superiority
8 Polyurethane

over tertiary amines because they are comparatively less volatile and less toxic. Metals
catalyse the isocyanate-hydroxyl reaction by complex formation with both isocyanate and
hydroxyl groups. The positive metal centre interacts with electron rich oxygen atom of both
the isocyanate and hydroxyl groups forming an intermediate complex, which by further
rearrangement results in the formation of urethane bonds. Difunctional low molecual
weight diols (ethylene glycol, 1,4-butanediol, 1,6-hexanediol), cyclohexane dimethanol,
diamines, hydroxyl-amines (diethanolamine and triethanolamine) are used as chain
extenders in PU synthesis while those with functionality 3 or > 3 are used as crosslinkers.
Since isocyanates are too sensitive to moisture or water even in traces, moisture scavengers,
which react more readily with water than an isocyanate, are incorporated to cut
off/eliminate the involvement of water during PU synthesis, e.g., oxazolidine derivatives,
zeolite type molecular sieves. Blowing agents are used to produce PU foams with cellular
structures by foaming process (e.g., hydrocarbons, CO2, hydrazine).

3. Chemistry of PU
PU are carbonic acid derivatives. The older term for them is an ester of a substituted
carbamic acid, polycarbamate, from carbamic acid. PU are formed by (i) the condensation
polymerization reaction of bischloroformates with diamine (Scheme 3) and (ii) addition
polymerization reaction of diisocyanates with di or polyfunctional hydroxy compounds, or
other compounds having a plurality of active hydrogen atom (Scheme 4). The latter method
is more important from the industrial point of view since in this method no by-product is
formed.

O O
O O
- HCl
+ H2N R' C R C R'
C R C
O O N N
Cl O O Cl NH2 H H n

Hydroxy compound wth

excess of Phosgene
Scheme 3. Reaction of bischloroformate with diamine

O O

C R C R'
OCN R NCO + R'
HO OH N N O O
H H
n
Scheme 4. Reaction of diisocyanate with di or poly hydroxy compound

The isocyanate reaction offers the possibility of producing tailor-made polymeric product
ranging from fibres to rubber. Generally, the isocyanate reactions are divided into two
 Polyurethane: An Introduction 9

classes, (a) addition (primary and secondary) reaction with compound containing active
hydrogen (Schemes 5 and 6), (b) self-addition reaction (Scheme 7). In some of the reactions,
CO2 is released which assists in the formation of PU foams.

Scheme 5. Primary addition reactions of isocyanate with (a) amine, (b) water, (c) alcohol, (d) carboxylic
acid, (e) urea.
10 Polyurethane

O
H O H N

R N C O + N C O
N C

O R O
(a)
Allophanate

HN
O
H N C
+
N NH N C O
H
R O
(b) Biuret

O
O
H N C
C
+ N C
N
H
R O
(c) Acylurea

Scheme 6. Secondary addition reactions of isocyanate with (a) polyurethane, (b) polyurea and (c)
polyamide

Wurts in 1848 discovered the basic reaction of isocyanate (Scheme 4). He found that
isocyanates having the structure R-N=C=O, where R= alkyl or aryl group, react rapidly at
room temperature with compounds containing active hydrogen atoms, like amine, water,
alcohol, carboxylic acid, urethanes and ureas (Scheme 8).

It is observed that a linear PU is formed when a diisocyanate react with diol whilst
branched or cross-linked PU results with the reaction of polyhydric compound (polyol). The
branched or cross- linked PU are also formed when a compound containing three or more
isocyanate groups reacts with a diol; however, this approach is of limited commercial
importance.
 Polyurethane: An Introduction 11

C
ine
Pyrid R N N R

C
2 R N C O

O Uretidione

R N C N R + CO 2

Carbodiimide

R C R
Strong base N N
3 R N C O
e.g. NaOMe C C
O N O

Isocyanurate

Very strong base C

x N C O
N
Low temp.
x

Polyamide

Scheme 7. Self -addition reactions of isocyanate

12 Polyurethane

H X R'

R N C O + R' X H N C

R O

Scheme 8. Reaction of isocyanate with active hydrogen compound

4. Mechanism
The reaction of an isocyanate with active hydrogen compounds is carried out with or
without a catalyst. The self-addition reactions of isocyanates do not usually proceed as
readily as reactions with active hydrogen compounds.

4.1. Reaction in the absence of a catalyst

The active compound itself acts catalytically in the reaction as follows (Scheme 9).

O
O
R N C
R N C O
R N C
+ X H
X H
R' X H R'
R'

H X R'
H X R'
+ R' X H
R N C O N C

R' X H R O
+

R' X H

Scheme 9. Isocyanate reaction in the absence of a catalyst

As given in Scheme 9, in the reactions proceeding in the absence of a catalyst, the

electrophilic carbon of the isocyanate is attacked by the nucleophilic centre of the active
hydrogen compound; hydrogen is added to –NCO group. The reactivity of the –NCO
 Polyurethane: An Introduction 13

groups is increased due to the presence of the electron withdrawing groups, and
decreases by the electron donating groups. While the aromatic isocyanates are more
reactive than the aliphatic isocyanates, steric hindrance at –NCO or HXR’ groups reduce
the reactivity.
The order of reactivity of active hydrogen compounds with isocyanates in uncatalyzed
systems is as follows:

Aliphatic amines> aromatic amines> primary alcohols> water>secondary alcohol> tertiary

alcohol> phenol> carboxylic acid> ureas> amides>urethanes.

4.2. Reaction in the presence of a catalyst

The isocyanate reactions of class (a) are also extremely susceptible to catalysis. The various
isocyanate reactions are influenced to different extents by different catalysts. Many
commercial applications of isocyanates utilize catalysed reactions. Tertiary amines, metal
compounds like tin compounds (as mentioned earlier in the chapter) are most widely used
catalysts for the reaction (Schemes 10 and 11). The mechanisms are similar to that of the
uncatalyzed reaction (Scheme 9).

The tertiary amines and metal salts catalyse the reaction as follows:

O
O
R N C
R N C O
R N C
+
R'' : N
3
R'' : N R'' : N
3 3

H X R'
H X R'
+ R' X H
R N C O N C

R O
R''3 : N
+

R'' : N
3

Scheme 10. Tertiary amine catalysed reaction

14 Polyurethane

+ R' X H
R N C O R N C O R N C O
+
M M
MX 2 X
X 2
2

H X R'

R N C O R N C O R N C O N C

H X M H X M H X M R O
X X +
X 2 2
2 R' R'
R'
MX 2

Scheme 11. Metal salts catalysed reaction

The catalytic activity of amines closely parallels to the base strength of the amines except
when steric hindrance becomes pronounced. This catalyst is also effective for self-addition
reactions while metal salt compounds generally have less influence; tin compounds are
particularly poor catalysts in these reactions.

5. Hazards
Although PU are chemically inert in their fully reacted form , the risks of asthmatic symptoms
arise on human exposure even in smaller concentrations due to the volatility associated with
isocyanates arise the risk of asthmatic symptoms on 12 human exposure, even in smaller
concentrations. On exposure to flames, hazards of ignition are feared. Isocyanates may also be
sensitive on our skin. Some isocyanates may also be anticipated as carcinogens. Thus, persons
working with isocyanates must be equipped with proper protection devices such as gloves,
masks, respirators, goggles, and others, as precautionary measures.

6. Conclusion
PU are thermoplastic and thermoset in nature. The type, position, and structure of
both the isocyanate and polyol determine the progress of PU forming reactions as well as
their properties and end-use applications. Hydrogen bonding also plays a key role
in determining the properties of final PU product. Due to the associated health hazards,
complete precautions are necessary while working with isocyanates. PU are available
as one-pack or two-pack PU. PU dispersions, waterborne PU, PU Interpenetrating
 Polyurethane: An Introduction 15

Networks PU, hybrids and composites are used in various applications such as paints and
coatings, adhesives, sealants, foams, absorbents, flame retardants, fuel binders, in
automobiles, in biomedical applications (urological stenting practices, carriers of
antituberculosis drugs, orthopaedics), extraction of metals, grouting technologies,
crashworthiness, treatment of industry wastewater, cast elastomers, and others as also
discussed in proceeding chapters.

Author details
Eram Sharmin and Fahmina Zafar*
Materials Research Laboratory, Department of Chemistry,
Jamia Millia Islamia (A Central University), New Delhi, India

Acknowledgement
Dr Fahmina Zafar (Pool Officer) and Dr Eram Sharmin (Pool Officer) acknowledge Council
of Scientific and Industrial Research, New Delhi, India for Senior Research Associateships
against grant nos. 13(8385‐A)/2010‐POOL and 13(8464‐A)/2011‐10 POOL, respectively. They
are also thankful to the Head, Department of Chemistry, Jamia Millia Islamia (A Central
University), for providing support to carry out the work.

7. References
Chattopadhyay D.K., Raju K.V.S.N. Structural Engineering of Polyurethane Coatings
for High Performance Applications. Progress in Polymer Science 2007; 32: 352–
418.
Desroches M., Escouvois M., Auvergne R., Caillol S., Boutevin B. From Vegetable Oils to
Polyurethanes: Synthetic Routes to Polyols and Main Industrial Products. Polymer
Reviews 2012; 52 (1): 38–79.
Lligadas G., Ronda J.C., Galia`M., Cadiz V. Plant Oils as Platform Chemicals for
Polyurethane Synthesis:Current State–of–the–Art. Biomacromolecules 2010; 11: 2825–
2835.
Malcolm P S. Polymer Chemistry An Introduction. 3rd Edn. New York: Oxford University
Press, Oxford; 1999.
Nylen P., Sunderland E. Modern Surface Coatings. London: John Wiley & Sons;
1965.
Paul, S. Surface Coating–Science and Technology. New York: John Wiley & Sons;
1985.
Petrović Z. S. Polyurethanes from Vegetable Oils. Polymer Reviews 2008; 48:109–
155.

* Corresponding Author
16 Polyurethane

Pfister D.P., Xia Y., Larock R.C. Recent Advances in Vegetable Oil–based Polyurethanes.
Chem Sus Chem 2011; 4(6):703–17.
Saunders K J. Organic Polymer Chemistry. 2nd Edn. New York: Chapman & Hall; 1981.
[Link] (accessed on 11th July 2012)
 Section 2

Synthesis and Properties

 Chapter 2

New Liquid Crystalline Polyurethane

Elastomers Containing Thiazolo [5,4d]
Thiazole Moiety: Synthesis and Properties

Issam Ahmed Mohammed and Mohamed Rashidah Hamidi

Additional information is available at the end of the chapter

[Link]

1. Introduction
Originally there are three states of matter; solid, liquid and gas. The emergence of an exotic
and extraordinary form of matter, which is known as liquid crystal has been considered as
one of the major breakthrough in polymer science. Liquid crystal can be defined as an
intermediate of solid (crystal) and liquid (Knight & Vollrath, 2002) where the molecules
have the capabilities to flow like a liquid (mobility) as well as possessing the common
property associated to solid, which is the degree of order (Doldeny & Alder, 1998). In
addition, liquid crystal materials are self assembling by nature and can offer a very elegant
and effective way of controlling and tuning the physical properties that ultimately define
the self-organizing and self assembly process (Zhang [Link]., 2008). One of the exciting
developments involving this unique material is the introduction of liquid crystalline
behavior in polyurethane elastomers (PUE) where the first of this kind was synthesized by
Iimura in 1981 (Lin [Link]., 2001).
Polyurethane [PU] is one of the most versatile class of polymeric materials known today.
Wide variety of structural changes can be produced with the different hydroxyl compounds
and isocyanates leading to a wide spectrum of properties and applications (Yeganeh [Link].,
2007). It contains a high concentration of polar groups, in particular the urethane group,
resulting from isocyanate-hydroxyl reactions. The interactions between these polar entities
are of great importance in determining the properties of PU of all types (Lee [Link]., 1999)
besides the composition and characteristic of the polyol, diisocyanates and the additives
utilized during the synthesis (Pachecho [Link]., 2009).

High toughness, excellent wear and tear properties and good oil resistance are among the
advantages displayed by PUE (Wright & Cumming, 1969). Moreover, not only they have
good mechanical and physical properties, PUE are also benefited with biocompatibility

©©2012
2012Mohammed
Mohammedand andHamidi,
Hamidi,licensee InTech.
licensee This
InTech. is aispaper
This distributed
an open under the
access chapter terms of the
distributed Creative
under the
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([Link] which
which permits unrestricted use,
permits unrestricted use, distribution, and reproduction in any medium, provided the original work is
distribution, and reproduction in any medium, provided the original work is properly cited.
properly cited.
20 Polyurethane

characteristics for biomedical applications (Barikani [Link]., 2009). Despite all the great
aforementioned properties, modifications and improvements are done to conventional PUE
in order to meet the qualities in more advanced applications.

Diisocyanates, polyol and low molecular weight diamine or diol (chain extender) are the basic
building blocks of conventional PUE (Yeganeh & Mehdizadeh, 2009). In order to synthesize
liquid crystal polyurethane elastomers (LCPUE), the low molecular weight diamine or diol
used in conventional PUE was substituted with the mesogenic unit. Incorporation of
geometrically anisotropic moieties (mesogenic unit) within polymer architecture can drive the
formation of liquid crystalline phase from strictly steric repulsion considerations (Abe &
Ballauf, 1991; Rowan & Mather, 2007). Furthermore, the insertion of mesogenic unit in the
backbone of PUE will impart unique physical properties to the polymer and also improve its
mechanical, optical and electrical characteristics (Jia [Link]., 1996).
Various mesomorphic behaviors are exhibited with different types of mesogenic units in
preparation of LCPUE. In this research work, mesogens consumed were thiazolo [5.4d]
thiazoles based and it is known as an important class of biycyclic aromatic molecule
comprising two fused thiazole rings (Knighton [Link]., 2010). Thiazolothiazole rigid fused ring
can enhance the rigidity of the polymer and the conjugation (Osaka [Link], 2007) which makes
it a best candidate to be part of the hard segment in the LCPUE network. The hard segments
consisted of either 2,5-bis(4-hydroxyphenyl) thiazolo-[5,4d] thiazole or 2,5-bis(4-hydroxy-3-
methoxyphenyl) thiazolo [5,4d] thiazole and 4,4’- methylene diphenyl diisocyanate (MDI).
As for the soft segments, polyethylene glycol (PEG) 1000, 2000 and 3000 were involved.
The ultimate aim of this work is to synthesize new LCPUE with the presence of thiazolo-
[5,4d] thiazole as a chain extender. Study and analysis were carried out to determine the
effects and consequences of the introduction of thiazolo-[5,4d] thiazole moiety and the
influence of various lengths of polyols on the properties of LCPUE.

2. Experimental
2.1. Materials
Vanillin and 4, 4’-methylene diphenyl diisocyanate (MDI) were purchased from Aldrich Co.
(United States). Rubeanic Acid (dithiooxiamide) and 4-hydroxybenzaldehyde were obtained
from MERCK Co. (Germany). Polyethylene glycol with molecular weight of 3000, 2000 and
1000 (PEG: Mn= 3000, 2000 and 1000) were purchased from Fluka Chemica (Switzerland).
All the chemicals were utilized as received without any further purification. N,N-
Dimethylformamide purchased from Aldrich (United States) was distilled over Calcium
Hydride (CaH2) through vacuum distillation before being used.

2.2. Synthesis of monomers and polymers

2.2.1. Synthesis of 2,5-bis(4-hydroxyphenyl)thiazolo-[5,4d] thiazole (I)
Briefly, 3 g (25 mmol) of dithiooxamide (Rubeanic acid) and 15 g (123 mmol) of 4-
hydroxybenzaldehyde with the presence of 9 g (97 mmol) of phenol were charged all at once
 New Liquid Crystalline Polyurethane Elastomers
Containing Thiazolo [5,4d] Thiazole Moiety: Synthesis and Properties 21

in a 500 ml round bottom flask fitted with condenser and left to be refluxed for 2h. Precipitates
were obtained by pouring the hot mixtures to the cold water. Subsequently, the yield was
filtered off and washed with ethanol followed by ether. The product obtained was dried at
70oC in a vacuum oven for 24 hours. Recrystallization from cyclohexanone was performed
giving an orange-yellowish powder. Yield: 35% with melting point 364oC. Fourier transform
infrared (FTIR; KBr, cm-1): 3492 (-OH), 1606 (C=N), 1596 (C=C), 855 (p-substituted benzene). 1H-
NMR (400 MHz, DMSO-d6 ppm): δH 7.12 (m, aromatic protons), 9.8 (s, -OH). Elemental
analysis: Found: C, 59.16; H, 3.28; N, 8.84, C16H10N2O2S2 Calc.: C, 58.89; H, 3.09, N, 8.59.

2.2.2. Synthesis of 2,5-bis(4-hydroxy-3-methoxyphenyl) thiazolo [5,4d] thiazole (II)

The same procedure was applied to the synthesis of 2,5-bis(4-hydroxy-3-methoxyphenyl)
thiazolo [5,4d] thiazole except that 4-hydroxybenzaldehyde was substituted with vanillin.
Orange-yellowish powder was obtained as the end product. Yield: 26% with the melting
point of 259oC. Fourier transform infrared (FT-IR; KBr disc): 3534 cm-1 (OH), 1608 cm-1(C=N),
1510 cm-1 (C=C), 842 cm-1 (-CH out of plane). 1H-NMR (400 MHz, DMSO-d6 ppm): δH 7.09 (m,
aromatic protons), 9.5 (s, -OH) and 3.87 (s, OCH3). Elemental analysis: Found: C, 55.60; H,
4.03; N, 6.89, C18H14N2O4S2 Calc.: C, 55.95; H, 3.62, N, 7.25.

2.2.3. Synthesis of liquid crystalline polyurethane elastomers (LCPUE)

Preparation of LCPUE was achieved by two steps solution polymerization reaction, where
isocyanate terminated pre-polymer was synthesized initially in the first stage. To produce
pre-polymer, 0.01 mol of PEG (Mw = 1000, 2000, and 3000) and 0.02 mol of MDI were mixed
in 500ml of reactor flask equipped with condenser, thermometer, nitrogen inlet and
mechanical stirrer. The mixture was allowed to be stirred and heated for 4h at 70oC in the
presence of 15 ml of DMF as solvent and nitrogen gas was kept flowing to provide inert
atmosphere. The reaction was followed by chain extension process, using either compound
(I) or (II), where the chain extender was added dropwise within 1h to complete the
formation of LCPUE. Subsequently, the temperature was increased to 100oC and the reaction
continued for another 9 hr. The hot viscous solution was then poured into 200ml of cold
water for precipitation, before subjected to filtration. Later, the filtered product was washed
with ethanol several times and finally with ether, before being dried overnight in a vacuum
oven at 60o C.

2.4. Measurements
100mg mixture of samples and KBr (grounded) were pressed into translucent disc before
being subjected to Nicolar Avatar Model 360 Fourier Transform infrared spectrometer
devices to obtain FT-IR spectra. Data was collected in the range of 4000-400cm-1. 1H-NMR
and 13C-NMR spectra were obtained using Bruker 400 MHz NMR spectrometer consuming
DMSO-d6 as solvent and TMS as internal standard. Thermal stability of LCPUE was
determined by thermogravimetric analyzer (Perkin Elmer Pyris series 6) under nitrogen
purge and with 10oC/min of heating rate and the heating was done up to 800oC. Liquid
crystalline behavior was verified by means of differential scanning calorimetry (DSC) to
22 Polyurethane

observe the behavior of polymers such as glass transition point (Tg), melting point (Tm) and
isotropic temperature (Ti). It was conducted utilizing Perkin Elmer Pyris Series 7 thermal
analyzer under Nitrogen flux at 100C/min rate of heating. Textures of mesomorphic phases
were displayed by Nikon Eclipse E600 polarized microscope equipped with MS600 Linkam
Hot stage and SONY CCD-IRIS Color Video Camera. The heating rate was 5oC/min and
10oC/min for the cooling rate. Sample was placed between two thin round glasses and it was
then transferred onto microscope fitted with the hot stage to be analyzed. Siemens X-ray
Diffractometer model D5000 equipped with a CuKα target at 40KV and 40mA was used in
obtaining X-ray scattering curve. Tensile strain properties of LCPUE films were measured
by Instron Testing instrument at a constant speed of 500mm/min (speed) where the
measurements were performed at room temperature. Brookfield viscometer was used to
measure the fluid viscosity where suitable spindle and speed were chosen and it was also
performed at room temperature.

3. Results and discussion

3.1. Preparation of chain extender
The preparation of 2,5-bis(4-hydroxyphenyl)thiazolo-[5,4d] thiazole and 2,5-bis(4-hydroxy-
3-methoxyphenyl) thiazolo [5,4d] thiazole were conducted according to the reaction shown
in Scheme 1. The starting reagent involved for the synthesis of both the compounds were
rubeanic acid and either 4-hydroxybenzaldehyde or vanillin with the presence of phenol.
Subsequently, both chain extenders prepared were being used in the preparation of LCPUE.
Identification of the chemical structures of the aforementioned products was monitored
primarily with FT-IR spectroscopy and further confirmation was carried out by 1H-NMR
spectrophotometer.

Scheme 1. Preparation of Compound I and II

 New Liquid Crystalline Polyurethane Elastomers
Containing Thiazolo [5,4d] Thiazole Moiety: Synthesis and Properties 23

3.2. Polymer synthesis

LCPUE based on thiazolo [5,4d] thiazoles moiety were synthesized from long chain of diol
(PEG 3000, 2000 and 1000) with an excess of diisocyanate (MDI) via addition reaction to give
the terminal reactive group which results in the formation of ‘extended diisocyanate’ or
isocyanate pre-polymer. Then, 2,5-bis(4-hydroxyphenyl) thiazolo-[5,4d] thiazole [I] and 2,5-
bis(4-hydroxy-3- methoxyphenyl) thiazolo [5,4d] thiazole [II] were added acting as a chain
extender in order to convert the pre-polymer into long chain LCPUE. The general route for
the preparation of LCPUE was outlined in Scheme 2, yield and viscosity of LCPUE were
listed in Table 1 and the data showed that the range of the viscosities and yields obtained
were 10,744 to 40 692 cP and 76-87 %, respectively. Range of the viscosities obtained also
provides the information of the molecular weight of each polymer synthesized where high
value of viscosity indicates high molecular weight of the polymer produced and vice versa
(Bagheri & Pourmoazzen, 2008). In this case, all LCPUE samples displayed fairly high
molecular weight in accordance with the results demonstrated.

Scheme 2. General route for the preparation of LCPUE VI (a-c) and VII (a-c)

3.3. Structural elucidation

FT-IR was employed to verify functional groups of the pre-polymer, compound I and II,
and LCPUE. Prior to the formation of LCPUE which is referring to the pre-polymer state,
in the region of 2270 cm-1 a peak was observed which was assigned to –N=C=O-
24 Polyurethane

(diisocyanate) whereas according to the IR spectra of compound I and II, a peak was
found at 3492 cm-1 and 3334 cm-1 which corresponds to –OH functional group in the
chemical structure. The disappearance of both the bands of -N=C=O- in pre-polymer and –
OH of compound I and II, indicates the completion of the reaction of preparation of
LCPUE and this fact was also supported with the appearance of new absorption bands at
3356.84cm-1 ( N-H- stretching ) and 1782.5cm-1 (carbonyl group) which were attributed to
the urethane linkage, –NHCOO- (Zhang et al., 2008; Issam, 2007). Furthermore, the peak
at 2884.89 cm-1 was ascribed to –CH stretching, whereas the band representing C=C
aromatic can be found at 1598.59 cm-1. Figure 1 displayed the FTI-R spectrum of LCPUE
VIIa and based on the results obtained, the characteristic absorption bands of FT-IR
spectra for the other LCPUE were almost identical to one another. The fact that
differentiates LCPUE VI and LCPUE VII was the presence of the methoxy group and it
was proven in the FTIR spectrum of LCPUE VIIa, where a peak displayed at the region of
1024.27 cm-1 corresponded to the methoxy group.

Further confirmation of chemical composition of LCPUE produced was carried out by

means of Nuclear Magnetic Resonance spectroscopy (NMR). 1H-NMR spectrum of LCPUE
VIIa was illustrated in Figure.2. A singlet peak centered at 8.76 ppm was assigned to –
NHCOO- and this proved the formation of urethane linkage. The appearance of multiplet
peaks at 7.53-6.99 ppm and singlet peak at 3.87 ppm was attributed to the aromatic protons
and the protons in methoxy group, respectively. Aliphatic chain of polyol (PEG 1000) was
detected in the region of 1.23-1.64 ppm.

Figure 1. FTIR spectrum of LCPUE VIIa

 New Liquid Crystalline Polyurethane Elastomers
Containing Thiazolo [5,4d] Thiazole Moiety: Synthesis and Properties 25

Figure 2. 1H-NMR spectrum of LCPUE VIIa

Figure 3. 13 C-NMR spectra of LCPUE VIIa

Other than FT-IR and 1H-NMR analysis, 13C-NMR was performed in order to clarify the
structure of LCPUE prepared. 13C-NMR spectra portrayed in Figure.3 which represents
LCPUE VIIa shows that the formation of urethane linkage (NHCOO) was determined by the
26 Polyurethane

appearance of the peak at 173.4 ppm. The methylene group presence in the soft segment of
PEG can be seen as a sharp and intense peak at 25-29 ppm. More peaks can be observed at
117.8 to 158.7 ppm and 56.2 ppm where they were assigned to the aromatic carbons and the
carbon in methoxy group respectively. Significant peaks in all characterization analysis (FT-IR,
1H-NMR and 13C-NMR) were consistent and adequately provide the evidences to support the

fact that the reaction of all materials took place and LCPUE was successfully prepared.

3.4. Thermal and liquid crystalline behavior of polymers

The DSC analysis was conducted at a heating rate of 10oC to understand phase separation
behavior of all synthesized LPCUE where the transition occurs, observed under polarizing
optical microscope (POM) equipped with heating stage and the results obtained from both
measurements were listed in Table 1. Based on the DSC thermograms, upon heating, one
step transition and two endothermic peaks were detected where each of them indicates glass
transition (Tg), melting endotherm, (Tm) and isotropic endotherm (Ti) respectively, which is
also the evidence of the existence of mesophase. LCPUE derived from 2,5-bis(4-hydroxy-3-
methoxyphenyl) thiazolo [5,4d] thiazole have transition temperatures lower than those
derived from 2,5-bis(4-hydroxyphenyl)thiazolo-[5,4d]thiazole. Methoxy group, which acts
as a substituent attached to the phenyl ring has the capability to lower the melting and
isotropization temperature and caused thermal suppression of the molecule to occur (Al-
Dujaili [Link]., 2001). The fact was supported by the results illustrated in Fig.4 where it depicts
the DSC thermograms of LCPUE. LCPUE VIIa displayed melting point (Tm) at 164oC and
isotropization temperature (Ti) at 187oC whereas for LCPUE VIa, Tm was detected at 176oC
and Ti at 205oC. The substituent could also act to reduce the coplanarity of adjacent
mesogenic groups and increase the diameter or decrease the axial ratio of the mesogens [Li
and Chang, 1991]. Due to the higher range between Tm and Ti of LCPUE VIa, the thermal
properties of this polymer are higher and more stable compared to LCPUE VIIa. The types
of diisocyanates also contribute to the thermal behavior of LCPUE, where MDI based PU
was known for having better order of the rigid chain that approaches the decomposition
temperature, giving high melting point to the polymer produced (Jieh & Chou, 1996). As for
glass transition, it involves mobility of the chain segments and the Tg will be affected by the
mobility restriction on the chain segments, (Suresh [Link]., 2008) it therefore explains the
varying pattern of the Tg values displayed in Table 1. The decreasing values of Tg can be
observed as the length of soft segments increases, indicating that the long chain of polyol
gave great flexibility characteristics towards the polymer chains where less mobility
restrictions occurred and hence resulting in the lower Tg values.

POM was utilized to investigate the type of mesophase by displaying the phase transition
that occurred, subsequently providing the polarizing optical microphotographs of the target
compounds. The morphology observed on heating and transition temperatures obtained
were given in Figures 5 and 6 and the results were summarized in Table 1. It was revealed
that all LCPUE showed mesophases upon melting temperature where the thread texture of
the nematic phases can be seen. From the photographs taken by POM, the crystal to
mesophase transition occurred at temperature ranging from 129 to 181oC. The samples were
 New Liquid Crystalline Polyurethane Elastomers
Containing Thiazolo [5,4d] Thiazole Moiety: Synthesis and Properties 27

further heated after the crystal-nematic transition temperature, and resulted in the
disappearing of the texture when reaching the isotropization stage. There were no traces of
mesophase transition during the cooling process from POM indicating all samples
possessed thermotropic type of liquid crystal. Phase transition temperatures observed
through POM were found to be consistent with the corresponding DSC thermograms.

Figure 4. DSC traces of (a) LCPUE VIa (b) LCPUE VIIa

DSC POM
PEG MOLECULAR Yield Viscosity
SAMPLE Tg Tm Ti Tm Ti
WEIGHT (%) cP
(oC) (oC) (oC) (oC) (oC)

LCPUE VIa 1000 85 11 108 25.1 176 205 181 200

LCPUE VIb 2000 83 26 456 22.5 153 174 162 180

LCPUE VIc 3000 77 40 692 19.1 139 156 133 161

LCPUE VIIa 1000 76 10 744 15.2 164 187 170 193

LCPUE VIIb 2000 80 22 453 11.8 143 163 148 170

LCPUE VIIc 3000 87 39 981 10.4 125 142 129 149

Table 1. Thermal properties of LCPUE VI (a-c) and LCPUE VII (a-c) by DSC and POM
28 Polyurethane

Figure 5. Polarized optical images of (a) LCPUE VIa (181oC), (b) LCPUE VIb (162 oC) and (c) LCPUE
VIc (133 oC)

Figure 6. Polarized optical images of (a) LCPUE VIIa (170 oC), (b) LCPUE VIIb (148 oC) and (c) LCPUE
VIIc (129 oC)

X-ray diffraction analysis of LCPUE was conducted at room temperature to obtain

information on both the mesophase structure and crystallinity of LCPUE. The
measurements exhibited several peaks in the range of 2θ= 15 – 25o as observed in Figure 7
 New Liquid Crystalline Polyurethane Elastomers
Containing Thiazolo [5,4d] Thiazole Moiety: Synthesis and Properties 29

and this indicated semi crystalline character possessed by LCPUE. The results obtained in
above range also provide details related to the d-spacing of 3.56 and 4.92 Å, thus supporting
the characteristic of nematic liquid crystalline phase (Jeh & The, 1994) as displayed through
POM.

Figure 7. X-ray diffraction scales of LCPUE VI (a-c) and LCPUE VII (a-c)

Thermal stability of prepared LCPUE was investigated by thermogravimetric analysis

(TGA). Incorporation of liquid crystalline properties into the polymer structure would
enhance the thermal properties (Jahromi [Link]., 1994) and the theory has proved to be
applicable from the results obtained. This may be partly due to favorable interactions
between hard domain interface and the liquid crystalline phase. All synthesized LCPUE
possessed good thermal stabilities, however, PU elastomers eventually undergo thermal
degradation when exposed to high temperatures. Degradation process occurred in two step
pattern where the initial degradation occurs in the hard segment involving the urethane
linkages, while the second stage indicated the degradation of soft segments. TGA curves in
Figure 8 demonstrated the thermal degradation of all LCPUE prepared where 10% weight
loss of LCPUE occurred at about 315-341oC and the maximum degradation temperature was
in the range of 430-470oC, signifying a high thermal stability property. Furthermore, it can
be observed that LCPUE VIIc demonstrated the lowest degradation temperature among the
others and this proved that the length of polyethylene glycol (soft segment) influenced the
thermal stability of LCPUE where the order of LCPUE due to their thermal stability can be
arranged as LCPUE VIa>VIIa>VIb>VIIb>VIc>VIIc.
30 Polyurethane

Figure 8. TGA curve of LCPUE VI (a-c) and LCPUE VII (a-c)

3.5. Tensile properties

Table 2 demonstrates tensile properties of the synthesized LCPUE. As seen, all of the
polymers possessed good elastic properties with high elongation at break. Due to the data
listed, the higher the molecular weight of the soft segments, the greater the elongation at
break, but decrease of tensile strength and tensile modulus can be observed. When the
molecular weight of polyol increased, the number of urethane groups in the polyol chain was
reduced at the same time, and hence the number of rigid segments is lower, consequently, the
possible number of intermolecular hydrogen bonds goes down in which –NH and C=O
groups are active (Kro & Pitera, 2008). However, the presence of enhanced rigid and high
aspect ratio mesogenic unit as part of hard segment in the synthesized LCPUE, is able to give
both high strength and good elastic properties to LCPUE even with long soft segments, which

Tensile modulus Tensile strength Elongation at break

Sample
(Mpa) (Mpa) (%)
LCPUE VIa 17.1 28.2 290
LCPUE VIb 13.4 24.1 450
LCPUE VIc 11.5 19.9 570
LCPUE VIIa 17.5 28.3 330
LCPUE VIIb 13.7 24.3 460
LCPUE VIIc 11.2 19.8 560
Table 2. Mechanical properties of LCPUE VI (a-c) and LCPUE VII (a-c)
 New Liquid Crystalline Polyurethane Elastomers
Containing Thiazolo [5,4d] Thiazole Moiety: Synthesis and Properties 31

is unusual in conventional PUE (Jeong [Link]., 2000). Better phase separation will lead to good
mechanical properties; hence the introduction of the mesogens unit as chain extender into
LCPUE can be said to easily induce the matter (phase separation) to occur.

Author details
Mohammed Ahmed Issam and Hamidi Mohamed Rashidah
University Sains Malaysia, Malaysia

Acknowledgement
The author would like to thank University Sains Malaysia for short term grant
[Link].6311031 and the fellowship scheme for funding the research.

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 Chapter 3

The Modification of Polyurethanes

by Highly Ordered Coordination
Compounds of Transition Metals

Ruslan Davletbaev, Ilsiya Davletbaeva and Olesya Gumerova

Additional information is available at the end of the chapter

[Link]

1. Introduction
One of the ways to influence the chemical structure of polyurethanes is to use metal
complex systems based on transition metal chlorides for their synthesis. The significance of
this trend is conditioned by the ability of metal complexes to order the macromolecular
chains, as well as affect the electrical properties of polyurethanes (Davletbaeva et al., 1996,
2001).
The synthesis of metal coordination polymers is a way of affecting the processes of
crosslinking of macrochains; interchain and intraionic interactions; and, thereby, preparing
polymer materials with special properties (Dirk et al., 1986; Kingsborough & Swager, 1999;
Reynolds et al., 1985; Thuchide & Nishide, 1977; Wang & Reynolds, 1988). From the
standpoint of designing materials with electric and magnetic properties, it is promising to
form in a polymer matrix chains of transition metal ions bound by exchange interaction.
Conventional methods for the creation of interactions of this type in a polymer are primarily
based on the presence of certain units in a macromolecule, e.g., those including the
phthalocyanine and azomethine moieties. For example, metal atoms in metal
phthalocyanine liquid crystalline complexes are bound to one another by chloride bridges
and play the role of a spacer between phthalocyanine units, thus promoting overlap of
electronic orbitals of parallel molecules (Shirai et al., 1977, 1979).

As a result, the electric conductivity of metal-coordination polymers obtained on the basis of

these complexes is increased by a few orders of magnitude relative to undoped systems. The
coordination bonding of comb-like liquid crystalline polymers can also give rise to stacked
structures. Interaction between metal ions is revealed in such polymers, which is realized
owing to the association of metal ions in an indirect manner, through ester oxygen bridges.

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licensee InTech.
licensee ThisThis
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distribution, and reproduction in any medium, provided the original work is properly cited.
34 Polyurethane

However, this approach is seriously limited and cannot be used for the creation of stacked
metal-coordinated fragments in a disordered polymer matrix (Brostow, 1990; Carrher, 1981;
Serrano & Oriol, 1995).

Metal complex structuring is promising in terms of the influence on properties of

polyurethanes. The significance of this trend is conditioned by the ability of metal
complexes to order the macromolecular chains, as well as affect the electrical properties of
polyurethanes.

2. Coordination compounds based on the aromatic isocyanates and

copper (II) chloride for the synthesis of polyurethanes
In the early studies (Davletbaeva et al., 1998) devoted to imparting special properties to
polyurethanes by their coordination bonding, it was shown that the interaction of aromatic
isocyanates with copper chloride (CuCl2) in the acetone medium in the presence of trace
amounts of water proceeded as a sequence of chemical transformations including simple
addition and decomposition reactions, redox processes, and subsequent complexation (Fig. 1).

The ultimate products are polynuclear complexes of azoaromatic compounds, in which

copper ions occurring in two variable oxidation states are connected by chloride bridges
(Fig. 1). As it is seen from the structural formulas, some copper ions are stabilized at the
initial degree of oxidation due to the formation of heterovalent pairs connected by сhloride
bridges. Free isocyanate groups present in these compounds are able to react with oligodiols
of different nature. Polyurethanes obtained in such manner form polymer network by
coordination bonding of urethane groups and azogroups which are the part of a
macrochain.

It is shown that the chloride bridges are replaced by heteroatoms that are present in
polymer chains while metal ions are coordinatively bound to macromolecules to crosslink
them and, occurring in two interacting variable oxidation states, to form local centers of
exchange interactions. As a result of electron transfer from one local coordinated unit to
another, which is mediated by electron-donating groups, such as an ester group, the
conductivity of polyurethane increases by several orders of magnitude.

3. Reactions of aromatic isocyanates and urethane prepolymers with

coordination compounds of iron (III)
Further studies established that similar structural units could be formed even in the
polyurethane matrix itself as a result of its modification with metal complexes synthesized
for this purpose. A characteristic feature of these coordination compounds is the presence of
chloride-bridged metal ions in their structure. One of such crosslinking metal complex
system was prepared by the reaction of iron chloride (FeCl3) with ethanolamine (EA). It was
found that reactions involving aromatic isocyanates and EA in the coordination sphere of
the iron ion (III) led to the formation of azoaromatic compounds shown in figure 2.
 The Modification of Polyurethanes by Highly Ordered Coordination Compounds of Transition Metals 35

OCN OCN OCN

+ H2O
H3C NCO H3C N OH H3C NH2
- CO2
O

OCN OCN OCN

2 CuCl2 + .
2 H3C NCO 2 H3C NH2 2 H3C NH
+
-2 H
OCN OCN
+. +.
H3C N N CH3 H3 C N N CH3
H H -2 e H H -2 e
NCO NCO

OCN NCO
-
+ +
H3C N N CH3 + 2 Cu + 4 H + 4 Cl

Cl Cl
Cu
CH3
H3C CH3 Ar N N Ar O C
C O Ar N N Ar O C
CH3
H3C CH3
Cu
Cu
Cl Cl
Cl Cl
Cu
Cu CH3
CH3 Cl
Cl O C
O C
CH3
CH3
2
Cl Cl
Cu
CH3
H3C CH3
Ar N N Ar O C
C O Ar N N Ar O C
CH3
H3C CH3
Cu
Cu
Cl Cl
Cl Cl

CH3

where Ar - NCO

Figure 1. Formation of polynuclear complexes of azoaromatic compounds.

36 Polyurethane

Cl

NH3 Cl O CH2
2 ArNCO
2nFeCl3 4 nNH2 CH2 CH2 OH 2 H2C Fe CH2
CH2 O Cl NH3

Cl
Ar N C O
n

NH3 Cl O CH2
2 H2C Fe CH2 2 n NH2 (CH2)2 OH NH3 (CH2)2 O
CH2 O Cl NH3

Cl n


NH2 (CH2)2 OH 
NH2 (CH2)2 OH
 
Ar N C O Ar N C O

NH3 Cl O CH2 NH3 Cl O CH2

2 H C Fe CH2 H2C CH2
2 2 Fe
CH2 O Cl NH3 Cl NH3 HO CH2 CH2 NH CH O
CH2 O
Cl Cl
n n

Ar N N Ar Cl

NH3 Cl O CH2 NH3 Cl O CH2

H2 C Fe CH2 CH2
H2 C Fe
CH2 O Cl NH3 Cl NH3
CH2 O
Cl
Cl
n/2 n/2 ,

CH3 O C HN CH3
O
NCO , , NCO , NCO
where Ar -
Figure 2. Scheme of formation of azoaromatic compounds.

The continuation of this reaction is the formation of stack coordination compounds in which
metal ions form coordination bonds with azogroups (Fig. 3).
 The Modification of Polyurethanes by Highly Ordered Coordination Compounds of Transition Metals 37

Fe

Ar N N Ar

Fe

Ar N N Ar

Fe

Ar N N Ar

Fe

Ar N N Ar

Fe
,
where
NH3. Cl
Fe = CH
Fe
CH
O
Ar =
CH3

NCO , ,

O C HN CH3
O
NCO ,

NCO

Figure 3. Formation of stack coordination compounds.

Mössbauer studies of iron coordinated compounds reveal that the magnetic ordering is
observed at relatively high temperature (80 K). Mössbauer spectrum obtained in
transmission geometry at the temperature of the sample being equal to 80 K consists of two
components, namely, a doublet in the middle of the spectrum corresponding to the residues
of the initial FeCl3, dissolved in the matrix (less than 10% of the total area under the
spectrum) and the magnetically ordered component with a hyperfine field average value of
about 430 kE and the isomer shift, indicating a high-spin state of the Fe (III) ion. The absence
of partial component in the middle of the spectrum is caused by the long average size of
supramolecular structures chains (Fig. 4).
38 Polyurethane

The Mössbauer study confirms the columnar structure of the obtained metal complexes, the
possibility of their fixation in a flexible-chain polymer matrix containing electron-donating
groups, and the existence of magnetic ordering at temperatures below 70 K. Sizes of very
thin magnetic fields correspond to high-spin state of iron(III) ions (S=5/2).

It is known that to achieve the effect of magnetic ordering it is necessary that the chain of
interacting ions of iron (III) should be long enough and combine up to a few thousand ions.
The criterion for judging the length of the chain of magnetic ordered iron ions is relatively
high blocking temperature of supermagnetism and the barrier value of effective anisotropy
field. In our view, due to significant anisotropy in the structure of the complex the most
likely assumption is the increasing of the potential barrier with the increase of chain length.
The longer the chain, the higher its strength and the ability to build columns in a polymer
matrix, and the specific properties of the structured polymer matrix are more pronounced as
well.

Figure 4. The Mössbauer spectrum of metal complex system based on FeCl3 and EA.

The metal complex system is used for structuring urethane prepolymer containing terminal
isocyanate groups. Considering the high flexibility of the urethane prepolymer chain, it can
be assumed that the urethane groups will be coordinately bound with iron ions. The result
of this interaction should be the formation of columnar structures directly in the polymer
 The Modification of Polyurethanes by Highly Ordered Coordination Compounds of Transition Metals 39

matrix. Mössbauer studies of urethane prepolymer confirm these assumptions. The

resulting spectra are also of superparamagnetic nature at temperatures below 47K
(Davletbaeva et al., 2006).
When polyurethanes are modified by coordination compounds synthesized on the basis of
FeCl3 and EA, the minimum values of specific volume electrical resistance (about 108
Ohm∙sm) are recorded in the concentration area of 0,1% in terms of iron chloride. It should
be noted that the ions of iron (III) in the above reactions do not change the oxidation level.

4. Modification of urethane prepolymer by coordination compounds of

copper (I, II)
In one of the worked out highly ordered coordination compounds of transition metals for
modification of polyurethanes N,N'-Diethylhydroxylamine (DEHA) is used as a ligand
exhibiting the properties of a reducing agent. The most appropriate transition metal
compound is copper (II) chloride. Some of the Cu (II) ions interacting with DEHA reduce
the oxidation level and turn into Cu (I) (see Fig. 5).

CH3CH2 CH3CH2
CuCl2 2 ArNCO
NOH N O Cu 2 Cl H
CH3CH2 CH3CH HO(CH2)2NH(CH2)2OH

Ar N N Ar Cu 2 Cl

CH3 O C HN CH3
O
NCO , , NCO , NCO
where Ar -
Figure 5. The mechanism of interaction of copper (II) chloride with DEHA.

It was ascertained that the metal complex system showed the ability to interact with
aromatic isocyanates to form azoaromatic compounds. The result was the formation of
columnar coordination compounds (Fig. 6).
It was established, that metal-complex modification of polyurethanes results in the change
of their physicomechanical properties and spasmodic reduction (by 3-4 orders) of
volumetric and superficial electric resistance. The reduction of the specific bulk electrical
resistance by 3-4 orders is the most significant effect accompanying the metal-complex
binding of polyurethanes. In this case the electrical resistance falls spasmodically depending
on the nature of flexible chains of polyurethanes, the range of transition -metal ions
concentrations. If the content of metal-complex modifying agent is increased further, the
electrical resistance increases to some extent. The main role in the mechanism of charge
transmission in metal-coordinated polyurethanes is assigned to electron-donating groups
which are included in the structure of flexible chains of polyurethane matrix and the
presence of transition metal ions having two degrees of oxidation in it.
40 Polyurethane

Ar N N Ar CH3
Ar N N Ar
Cl Cu Cl NCO , ,
Cl Cu Cl
O C HN CH3
Ar N N Ar
Ar N N Ar O
NCO ,
Cl Cu Cl
Cl Cu Cl
Ar N N Ar
NCO
, where Ar -
Figure 6. Formation of columnar coordination compounds.

5. Modification of polyurethanes by heteronuclear complexes based on

molybdenum (V) and copper (II) chlorides
To study the effect of the coordination compounds structure on the electrophysical
properties of the modified polyurethanes the heteronuclear metal complexes based on
transition metals of IV and V periods were synthesized. CuCl2 was used as the chloride of
3d-metal, and MoCl5 was used as the chloride of the 4d-metal. DEHA was used as a ligand.
Cu (II) has 3d-orbitals that are involved in coordinating binding, in the case of Mo (V) this
role is performed by 4d-orbitals. Therefore, it is assumed that when heteronuclear
complexes of the columnar structure are formed, where the CuCl2 is in excess, the ions of
molybdenum could cause the interruption of chains of exchange interactions between 3d-
ions (Fig. 7). It is found that the metal complex system, obtained on the basis of
[CuCl2]:[DEHA] = 1:0,7 has ρv = 2600 [Link] at room temperature, while the system based
on [MoCl5]:[DEHA] = 1:0,7 has ρv = 1300 [Link]. The heteronuclear complex obtained at
the ratio of [CuCl2]:[MoCl5]:[DEHA] = 0,9:0,1:0,7 at room temperature exhibits ρv = 5250
[Link], while the complex obtained at ratio of [CuCl2]:[MoCl5]:[DEHA] = 0,8:0,2:0,7 has
already ρv = 73800 [Link].

Homonuclear and heteronuclear metal complexes were used for polyurethane modification.
It was found that both modifying systems were able to react with the urethane prepolymer.
When the metal complex structuring of polyurethanes by heteronuclear complexes based on
3d-and 4d-ions took place ρv values remained similar to the unmodified sample. With the
increase of the concentration of heteronuclear complex the specific volume electrical
resistance of polyurethanes actually increased slightly (Fig. 8). Another situation is observed
in the case of polyurethanes modification by homonuclear coordination compounds. In this
case the introduction of metal complexes based on copper led to the decrease of ρv by three
orders. However, when polyurethanes were modified by homonuclear metal complex
compounds based on Mo (V) ρv decreased by 5 orders.
 The Modification of Polyurethanes by Highly Ordered Coordination Compounds of Transition Metals 41

Cl Cl
Cu Cu

Cl Cl
Cu Cu

Cl Cl
Mo Cu

Cl Cl
Cu Cu

Cl Cl
Cu Cu

C2H5
O N
H5C2 Cu C2H5
Cu = N O
H5C2

Figure 7. Scheme of the formation of columnar homonuclear and heteronuclear coordination

compounds of transition metal.

Figure 8. Dependence of ρv ([Link]) of polyurethanes on the concentration (%) of metal complexes

based on: 1-MoCl5-DEHA; 2-CuCl2-DEHA; 3-CuCl2-MoCl5-DEHA.
42 Polyurethane

6. Catalytic properties of coordination compounds of copper in the

reaction with isocyanate and urethane groups
The next step was to change the ligand composition of metal complex modifying system
based on CuCl2 and DEHA. The aminopropyltriethoxysilane (AGM) was used as a part of
modifying system. The use of the AGM as an additional component to the DEHA was
caused by some reasons. The first reason is that the AGM is able to take part in the reactions
of sol-gel synthesis, resulting in the hydrolysis of ethoxy-component and subsequent
polycondensation of the forming silanol groups. The second reason is the presence of
electron-donor amine groups in the AGM which are able to form complexes. Besides,
amines can lead to reduction of copper (II) to copper (I). Thereby this substance is
interesting in terms of the influence on the reactivity of isocyanate groups and the
supramolecular structure of polyurethane, which has domain nature.

Titrimetric determination of concentration of isocyanate groups in UPTI during its

interaction with metal complex system based on CuCl2, DEHA and AGM at 100ºC, was
carried out. UPTI is industrial prepolymer synthesized on the base of 1 mol
polyoxitetramethyleneglicol and 2 mols 2,4-toluene diisocyanate.

It was found that at relatively low concentrations of metal complex (0.01 and 0.05% in terms
of CuCl2) in the first ten minutes from the start of the reaction process, the concentration of
isocyanate groups started to rise, and only after that it fell. When the content of metal
complex was 0.1, 0.5 and 0.75% in terms of CuCl2 the concentration of isocyanate groups
began to fall significantly (see fig. 9).

Figure 9. Isocyanate groups consumption curves in system UPTI – CuCl2-DEHA-AGM, Т=100°С, at a

content of CuCl2: 1 - 0,05%; 2 - 0,1%; 3 - 0,25%; 4 - 0,5%; 5 - 0,75% (wt.).
 The Modification of Polyurethanes by Highly Ordered Coordination Compounds of Transition Metals 43

The titration data confirm the results of IR-spectroscopic studies. It is established that the
absorption band at 1731 sm-1 due to the stretching vibrations of carbonyl component of
urethane group decreases at low concentrations of metal complex in the first ten minutes
from the start of the reaction process. At the same time the intensity of the absorption band
at 2273 sm-1 due to the stretching vibrations of isocyanate group grows. Later the growth of
the intensity of the absorption band at 1731 sm-1 and the decrease at 2273 sm-1 are observed.
Besides in the first ten minutes from the start of the reaction the IR-spectroscopy shows the
reduction of the intensity of the absorption band at 3293 sm-1 due to the stretching vibrations
of N-H-bond that is a part of urethane group. At relatively high concentrations of metal
complex (≥0.25%) the interaction is accompanied by the growth of the intensity of the
absorption band at 2120 sm-1 due to the formation of carbodiimide group.

The research suggested that at relatively low concentration of metal complex the urethane
group dissociates to isocyanate and hydroxyl groups, while at high concentrations of metal
complex the isocyanate groups consume to the formation of carbodiimide groups. The part
of isocyanate groups is hypothetically consumed on the formation of the azoaromatic
groups. It is known that it is impossible to analyze azoaromatic groups using infrared
spectroscopy. In this regard, studies were carried out using electron spectroscopy.

Electronic spectrum (Fig. 10) showed absorption at 350 nm, typical for trans-azoaromatic
compounds. The absorption in the area 480 nm characterizes the coordination compounds
of copper (II).

Figure 10. Electron spectrum of urethane prepolymer (1) and prepolymer (2) modified by 0.5% (wt.)
metal complex system based on CuCl2 - DEHA – AGM.
44 Polyurethane

Metal complex system, derived on the basis of CuCl2, DEHA and AGM was further used to
modify polyurethanes. We measured the dependence of the volume resistivity (ρv) of
polyurethanes on the concentration of metal complex modifier (Fig. 11).

It turned out that the use of the worked out metal complex system caused the leap of ρv by 4
orders (10 000 times) observed at low concentrations of metal complex 0.01%. Here we
should note that while using metal complex system based on CuCl2 and DEHA (no AGM) a
stepwise drop of ρv was observed at much higher concentration of the complex - 0.1%.

1
2

Figure 11. Volume resistivity-concentration diagram of modified polyurethanes under molar ratio of
[UPTI]: [Diamed-X] = 1:Y:

1. [CuCl2]:[АGМ]=1:4 (Y=0.9);
2. [CuCl2]:[DEHA]:[АGМ]=1:1,48:0,25 (Y = 0.9);
3. [CuCl2]:[ DEHA]:[АGМ]=1:1,48:0,25 (Y = 0.7);
4. [CuCl2]:[ DEHA]:[АGМ]=1:1,48:0,25 (Y = 0.5).

It was found that the use of metal complex systems based on CuCl2, DEHA and AGM could
significantly reduce the dosage of curing agent 4,4-methylene-bis-o-chloroaniline (Diamed-
X) for urethane forming system based on UPTI.
 The Modification of Polyurethanes by Highly Ordered Coordination Compounds of Transition Metals 45

7. The use of highly ordered coordination compounds of copper for

receiving the rigid polyurethane foam
Metal complexes derived from CuCl2, DEHA and AGM were also tested as modifiers of the
polyol component used in the manufacturing of rigid polyurethane foam. It was found that
metal complex system based on CuCl2, DEHA and AGM had a significant impact on the rise
and curing time of foam, reducing it (Fig. 12).

Figure 12. Rise (1) and curing (2) time of foam as a function of metal complex concentration based on
[CuCl2]:[DEHA]:[АGМ]=1:1,48:0,25 in terms of CuCl2 (%)

It was also established that the increasing of the molar ratio of the AGM in metal complex
system led to even greater decrease in rise and curing time of foam (Fig. 13).
In order to establish the role of the AGM in the foaming process it was loaded alone in
polyol component (Figure 14). It was found that the AGM also reduces the rise and curing
time of the foam. However, these parameters were more than two times higher than the
parameters that caused the addition of metal complex system.
We also used metal complex system based on CuCl2 and DEHA as the control modifying
system. In this case, in the wide range of concentrations of modifier the foam "collapsed".
That is, the foam rose and the subsequently settled out. It should be also mentioned that the
density of foam produced using metal complex system CuCl2 - DEHA - AGM did not
change in comparison with polyurethane foam obtained by the unmodified polyol
component.
Thus, these studies show a significant catalytic effect of the metal complex modifier on
foaming. In this connection it should be noted that the polyol component is a complicated
balanced system that contains catalysts of amine nature and organotin compounds already.
Our results suggest that the metal complex systems act as a cocatalyst.
46 Polyurethane

Figure 13. Rise (1) and curing (2) time of foam as a function of modifier concentration based on
[CuCl2]:[DEHA]:[АGМ]=1:1,48:X, where Х is a mole fraction of AGM in the metal complex overall
concentration (mol)

Figure 14. Rise (1) and curing (2) time of foam as a function of AGM concentration.
 The Modification of Polyurethanes by Highly Ordered Coordination Compounds of Transition Metals 47

The next step was the research of such polyurethane foam key indicators as moisture
absorption (Fig. 15) and water absorption (Fig. 16-17). It was found that the modified foam
had enhanced characteristics as compared with unmodified polyurethane foam.

Figure 15. Moisture absorption of rigid foam as a function of metal complex concentration based on
[CuCl2]:[DEHA]:[АGМ]=1:1,48:0,25 in terms of CuCl2 (%)

Figure 16. Water absorption of rigid foam as a function of metal complex concentration based on
[CuCl2]:[DEHA]:[АGМ]=1:1,48:0,25, where in terms of CuCl2 (%)
48 Polyurethane

Figure 17. Water absorption of rigid foam as a function of modifier concentration based on
[CuCl2]:[DEHA]:[АGМ]=1:1,48:X, where Х is a mole fraction of AGM in the metal complex overall
concentration (mol)

In conclusion, it should be noted that in order to achieve a positive result very small
amounts of modifiers are required.

8. Conclusion
We considered the methods of obtaining transition metal coordination compounds that
were active in reactions with isocyanate and urethane groups.

The feature of these metal complexes is that the metal ions are arranged in a chain of atoms
linked together by chloride bridges. It is established that the chain of exchange-coupled
transition metal ions remains in the polyurethanes structured by metal complex
compounds. This circumstance is the cause of stepwise decrease in the specific volume
resistivity of the modified polyurethanes.

It seems to be interesting for further research in this field to study the effect of metal
complex binding on the physical and mechanical properties of polyurethanes. The most
promising materials in terms of improving strength properties and heat resistance are
thermoplastic urethanes.
 The Modification of Polyurethanes by Highly Ordered Coordination Compounds of Transition Metals 49

Author details
Ruslan Davletbaev, Ilsiya Davletbaeva and Olesya Gumerova
Kazan National Research Technological University, Russia

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Thuchide E.,Nishide H. (1977). Polymer-metal complexes and their catalytic activity.
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50 Polyurethane

Davletbaeva I. M., Pyataev A. V., Kalachev K. E., Sadykov E. K. & Manapov R. A. (2006)
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pp.(612–617)
 Chapter 4

Bottom-Up Nanostructured Segmented

Polyurethanes with Immobilized in situ
Transition and Rare-Earth Metal Chelate
Compounds – Polymer Topology – Structure
and Properties Relationship

Nataly Kozak and Eugenia Lobko

Additional information is available at the end of the chapter

[Link]

1. Introduction
The formation of the polyurethanes (PU) with immobilized in situ co-ordinating metal
compounds allows obtain structurally homogeneous systems with uniform dispersed
nanosize metal containing sites. Aggregation of these metal chelate compounds is prevented
due to complexing with polar groups of the polymer matrix.

At the same time due to complex formation between the metal compound and polymer
functional groups, the structuring of the forming matrix occurs on a nanoscale level. As a
result, in the presence of small amounts of metal chelate compound (0,5-5%wt) both change
of the polyurethane structure and properties can be observed. To understand the nature of
above phenomena the influence of the weak interactions «macromolecule - metal» were
analyzed on the metal-containing PUs structure, molecular dynamics and properties.
The present study investigates the formation of nanostructured linear and cross-linked
polyurethanes (LPUs and CPUs, respectively) with immobilized in situ mono- and poly-
heteronuclear chelate compounds of rare-earth and transition metals. Influence of PU topology
on self organization processes in polymer matrix and its properties is also subject of analysis.

1.1. Materials, methods and instrumentations

Polypropylene glycol (PPG, MW 1000) was dried under vacuum at 120 oC for 2 h. Tolylene
diisocyanate (mixture 80/20 of 2,4- and 2,6- isomers) (TDI) was distilled under vacuum.

©©2012
2012Kozak
Kozakand
andLobko, licensee
Lobko, InTech.
licensee ThisThis
InTech. is aispaper distributed
an open under the
access chapter terms of the
distributed Creative
under Commons
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License ([Link] which use,
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distribution, and reproduction in any medium, provided the original work is properly cited.
52 Polyurethane

Diethylene glycol (DEG) was distilled under vacuum at 105 oC. Trimethylol propane (98%)
(TMP) was dried under vacuum at 40-45 oC for 2-4 h. Dichloromethane (CH2Cl2), 1,4-
dioxane and N,N- dimethylformamide (DMF) were distilled at 40 oC, 101 oC, 153 oC,
respectively. The following chelate compounds of transition and rare-earth metals as PU
modifier were used:

(R=-CH3)
Cu(acac)2 - Copper(2+) acetylacetonate
R1
O Ni(acac)2 – Nickel(2+) acetylacetonate
Met (R = -OC2H5)
O
CH3 2 Cu(eacac)2 - Copper (2+) ethyl acetoacetate
(R = --CF3).
Cu(tfacac)2 - Copper (2+)trifluoro acetylacetonate
(R1=R2=-CH3 )
Co(acac)3 – Cobalt (3+) acetylacetonate
Cr(acac)3 – Chromium (3+) acetylacetonate
Gd(acac)3 – Gadolinium (3+) acetylacetonate
R1
O Nd(acac)3 – Neodymium (3+) acetylacetonate
Met Er(acac)3 – Erbium (3+) acetylacetonate
O (R1 =-C(CH3)3 , R2 =-(CF2)2-CF3)
R2 3
Eu(fod)3 – Europium (3+) tris(6,6,7,7,8,8,8-heptafluoro-
2,2-dimethyl-3,5-octanedionate)
(R1 =- thiophene , R2 =- CF3)
Eu(TTA)3 – Europium (3+) thenoyltrifluoroacetonate
(R1 =- thiophene , R2 =- CF3 ; L4= phen)
Eu(TTA)3 phen – Europium (3+)
R1
O tris(thenoyltrifluoroacetonate) phenantroline
L4 Eu (R1 =- thiophene , R2 =- CF3 ; L4= triphenylphosphine oxide)
O
R2 3 Eu(TTA)3 TPPO –Europium (3+)
tris (thenoyltrifluoroacetonate)
(triphenylphosphine oxide)
k=2, m=1, n=0, p=3, q=3, r=0, t=1,
 Met1k Metm 2
Metn3 R1p Rq2 Rr3   Solt R1=NCS, R2=Me2Ea, Sol= CH3CN
 
p , q , k , m  1, 2 , 3, 4; [Cu2Zn(NCS)3(Me2Ea)3]CH3CN
n , r , t  0,1; k=2, m=3,n=0, p=6, q=4, r=0, t=2,
where R1=Br, R2=Me2Ea, Sol= dmso
Me2Ea = deprotonated residue of [Cd2Cu3Br6(Me2Ea)4(dmso)2]
dimethyl aminoethanol k=1, m=2, n=2, p=3, q=4, r=4, t=0,
Dea = doubly deprotonated R1= H2Dea, R2= NCS, R3= Dea
residue of diethanolamine [Ni(H2Dea)2][CoCu(Dea)2(H2Dea)
(NCS)]2(NCS)2
Table 1. The PU modified chelate compounds of transition and rare‐earth metals.
 Bottom-Up Nanostructured Segmented Polyurethanes with Immobilized in situ Transition and
Rare-Earth Metal Chelate Compounds – Polymer Topology – Structure and Properties Relationship 53

In metal chelate compounds used as PU modifier metal ions are already surrounded with
organic ligands. This facilitates solvation of modifier in polymer. The listed above transition
and rare-earth metal chelate compounds are commercial products (Aldrich). The heteroligand
rare-earth metal compounds were synthesized by Professor Svetlana B. Meshkova’s group
(A. V. Bogatsky Physic-Chemical Institute of National Academy of Sciences of Ukraine,
Odessa). Polyheteronuclear metal complexes of Cu (2+), Cd (2+), Zn (2+), Ni (2+) and Co (3+),
described in (Skopenko et al., 1997; Vinogradova et al., 2002), were provided by Prof.
V. Kokozay’s goup (Kiev Taras Shevchenko University). Polyheteronuclear metal chelate
compounds can realize unexpected coordination states of transition metal ions. That, in turn,
can give new properties to a polymer formed in their presence.
PUs were synthesized in two stages according to standard procedure described in detail
elsewhere (Saunders&Frish,1968; Wirspza,1993) using PPG-1000 and TDI based prepolymer.
DEG was used as chain extender to obtain LPU (Scheme 2). TMP was used as cross-linking
agent to obtain CPU (Scheme 3). Metal chelate compounds were added into reaction mixture
as solution in CH2Cl2, 1,4-dioxane or DMF to obtain the metal containing PUs with
homogeneous distribution of modifier (from 0,5 to 5 %wt.) in polymer matrix. High ability
of metal chelate compound to complex formation leads to enrichment of PU matrix with
heteroligand macro complexes of 3d- and 4f-metal with prevalence of outer-sphere
coordination of macro chains. Such macro complexes act like coordination linkages between
polymer chains and form “coordination nodes” in PU (Scheme 1).

Scheme 1. The coordination junction of PUs networks.

Thus, in the LPU (Scheme 2) in the presence of chelate metal compounds the “coordination
nodes” can form.

H H H H
C N N C O CH2 CH O C N N C O CH2 CH2 O CH2 CH2 O
O O CH3 nO O
H3C H3C m

Scheme 2. The general formula of LPU.

54 Polyurethane

In the metal containing CPU both the chemical linkages (Scheme 3) and the “coordination
nodes” can form (Scheme 1).

H H H H
CH 2 O C N N C O CH 2 CH O C N N C O
O O CH 3 n O O
H 3C H 3C
H H H H
C 2 H 5 C CH 2 O C N N C O CH 2 CH O C N N C O
O O CH 3 n O O
H 3C H 3C
H H H H
CH 2 O C N N C O CH 2 CH O C N N C O
O O CH 3 n O O
H 3C H 3C

Scheme 3. The fragment of PU network with cross‐linkage.

Wide-angle X-ray scattering (WAXS) profiles of studied samples were recorded on a Dron-4-
07 diffractometer with Ni-filtered Cu-Kα radiation and Debay-Sherer optical schema.
Distance between PU atomic layers (d) was estimated using the Bragg equation:

λ  2d sin θ (1)

where λ – the X-ray wave length (λ = 0,154 nm); θ - the diffraction maximum angular
position, degrees.
Small-angle X-ray scattering (SAXS) profiles were recorded using KPM-1 X-ray camera
(Kratky et al., 1966). The Schmidt's method (Schmidt & Hight, 1960) was used to smooth out
the SAXS-profiles to point collimation. X-ray measurements are carried out using
monochromatic Ni-filter of Cu-Kα radiation at temperature 22±2 оС. The Bragg’s period of
uniform electronic density scattering elements was estimated through the equation:

D  2 / q (2)

The X-band EPR-spectra were recorded at temperature 20оС using radio spectrometer РE-
1306 equipped with frequency meter ChZ-54. The magnetic field was calibrated using 2, 2-
diphenil-1-pycrilhydrazyl (DPPH) (g=2,0036) and ions of Mn(2+) in MgO matrix (g=2,0015).
Stable nitroxide radical 2,2,6,6-tetramethylpiperidinyl-1-oxy (ТЕМPО) was used as
paramagnetic spin probe (SP). Nitroxide SP was introduced into PU films via diffusion of its
saturated vapor at 30oC for 2 hours with subsequent keeping at 20oC for 24 hours.
Correlation time () of SP rotational diffusion in the range of its fast motion (10-11 <  <10-9s)
was calculated according (Vasserman & Kovarskii, 1986) as follows:

τ 6 , 65H( 1) ( ( I 1 / I 1 )  1)  1010 c , (3)

where Н (+1) – is width of the low-field- component of ТЕМPО EPR-spectrum, І+1 and І–1 -
are intensities of low-field and high-field components of the spectrum, respectively.
 Bottom-Up Nanostructured Segmented Polyurethanes with Immobilized in situ Transition and
Rare-Earth Metal Chelate Compounds – Polymer Topology – Structure and Properties Relationship 55

The differential scanning calorimetry in temperature interval from 223 to 750 K was performed
using Perkin Elmer DSC 2 instrument with the IFA GmbH’s software. The heating rate was
0,05-2 grad/min.

Micro images in light transmission were obtained using an optical microscope XY-B2 (NS
Instr. Co.) equipped with digital video ocular ICM 532 and AMCAM/VIDCAP (Microsoft)
image processing system.

The surface tension of PUs (sg) was determined according to Elton’s equation (Tavana et al.,
2004) using measurement of contact wetting angle with ethyleneglycol (EG) as wetting
liquid at 20oC:

γ sg  0 , 5γ lg (1  cosθ ) (4)

where sg and γlg are the surface tension on solid-gas and liquid-gas boundaries,
respectively;  is the boundary wetting angle; solid is PU; liquid is EG.

The mean value of γsg was calculated as average of 5 different measurements and error of
measurements did not exceed the value of 0,5 mN/m.

The spectra of luminescence were obtained using the luminescent spectrometer SDL-1 (LOMO)
in an excitation by the mercury lamp. The emission of the most intensive line with the
maximum on 365 nm was selected with light filter UFS-2.

Two-electrode method measurements of conductivity at a direct current (dc) were conducted

using a Hiresta UP high resistivity meter (Mitsubishi Chemicals, Japan). A dc voltage of
10 V was applied across the sample thickness. The samples were dried over night in an oven
at 40°C under vacuum and then kept in dried environment, for the elimination of any
moisture effects.

Dielectric relaxation analysis was performed using dielectric spectrometer on the base on
alternating current bridge R5083. Complex dielectric permittivity, ε* = ε’ – iε’’, of disc-like
specimens (diameter: 20 mm) sandwiched between gold-coated brass electrodes was
measured over the frequency window from 102 to 105 Hz in the temperature interval from --
40 to 120 °С. They have been analyzed from the traditional point of view (Pathmanatham &
Johari, 1990; Pissis & Kanapitsas, 1996). Additional formalisms such as: complex admittance
σ*, electrical modules М* and impedances Z', Z" were used according to formulas.

ε '  С 1 / С о , tgδ  ωRС1and ε " ε ' tgδ (5)

σ *  σ ' σ ”, σ ' ωε " , σ " ωε ', (6)

M*  
ε "/ ε '2  ε "2 ,M" 
M' M",M'  
ε '/ ε '2  ε "2   (7)

Z'  M"/(ωC o ), Z"  M'/(ωC o ) (8)

Со and С1 – are instrument and standard capacitor capacities, ω – cyclic frequency.

56 Polyurethane

The electron spectra of the copper (2+) containing PU films and of copper (2+) chelate
compounds solutions in dichloromethane (c = 10-2M) in the ultra-violet and visible region
were recorded using the spectrometer Specord UV-VIS.
The quasi-elastic neutron scattering (QENS) was recorded using the multi detector
spectrometer “NURMEN” on the atomic reactor ВВР-М (The institute of the nuclear
research of the NAS of Ukraine). The self-diffusion of chloform used as low molecular probe
liquid in swelled PU films was analyzed.

2. Heterogeneity of metal containing polyurethanes

2.1. Structural heterogeneity of PU according to X-ray data
Formation of a polymer matrix in the presence of metal chelate compounds favours creation
of a new hierarchy in structural organization of the polymer as compared with metal free
system. This effect is caused by complex formation between metal chelate compound and
functional groups of the forming polymer (Ying, 2002; Kozak et al., 2000).
Figure 1 represents the WAXS and Figure 2 presents SAXS intensity profiles of metal-free PU
and PU modified with metal -diketonate. The asymmetric diffuse diffraction maxima
(Figure 1) point on the amorphous structure of the metal-free and metal containing CPU and
LPU. For the LPUs the short-range order parameter d (equation 1) is equal to 0.44 nm and don’t
depend on the metal chelate compound amount (table 1). For the CPU the Bragg’s period (d)
changes from 0.44 to 0.46 nm with increasing of the modifier amount from 0,5 to 5% wt.

The PU’s SAXS profiles are characterized by the presence of one amorphous maximum with
qm positions varying from 1,7 to 2,0 nm-1 (Figure 2). Such maximum points on the existence
of changeover period of uniform electron density scattering elements and areas of uniform
distribution of hard and flexible blocks in PU. The Bragg’s period (D) falls from 3,7 to 3,1 nm
with increasing of the modifiers amount from 0,5 to 5% wt. (table 1).

Figure 1. The WAXS intensity profiles of CPU (a) and LPU (b): metal-free (1), modified with 0,5% (2),
1% (3), 3% (4) и 5% (5) Eu(fod)3.
 Bottom-Up Nanostructured Segmented Polyurethanes with Immobilized in situ Transition and
Rare-Earth Metal Chelate Compounds – Polymer Topology – Structure and Properties Relationship 57

System 2θ, degree d, nm qm, nm-1 D, nm

CPU-0 20 0.44 1.7 3.7
CPU-0,5% Eu(fod)3 20 0.44 1.7 3.7
CPU-1% Eu(fod)3 19.9 0.45 1.76 3.6
CPU-3% Eu(fod)3 19.9 0.45 1.76 3.6
CPU-5% Eu(fod)3 19.4 0.46 2.0 3.1
LPU-0 20 0.44 1.7 3.7
LPU-0,5% EEu(fod)3 20 0.44 1.7 3.7
LPU-1% Eu(fod)3 20 0.44 1.9 3.3
LPU-3% Eu(fod)3 20 0.44 1.8 3.5
LPU-5% Eu(fod)3 20 0.44 1.9 3.4
2 θ - the diffraction maximum angular position, degrees;
d – distance between PU atomic layers from WAXS, nm;
qm - value at maximum intensity of I(q) relationship, nm-1;
D - changeover period of uniform electronic density scattering elements from SAXS, nm.

Table 2. X-ray structural characteristic of LPU and CPU

Figure 2. The SAXS intensity profiles of CPU (a) and LPU (b): metal-free (1), modified with 0,5% (2), 1%
(3), 3% (4) and 5% (5) Eu(fod)3.

Analysis according (Porod, 1982) of heterogeneity range (lp) and average diameter (l1, l2) of
different scattering elements in CPU-0, CPU-Cr and CPU-Со indicate existence of two types
of nanosize heterogeneities in the bulk of PU. The first one (with l1 < D ) is inherent to
segmented PU. The second one (with l2 > D) is generated in the presence of transition metal
chelate compound. We can define the latter structures as “metal chelate compound –
polyurethane” complexes with polymer chains as macro ligands (Kozak et al., 2006;
Nizelskii & Kozak, 2006) (Scheme 1).

Thus, the immobilization in situ of metal chelate compounds in polyurethane is

accompanied with enrichment of polymer matrix with the nanosize heteroligand macro
complexes of metal formed simultaneously with organic nanosize structures typical for
metal-free polymer.
58 Polyurethane

2.2. Dynamic heterogeneity of PU according to EPR data

The structural heterogeneity of PU influences the local segmental mobility of macro chains,
resulting in “dynamic heterogeneity” of the systems. The analysis of mobility of SP
introduced into the polymer gives information concerning such heterogeneity.

Calculated values of  are listed in the table 2. They characterize the hindered rotation of SP
in PUs of different topology. The greater value of  is, the harder rotation of the probe occurs
in polymer matrix.

System τ·10-10, c System τ·10-10, c

CPU-0 45 LPU-0 48
CPU-1%Cu(eacac)2 43 LPU-1%Cu(eacac)2 69
CPU-1%Ni(acac)2 42 CPU-1%CuCd 45
CPU-1%Cr(acac)3 50 CPU-1%CuZn 32
CPU-1%Co(acac)3 49 CPU-1%CuNiCo 51
Table 3. The correlation time of TEMPO in CPUs and LPUs, modified with 1% of metal chelate
compounds.

As it can be seen from the table 2, in CPU modified with 1%wt. Co(3+) and Cr(3+) chelate
compounds the values of  increase indicating reduction of SP mobility as compared with
metal-free CPU. In the contrary, for CPUs modified with 1%wt. Cu(2+), Ni(2+) values of 
decrease as compared with metal-free CPU. This means that Co(3+) and Cr(3+) containing
CPUs have more dense macro chain packing as compared with metal free CPU. Where as
Cu(2+) and Ni(2+) containing CPUs possess looser macro chain packing. Similarly to
(Lipatov et al., 2000), the effect we can relate to difference in metal chelate compounds
electron configuration and symmetry. In addition, the influence of metal chelate compound
on PU dynamic depends also on the polymer topology. For example, it can be seen the
opposite influence of Cu(2+) chelate compounds on the macro chain mobility in LPU and
CPU (Table2).

The analysis of SP EPR-spectrum shape and hyperfine splitting (HFS) gives additional
information concerned probed medium. In PU matrices that contain metal chelate
compounds the EPR spectra of SP have asymmetric shape (Figure 3). In all of the spectra
occur essential increasing of central component and broadening of all components as
compared with TEMPO spectrum in homogeneous glycerol matrix. In many spectra there is
noticeable splitting of low-field and/or high-field components of SP spectrum.

The peculiarities observed are most likely the result of signal superposition of “fast” and
“slow” probes located in polymer regions with different mobility. In conformity with above
supposition the temperature increasing brings on enhancement of the SP EPR spectra
isotropy (Figure 3). Initially asymmetric ESR spectrum becomes more isotropic
while heating the sample. The spectrum components narrow and the intensity of central
component diminishes.
 Bottom-Up Nanostructured Segmented Polyurethanes with Immobilized in situ Transition and
Rare-Earth Metal Chelate Compounds – Polymer Topology – Structure and Properties Relationship 59

As a result of heating the equalizing of polymer segments mobility and „unfreezing” of

„slow” SP rotation diffusion occurs. The correlation time decreases with the rise of
temperature due to increasing of molecular mobility and “softening” of PU matrix. Figure 4
represents the relationship  (Т) for CPU.

1
2
3
B
4
5
1mT
6

Figure 3. The spectra of the TEMPO introduced in CPU+%Er(acac)3 at the various temperatures: 18 оС
(1); 26 оС (2); 44 оС (3) ; 90 оС (4); 114 оС (5); 21 оС (30 min after thermal heating) (6); 18 оС (2 days after
thermal heating) (7).

10
*10 , c

40 1 CPU-0
2 CPU-0.5% Er(acac)3
3 CPU-5% Er(acac)3
30

20

10 3
1
2
0
280 300 320 340 360 380 400
T, K
Figure 4. The thermal dependence of correlation time of the TEMPO in CPU-0 (1), CPU, modified with
0,5%wt. (2) and 5%wt. (3) of Er(acac)3.

2.3. Thermodynamic heterogeneity of PU according to DSC data

The PU’s thermodynamic heterogeneity is closely associated with above discussed types of
heterogeneities. The influence of the metal chelate compounds on the thermodynamic
60 Polyurethane

heterogeneity and thermo-physic properties of PUs was analyzed by DSC. Figure 5

illustrates the temperature dependences of specific heat capacity of CPUs modified with 0,5;
1; 3; 5%wt. of Cu(acac)2. The thermo-physic characteristics of copper-containing CPUs are
given in Table 3.

2,4
5
4
2,1 3
2
1
Cp, J/(g·K)

1,8

1,5
1 СPU-0
2 СPU-0,5% Cu(acac)2
1,2 3 СPU-1% Cu(acac)2
4 СPU-3% Cu(acac)2
0,9 5 СPU-5% Cu(acac)2

220 240 260 280 300 320 340 360 380 400
T,K

Figure 5. Temperature dependence of specific heat capacity for copper-containing CPU.

System Tg, K ΔT, K C p , J/ (g·K) C p(CPU Сu )

C p(CPU  0 )
CPU-0 258 18 0,25 1
CPU-0,5%Cu(acac)2 256 16 0,38 1,52
CPU-1%Cu(acac)2 258 18 0,43 1,72
CPU-3%Cu(acac)2 260 21 0,50 2,00
CPU-5%Cu(acac)2 271 20 0,55 2,20
Table 4. The thermo-physical properties of copper-containing CPU.

It is evident from fig. 5 and table 3 that for the CPUs the specific heat capacity (̣ΔCp) grows
with increasing of Cu (2+) chelate content from 0,5 to 5% wt. comparing with CPU‐0. In
addition, the high temperature shifting of glass temperature (Tg) and the broadening of the
temperature interval of glassing (̣ΔT) for CPU- 3%Cu and CPU-5%Cu are observed. The
similar effect was discussed in (Lipatov et al., 1999) for CPUs, modified with 1%wt of
various transition metals chelate compounds. That effect we can relate to formation of
coordination bonds between functional groups of CPU and copper (2+) chelate compound.

Thus, growth of Tg and ΔCp values with increasing of Cu(acac)2 amount corresponds to rise
of polymer segments with decreased mobility due to complexing.

The ratio of ΔCp(CPU-Сu) to ΔCp(CPU-0) allows estimate the degree of PU’s thermodynamic
heterogeneity (Bershtein. & Yegorov, 1990) and analyze the influence of metal chelate
modifier content on this type of heterogeneity (table 3). As it can be seen the thermodynamic
 Bottom-Up Nanostructured Segmented Polyurethanes with Immobilized in situ Transition and
Rare-Earth Metal Chelate Compounds – Polymer Topology – Structure and Properties Relationship 61

heterogeneity degree of CPU correlates with modifier amount in the system. This result
agrees with X-ray data (section 2.1).

2.4. The formation of ordered micro regions in metal containing PUs

The segregation of metal containing micro crystals in CPU-5% Co and CPU-5%Cr was
revealed in (Kozak et al., 2006):. Such unexpected segregation seemed unlikely due to
homogeneous dispersion of metal chelate compound solution in reaction mixture (see 2.1)
and coordination immobilization of metal chelate compounds in PU matrix. Nevertheless,
the further X-ray study of CPU-5%Cu, LPU-5%Cu (fig. 6) and microscopy data (see 2.5)
confirm partial segregation of metal-containing sites in PU matrices. This effect can be
explained by different complex ability of segmented PU soft and hard components towards
metal chelate compound as well as by higher mobility of PU’s soft component.

The Scherer’s equation (Stompel & Kercha, 2008) for the average diameter (L) of crystallite in
amorphous media allows estimate dimensions of the particles in metal-containing PU.

L  kλ / ( βcosθm ) (9)

Here X-ray wavelength  = 1,54 Ǻ, k is the shape factor assigned to 0,9, L is the average
diameter of the crystals in angstroms, m is the Bragg’s angle in degrees, and  is the half-
height of diffraction angle in radians. The value of L is equal to 3 nm for CPU-1%Co, it is
equal to 4 nm for CPU-1%Cr and it is equal to 10 nm in LPU-1%Eu. The evaluated
dimensions of the aggregates in copper containing PUs are ranged from 8 to 12 nm.

1 Cu(acac)2
2 CPU-0
3 CPU-0,5% Cu(acac)2
4 CPU-1% Cu(acac)2
5 CPU-3% Cu(acac)2
Intensity, pulses

6 CPU-5% Cu(acac)2

6
5
4
3
2

1
0 5 10 15 20 25 30 35 40
2, degree
Figure 6. The WAXS diffractograms of the CPU-%Cu(acac)2 films.

Segregation of the micro crystals detected via WAXS study has been also fixed by optical
light transmission microscopy and by the scanning electron microscopy (SEM) (Figure 7).
The micro crystals detected by optical microscopy are coloured like metal chelate
compounds used as PU modifier. Such colouring indicates enrichment of the crystals with
corresponding metal ions. The crystalline regions can be formed by the modifier itself
and/or by complexes of modifier with PU chains as macro ligand. The last conclusion agrees
62 Polyurethane

with the X-ray data that register several discrete peaks in Cu(2+), Cr(3+) and Co(3+)
containing PUs (Figure 6).

(a) (b) (c)

Figure 7. The optical microscopy (a, b) and SEM microscopy micro images of the LPU-0,5%Cu(acac)2
(in polarized light) (a), LPU-5%Cu(acac)2 (b) and CPU-5%Cr(acac)3.

Optical microscopy allows obtain information concerning two surfaces of one PU film.
One of them formed on the boundary “polymer-support” (the PU’s surface formed on the
Teflon support) and another formed on the boundary “polymer-air” (the PU’s surface
formed on the air).

(a) (b)

(c) (d)
Figure 8. Micro images of LPU-1%Eu(fod)3 (a,b) and CPU-1%Cr(acac)3 (c, d) surfaces formed at the
“polymer-air” boundary (а, c) and the “polymer- support” boundary (b, d).
 Bottom-Up Nanostructured Segmented Polyurethanes with Immobilized in situ Transition and
Rare-Earth Metal Chelate Compounds – Polymer Topology – Structure and Properties Relationship 63

Figure 8 illustrates the typical differences in surfaces of PU films. As it can be seen, at

surface formed at the boundary “polymer-support” (fig. 8, a) the size and quantity of
crystals are larger. Where as, at surface formed at the “polymer-air” boundary (fig. 8, b) the
size and quantity of crystals are significantly smaller. For example, the mean size of crystals
in LPU-1%Eu changes from the one surface to another from 20 μm to 0,5 μm.

Detailed analysis of PUs surface properties depending on the boundary nature can give
additional information.

3. Influence of metal chelate modifiers on surface properties of

polyurethanes
The presence of metal chelate compounds in reaction mixture can influence the surface
tension of the formed polyurethane. In (Lipatov, 1997) the surface properties were studied
of PU with metal ions introduced through in four different ways. There are filling, metal ion
cross-linking, metal ion chain-extending and diffusion of metal chelate compound from its
solution to polymer being formed earlier. It has been shown that the surface properties of
metal containing PU depend on metal quantity much less than on the way of metal chelate
compound introduction in polymer. For example, the γsg of PU filled with Cr(acac)3
(0.18% wt.) changes up to 8 mN/m. On the contrary the γsg of Pb (15% wt) cross-linked PU
changes up to 0.3 mN/m as compared with metal free PU.

Obviously, the PU’s surface structure depends on the boundary “polymer-support” or

“polymer-air”. Data of ESCA and IR-spectroscopy by (Lipatova et al., 1987; Lipatova &
Alexeeva, 1988) point on possibility of the chemical unequivalenсe of the polymer surfaces
formed at the different boundaries. In addition in (Kozak et al., 2010) it was observed
substantial difference in luminescence intensity at different surfaces of the PU films
modified with europium (3+) chelate compounds. Therefore, the surface properties of
europium containing LPU and CPU were compared for surfaces formed at the “polymer-
air” and “polymer-support” boundary using measurement of contact wetting angle. The
data obtained are listed in the table 4.

The values of surface tension of metal containing PU obtained using Wilgelmy method(with
water as wetting liquid) (Lipatov et al., 1997) are consistent with values of the surface
tension calculated using measurement of contact wetting angle (Table 5) of standard liquid.

The wetting angles at the „polymer-air” boundary for all of CPU and LPU are from 5.5 to
15.5 degrees less than the wetting angles at the „polymer-support” boundary (table 4).
The difference between relative values of surface tension (1-2) takes values from 2.18 to 5.59
mN/m. As it is known, the higher compound polarity is the greater surface energy and
surface tension it possesses. Obtained results allow conclude that PU surface formed at the
„polymer-air” boundary is enriched with more polar groups (e.g. urethane ) and PU surface
formed at the „polymer-support” boundary is enriched with less polar groups (e.g. glycol
segments).
64 Polyurethane

Concentration of PU less polar groups that form the weak complexes with metal chelate
compound at the „polymer-support” boundary can facilitate the partial segregation of metal
containing centres at this boundary. That conclusion is consistent with microscopic data and
photoluminescence measurements.

θ, degree γЕG-PU, mN/m

θ2 (the γ2 (the
θ1 (the γ1 (the θ= θ2 –θ1, = 1-2,
System „polymer- „polymer-
„polymer-air” „polymer-air” degree mN/m
support” support”
boundary) boundary)
boundary) boundary)
CPU-0 55 65 38,06 34,50 10 3,56
CPU-1% Eu 53 64 38,74 34,67 11 4,07
CPU-3% Eu 51 66 39,39 33,95 15 5,44
CPU-5% Eu 56 64 37,70 34,77 8 2,93
LPU-0 58 70 37,00 32,45 12 4,55
LPU-1% Eu 61 67,5 35,95 33,43 6,5 2,52
LPU-3% Eu 67,5 73 33,43 31,25 5,5 2,18
LPU-5% Eu 59 74,5 36,63* 30,64 15,5 5,99
θ1, θ2 – the wetting angles at the „polymer‐air” and the „polymer-support” boundaries, respectively, degree;
γ1, γ2 – the surface at the „polymer‐air” and the „polymer-support” boundaries, respectively, mN/m;
* the unbalanced wetting angles

Table 5. The contact wetting angle (θ) and surface tension () of PU films. The standard liquid is
ethylene glycol (EG) γЕG-air = 48,36 mN/m.

Varying of the metal containing modifier amount (from 0,5 to 5% wt.) in CPU practically
does not affect surface tension. In the contrary, change of metal chelate compound content
in LPU from 0,5 to 3%wt. lead to decreasing of both 1 and 2.

The difference of the tendency in changing of surface tension in LPU and CPU clearly
depend on polymer topology. Different PU topology results in different segmental mobility
of the polymer, that agrees with DRS data. This effect described detailed in Section 5 and
Section 2.4. At that time we can’t formulate the certain reason for non monotonous influence
of the modifier’s amount on the surface tension.

4. The influence of polymer topology and modifier content on the

luminescent properties of segmented polyurethanes
According to (Lobko et al., 2010) the PU matrix can intensify the photoluminescence of
europium chelate compounds introduced into polymer in situ. Taking into account that
immobilization in situ of metal chelate compounds in polymer matrix can influence both
structure and properties of the hybrid system (Nizelskii & Kozak, 2006; Nizelskii et al., 2005)
the investigation of rare-earth metal compounds in polymeric environment is a way for
creation of new optically active materials.
 Bottom-Up Nanostructured Segmented Polyurethanes with Immobilized in situ Transition and
Rare-Earth Metal Chelate Compounds – Polymer Topology – Structure and Properties Relationship 65

LPUs and CPUs modified with Eu(3+) chelates when exposed in 365 nm UV-light
demonstrate the intensive photoluminescence in red region. Figure 9 represents
the luminescent spectra of LPU and CPU, modified with various amount of Eu(fod)3.

The luminescent spectra of europium containing PU are diffuse, while luminescence

spectrum of Eu(fod)3 is enough well-resolved. According to (Poluectov et al., 1989)
the luminescence spectra of europium β-diketonate solutions contain bands corresponding
to the 5D0-7Fі -transitions (where і = 0,1,2,3,4). The spectra of Eu β-diketonate in PU matrices
demonstrate the intensive wide band of photoluminescence in the region of λ=610-635 nm
(5D0-7F2-transition), narrow band λ=660 nm (5D0-7F3 –transition) and bands of 5D0-7F0, 1, 4-
transitions (580, 600,700 nm, accordingly) of low-intensity. It is possible to explain
the diffuse spectrum of luminescence of europium containing PU in the region of λ =610-635
nm by distortion of the Eu (3+) chelate geometry in PU due to complex “polymer-metal
chelate compound” formation and due macroligand steric hindrances.

Figure 9. The spectra of luminescence of LPU (a) and CPU (b), modified with europium chelate (λUV =
365 nm): (1) 0.5%; (2) 1%; (3) 5%.

The intensity of PU-Eu luminescence depends both on the europium chelate content and
polymer topology. The luminescence intensity increases with increasing of europium
chelate compound content. The luminescence intensities of 5D0 → 7F2 transition (λ=612nm)
for LPU with 05%, 1% and 5%wt. of Eu(fod)3, correspond as 1:1,8:2,4. The relationship of
luminescence intensity vs. modifier percentage in CPUs is linear (1:3,3:9,2). The CPU-Eu
with low modifier content has the lower luminescent intensity as compared with LPU-Eu.
Where as CPU-5%Eu luminescence intensity is 1,5 higher, than LPU-5% Eu luminescence
intensity. Taking into account data of Sections 2, 3, 6 we can suppose that due to difference
in PU topology this effect is associated with higher concentration of polymer photo
transmitting sites near the modifier in CPU as compared with LPU.

The tetra coordinated Eu (3+) chelate compounds with different additional ligands in an
external coordination sphere were used to analyse the influence of additional coordination
66 Polyurethane

of europium chelate compounds on the intensity of their luminescence. The fig. 10, a
illustrates the luminescent spectra of isolated Eu (3+) chelate compounds. The fig. 10, b
represents the spectra of luminescence of CPU films, modified with 1%wt. of Eu (3+)
compounds.

(a) (b)

Figure 10. The luminescence spectra (λex. = 365 nm) of the europium (3+) chelate compounds (a) and of
CPU films with 1%wt. of these chelate compounds (b): Eu(TTA)3phen (1); Eu(TTA)3ТРРО (2); Eu(TTA)3
(3); Eu(fod)3 (4)

As it can be seen the luminescence of Eu (3+) chelate compounds introduced into PU matrix
(only 1%wt.) is more intensive than luminescence of isolated metal chelate compounds
(100% wt). In addition, the intensity of luminescence of tetra coordinated Eu(3+) chelate
compounds (Eu(TTA)3phen and Eu(TTA)3TPPO) both isolated and introduced into CPU
matrix, considerably exceeds such intensity for 3-coordinated Eu(3+) chelate compound
Eu(TTA)3 that does not contain additional ligands The intensity of photoluminescence of
Eu(fod)3 also is considerably lower.

Estimation of Eu (3+) environment symmetry in various complexes via the coefficient of

asymmetry (η) defined as ratio of intensity of 5D0 → 7F2 –transition to intensity of 5D0 → 7F1
transition. (Haopeng et al., 2008) shows that the greatest coefficient of asymmetry (η = 9) has
CPU-1%Eu(TTA)3phen characterized by the greatest intensity of luminescence.
Consequently, the presence of additional ligand in the external coordination sphere of
Eu (3+) favours increasing of luminescence intensity. Then increasing of Eu-chelate
compounds luminescence intensity in PU can be explained in particular by additional
coordination of lanthanide ion with the functional groups of PU and/or by formation of
 Bottom-Up Nanostructured Segmented Polyurethanes with Immobilized in situ Transition and
Rare-Earth Metal Chelate Compounds – Polymer Topology – Structure and Properties Relationship 67

donor-acceptor complexes between aromatic fragments of PU and quasi-aromatic chelate

rings of chelate compounds of rare-earth metals.

5. Dielectric relaxation and conductivity

The dielectric properties of PU were studied by broad band DRS measurements in wide
range of temperature (-40 to 120 oC). The data are analyzed within the various formalisms.
The direct current conductivity was both measured using two-electrode method and was
estimated using DRS complex electric resistance dс =d/(ARdc) and Z”(Z’) isotherms (Cole-
Cole diagram). Figure 11-13 illustrate obtained dielectric spectra. Calculated conductivity
values are listed in Table 5.
According to two-electrode method the direct current conductivity of PU can drastically change
in the presence of some metal chelate compounds. At the room temperature dc for the
CPU-5%Eu increases by one order as compared with CPU-0. In the presence of
polyheteronuclear metal chelate compounds d enlarges from 2 to 3 orders (fig. 13, table 5). DRS
analysis of complex dielectric permittivity as well as complex admittance σ*, complex electrical
modulus М* and impedances Z', Z" allows reveal the nature of the observed conductivity.

a) dc, Sm/cm b) dc, Sm/cm a) dc, Sm/cm b) dc, Sm/cm

System System
20oC 40oC 20oC 20oC
CPU-0 1,78 10-12 1,310-11 LPU-0 4,6510-12 4.610-12
CPU-Cu 2,86 10-11 210-9 LPU-Cu 4,2510-11 3.810-11
CPU-Cu2Zn 2,47 10-9 0,710-8 LPU-Cu2Zn 1,5110-9 1.210-10
*CPU2000-0 - 1*10-10 *CPU2000-Cu2Zn - 1*10-7
*CPU2000-Cu - 1*10-9
* The PU films synthesized with PPG-2000
a) dc measured using two-electrode method and b) dc obtained using DRS data

Table 6. PUs conductivity at a direct current

-1
10
0
0 120 C
0
0
80 C 100 C
60 C
M''

-2
10

2 3 4 5
10 10 10 10

f,Hz
Figure 11. Log-log plots of the imaginary part of complex electrical modulus M” vs. frequency for
CPU–5%Eu at several temperatures
68 Polyurethane

0
T,C
120 110 100 90 80 70

0,5% Eu(fod)3
-3 -3
10 10
0% Eu(fod)3


-4
5% Eu(fod)3 -4
10 10

1% Eu(fod)3

2,6 2,8 3,0

-1
1000/T,K
Figure 12. The thermal dependence of the relaxation time (τmax) for the CPU with various content of
Eu (3+) chelate compound.

-4,5

-5,0

-6 -5,5 4

-6,0
lgdc, S/cm

-7 3
1 -6,5
lgdc(S/cm)

2
-8 -7,0

-7,5
2
-9
-8,0
3
1
-10 4
-8,5

5 -9,0
-11
2,5 3,0 -9,5
2,4 2,6 2,8 3,0 3,2 3,4
-1
1000/T,K -1
1000/T(K )

Figure 13. The logdc vs. 1/T for CPU: (a) CPU with various length of flexible component: CPU (PPG-
2000) – 1%Cu2Zn (1); CPU (PPG-1000) – 1% Cu(eacac)2 (2); CPU (PPG-2000) – 1% Cu(eacac)2 (3);
CPU (PPG-2000) – 0 (4); CPU (PPG-1000) – 0 (5) and (b) CPU-0 (1) and CPU-Cu2Zn formed in the
presence of various solvents: 1, 4-dioxane (2); dichloromethane (3) and DMFA (4).

The curves on the fig. 11 have well defined maxima in temperature region of 60 to 120oC.
According to (Pathmanatham & Johari, 1990; Kyritsis & Pissis, 1997) these maxima
correspond to conductivity relaxation. Increasing of temperature is accompanied with
shift of conductivity relaxation maxima to higher frequencies (fig. 11). The fact concerned
to increasing of segmental mobility in PU. The metal chelate compounds introduction
and increasing of their content in the system result in increasing of PU segmental
mobility.
 Bottom-Up Nanostructured Segmented Polyurethanes with Immobilized in situ Transition and
Rare-Earth Metal Chelate Compounds – Polymer Topology – Structure and Properties Relationship 69

1
Experimental dependences of relaxation time ( τ max  ) in log scale vs. 1/T (fig. 12) for
2 πf max
metal-containing PU are linear indicating the Arrhenius-type of temperature dependence of
τmax.

Decreasing of max value with the increasing of Eu(3+) content in PU confirm increasing of
macro chains mobility in metal-containing CPU (Kozak et al., 2006). The activation energy of
conductivity relaxation for CPU-0, CPU-0,5%Eu, CPU-1%, CPU-5% are approximately
similar. Experimental dependences of logdc vs. 1/T are non-Arrenius both for PU-0 and
metal containing PUs. It fit the theoretical curves of Vogel–Tamman-Fulcher (VTF) equation
σdc=σoexp(-B/(T-To) (fig. 13) indicating influence of the PU free volume on charge transport.
The results obtained give evidence of significant influence of structural organization in the
modified PU on its conductivity level.

As it can be seen PU’s direct current (σdc) conductivity grows with increasing of temperature
and that is characteristic to ionic conductivity. The metal ion participation as current carrier
is unlikely because to small amounts of metal ion in the modified PUs (~ 0.025-0.25% wt.).
That fact and coordination immobilization of the modifiers in polymer makes unlikely
increasing of the conductivity due to the metal chelate compound conductive properties. On
the other hand ionic mechanism of conductivity and adequate amount of protons presented
in PU matrix as well as observed increasing of polymer chain mobility in modified PU
allows us to suppose proton participation in the process of charge transport.

Comparison of direct current conductivity of CPU based on PPG-2000 with conductivity of

CPU based on PPG-1000 shows increasing of conductivity at the direct current of such system
up to 10-7Sm/sm at the 40оС due “softening” of PU. Nevertheless it can be seen that
conductivity level of maximum soft LPU is at least one order lower then conductivity of CPU.

6. “Metal chelate compound - polymer” complexing and formation of the

additional network of coordination bonds in metal containing PU
Mutual influence of metal chelate compound and polymer matrix due to complex formation
is a decisive reason of observed changes of structural, dynamic, relaxation etc.
characteristics of the metal contained PU. The complexing of metal chelate compounds with
PU matrix was analysed using electron spectroscopy and EPR.

6.1. The complexing of the metal chelate compound with PU matrix according to
the electron spectroscopy
The electron spectroscopy allows analyse both character of complexing of metal chelate
compound with the polymer matrix and state of metal chelate compound in PU.
The electron spectra of transition and rare-earth metal chelate compound in PU indicate
presence of the band of d-d-transitions for the transition metal chelate compound introduced
into PU (fig.14) and band of π-π-transitions for the rare-earth metal chelate compounds
70 Polyurethane

introduced into PU. That points on saving of chelate structure of the complexes in polymer
matrix. While the change the band intensity, its broadening and shift to a long-wave region
testifies their participation in complexing with PU.

Figure 14. The electron spectra of transition metal chelate compounds in dichloromethane (a) and LPU
(b): Cu(tfacac)2 (1), 1%Cr(acac)3 (2), Cu(eacac)2 (3); Co(acac)3 (4); LPU Cu(tfacac)2 (ε = 28 l/molsm) (1);
LPU-1%Cr(acac)3 (ε = 33 l/molsm) (2); LPU-1%Cu(eacac)2 (ε = 40 л/ l/molsm) (3); LPU-1%Co(acac)3(ε =
117 l/molsm) (4)

Figure 14 represents comparison of electron spectra in the visible region of the LPU films
with 1%wt. of transition metal (copper, chrome, cobalt) chelate compounds (fig. 14, a) and
the spectra of this metal chelate compounds dissolved (c= 10-2 M) in dichloromethane
(CH2Cl2) (fig. 14, b).
In addition to described above changes in electron spectra the influence of fluorine on
complex ability of metal chelate compound in PU is evident due to, the rise of absorption
level (ε = 40 l/molcm) and hypsohromic shift of maxima of band of d-d-transitions for LPU
- 1% Cu(eacac)2 as compared with LPU-1% Cu(tfacac)2 that have fluorine in ligand (ε =
28 l/molcm). Fig. 15 illustrates the detailed analysis of electron transitions of copper ion in
β-diketonates (4 transitions for D2h symmetry). Calculated maxima positions of Gaussian
components of adsorption band corresponding to electron d-d-transitions of copper ion for
Cu(tfacac)2 and Cu(eacac)2 in solution and in PU are listed in the table 6.

υ, cm-1
System dчн  dz2 dчн  dx2  y 2 dчн  dyz
dчн  dxz
Cu(tfacac)2 in CH2Cl2 13658 15386 17930 19579
LPU -1% Cu(tfacac)2 13435 15179 16322 17628
Cu(eacac)2 in CH2Cl2 13715 15376 16686 18261
LPU-1% Cu(eacac)2 12771 14497 16059 17738
Table 7. The allocation of Gaussian components of copper chelate compounds adsorption band.
 Bottom-Up Nanostructured Segmented Polyurethanes with Immobilized in situ Transition and
Rare-Earth Metal Chelate Compounds – Polymer Topology – Structure and Properties Relationship 71

Figure 15. The adsorption band of LPU+1%Cu(tfacac)2 with Gaussian components allocation.

The maxima of dxz and dyz transitions of Cu(2+) ion in copper chelate compounds,
immobilized in PU matrix are shifted to the long-wave region, as compared to
corresponding transitions of copper chelate compounds in solution (table 6). Visible
broadening of the dz2 component of absorption band of Cu (2+) chelate compounds in PU
indicates the prevalence of axial coordination of macro ligand in “PU-metal chelate
compound” complexes.

6.2. Complex formation in the “polymer-modifier” system according to EPR data

The EPR data confirm the complexing between the metal chelate compound and PU
functional groups. The state of paramagnetic Cu(2+) containing chelate compounds in PU
can be directly analyzed using EPR due to sensitivity of spin-electron parameters АII and gII
(see table 7) of the tetragonal copper chelate compounds to symmetry and chemical nature
of the copper nearest environment.

Decreasing of АII and increasing gII of Cu(acac)2, Cu(tfacac)2, Cu(eacac)2

and (Cu2Zn2(NH3)2Br2(HDea)4)Br2 immobilized in PU as compared with undisturbed
compounds indicate the participation of the modifiers in the complexing with PU electron
donor groups.

Figure 16 illustrates the representative EPR spectra of some copper containing modifiers
both isolated and immobilized in PU with different topology (linear and cross-linked).
The EPR spectra of polyheteronuclear powdered crystalline samples have anisotropic shape
with weakly resolved HFS due to broadening of the spectrum components and possible
tetrahedral distortion of the copper ion surrounding in the polyatomic complex.
Immobilization of such chelate compounds in a PU network resulted in decreasing of the
EPR signal intensity.
72 Polyurethane

AII 10-4 A┴10-4 a0*10-4

System gII g┴ g0
сm-1 cm-1 cm-1
1 Cu(tfасас)2 * 2,271 187 2,052 23 - -

2,275 172 2,131 71

CPU-1% Сu(tfacac)2 2,059 21
2,290 151 2,136 64

2,283 162 2,127 67

LPU-1% Сu(tfacac)2 2,049 19
2,302 141 2,133 60
1 Cu(eacac)2 * 2,276 187 2,055 22 2,128 68

CPU-1% Cu(eacac)2 2,249 150 - - - -

LPU-1% Cu(eacac)2 2,298 173 - - - -

1 Cu(acac)2 * 2,250 189 2,052 24 2,118 75

CPU-1% Cu(acac)2 2,269 182 - - - -

LPU-1% Cu(acac)2 2,254 188 2,052 29 2,119 82

2 (Cu2Zn2(NH3)2Br2(HDea)4)Br2 2,370 122 - - - -

2,370 132
CPU-1% CuZn - - - -
2,300 142

LPU-1%CuZn - - - - - -
undisturbed Cu(2+) complex in glassy matrix chloroform/toluene (40/60) (at -196oC)
1)

2)powder of polycrystalline sample

* (Lipatova & Nizelskii, 1972)

Table 8. Electron-spin parameters of isolated and polymer immobilized copper complexes.

The most reasonable explanation for this effect is distortion of the modifier’s symmetry or
geometry in PU-CuZn. The shape of EPR signal in PU network modified with
(Cu2Zn2(NH3)2Br2(HDe)4)Br2 indicates formation of complexes of various content and
structure.

6.3. Low molecular probes dynamic and formation of additional network of the
coordination bonds in metal containing polyurethanes
Using QENS and EPR with paramagnetic probes of various natures it was shown that
complex formation of metal containing modifier with macro chains results in appearance of
additional spatial obstacles for probe diffusion as compared with metal free network. The
dynamic of low molecular probes and complex formation in the nanostructured
polyurethane network containing Co (3+) chelate compounds immobilized in situ were
analyzed.
 Bottom-Up Nanostructured Segmented Polyurethanes with Immobilized in situ Transition and
Rare-Earth Metal Chelate Compounds – Polymer Topology – Structure and Properties Relationship 73

(a) (d) (g)

(b) (e) (h)

(c) (f) (i)

Figure 16. EPR – spectra of matrix isolated Cu(eacac)2 (a), Cu(acac)2 (b), (Cu2Zn2(NH3)2Br2(HDea)4)Br2
(c) in chloroform-toluene at -196oC; LPU with 1%wt. of Cu(eacac)2 (d), Cu(acac)2 (e),
(Cu2Zn2(NH3)2Br2(HDea)4)Br2 (f) and CPU with 1%wt. of Cu(eacac)2 (g), Cu(acac)2 (h),
(Cu2Zn2(NH3)2Br2(HDea)4)Br2 (i).

According to EPR data obtained using complex spin probe (Kozak et al., 2006) it was
demonstrated that in cobalt containing CPU the complexes “polymer-metal chelate
compound” of two types are formed. The analysis of rotational diffusion of nitroxyl spin
probe TEMPO (see table 2) reveals the decreasing of PU segmental mobility due metal
chelate compound introduction and/or it content increasing. The dynamic of solvent
molecules diffusion in swelled CPU-0, CPU-5%Co films and in probe liquid was
analysed to compare the ratio of one-particle and collective modes of the solvent
molecules motion.
74 Polyurethane

DF ·10-6, DL/D,
System D·10-6, cm2/с DL·10-6 , cm2/с
cm2/с %

Probe liquid 3,52 3,18 0,35 8,0

The solution of Со(асаса)3 5%wt.

3,33 3,04 0,29 8,7
in the probe liquid

CPU-0 (CH2Cl2) 2,71 2,40 0,31 11,5

CPU-Со5% (CH2Cl2) 1,85 1,32 0,53 28,6

CPU-Со5% (DMF) 1,25 0,89 0,36 28,8

where DF – one-particle (“Frenkel ”) diffusion coefficient ;
DL – collective (“Lagrangian”) diffusion coefficient.

Table 9. The diffusion parameters of the probe molecules in the swelled PU films

The sharp decreasing of both the general and one-particle component of diffusion coefficient
for the metal containing PU as compared with the metal-free PU indicates the appearance of
the spatial hindrances for the liquid molecule dynamics.

7. Conclusion
Immobilization in situ mono- and polyheteronuclear chelate compounds of transition and
rare-earth metal in linear and cross-linked polyurethanes results in nanoscale structuring of
forming polymer and is accompanied with polymer matrix enrichment by the nanosize
heteroligand macro complexes of metal formed simultaneously with organic nanosize
structures characteristic for metal-free polymer. Nanostructuring of formed in this way
polyurethane favours creation of a new hierarchy in structural organization of the polymer
as compared with metal free system as well as changes in dynamic, relaxation, optical,
dielectric, surface etc. properties of the modified polyurethane.

Analysis of structural heterogeneity of metal-modified polymer indicates existence of two

types of nanosize heterogeneities in the bulk of polyurethane. One of them is inherent to
segmented PU and another is generated in the presence of transition metal chelate
compound. The structural heterogeneity of PU influences the local segmental mobility of
macro chains, resulting in “dynamic heterogeneity” as well as in “thermodynamic
heterogeneity” of the systems.

The possible origin of the formation of the ordered micro regions is segmental structure of
PU containing the soft and hard blocks with different complex ability relative to metal
chelate compound. The PU’s surface structure depends on the boundary “polymer-support”
or “polymer-air”. Concentration of PU less polar groups that form the weak complexes with
metal chelate compound at the „polymer-support” boundary can facilitate the partial
segregation of metal containing centres at this boundary.
 Bottom-Up Nanostructured Segmented Polyurethanes with Immobilized in situ Transition and
Rare-Earth Metal Chelate Compounds – Polymer Topology – Structure and Properties Relationship 75

The essential increasing of luminescence intensity of the rare-earth metal in the

polyurethane environmental is a way for creation of new optically active materials. The
intensity of PU-Eu luminescence depends both on the europium chelate compound content
and polymer topology. Contrary to LPU the relationship of luminescence intensity vs.
modifier percentage in CPUs is linear.

Increasing of the polyurethane conductivity to semi-conducting level is caused by the

drastic increasing of macro chain mobility in the presence of polyheteronuclear modifiers.
Conductivity level of LPU is at least one order lower then conductivity of CPU.

The results obtained indicate significant influence of structural organization of the modified
polyurethane on its properties. The effect is caused by complex formation between metal
chelate compound and functional groups of the forming polymer. The analysis of dynamic
of low molecular probes and complex formation in the nanostructured polyurethane gives
experimental evidence of existence of additional coordination bond network in metal-
contained polyurethanes.

Author details
Nataly Kozak and Eugenia Lobko
Institute of Macromolecular Chemistry National Academy of Sciences of Ukraine, Ukraine

Acknowledgement
We would like to express our sincere gratitude to Professor Svetlana B. Meshkova
(A. V. Bogatsky Physic-Chemical Institute of National Academy of Sciences of Ukraine,
Odessa) and Professor Vladimir N. Kokozay (Taras Shevchenko Kyiv University) for
synthesized heteroligand rare-earth metal’s and polyheteronuclear chelate compounds,
respectively.

8. References
Bershein, V.A. & Yegorov, V.M. (1990). Differential Scanning Calorimetry in Polymer Physic. (in
Russ.). Chemistry, ISBN 5-7245-0555-X, St. Petersburg
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 Chapter 5

Thermal Analysis of Polyurethane

Dispersions Based on Different Polyols

Suzana M. Cakić, Ivan S. Ristić and Olivera Z. Ristić

Additional information is available at the end of the chapter

[Link]

1. Introduction
1.1. Water-based polyurethane dispersions
Water-based polyurethane dispersions (PUD) are a rapidly growing segment of
polyurethane (PU) coatings industry due to environmental legislations such as the clean air
act and also due to technological advances that made them an effective substitute for the
solvent-based analogs. Water-based or waterborne PUD have gained increasing importance
in a range of applications, due in large part to properties such as adhesion to a range of
substrates, resistance to chemicals, solvents and water, abrasion resistance and flexibility.
Water-based PUD show very good mechanical and chemical properties and match the
regulatory pressures for low volatile organic compound (VOC) containing raw paints. The
continuous reduction in costs and the control of VOC emissions are increasing the use of
water-based resins, motivating the development of PU dispersed in water. PU obtained
from water-based PUD have superior properties when compared with similar materials
obtained from organic media. Water-based PUD are used in many application areas to coat
a wide range of substrates - for example footwear adhesives, wood lacquers for flooring and
furniture, leather finishings, plastic coatings, printing inks and automotive base coats
(Rothause et al., 1987; Kim et al., 1994; Ramesh et al., 1994).

Regarding the chemical nature of PU, the water based PU are applied with higher solids
content, compared to the solvent based PU, because their viscosity does not depend on the
molecular weight of PU, as is the case for solvent based PU (Gunduz & Kisakurek, 2004).
Thus waterborne PUD can be prepared at high solid contents with a molecular weight
enough to form films with excellent performance resulting solely upon “physical drying”.
This means that the film formation occurs by simple evaporation of water even at room
temperature.

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Cakić al.,al.,
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80 Polyurethane

Waterborne PUD are fully-reacted PU systems produced as small discrete particles. 0.1 to
3.0 micron, dispersed in water to provide a product that is both chemically and colloidally
stable, which only contains minor amounts of solvents and does not emit VOC. Polymeric
structure of waterborne PUD is formed by usually reacting an excess of aliphatic isocyanates
(mainly IPDI or HDI based), with a polyol or a mixture of polyols to form a prepolymer
containing the so called soft segment. The polyols are generally polyesters, polyethers, or
polycarbonates. The hard segment is generally formed by chain extending the prepolymer
with short chain diamines and from the short chains containing ions. Due to incompatibility
between the two segments of the polymer chain, the hard segment separates and aggregates
into domains that act as reinforcing fillers to the soft segment. The degree of phase
separation as well as the the concentration of the hard segments are contributing factors to
the good properties of PUD. PU backbone with a minority of the repeat units contains
pendant acid or tertiary nitrogen groups, which are completely neutralized or quarternized,
respectively, to form salts. Such ionomeric groups are absolutely necessary for the formation
of dispersions, because they act as internal surfactants, and are not incorporated in the chain
of the solvent-based PU. Ionic centers in the hard segment generally favor segregation and
cohesion within the hard segment domains due to their strong electrostatic forces and
thermodynamic incompatibility with the polymer matrix. Water-based PUD can be divided
into two classes. The first group consists of polymers stabilized by external emulsifiers, and
second one achieves stabilization by including hydrophilic centers in the polymer. Such
hydrophilic centers may be one of the three types: non-ionic, cationic groups and anionic
groups. These hydrophilic groups fulfill the function as internal emulsifiers and make
possible to produce stable water/based emulsions. Water–based PUD can be classified into
anionic, cationic and nonionic systems (Rothause & Nechtkamp, 1987; Kim et al., 1996).

Several processes have been developed for the synthesis of PUD. All of these have in
common the first step, in which a medium molecular weight polymer (the prepolymer) is
formed by the reaction of suitable diols or polyols (usually macrodiols such as polyether or
polyester) with a molar excess of diisocyanates or polyisocyanates. In this reaction mixture,
an internal emulsifier is added to allow the dispersion of the polymer in water; this
emulsifier is usually a diol with an ionic group [carboxylate, sulfonate, or quaternary
ammonium salt) or a nonionic group poly(ethylene oxide)]. The internal emulsifier becomes
part of the main chain of the polymer. The critical step in which the various synthetic
pathways differ is the dispersion of the prepolymer in water and the molecular weight
build-up. The most important dispersions are emulsifier-free ionomer dispersions. The
resulting dispersions are mainly anionic or non-ionic, that have the potential for wide
variations in composition and property level. They can be obtained by different processes,
however, the earliest process to prepare the aqueous PUD is known as acetone process and
this process has remained technically important so far (Hepburn, 1992; Oertel, 1985). Within
the last three decades several new processes have been developed such as prepolymer
mixing process, hot melt process and ketamine/ketazine process.

The facts that aqueous/water PUD have become increasingly important for industrial and
academic research in recent years is due to the following reasons:
 Thermal Analysis of Polyurethane Dispersions Based on Different Polyols 81

1. the environmental law requires for the development of ecological-friendly products for
which the emissions of volatile organic compounds (VOC) have been reduced to a
minimum,
2. the economic reasons (substitution of expensive organic solvents in conventional PU
with water),
3. the water PU surpasses performance of conventional isocyanate- and/or solvent-
containing PU,
4. continuous increase in solvent prices, low raw material costs and easy to clean up the
reactor system made waterborne PU system more popular in the industry.

2. Ingredients for water–based PUD

The basic components used to build up PUD include long–chain polyether, polyester or
polycarbonate polyol, diisocyanate, aromatic or (cyclo)aliphatic, low molecular weight
glycol and /or diamine, bis–hydroxycarboxylic acid and a neutralization base. In general, an
excess of diisocyanate is treated with a long-chain linear polyol, bis-hydroxycarboxylic acid
and other low-molecular-weight glycol to form an isocyanate-terminated prepolymer with a
segmented structure. In this polymer, the long-chain polyol units form soft segments, and
the urethane units-built up from diisocyanate, glycol and bis-hydroxycarboxylic acid form
hard segments. The pendant carboxylic acid groups are neutralized with base to form
internal salt group containing prepolymers that can be easily dispersed in water. The
microphase separation between the incompatible soft- and hard-segment sequences
contributes to the unique properties of PUD. The PU chains with NCO terminating groups
can be extended with glycol forming urethane groups. Chain extenders are low molecular
weight, hydroxyl and amine terminated. Aliphatic isocyanates: hexamethylene diisocyanate
(HDI), isophorone diisocyanate (IPDI) and (4,4’–diisocyanatodicyclohexylmethane
(H12MDI), improve thermal and hydrolytic stability, resistance to UV degradation and they
do not yellow (Bechara, 1998).

Aliphatic diisocyanates are less reactive than aromatic ones and they must be used with
certain catalysts. Aromatic isocyanates: methylene diphenyl diisocyanate (MDI), toluene
diisocyanate (TDI) and 1,5–naphthalenediisocyanate (NDI) on the other hand, provide for
toughness but yellow upon exposure to UV light. Although early water dispersed PU resins
heavily utilized TDI, there is a high tendency to shift to aliphatic diisocyanates or to the
aromatic diisocyanates with NCO groups not directly attached to an aromatic nucleus
(Gunduz & Kisakurek, 2004).

The two key classes of polyols are polyethers and polyesters. Polyester polyols have been
largely used in PUD paints as they exhibit outstanding resistance to light and aging. There
are four main classes of polyester polyols: linear or lightly branched aliphatic polyester
polyols (mainly adipates) with terminal hydroxyl groups, low molecular weight aromatic
polyesters for rigid foam applications, polycaprolactones, polycarbonate polyols. Polyether
polyols are susceptible to light and oxygen when hot, however, they improve water
dispersion, and impart chain flexibility. These are made by the addition of alkylene oxides,
82 Polyurethane

usually propylene oxide, onto alcohols or amines which are usually called starters or
‘initiators’. Polyether based on propylene oxide contains predominantly secondary hydroxyl
end–groups. Secondary hydroxyl end–groups are several times less reactive with
isocyanates than primary hydroxyl groups and for some applications, polyether based only
on propylene oxide may have inconveniently low reactivity. The primary hydroxyl content
may be increased by a separate reaction of the polyoxypropylene polyols with ethylene
oxide to form a block copolymer with an oxyethylene tip.

In the choice of polyol for PU application, selected polyols must be competitive with other
polyols and also enable the final PU product to be cost competitive with other materials in
the end application.

In a typical anionic PUD process, anionic groups (carboxylic and sulfonic) are introduced
along the length of the polymer chain by using hydrophilic monomers or internal
emulsifiers. As the hydrophilic monomer, dimethylol propionic acid (DMPA) is the most
widely used acid, which has two hydroxyl groups, therefore, it can be one of the main
constituents of the PU backbone. DMPA improves the hydrophilic property by serving as
the potential ionic center with N–methyl pyrrolidone as the co–solvent. Tartaric acid (TA)
can also be used, but it usually results in branching. However, TA improves the mechanical
properties of PU paint. Study has shown that the particle size of dispersion depends on the
content of DMPA. Therefore, increased amount of DMPA leads to more ionic centres in the
PUD backbone and thereby increasing hydrophilicity of the polymer and hence reductions
in particle size (Dieterich, 1981; Jacobs & Yu, 1993; Rosthauser & Nachkamp, 1986).

The chain extension step also has a high influence on the properties of the resin produced,
not only due to the structure and concentration of the extender but also due to process
variables that influence the particle size distribution. Chain extenders are difunctional
glycols, diamines or hydroxyl amines. If a diol of low molecular weight reacts with the NCO
terminated PU chains in the chain extension reaction step, urethane linkages will be formed
but if a diamine is used as chain extender, the NCO terminated PU chains will form urea
linkages. The higher density of hydrogen bonds of polyurea hard segments is responsible
for the improved mechanical properties of polyurea and PU/urea products. Typical chain–
extending agents are as follows: water, diethylene glycol, hydroquinone dihydroxyethyl
ether, bisphenol A, bis(hydroxyethylether), ethanolamine, hydrazine, ethylene diamine.
Aliphatic diamines such as hydrazine or ethylene diamine are used as chain extenders in
processes directed to preparing waterborne PUD. In the chain extension step, it is most
important to control the extremely fast reaction between NCO groups and NH2 groups
accompanied by the viscosity rise. Molecular weight of PUD increases by the formation of
urea linkages through the chain extension step and it is the most important step to
determine the molecular weight of PUD (Kim, 1996; Delpech & Coutinho, 2003).

In the synthesis of PUD, to neutralize the carboxyl and/or sulfo groups, are used agents that
contain one or more bases and to form internal salt groups containing prepolymers that can
be easily dispersed in water. During the neutralization, carboxyl and/or sulfo groups serve
for anionic modification or stabilization of the PUD. Tertiary amines and in particular
 Thermal Analysis of Polyurethane Dispersions Based on Different Polyols 83

triethylamine are preferably used. The structure of waterborne anionic PUD is illustrated in
Scheme 1.
Most commonly used catalysts in PU chemistry are tertiary amine catalysts and metal
catalysts, especially tin catalysts. Tertiary amines are catalysts for the isocyanate–hydroxyl
and the isocyanate–water reactions. Organotins are the most widely used, however
organomercury and organolead catalysts are also used but have unfavourable hazardous
properties.

Soft segment in
hard domain

Hard segment in
soft segment
Hard domain

−
OOC− -COO−
N+ N+

−
OOC-
N+

Soft domain

Macropolyol Reacted diisocyanate

Urethane or urea linkage
-COO− DMPA and counterion
N+ Hydrogen bonding

Scheme 1. Structure of waterborne anionic PUD (Tawa & Ito, 2006)

2.1. Various methods for preparing water–based PUD

The most important process is the prepolymer mixing process that has the advantage of
avoiding the use of a large amount of organic solvent. In this process hydrophilically
(carboxylate molecule) modified prepolymer is directly mixed with water. If the mixture
viscosity is too high, a small amount of a solvent such as N–methyl pyrrolidone can be
added before the dispersion step. Chain extension is accomplished by the addition of di– or
polyamines to the water–based prepolymer dispersion.
The acetone process can be considered the link between the solvent synthesis and the
prepolymer mixing process. In effect, the prepolymer is synthesized in a hydrophilic organic
solvent, for example acetone solution and afterwards it is subsequently mixed with water.
The hot melt process explains the process of obtaining a PUD by the reaction of NCO–
terminated ionic modified prepolymer with, for example ammonia or urea resulting in a
prepolymer with terminal urea or biruet groups, respectively. The terminal urea or biruet
prepolymer is methylolated with formaldehyde and mixed with water, forming dispersion
84 Polyurethane

spontaneously. By polycondensation (lowering the pH, increasing the temperature), chain–

extension or cross–linking was obtained.

Ketamine and ketazine process explains the process of obtaining a PUD by reaction of
NCO–prepolymers containing ionic groups mixing with a blocked amine (ketamine) or
hydrazine (ketazine) without premature chain extension. These mixtures can be emulsified
with water even in absence of co–solvents. The reaction with water liberates the diamine or
hydrazine, which then reacts with the prepolymer.

Non–ionic dispersions are obtained similar to ionomer dispersions if the ionic centre is
replaced by lateral or terminal hydrophilic ether chain. The temperature of dispersing
process has to be kept below 60 °C. Non–ionic dispersions are stable towards freezing, pH
changes and addition of electrolytes.

3. Thermal analysis of PU
Thermal analysis techniques have been used for many years in many scientific and
industrial laboratories for studying the thermal decomposition of polymeric materials.
Among them thermogravimetry (TG) is one of the most common since the mass of a sample
is easy to measure accurately and valuable information regarding the nature of the process
can be extracted from a mass loss against time or temperature plot. The thermal
decomposition of PU (their degradation attributed to absorbed thermal energy) is important
phenomenon from both fundamental and industrial applications (Pielichowski et al., 2004).
The understanding of degradation processes allows determination of optimum conditions
for designing PU in order to obtain high-performance polymer materials. Fundamental
research has established that the thermal decomposition of PU is a complex heterogeneous
process and consists of several partial decomposition reactions (Scaiano, 1989). The study of
the decomposition of PU is particularly difficult since they degrade with the formation of
various gaseous products and a number of decomposition steps are typically observed in
thermogravimetric analysis (TGA) experiments. Some authors claim that the study of the
thermo-degradation behavior of PU at high temperatures provides a fingerprint of the
material that has to do not only with the characteristics of the original material, but also
with its processing and the final quality of the end use products (Prime et al., 1988). The
thermal stability of a material is defined by the specific temperature or temperature-time
limit within which the material can be used without excessive loss of properties
(Chattopadhyay & Webster, 2009). With respect to commercial applications, the
investigation of thermal decomposition processes has two important aspects. The first
concerns the stabilization of a polymer to obtain novel materials with a desired level of
thermal stability that will be able to fulfill the demands of contemporary materials
engineering. The second is to understand material behavior at higher temperature as well as
to obtain characteristic thermal decomposition data.

A waterborne PUD can be defined as a binary colloidal system in which PU particles are
dispersed in a continuous aqueous medium. PUD are usually prepared as low molecular
weight NCO-terminated prepolymers for ease of dispersion. Then, diamines are generally
 Thermal Analysis of Polyurethane Dispersions Based on Different Polyols 85

used to increase the molecular weight by reaction with the terminated NCO end groups
(chain extension). The presence of ionic species in PUD has a considerable effect on the
physical properties. PUD are now one of the most rapid developing and active branches of
PU chemistry.

PU are synthesized by the prepolymer reaction of a diisocyanate and a polyol (mainly

polyethers and polyesters). If a diol of low molecular weight reacts with –NCO-terminated
prepolymers in the chain extension reaction step, urethane linkages will also be formed but
if a diamine is used as chain extender, the reaction between the –NH2 groups and the –NCO
terminated prepolymers will form urea linkages. In this case, poly(urethane-urea)s, which
are the most important class of polyureas, are produced. These copolymers show reduced
plasticity in comparison to homopolyurethanes. The resulting PU or poly(urethane-urea)
chains consist of alternating short sequences forming soft (flexible) and hard (rigid)
segments. The soft segments, originated from the polyol, impart elastomeric characteristics
to the polymer. The hard segments are mainly produced by reacting the isocyanate and the
chain extender. They are polar and impart mechanical properties to PU. The hard segments
contain the highly polar urethane linkages. Due primarily to interurethane and urea
hydrogen bonding, the two segment types tend to phase-separate in the bulk, forming
microdomains. The hard segments act as physical crosslinks and, as a consequence, the
physical, mechanical and adhesive properties depend strongly on the degree of phase
separation between hard and soft segments and interconnectivity of the hard domains. The
urethane linkages in PU can serve as H-bond acceptor and donor. In polyether-based PU,
the urethane –NH can bond to either the polyether –O– linkage or the urethane –C=O
groups. In the case of poly(urethane-urea) formation, there is an additional –NH from urea
linkage participating in the interactions (Delpech & Coutinho, 2000). The degradation of
thermoplastic PU has been extensively studied, and a number of reviews are available (Lu et
al., 2002; Fambri et al., 2000). Thermal degradation of ester- and ether-based thermoplastic
PU is performed under vacuum, air and nitrogen, allowing investigators to determine the
mode of degradation (Dulog & Storck, 1996).

Polyester-based thermoplastic PU exibit rapid degradation in air and nitrogen, indicating

that a nonoxidative mechanism is involved. In contrast, the significantly improved thermal
stability of ether-based PU under vacuum and nitrogen indicates that the oxidative process
plays a major role in the decomposition of ether-based thermoplastic PU. In general, the
ester-based PU normally exibit better thermal and oxidative stabilities than the ether-based
ones. The mechanism of thermal degradation of PU is very complex due to the variety of
products formed.
It is proposed that the thermal degradation of thermoplastic PU is primarily a
depolycondensation process, which starts at about 200 oC (Cakić et al., 2006 a). The first
stage of decomposition is because of degradation of hard segments and starts at about 200
oC and at ~ 360-380 oC, while the second step of degradation is because of degradation of

soft segments and ends above 480 oC. Waterborne PU should exhibit some different features
in thermal degradation due to their unique chain structure, for example, salt-forming
groups. Therefore, it is necessary to analyses their thermal degradation behavior to
86 Polyurethane

understand the structure-property relationship. The properties of PUD are mainly

determined by the interactions between the hard and soft segments, and by the interactions
between the ionic groups. The ionic group content, solids content, segmented structure,
molecular weight of the macroglycol, the type of chain extender and the hard/soft segments
ratio, determine the properties of PUD.

In the following sections, we will review typical results to demonstrate the utility of TGA in
deducing the structural and bonding information about waterborne PUD based on different
polyols. The thermal stability of PU and poly(urethane –urea)s cast films with anionomer
character, obtained from waterborne dispersions and based on isophorone diisocyanate
(IPDI), dimethylolpropionic acid (DMPA), poly(propylene glycol) (PPG), polycarbonate diol
(PCD) and glycolized products obtained from recycled poly(ethylene terephthalate)(PET) is
also compared. Three types of chain extenders were used: ethylene glycol (EG), propylene
glycol (PG) and ethylene diamine (EDA). The effect of type of polyols, chain extender, type
of catalyst, ionic content, length of soft segment, hard segment content and the presence of
urea or urethane linkages on the thermal stability of the waterborne anionic PUD are
discussed.

4. Water-based PUD based on poly(propylene glycol) and selective

catalyst
One of the inherent drawbacks of waterborne PU technology is the formation of carbon
dioxide due to the side reactions of isocyanate with water. When an isocyanate reacts with
water, the products are a urea linkage (via an amine intermediate) and carbon dioxide. The
carbon dioxide formation is problematic in that it causes imperfections in the coating
during cure, such as blistering and pin-hole formation. The main aspect in the development
of waterborne PU is in the first place to find methods for preventing the undesired
secondary reactions with water and achieving the best crosslinking. This reaction is reduced
to a minimum by the use of non-tin catalysts. One novel approach to control the water side
reaction is the use of catalysts which selectively catalyze the isocyanate-polyol reaction and
not the isocyanate-water reaction (Colling et al., 2002; Blank &Tramontano, 1996).

The relative selectivity (S) obtained from equation S = Purethane/Purea, was measured as
urethane IR peak area (Purethane)/ urea IR peak area (Purea) ratio, by method given by Blank
(Blank et al., 1999). After the integration of characteristic absorption max of urethane (1700
cm-1, 1540 cm-1) and urea (1640 cm-1, 1570 cm-1) was done, the relative selectivity was
calculated. The manganese catalyst, a complex of Mn(III)–diacetylacetonatomaleate with
various ligands based on acetylacetonate and maleic acid, used in some of the experiments
(Stamenković et al., 2003; Cakić et al., 2006), has shown a high selectivity for the isocyanate–
hydroxyl reaction in comparison to the commercially available zirconium catalyst (Blank et
al., 1999). Zirconium catalyst is a proprietary zirconium tetra-dionato complex in the
reactive solvent with the metal content of 0.4%.

TG is a suitable method to evaluate the thermal properties of several types of PU elastomers.

The thermal stability of PU has been studied extensively because of the great importance of
 Thermal Analysis of Polyurethane Dispersions Based on Different Polyols 87

this group of materials (Chang et al., 1995). These thermoplastic elastomers generally are not
very thermally stable, especially above their softening temperatures (Wang & Hsieh, 1997),
and their mechanism of thermal degradation is very complex due to the variety of products
formed. Commonly, it presents a bimodal profile where the first mode is related to the hard
segments of PU. Usually, at a low heating rate, the degradation process results in differential
weight loss (DTG) curves with several peaks, which is an indication of the complexity of the
degradation (Delpech & Coutinho, 2000).

4.1. Experimental
Poly(propylene glycol) (PPG) ), (Mn = 1000, hydroxyl value 111 mg KOH/g, dried under
vaccuum, at 120 oC), isophorone diisocyanate (IPDI) and dimethylolpropionic acid (DMPA),
were obtained from Aldrich Chemical Co. 1-methyl-2-pyrrolidone (NMP), dimethyl
formamide (DMF) and triethyl amine (TEA) were received from Merck (Darmstadt,
Germany). Ethylene glycol (EG) and propylene glycol (PG) obtained from Zorka Co.(Šabac
Serbia). Dibutyltin dilaurate (DBTDL), was supplied by Bayer AG. Zirconium catalyst
(ZrCat) was supplied by King Industries Inc., Norwalk, CT, USA. Manganese catalyst
(MnCat) has been used in the reactive diluent with a metal content of 0.4% (Stamenković et
al., 2003; Cakić et al., 2006 b). Water–based PUD from PPG with selective catalyst were
prepared using the prepolymer method has been described in detail in our previously work
(Cakić et al., 2009).

In the first step, PPG and DMPA were dispersed in DMF to obtain a homogeneous mixture
and heated at 70 oC. IPDI and DBTDL were added to the homogenized mixture at 80 oC. An
NCO/OH equivalent ratio of 3.0 was used. Hard : Soft segment ratio was defined as a ratio
between IPDI weight and polyol weight in the starting formulation and is calculated as 1.5.
The reaction times were determined by the dibutyl amine back titration method. After
obtaining completely NCO terminated prepolymer, the mixture was cooled to 60 oC and the
carboxylic groups were neutralized with TEA (DMPA equiv) dissolved in NMP. In second
step the chain extension was carried out with EG or PG. The selective catalysts, ZrCat or
MnCat, at concentration of 2% relative to the resin solids, have been added to the reaction
solution. Water was added to the mixture and stirred to obtain dispersion of organic phase
in water. The waterborne PUD contains 40 wt% solids (Cakić et al., 2009). Films were
prepared by casting the waterborne dispersions on leveled surfaces and allowing them to
dry at room temperature, for 7 days, and then at 60 oC, for 12h (Coutinho, 1996, 2003). When
chain extenders were EG and PG, the PUD had to be cast in Teflon surfaces due to the high
adhesiveness observed on the glass surface, making demoulding impossible. After
demoulding, the films were kept into a desiccator to avoid [Link] polyurethanes
were formed.

4.2. Results and discussion

Degradation profile of waterborne PUD is influenced by the variation of chain extender
presented in Fig.1. It was verified that the thermal stability was influenced by chain
88 Polyurethane

extender type. In a general way, thermal stability was higher when EG chain extender was
used, in comparison to PG, probably because of the higher reactivity of the primary
hydroxyl groups. The onset temperatures calculated for the first stage for PU chain-
extended with EG were about 234 oC and 140 oC for PG. Unsymmetrical structure of IPDI
enables easier diffusion of EG (Gunduz & Kisakurek, 2004).

Figure 1. TG curves of PUD without catalyst with EG (1) and PG (2) as chain extender

Fig. 2 shows the degradation profile of PUD with variation of catalyst using catalysts of
different selectivity. EG and PG formed urethane linkages by reaction with terminal NCO
groups. The initial onsets observed are: 234 oC when EG was employed, 275 oC and 311 oC,
when the chain extender was EG with ZrCat and EG with MnCat, respectively. The initial
onsets observed are: 140 oC when PG was employed, 290 oC and 305 oC, when the chain
extender was PG with ZrCat and PG with MnCat, respectively. The thermal stability was

Figure 2. TG curves of PUD with EG as chain extender (a), PG as chain extender (b), and MnCat (1),
ZrCat (2), without catalyst (3)
 Thermal Analysis of Polyurethane Dispersions Based on Different Polyols 89

higher when MnCat was used, in comparison with the use of ZrCat. This result suggested that
all the residual NCO groups in PU particles did not react with the chain extender completely.
Because the viscosity of particle is high at low temperature in the chain extension step, it
would take long time for chain extenders to diffuse into the particle. Therefore, the efficiency
of chain extension increased as total surface area of particles increased (Jang et al., 2002; Cakić
et al., 2007 a). In general, the presence of more selective catalyst has also been found to have a
stabilizing effect on the resultant PU, as can be observed in the curves obtained for the samples
chain-extended with EG and PG, in comparison to the samples obtained without selective
catalyst probably due to favoring of isocyanate-polyol reaction and not the isocyanate-water
reaction. The PUD was formed with higher hard segment proportions.
The DTG curves show that there are different stages of degradation which are not
perceptible in TG curves, showing the close relation and mutual influence between the
degradation process of hard and soft segments.
Fig. 3a shows the DTG curves corresponding to the TG degradation profiles presented in
Fig. 2a, in which the catalysts were varied (MnCat or ZrCat). The chain extender employed
was EG. Two peaks are observed. The first group of peaks, corresponding to the
degradation of rigid segments formed by urethane and urea linkages, presents maximum of
the peak from 200 to 250 oC. The second group, related to the degradation of PPG soft
segment, varying maximum of the peak from 375 to 418 oC . The peaks shifting towards
higher temperatures resulting from addition of more selective catalyst confirm the
assumption that all isocyanate groups had not reacted with the added chain extender.
Selective catalyst isocyanate-polyol reaction causes greater incorporation of chain extender
in hard segments, which is reflected on higher thermal stability of hard segments (Jang et al.,
2002; Lee et al., 1995; Cakić et al., 2007 b).
Fig. 3b depicts DTG curves related to TG profiles observed in Fig. 2b, in which the catalyst
were varied (MnCat or ZrCat). The chain extender employed was PG. The first group
of peaks presents maximum of the peak appearing in the range from 160 oC to 195 oC. The

Figure 3. DTG curves of PUD with EG as chain extender (a), PG as chain extender (b), and without
catalyst (1), ZrCat (2), (3) MnCat
90 Polyurethane

second group can be observed in the range, varying maximum of the peak, from 267 to
347 oC, for PPG soft segments. A marked difference can be observed, promoted by changing
the type of chain extender in DTG profiles, especially in the first stage of weight loss,
corresponding just to urethane (EG or PG as chain extender) linkage degradation. The soft
segment, formed only by PPG degradation step seemed to be also affected. The rigid
segment formed from EG retarded the weight loss of PPG chains (peak at 375 oC), while PG
showing peaks at 267 oC (Cakić et al., 2006, 2007 c). All DTG curves showed that there are
different stages of degradation which are not perceptible in TG curves, showing the close
relation and mutual influence between degradation of hard and soft segments.

The degradation profiles of PU cast films obtained from water-based dispersions were
influenced by the type of chain extender, length of the hard segment and type of catalysts.
The presence of more selective catalysts, which formed urethane linkages with higher hard
segment proportions, had a marked influence on the degradation of the polymers, especially
in elevated quantities, improving the thermal stability of the materials. The DTG curves
showed that the length of the hard segment had a strong influence on the thermal profile of
the samples as a whole. The type of chain extender, forming urethane linkages, affected the
whole process of degradation and the presence of more selective catalyst improved the
thermal resistance of the chains.

5. Water-based PUD based on glycolized products obtained from

recycled poly (ethylene terephthalate)
Recycling of polymers has received a great deal of attention (Atta et al., 2006, 2007).
Although several methods have been proposed for recycling waste poly(ethylene
terephthalate) (PET), it is suggested that the most attractive method is glycolysis of
chemicals into the corresponding monomers or raw chemicals that could be reused for the
production of plastics or other advanced meterials (Patel et al., 2007).

Two-stage PUD synthesis was applied: the first, glycolysis of PET using different types of
glycols (PG), triethylene glycol(TEG) and poly(ethylene glycol) (PEG 400), with different
molar ratio of PET repeating unit to glycol (1:2 and 1:10); the second, preparation of PUD of
the products formed.

PUD are prepared by anionic dispersion process (Cakić et al., 2011), using IPDI, glycolyzed
products, DMPA as potential ionic center which allow water dispersibility and ethylene
dimine (EDA) as chain extender.

5.1. Experimental
Example 1 of glycolysis reaction: Small pieces of PET waste (100 g), equivalent to 0.5 mol
repeating unit ([Link]. 192 gmol-1) were added to 88.64 g PG ([Link]. 76.09 gmol-1), 173.07 g
TEG ([Link].150 gmol-1) or 461.5 g PEG 400 ([Link]. 400 gmol-1), such that the molar ratio of
PET repeating unit to glycol was 1:2.
 Thermal Analysis of Polyurethane Dispersions Based on Different Polyols 91

Example 2 of glycolysis reaction: In the second experimental runs of depolymerisation,

appropriate amount of PET waste were added to 396.1 g PG, 750 g TEG or 2173 g PEG 400,
so that molar ratio of PET repeating unit to glycol was 1:10. These mixtures (with different
molar ratio PET/glycol) and 0.5 wt.% zinc acetate (based on the weight of PET as
transesterification catalyst) were charged to a glass reactor, which was fitted with stirrer,
reflux condenser, nitrogen inlet and temperature controller. This reactor was immersed in
an oil bath and the content of the reaction kettle was heated at 190 oC for 2 h, subsequently
the temperature was raised to 210 oC until all the solids disappeared.

The obtained glycolyzed oligoester polyols were analysed by the hydroxyl value (HV)
determination according to the conventional acetic anhydride/pyridine method (Cakić et al.,
2011). The hydroxyl value of the oligoester polyol obtained in the glycolysis reaction based
on molar ratio of PET repeating unit to glycol, 1:2, with PG was HBPG=490 mg KOH/g, TEG
HBTEG=370 mg KOH/g and PEG HBPEG400=297 mg KOH/g.

The hydroxyl value of the oligoester polyol obtained in the glycolysis reaction based on
molar ratio of PET repeating unit to glycol, 1:10, with PG was HBPG=201 mg KOH/g, TEG
HBTEG=209 mg KOH/g and PEG HBPEG400=192 mg KOH/g.

5.2. Synthesis of PUD based on glycolyzed products with molar ratio PET/glycol,
1:2
Anionic PUD based on glycolyzed products with molar ratio PET/glycol, 1:2, were prepared
by modified acetone process. Acetone was added to the prepolymer and the dispersion is
formed by the addition of water to this solution. Procedure for synthesis of anionic PUD has
been developed adjusting the molar ratio of DMPA as a hydrophilic monomer to IPDI as 1:3.3.
Mass of oligoester polyol, obtained by PET glycolysis, according to example 1, with a hydroxyl
number which is equivalent to the hydroxyl number of 0.06 mol of poly(propylene glycol)
PPG1000 (110 mg KOH/g), was for PG 15 g, TEG 20 g, poly (ethylene glycol) (PEG 400) 25 g.

The oligoester polyol and hydrophilic monomer (8 g, equ. 0.06 mol) was mixed in the
cosolvent DMF (50:50 w/w), in a 250-ml round four-neck glass reactor connected to a stirrer, a
thermometer, a reflux condenser and a nitrogen gas inlet. The reaction was carried out at 70 oC
for 30 min to obtain a homogeneous mixture and the uniform distribution of hydrophilic
monomer to PU backbone. IPDI (44.4 g, equ.0.2 mol) and catalyst DBTDL (0.03% of the total
solid) were added to the homogenized mixture at 80 oC for about 4h until the amount of
residual NCO groups reached a theoretical value, as determined by the dibutyl amine back-
titration method. To reduce the viscosity and obtain a homogenous mixture of NCO
prepolymers, acetone was added 50 wt% to the solid reaction mass. The theoretical value of
NCO groups for PUD based on oligoester polyol obtained from the glycolysis with molar ratio
of PET repeating unit to glycol, 1:2, was 19.2% for PG, 17.7%, for TEG and 16.1% for PEG.

After obtaining completely NCO terminated prepolymer, the mixture was cooled to 60 oC
and the carboxylic groups in hydrophilic monomer were neutralized with TEA (DMPA
equ). TEA was dissolved in NMP by stirring the solution for 60 min.
92 Polyurethane

PU anionomer was cooled to 30 oC then dispersed in water (50% of total mass) under high
speed stirring for 30 min. The rate of water addition to the mixture was carefully controlled,
to obtain a stable inversion. Upon completing the phase inversion, EDA (0.03 mol) was
added for 60 min. at 35 oC. PUD of about 30 wt% solids was obtained upon removal of
acetone by rotary vacuum evaporation at 35 oC.

5.3. Synthesis of PUD based on glycolyzed products with molar ratio PET/glycol,
1:10
Anionic PUD based on glycolyzed products with molar ratio PET/glycol, 1:10, were
prepared by prepolymer mixing method in two steps: synthesis of NCO-terminated
prepolymers and the preparation of dispersions by introducing anionic centers to aid
dispersions (Athawale & Kulkarni, 2009). The prepolymer mixing method has been
developed adjusting the molar ratio of DMPA to IPDI as 1:3, which was increased compared
to the previous procedure. Mass of oligoester polyol, obtained by PET glycolysis, according
to example 2, with a hydroxyl number which is equivalent to the hydroxyl number of 0.1
mol of poly(propylene glycol) PPG1000 (110 mg KOH/g), was for PG 54.5 g, TEG 52.6 g, poly
(ethylene glycol) (PEG 400) 57.3 g. The mass of oligoester polyols and hydrophilic monomer
was the same as in the previous procedure, but the mass of IPDI was (66.6 g, equ.0.3 mol).
determined by molar ratio of a hydrophilic monomer to IPDI as 1:3. In order to obtain NCO
terminated prepolymer, synthesis was controlled by determing the NCO groups by the
dibutyl amine back-titration method until a theoretical value was achieved. The theoretical
value of NCO groups for PUD based on oligoester polyol obtained from glycolysis with
molar ratio of PET repeating unit to glycol, 1:10, was 14.2% for PG, 13.7%, for TEG and
13.9% for poly(ethylene glycol). The neutralization of the carboxylic groups in hydrophilic
monomer, extension chain with EDA and the preparation of stable dispersion was done as
in the previous modified acetone process. The solid content in this dispersion was 30%.
Films were prepared by casting the aqueous dispersions on the glass surface and allowing
them to dry at room temperature for 7 days and then at 60 oC, for 12h (Coutinho, 1996,
2003). Films were cast by 100 μm applicators from the solutions onto glass surface (7cm x 2
cm) to obtain dry film thickness of 25-30 μm, making demoulding impossible. After
demoulding, the films were kept into a desicator to avoid moisture. TG experiments were
performed in a Perkin-Elmer TG-7 analyser. Film samples about 20 mg were placed in a
platinum sample pan and heated from 30 to 600 oC, with an air flow of 200 mL min-1 and
heating rates of 10 °C min-1. During the heating period, the weight loss and temperature
difference were recorded as a function of temperature.
TGA was used to analyze decomposition behavior of cured films of PUD synthesized with
glycolized products obtained from PET waste. TG curves are depicted in Figs. 4a,4c and 4e
(curve marked as 1 a show lower molar ratio of PET / glycol (1:2) in the glycolized oligoester)
represents the degradation of PUD influenced by the variation of oligoester polyols. It was
verified that the thermal stability was influenced by glycol type and different molar ratio of
PET repeating unit to glycol in glycolysis reaction. Figs. 4b, 4d and 4f depict the behavior of
corresponding differential weight loss (DTG) curves.
 Thermal Analysis of Polyurethane Dispersions Based on Different Polyols 93

Figure 4. TG curves (a) and DTG curves (b) of PUD synthesized from glycolized oligoester PET/PG with
molar ratio 1:2 (1) and 1:10 (2). TG curves (c) and DTG curves (d) of PUD synthesized from glycolized
oligoester PET/TEG with molar ratio 1:2 (1) and 1:10 (2). TG curves (e) and DTG curves (f) of PUD
synthesized from glycolized oligoester PET/poly(ethylene) glycol 400 with molar ratio 1:2 (1) and 1:10 (2).
94 Polyurethane

PUD (synthesized from glycolized oligoester PET/PG (1:2), Fig. 4b) synthesized from
depolymerised oligoesters with lower molar ratio of PET repeating unit to glycol in
glycolysis reaction showed lower thermal stability in the initial stage of degradation may be
due to the presence of greater amount of aromaticity in polyester backbone which makes the
PU chains susceptible to scission and relieves the structure crowing (Athawale & Kulkarni,
2010). In later stage (above 300 oC), it showed enhanced thermal stability. It has also been
proved that two or three peaks of first decomposition were well correlated with the higher
value of polydispersity of GPC results (1.65), for oligoester polyols PET/PG (1:2) compared
to the values of polydispersity (1.20), for oligoester polyols PET/PG(1:10). Curve marked as
2, in Figures 4b, 4d and 4f, which shifted third decomposition step temperature to the higher
values, shows that glycolized oligoester obtained with higher molar ratio of PET/glycol of
1:10 have better thermal stability of obtained PUD.

Because of the presence of oligoester polyols wich lower molecular weight in glycolysis
reaction and a diamine were used in the synthesis of PUD, two kinds of hard segments are
formed, urethane and urea. It has been estabilished that the urethanes have lower thermal
resistance than urea and therefore the first decomposition process at about 190 - 250 oC and
the second at about 270 – 290 oC of PUD should correspond to the urethane and urea hard
segments, respectively. The decomposition temperature of the soft segment is observed at
400-430 oC. The decomposition temperature for investigated samples are listed in Table 1.

Second Third
First decomposition
Sample decomposition decomposition
T1on (oC) T1max (oC) T2 (oC) T3 (oC)
190.2
PET/PG (1:2) 270.7 349.7 400.3
247.0
PET/TEG (1:2) - 288.0 335.1 401.9
PET/PEG400 (1:2) 248.6 - 316.5 403.4
PET/PG (1:10) 251.7 288.1 327.0 411.3
PET/TEG (1:10) - 277.6 379.6 416.4
PET/PEG400 (1:10) - - 305.4 422.4
Table 1. Temperature of decomposition of PUD

The degradation profile of PUD was dependent on mole ratios of PET to glycol in
glycolyzed products.

The samples based on PET/glycol, at molar ratio of 1:10, had better thermal stability than
samples based on PET/glycol, at molar ratio of 1:2. The higher values of temperature for
third decomposition stage, for samples with molar ratio of 1:10, probably is due to the
increased length of glycol in glycolyzed oligoester polyol.
 Thermal Analysis of Polyurethane Dispersions Based on Different Polyols 95

6. Waterborne PUD based on polycarbonate diols (PCD)

The polyols used in PUD synthesis are of polyether-, polyester-, polycaprolactone- and
polycarbonate- origin. The use of individual types of polyol chains and their functionalities
depend on the purpose of the potential use, e.g.; PUD made from polyesters can have
slightly elevated strength and oil resistance compared to polyether-based PUD and have
been largely used in PU paints as they exhibit outstanding resistance to light and aging.
Polyether polyols are susceptible to light and oxygen when hot, however, they improve
water dispersion, and impart chain flexibility (Gunduz & Kisakurek, 2004). The use of PCD
in PUD, as compared to other polyols, imparts better hydrolysis resistance, improved ageing
and oil resistance, excellent elastomeric properties even at low temperature, improved
mechanical properties, good weathering and fungi resistance (Garcia et al., 2010). PCD used
as the soft segment component in PUD synthesis are usually obtained from
dimethylcarbonate or ethylene carbonate and a linear aliphatic diol (Foy et al., 2009). The
properties of PUD are related to their chemical structure (Cakić et al., 2009; Athawale &
Kulkarni, 2010) and are mainly determined by the interactions between the hard and soft
segments, and the interactions between the ionic groups (Garcia et al., 2011). The properties
of PUD are strongly influenced by composition and ionic content, an important target in an
investigation of the role of the composition (Lee at al., 2004, 2006).

6.1. Experimental
Water-based PUD derived from IPDI, with different molar ratio PCD to DMPA, were
prepared by the modified dispersing process. The ionic group content in PU-ionomer
structure was varied by changing the amount of the internal emulsifier, DMPA (4.5, 7.5 and
10 wt% to the prepolymer weight).

Three waterborne PUD were prepared using NCO/OH = 1.5 by method in which the
dispersing procedure was modified (Lee et al., 2006). In the modified procedure only the
dispersing stage was varied compared to the standard procedure. The prepolymer solution
was mixed with a small amount of deionized water for dispersion of polymer in water.
Solvent was added for reducing the viscosity, if necessary.

Into a 250 ml glass reaction kettle, equipped with a mechanical stirrer containing a torque
meter, a thermometer, a condenser for reflux and nitrogen gas inlet, was added 60 g (0.03
mol) of PCD (dried under vacuum at 120 oC); and 4, 8 or 12 g (0.03, 0.06 or 0.09 mol) of
DMPA dispersed in 30 ml DMF. The reaction mixture was heated at 70 oC for 0.5 h to obtain
a homogeneous mixture. This step is important for the resulting equal uniform distribution
of hydrophilic monomer, DMPA, on PU backbone. After that 20, 32 or 40 g (0.09, 0.15 or 0.18
mol) of IPDI and DBTDL (0.03 wt. % of the total solid) were added to the homogenized
mixture and stirred at 80 oC for 2.5 h. Dibutyl amine back titration method was used for the
determination of the reaction time necessary to obtain completely NCO-terminated
prepolymer. Then the mixture was cooled down to 60 oC and carboxylic groups (DMPA
equiv) were neutralized with TEA dissolved in NMP (2 wt % of the total reaction mass) by
stirring the reaction mixture at 60 °C for 1h.
96 Polyurethane

Subsequently, the prepolymer solution was mixed with 0.3 ml of deionised water for
dispersion step-by-step. Stirring was increased during the addition of water, and the
mixture was diluted with NMP. Waterborne PUD was obtained by drop-wise addition of
water to the mixture in order to obtain PUD with solid content of about 30% at 30 oC for 1h.
The chain extension was carried out with solution of 0.9 or 1.8 g (0.015 or 0.03 mol) of EDA
in 2 ml of deionised water at 35 oC for 1h. The mixture was heated to 80 oC under vacuum in
order to remove NMP and to obtain PUD with solid content of about 30%.

The thermal stability of PU was determined by TG. The DTG thermogram of cured films of
PUD based on PCD showed several degradation steps (Fig.5b). Detailed analysis of the
thermogram is represented in Table 2. The decrease in the DMPA content produces a slight
increase in the decomposition temperature (Fig.5a). However, the degradation mechanism
was very complex due to the different stability of the hard and soft segments.

The removal of residual water due to incomplete drying of PU was produced at around
130 oC. The DTA thermogram of the used aliphatic PCD shows the main degradation at 350 oC
and other less important at 265 oC (Garcia, 2010, 2011). Because this diol and EDA were used in
the synthesis of PU, two kinds of groups in hard segments have been formed, i.e., urethane
and urea ones. The decomposition temperature of PUD is mostly influenced by the chemical
structure of the component having the lowest bond energy (Coutinho et al., 2003; Cakic et
al.,2009). The urethane bond has lower thermal resistance than the urea bond and thus the first
decomposition process at about 280 oC corresponds to the beginning of the urethane part of
hard segment degradation and second at about 300 oC to the degradation of the urea part of
hard segment. The degradation in PU at 264–268 oC is characteristic of the polyol. The
degradation of soft segment (mainly composed of polyol) is produced at 329–338 oC. The soft
and hard segments content were quantified from the weight loss at above mentioned
temperatures (265 oC from PCD degradation, 280 oC and 300 oC correspond to the urethane
and urea hard segment degradation, and 330 oC from degradation of soft segment).

According to Table 2, the decrease in DMPA content produced a slight increase in the
decomposition temperature and a decrease in the weight loss for the decomposition of
urethane and urea hard segments, which can be ascribed to a decrease in the amount of hard
segment. The decomposition temperature of the soft segments is produced at 329–338 oC
and the weight loss increase by decreasing DMPA content 20.9 and 23.5 to 6.2wt.% in PU
ionomers.

Residual water Soft segment Hard segment

Sample
Weight loss Weight loss Weight
PUD T (oC) T (oC) T (oC)
(wt%) (wt%) loss (wt%)
4.5%DMPA 129.8 1.1 268; 329 10.1; 20.9 282; 301 23.5; 45.4
7.5%DMPA 137.3 1.0 264; 338 3.8; 23.5 290; 304 17.5; 53.7
10%DMPA 128.8 0.9 267; 331 10.5; 6.2 280; 301 22.9; 59.3
Table 2. Temperature of decomposition and weight loss of PUD (obtained by TG measurements)
 Thermal Analysis of Polyurethane Dispersions Based on Different Polyols 97

The decrease in DMPA content produces a decrease in the hard segment content of PU
ionomers. The resistance to thermal degradation of PU ionomer increased by decreasing the
DMPA content due to the lower hard segment content.

Figure 5. TGA curves (a) and DTA curves (b) of cured films of PUD based on PCD with 4.5% DMPA
(1), 7.5% DMPA (2), 10% DMPA (3).

7. Conclusions
The wide application of PUD makes necessary better understanding of the chemistry-structure
relationship that improves the thermal stability as this is important prerequisite to obtain
tailor-made products for high performance applications. In this work, the investigation on
thermal degradation of PUD with well-defined architectures indicated that diol types and
DMPA content had great influence on thermal stability. PUD with lower DMPA content has
shown enhanced thermal stability. The degradation profiles of PU aqueous dispersions were
influenced by the type of chain extender, length of the hard segment and type of catalysts. The
TG curves showed that the length of the hard segment had a strong influence on the thermal
profile of the samples as a whole. The possibility for using glycolysis products of waste PET in
PUD manufacturing was confirmed. The effects of glycol type and the different mole ratios of
PET to glycol on thermal properties of PUD have been described. The degradation profile of
the dispersions was dependent on mole ratios of PET to glycol in glycolyzed products. The
samples based on (PET/glycol molar ratio 1:10) have shown enhanced thermal properties,
which can be ascribed to increased length of glycol in glycolyzed oligoester polyol.

Author details
Suzana M. Cakić and Olivera Z. Ristić
University of Niš, Faculty of Technology, Leskovac, Serbia

Ivan S. Ristić
University of Novi Sad, Faculty of Technology, Novi Sad, Serbia
98 Polyurethane

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[3] Athawale V.D. & Kulkarni M.A. (2009) Preparation and properties of urethane/acrylate
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 Thermal Analysis of Polyurethane Dispersions Based on Different Polyols 99

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 Chapter 6

Polyurethane Flexible Foam Fire Behavior

Ahmadreza Gharehbagh and Zahed Ahmadi

Additional information is available at the end of the chapter

[Link]

1. Introduction
Polyurethanes are a broad range of polymers, which are formed from the reaction
between diisocyanates or polyisocyanates with diols or polyols. According to the types
and amounts of, polyols, isocyanate, ingredients and the overall reaction circumstances,
a broad range of products like flexible foams, rigid foams, elastomers, coatings and
adhesives are produced.

Since the polyurethane products specially foams are playing an indispensable rule in our
daily life because of wide range of applications in automotive, household, refrigerators,
insulations, reducing of the fire risk of such a products are become more vital.

Conventional polyurethane flexible foams are easily ignited by a small flame source and
burn rapidly with a high rate of heat release and smoke and toxic gases. This high
flammability of polyurethane flexible foam is related to its cellular and open cell structure
and low density of such foams. Oxygen can easily pass through the cells of the combustible
material and in subjecting with an accident, smoldering cigarette or an electrical shock, foam
catch fire [1].

Polyurethanes can be resisted against fire by different ways. Depends on the types and
applications of them, fire resisting could be done by the flame retardants using or by
changing in the polymer structure. In the whole picture the polymer ignition can be
controlled by the following factors.

1. Extinguishing material reduction

2. Air supplying source reduction
3. Fire diffusion and heat generation reduction4. Increasing of the energy needed for
entire combustion process

Different types of the fire retardants could be used according to one of the above mentioned
categories. The flame retardants are acting according to one of the following mechanisms.

©©2012
2012Gharehbagh
GharehbaghandandAhmadi,
Ahmadi, licensee InTech.
licensee This
InTech. is aispaper
This distributed
an open under the
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permits unrestricted use, distribution, and reproduction in any medium, provided the original work is
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properly cited.
102 Polyurethane

1. Reaction with the flame and preventing of the spreading of the fire by the created free
radical blocks.
2. Preventing of the oxygen diffusion into the polymer
3. Lowering of the flame temperature with removing energy from the system
4. Char creation and creating a free place between the solid polymer and the disposed
area.
5. Polymer expansion and making a free place between the fire and the decomposed
polymer.

There are lots of materials which are known as the fire retardants according to the following
groups.

 Halogenated flame retardants which are acting in the gas phase with disturbing the
hydrogen-oxygen reaction. They react with hydrogen and create the halogen free
radicals then they block free radicals of decomposed polymer.
 Metal oxides which act in solid or gas phase and some of the members of this group
cause to reduce the flame temperature.
 Phosphorous containing compounds which create char on the extinguishing area of the
polymer and prevent the oxygen feeding to the flame.
 Halogen free FR which the two main candidates are EG and Melamine. The heat
stability of the polyurethanes especially the rigid foams at high temperatures depend
on the isocyanurate to allophanates and biurets cross-linked bond ratio. Carbodiimide
is produced by the condensation reaction of isocyanate with lose of CO2 (Fig.1). This
reaction can be catalyzed by the cyclic phosphine-oxide. Generated carbodiimide is
used as an unti-hydrolyze agent in the polyurethanes. The heat stability of the diverse
products of polyurethanes is classified in Table (1).

Figure 1. Condensation reaction of isocyanate to make Carbodiimide

 Polyurethane Flexible Foam Fire Behavior 103

Bonds Decomposition Temperature(ºC)

allophanate 100-200
biuret 115-125
Urea 160-200
Urethane 180-200
Substituted Urea 235-250
carbodiimide 250-280
Isocyanurate 270-300
Table 1. Heat stability of the diverse products of polyurethanes

2. Polyurethane foam morphology

Polyurethane morphology plays a vital rule on the fire properties of the polyurethane foam.
The porous structure of the foam helps to diffuse the oxygen easily in to the foam and
accelerate the ignition process. Fig.2 shows the SEM Picture of the polyurethane flexible
foam with no filler inside. As it is clear, the cell structure of the foam includes Cell window,
Strut and Strut joint [1].

Figure 2. Fundamental concepts of polyurethane foam Cell Structure (SEM×200)

3. Polyurethane flexible foam fire retardants

3.1. Halogenated phosphorous flame retardants
In recent years the phasing out of some types of halogenated FR (flame retardant) due to
persistence at environment and bioaccumulation and toxicity has been more investigated.
104 Polyurethane

TMCP (Tris (2-chloroisopropyl) phosphate) and TDCP (Tris (1, 3-dichloroisopropyl

phosphate) are two well-known liquid FR which are used in polyurethane flexible foam to
make fire resisted (Figure3-4). Table (2) illustrate some important parameters of the
mentioned fire retardants. [2]

Figure 3. Chemical structure of TMCP

Figure 4. Chemical structure of TDCP

Property TMCP TDCP

CL content (%) 32.5 49
Mw(g/mol) 327.55 430.91
P content (%) 9.5 7.1
physical state at 25°C clear liquid clear liquid
Water solubility(%) < 0.05 < 0.05

Table 2. Properties of TMCP and TDCP

 Polyurethane Flexible Foam Fire Behavior 105

Studies show that in the foams with only liquid FR (TMCP , TDCP) a very divergent
combustion behaviour has been indicated. TMCP containing foams show lower TWL(total
weight loss) and shorter burn time compared to TDCP containing [Link], TMCP
containing foams didn’t show any significant dripping and subsequent hole formation, a
phenomenon seen at all levels of TDCP addition. TMCP and TDCP addition leads to
decrease in the THE( total heat evolved) but an increase in the amount of smoke and carbon
monoxide produced and this is why normally some amount of other FR such as melamine is
added to the TMCP and TDCP containing foams to decrease total heat evolved, total smoke
produced and CO emission significantly[2,3].

3.2. Halogen-free flame retardants

Due to the above mentioned reasons it has been a driving force to move toward the halogen
free FR to compensate those weakness of halogenated FR, despite of some disadvantages
that the halogen free FR have e.g. they are mostly in solid state and they show process
difficulties. There are different types of halogen-free flame retardants which are behaving
with different mechanisms. First group acts according to the expansion inside the polymer
and oxygen-diffusion prevention and second group does by the cooling of the ignited
surface of the polymer. One important example of the above mentioned groups are leaded
by expandable graphite (EG) and Melamine powder respectively.

3.2.1. Expandable graphite

EG is a graphite intercalation compound in which some oxidants, such as sulfuric acid,
potassium permanganate, etc. are inserted between the carbon layers of the graphite [4].
Fig.5 illustrates the chemical structure of Graphite, diamond and C60 [1].

Figure 5. Comparison of Lattice graphite, Diamond and C60

106 Polyurethane

When EG is subjected to a heat source, it expands to hundreds of times of its initial volume
and creates voluminous, stable carbonaceous layer on the surface of the materials. This layer
limits the heat transfer from the heat source to the substrate and the mass transfer from
the substrate to the heat source resulting in protection of the underlying material [5, 6].
The redox process [7] between Sulfuric acid and graphite generates the blowing gases
according to the reaction:

The fire retardancy of EG is done by two steps [1]:

 The EG expands under the impact of Heat up to about 500 times of its original volume
and creates a very large surface. It allows a quick oxidation of the carbon. The oxygen is
taken out of the air and makes the air almost inert. This inert air extinguishes the fire.
 EG doesn’t create flames while oxidation and will extinguish if no more heat will be
applied to the glowing graphite. Therefore, no source of fire will be generated by the
oxidizing graphite.

The more characteristic factors for EG which should be considered are:

 SET (start expansion temperature)

 Expansion volume
 Strength

Figure (6, 7) show particle size and distribution of two types of EG with different sizes
(0.18mm, 0.25mm)

Figure 6. Particle size and distribution of 8% of EG (0.18mm) (SEM ×200)

 Polyurethane Flexible Foam Fire Behavior 107

Figure 7. Particle size and distribution of 8% of EG (0.25mm) (SEM×200)

3.2.2. Melamine
Melamine acts as fire retardant and smoke-suppressant according to the following
combined mechanisms [8].

 Melamine is believed to act as a heat sink, increasing the heat capacity of the
combustion system and lowering the surface temperature of the foam. Thus the rates of
combustible gas evolution and burning are reduced.
 The nitrogen content of the melamine may partly end up as nitrogen gas when
melamine burns, providing both a heat sink and inert diluents in the flame. The
presence of melamine in the foam results in less heat generated by the flame,
consequently less heat fed back to the foam and the rate of foam pyrolysis, i.e.
generating of volatile fuel is reduced.
 Due to a chemical interaction between melamine and the evolved isocyanate fraction
creating from degradation of polyurethane foam. This interaction reduces the amount
of diisocyanate the main contributor to the smoke and CO release (Fig.8).
108 Polyurethane

Figure 8. Chemical reaction between melamine and diisocyanate (MDI)

Figure (9) shows particle size and distribution of melamine powder inside the flexible foam.

Figure 9. Particle size and distribution of 8% of melamine (SEM ×200)

 Polyurethane Flexible Foam Fire Behavior 109

4. Properties of the polyurethane flexible foam with different types of

fire retardants
Comparison between halogenated flame retardants which are mainly liquid with halogen
free flame retardants ( expandable graphite and melamine powder) which both are solid can
be categorized as four items.

 Processing
 Reactivity
 Fire properties
 Physical properties.

4.1. Foaming process

The best choice for the processing as it is clear will be the liquid grade which has a good
dispersion inside the polyol and less side effects.

Expandable Graphite has a limit pot life (3-4 hours) and when it subjects with the polyol
component, it attacks to the catalyst of the polyol and destroys the catalyst during the foaming
process. For the foam producing, the highly recommendation is the EG containing polyol
should react with proper isocyanate before the EG pot life reaches or the EG should be
injected by an individual stream and mix with the polyol stream in the mixing head instead
of pre-mixing with polyol. Otherwise the produced foams will be collapsed. The other
disadvantage of this technology is related to the fact that EG is very corrosive and make the
mixing head to be damaged and it is preferred to be used a hardened grade of mixing head, a
damaged mixing head needle picture is showed in (Fig.10)[9].

The advantages of this technology is the good homogeneity of the EG particles inside the
polyol.

Figure 10. Mixing head needle corrosion by EG

110 Polyurethane

Despite the EG, melamine has the longer pot life inside the polyol, which is around 24 hours
but the fast sedimentation of the melamine powder in the polyol will be the main
disadvantages so we need a suitable method to disperse the melamine powder in the polyol
very well to achieve a homogeneous mixture.

4.2. Reactivity
Foam reactivity is determined by the following parameters:
- Cream time (sec): Cream time is the time when the polyol and isocyanate mixture
begins to change from the liquid state to a creamy and starts to expansion subsequently.
- Gel time (sec): Gel time is the time the foam start to stiffen
- Rise time (sec): rise time is the time the foam reach to its maximum height
- Recession factor (%): the height percentage the foam is settled after 5 min after the rise
time
- Expansion factor (cm/kg): the proportion of the maximum height of the foam to foam
weight.
The flame retardants would affect on the foam reactivity depend on the types of them,
whether they are solid or liquid. Because they make changes in cell structure and total
system heat capacity. The recession factor goes up with addition of EG and melamine but
with different slopes. This is due to the increase in the average cell size of the foam. The
bigger the flake size, the larger the cells and higher the recession factor. On the other hand
melamine powders with small sizes are embedded on struts and joints and increase the
viscosity and reduce the drainage rate which consequently, decreases the number of cells
with bigger sizes [10]. Melamine powders with bigger size (bigger than struts and joints) are
embedded inside the cell walls and open the cells.
Expansion factor which is related to the free rise density (FRD) reduces with addition of the
EG and melamine in the foam. This is due to the increase the heat capacity of the entire system
because of high heat capacity of melamine and EG. When melamine and EG content increases
in the system, the heat capacity of the system increases and the system temperature reduces,
therefore, the foam height and consequently expansion factor reduces [11].

4.3. Fire properties

The fire properties of the polyurethane flexible foams have been evaluated by different
types of methods depends on the customer requirements. For example, the automotive,
railway and airplane industries have their own standards.
The most important parameters which have been tested are: Cone calorimetry, flammability,
smoke density and toxicity.

4.3.1. Cone calorimetry ISO 5660

The principle of the calorimetry by oxygen consumption (cone calorimeter) is based on the
relation between the oxygen consumption and the heat release during the combustion. The
 Polyurethane Flexible Foam Fire Behavior 111

ratio between the heat release and the weight of oxygen consumed is a constant (Huggett
constant) equal to 13100 kJ/kg. It has been previously demonstrated that cone calorimeter
results are in good correlation with results obtained in full scale fire test on upholstered
furniture [3].

Samples of flexible foams (10*10*5cm) were exposed in a Stanton Redcroft Cone Calorimeter
according to ASTM 1356-90 under a heat flux of 35kW/m2 (case of fully involved real firs).
This flux was chosen because it corresponds to the evolved heat during a fire. An electrical
spark igniter ignited volatile gases from the heated specimen. At least three specimens have
been tested for each formulation. Data were recorded with a computer connected to the cone
calorimeter. The test gives the opportunity to evaluate:

- RHR: Rate of Heat Release (kW/m2)

- Figra: fire growth rate: RHR/time (kW/m2/s)
- Weight loss (wt. %)
- Emission of carbon monoxide (ppm)
- TVSP: Total volume of smoke production (m3)
- THE: total heat evolved (kJ/cm2/g)

The combustion of flexible polyurethane foams is a two steps process (Fig.11).

The first step corresponds to the melting of the foam into a tar and the second to the
combustion of the tar previously produced. [3]

These two degradation steps lead to two distinct peaks of rate of heat released.

 The RHR1 values (the values of RHR of the first and second RHR peaks).
 The T1 and T2 values (times at which RHR1 and RHR2 occur).
 The Figra2 values (the two maximum peaks on the Figra curve).

Figure 11. Combustion of flexible polyurethane foams: a two-stage process

112 Polyurethane

4.3.2. Flammability
Flammability of the polyurethane foam is running with wide range of test methods depends
on the applications and customers specification. Some fire tests standards include: FMVSS
NO.302, British Standard 5852, ISO 9772 and FAA/JAA 25.853 Appendix F. as an example
the airplane seat foam fire tests according to FAA/JAA 25.853 Appendix F have been
investigated.

In this test 5 samples with 75mm*305mm*13mm dimension have been subjected with flame
vertically for 12 sec and the following parameters have been investigated.

Burning time (the time that burning is continuing after removing the flame source) Burned
length (the length of the foam which is damaged by the burning process) Time of dripping
(the time which droplet continues to burn).

Synergetic effect

The synergetic effect of different types of FR has been observed. for instance, the fire
properties of the EG loaded foams is much worse than when it is used by mixing with a
liquid FR such halogenated phosphorous flame retardant. Also when some amount of
melamine is added to the TMCP and TDCP containing foams it helps to decrease total
heat evolved, total smoke produced and CO emission significantly[2].

Also the mixing of the liquid FR could boost the fire properties of the melamine loaded foam
considerably.

4.3.3. Smoke density and toxicity

Smoke density and Toxicity are measured according to Airbus Directive ABD0031 (2005) on
two categories:
1. Flaming
2. Non-flaming

Samples with 76mm*76mm*13mm are chosen to do the above mention tests against them in
flaming and non-flaming status.

4.4. Physical properties

Physical and mechanical properties of the flexible polyurethane foams are evaluated by
different types of tests in order to make an entire picture from the foam part performance
during the consuming by the customer. For instance, flexible polyurethane foam is widely
used as car seat foam and it has to keep its shape and other properties such as hardness and
compression set during the time which is used. The most important properties of the
polyurethane flexible foam as car seat foam according to RENAULT specifications are
viewing as below.

 Core Density
 Polyurethane Flexible Foam Fire Behavior 113

 Compression Load Deflection (CLD: P25/5) and Sag-Factor according to D411003

 Compression Set according to D451046
 Tensile strength & Elongation at break according to
 Tear Strength according to D411048
 Resilience in 1st and 5th cycle according to D455128

When the polyurethane flexible foam is going to be fire resisted, some fire retardants in
liquid or solid forms are entered in to the foam structure and make some changes in the
physical properties of the final foam part. Mostly the valuable changes have been observed
by the solid FR addition rather than the liquid one.

Depending on the fire retardant nature, shape and size, their addition may have some
positive or negative effect on foam physical-mechanical properties. By loading the solid FR
with the same amount, the foams become softer, because both additives have a similar size
as cell windows and make the foam inhomogeneous. With EG, the homogeneity would be
less than the foam loaded by melamine, because of its bigger size and flake shape which
makes the foam much softer [1].

Sag-factor or the comfort index [12] increasing when the percentage of EG and melamine
increases. It means that by adding solid FR, the comfort index would change considerably.
Compression set, which is another very important factor, has increased by rising the EG
percentage, but there was almost no changes in CS by increasing the melamine content. This
effect is due to destroying effect of the cells structure by both additives but mainly by the EG.

Tear strensgth of the foams has improved by increasing the EG which could be related to the
rigidity of EG flakes but deteriorates when melamine is added.

Finally, the resilience in 1st cycle is decreased for all additives but it is recovered in 5th cycle,
because in 1st cycle the polymer chains have lost their flexibility due to rigid particles but
after 5 cyclic movements the particles are embedded in struts and joints and the foam
restores its flexibility.

5. Statistical method
Principle component analysis (PCA) is a useful method to illustrate relations between
different parameters by using STAT-BOX-ITCF [13, 14].

Interpretation of the results consists first in the checking the representation of the variables
in the circles of correlation. The correlations between variables are deduced from the relative
position and the length of their corresponding vectors on the circle of correlation. An
example of interpretation is done in (Fig.12); the angle between two vectors defines the
intensity of the correlation (vectors 1 and 5). If α is=90⁰, no relation exists between the
variables. The strength of the correlation is higher when the angle is close to 0⁰ or 180⁰. So,
orthogonal vectors (vectors 1 and 2) mean no correlation between the variables. Data are
strongly correlated if their vectors are collinear (vectors 1 and 3, and vectors 1 and 4). The
nature of the correlation also depends on the direction of the vectors: if vectors have the
114 Polyurethane

same direction (vectors 1 and 4) the variables are correlated, i.e. an increase in the variable
linked to the vector 1 corresponds to an increase in the variable linked to the vector 4.
Inversely, if vectors are opposite (vectors 1 and 3), the variables are anti-correlated.

The correlation between two variables is also a function of the length of the vectors. As
example, vectors 2 and 6 are co-linear and so should be anti-correlated. But the weak length
of the vector 6 means that its corresponding variable does not influence the variable linked
to vector 2 [2].

Figure 12. Interpretation of principal components analysis

5.1. Cone calorimeter–FMVSS 302

The principal components analysis from cone calorimeter and FMVSS 302 data shows the
following correlations (Fig.13)

 RHR1 is moderately correlated with Figra1: Figra1 is a variable that depends on the first
peak of HRR (also called q1max), d the time it occurs. So, it seems quite coherent to find
this kind of relation if the relative variation of the time is low.
 RHR1 is correlated with Figra2. In the cone calorimeter, the foam degradation occurs in
two main steps. It is obvious that an important consumption of fuel in the first step
leads to a lower Figra2.
 FMVSS is strongly correlated with Figra1 and Figra2 and inversely correlated with
RHR2. The lower Figra1 and Figra2, the slower the flame spread. A high RHR2 means
loss of heat by dripping.
 Polyurethane Flexible Foam Fire Behavior 115

Figure 13. Correlation circle—relationship: cone calorimeter/FMVSS.

From the energy assessment of the foam consumption during 1s, we can find a relation
between the propagation speed of the flame and the energy of the tar produced by the
combustion (Fig.14).

Figure 14. Principle of FMVSS.

As a first hypothesis, we can consider the following relation:

q1 + q2 - ∆Q = Q = constant
 ∆Q corresponds to the part of heat used to melt the polymeric matrix leading to
dripping.
116 Polyurethane

 q1 corresponds to the energy released during the first stage of the combustion that leads
to the formation of the tar (Figra1).
 q2 corresponds to the energy released by the combustion of the tar (Figra2).

This relation indicates the different strategies to decrease the value of RHR1 (and so Figra1),
that is to say the flame spread in the FMVSS 302 tests:

 To decrease the total heat evolved Q using specific FR additives.

 To decrease the heat released during the first stage of degradation of the foam and as a
consequence to decrease the heat fed back to the virgin polymer (decrease in Figra1).
 To increase RHR2, that is to say to reduce the energy of combustion by dripping.
 To delay the heat released by the tar. When the foam is molten, the tar starts to burn
and this tar is not immediately lost by dripping. Hence, it is of interest to delay the
combustion of this tar to enable it to drip (decrease in Figra2). An increase in RHR2 is
not sufficient to reduce the flame spread and it is important that the high energy tar
degrades at a later stage.

Hence, we may propose that the flame propagation rate in FMVSS 302 testing is much lower
when easy melting and dripping allows heat reduction and tar dripping. It may be proposed
that q2 corresponds in fact to the almost complete combustion of the tar.

Comparing the RHR curves of foams processed with variable water level, we note that the
density of the foam strongly influences the first RHR peak (Fig.15). The higher the water
content (the lower the density) the faster the step of melting under cone calorimeter
conditions.

The effect of density on RHR1 may explain the previous correlation found between density
and FMVSS 302. Low density leads to rapid melting and to a high flame propagation rate.

Figure 15. Effect of density on the melting stage of polyurethane during combustion
 Polyurethane Flexible Foam Fire Behavior 117

5.2. Cone calorimeter–British Standard

Ignition Source Crib 5 test to SI 1324 Sch. 1 Pt. 1

The statistical computation was made considering the two different sets of foams: the foams
containing TMCP–melamine and the ones containing TDCP–melamine. The level of fire
retardant additives has been included in the computation but is not shown on the circles of
correlation.

Considering the TMCP–melamine foams (Fig.16) it is of interest to note that the lower are
Figra1 and Figra2, the lower are the burn times, TWL and DWL. We also note that T2 is
strongly inversely correlated with the data of SI 1324 Sch. 1 Pt. 1, that is to say the higher T2
the

Better results under the SI 1324 test (lower TWL, DWL and burn time).

The statistical computation of the data from the formulations TDCP–melamine clearly
shows that the fire behavior of these foams in the SI 1324 test is linked to the second stage of
degradation of the foam in the cone calorimeter (Figra2 and T2). Indeed, the Figra curve
represents the fire growth rate of foam during combustion.

Figure 16. Correlation circle—relationship: cone calorimeter/SI

1324, TMCP–melamine formulations

A high Figra means a high rate of flame propagation and so leads to a high weight loss of
the material. Hence, it is not surprising that Figra curves are strongly linked to the BS5852
118 Polyurethane

results. The combustion of PU foam occurs in two steps: the “melting” of the foam and the
combustion of the tar. The tar combustion is the most exothermic part of the combustion. A
decrease in the heat released by the tar reduces the flame propagation and leads to a
decrease in the weight loss of the foam (Fig. 17).

The TDCP and TMCP additives differ in their chlorine and phosphorus content and also in
their temperature of degradation. TMCP degrades earlier than TDCP (150 ⁰C and 210 ⁰C,
respectively); this temperature corresponds to a 5 wt. % weight loss under thermo
gravimetric analysis conditions). A previous study [15] has clearly shown that TMCP is
efficient in the early stage of combustion but no interaction with melamine is observed
(temperature of 5 wt. % weight loss of melamine is 290 ⁰C). TDCP acts later and when
melamine starts to degrade about 50 wt. % of TDCP is available in the system, so a strong
TDCP–melamine synergy is observed. The use of TDCP or TMCP in combination or not
with melamine leads to very distinctive fire properties of the foams.

Figure 17. Correlation circle—relationship: cone calorimeter/SI

1324, TDCP–melamine formulations

Considering the TMCP–melamine foams, it is of interest to note that the higher the TMCP
content the lower is RHR1. That confirms the early effect of TMCP that acts by decreasing
the heat released by the foam in the first stage of the combustion. Secondly, the melamine
content is inversely correlated with RHR2. As described previously, the temperature of
decomposition of melamine is high (290 ⁰C) and this inverse correlation indicates an
efficiency of melamine during the combustion of the tar.
 Polyurethane Flexible Foam Fire Behavior 119

Regarding the TDCP–melamine formulations, we note a positive effect of the TDCP amount
on the RHR1 peak. Even if TDCP degrades later than TMCP, a part of the TDCP is efficient
in the first stage of the combustion.

The melamine content is strongly correlated with the SI 1324 data. High melamine content
leads to a decrease in TWL, DWL burn time and maximum rate of weight loss.

The Figra2 and RHR2 peaks are also correlated with these data.

5.3. Properties–FMVSS 302

The statistical treatment shows that the FMVSS 302 rating is an inverse function of the density
of the foam which is itself a function of the water index (Fig. 18). No significant relations may
be proposed between FMVSS 302 and porosity or TDI index because data did not show any
variation of the porosity (same SnOct content) and only a low variation of the TDI index.
The porosity index of the foam is strongly correlated with the SnOct range used in the foam
manufacturing.
The previous study of conventional foams has revealed correlations between the FMVSS 302
testing and these parameters. The PCA study shows the absence of correlation between the
EO content, the porosity (and so the SnOct range) and the index of the foam with the FMVSS
302 testing. However, it clearly shows that FMVSS 302 is strongly and inversely correlated
with the density of the foam as it has been previously supposed.

Figure 18. Correlation circle—relationship: physical properties/FMVSS.

120 Polyurethane

Author details
Ahmadreza Gharehbagh
Iran Polyurethane [Link]. NO.30, Tehran, Iran

Zahed Ahmadi
Color and Polymer Research Center, Amirkabir University of Technology, Tehran, Iran

6. References
[1] R. Bashirzadeh, A. Gharehbaghi, Journal of Cellular Plastics December 30, 2009, An
Investigation on Reactivity, Mechanical and Fire Properties of Pu Flexible Foam
[2] Jerome Lefebvre and Michel Le Bras, Benoit Bastin and Rakesh Paleja, Rene Delobel,
Journal fire sciences, Vol.21-september 2003
[3] Jerome Lefebvre, Benoit Bastin, Michel Le B, Sophie Duquesne,Christian Ritter, Rakesh
Paleja, Franck Poutch , Flame spread of flexible polyurethane foam: comprehensive
study, Polymer testing, 23(2004) 281-290
[4] Lei Shi, Zhong-Ming Li, Wei Yang, Ming-Bo yang, qiu-Ming Zhou, Rui Huang, Powder
Technology 170(2006) P.178-184.
[5] Bourbigot, S.; Le, B.M.; Decressain, R.; Amoureux, J.P. [Link].-Faraday T.1996, 92(1),
149-158.
[6] Delobel R, Lebras M, Ouassou N, alistiqsa F. JFire Sci 1990; 8:85-108.
[7] Camino G,Duquesne S, Delobel R, Eling B,Lindsay C,Roels [Link] and polymers. In:
Nelson GL, Wilkie CA, [Link] and solutions for hazard prevention.
Washington DC: ACS Pub; 2001.P.90.
[8] Dennis Price, Yan Liu, [Link] Milnes, Richard Hull, Baljinder [Link] and [Link]
Horrocks Fire and Materials .2002; 26:201-206.
[9] Gharehbaghi, R. Bashirzadeh, and Z. Ahmadi, Polyurethane flexible foam fire resisting
by melamine and expandable graphite: Industrial approach, Journal of Cellular
Plastics, online published on 19 September 2011
[10] Turner, R.B., Nichols, J.B. and Kuklies, R.A. (1988). The Influence of viscosity in Cell
opening of Flexible Molded Foams, In: Proceedings of the SPI, 31st Conference,
Technomic, Lancaster, PA.
[11] [Link], [Link] and T. Hirth, [Link], [Link] Cellular plastics Vol.44-Nov.2008
[12] Kaneyoshi Ashida, Polyurethane and Related Foams, Chemistry and Technology (2007)
[13] G. Philippeau, Comment interpre´ter les re´sultants d’une analyse en composantes
principales, I.T.C.F, Paris, 1986.
[14] H. Harman, Modern factor analysis, The University of
[15] Chicago Press, Chicago, 1976.
[16] [Link], R. Paleja, [Link], in: Polyurethanes EXPO 2002, API Conference, Salt Lake
City, Utah,2002,p.244.
 Section 3

Applications
 Chapter 7

Polyurethane in Urological Practice

Valentina Cauda and Furio Cauda

Additional information is available at the end of the chapter

[Link]

1. Introduction
Polyurethane (PU) is one of the most bio- and blood-compatible materials currently used for
fabrication of various medical devices, e.g. blood bags, vascular/ureteral catheters and
artificial heart. Originally, PU was conceived with other copolymers, aiming at similar goals,
i.e. enough versatility to successfully meet biomedical devices constraints, such as
biocompatibility, resistance to sterilization, physical features invariance over time and
infection resistance during indwelling. PU in particular, has also other key properties
particularly suited to biomedical industry, including strength, versatility and low cost. The
surface of PU can be chemically functionalized with organic and biologically active
molecules, resulting in improved durability, compliance, acceptance and tolerance in the
human body during implantation. These features additionally strengthen PU as an
appealing candidate for biomedical applications.

Normally, several polymers such as natural rubber, polyethylene, polyvinylchloride,

fluoropolymers, hydrogels and silicon are used in biomedical applications. Despite the
widespread use of these materials, PU still covers a relevant and dominant role, thanks to its
high blood and tissue biocompatibility for improving the quality of patient’s life. It
conjugates a good stability over long implantation times, excellent physico-mechanical and
surface tuning properties via anchoring of molecules. PU has simply a unique mix of
features, highly required for almost any medical device.

PU is also widely used in cardiovascular applications, in particular for the preparation of

venous and intravenous catheters and balloons for angioplasty and angiography. It has also
been successfully used for tissue replacement and augmentation in breast implants, facial
reconstruction and body joints. Artificial organs based on PU such as heart, kidneys and
lungs have already been developed. Thanks to its above described unique features, PU has
recently been proposed for new promising application fields, e.g. controlled drug delivery
devices. A deep review on the use of PU in medicine and medical devices is also available
(Zdrahala and Zdrahala 1999).

©©2012
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licensee ThisThis
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the terms of
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([Link] which
which permits unrestricted use, permits
unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.
distribution, and reproduction in any medium, provided the original work is properly cited.
124 Polyurethane

Given its large use, in this chapter we will focus on the use of PU in urological applications,
in particular as ureteral catheter, or stent, in endourology routines.

In urology, catheterization is defined as the insertion of tubes (stents), such as urinary

catheters, into the patient's bladder through the urethra. A stent is usually a tube with
ending coils at both sides (pig-tails), or with lateral holes to further improve urine drainage
(JJ or double-J). Urethral stents are usually in latex, silicone or polyurethane, allowing
patients' urine to drain freely from the bladder. Stents can also be used to inject liquids for
treatment or bladder conditions diagnosis. A patient is typically catheterized in the case of
acute or chronic urinary retention, orthopedic procedures that may limit movement, benign
prostatic hyperplasia, incontinence, and effects of various surgical interventions involving
bladder and prostrate.

In endourology, urine is drained by indwelling a catheter between the kidney and the
patient’s bladder, hence inserting the stent into the ureter. Nowadays, ureteral stenting has
become a common procedure for safe urine drainage. It is effective for managing several
diseases, such as ureteral obstruction by stones or clots, benign or malignant ureteral
obstruction, or post-surgical treatments, i.e. ureteroscopy and ureteral surgery. Ureteral
stents almost painlessly keep the ureteral lumen open, ensuring that urine flows while
maintaining the correct renal function. Stents also promote ureteral healing and prevent
strictures formation.

From a general urological viewpoint, these devices must be easily maneuverable, affordable,
and radiopaque for a correct positioning under fluoroscopic guidance. Hence, ureteral stents
are mainly fabricated in PU or silicone since some patients can be allergic or sensitive to
latex after long-term use. Radiopacity is ensured by adding metallic salts, e.g. based on
barium. According to a critical study on materials (Mardis et al. 1993), the use of strong
materials, e.g. PU, permits the reduction of the stent wall thickness, enlarging the inner
lumen and the size or number of lateral holes and increasing urine flow. Silicone stents are
weaker than PU, and need to be fabricated with smaller inner diameters, compromising
urine flow and increasing the lateral compressibility.

Despite the numerous advantages enabled by PU, some complications and challenges
remain. Indeed, PU is not perfectly biocompatible, in the sense that it somehow affects the
epithelial cells of the ureter (urothelium): urothelial ulceration and erosion may occur. Other
complications are related to stent migration or fracture, erosion, development of uretero-
arterial fistula, fever, infection, voiding symptoms including dysuria and hematuria (Arshad
et al. 2006). Among these, the stent encrustation represents one of the most serious
complications resulting from the use of PU double-J stents: a stent can be encrusted by
inorganic salts flowing with urine, and bacterial colonies can grow on the surface. These
infections are very common among the general population, sometimes leading to death.
During infections, the bacteria grow in the internal lumen of the stent, forming the so-called
"biofilm", normally an aggregation of bacteria with their extracellular products and several
inorganic salts (Costerton 2007). This matrix covers the cells, leading to a reduced
susceptibility to prophylactic antibiotics (Tenke et al. 2004). Moreover, the development of
 Polyurethane in Urological Practice 125

these encrustations can obstruct the device and impair the urinary flow, compromising with
patient care and leading to kidney infections, sepsis and shock (Warren et al. 1994).

Temporary prevention from encrustation includes stent replacement at regular intervals,

modification of the type or size of catheters, washing the catheter and bladder with acidic,
antiseptic or saline solutions (Arshad, Shah and Abbasi 2006). Antibiotics are still orally
administered whenever stent is replaced or inserted for preventing infections (Reid 2001).

However all these approaches are mostly ineffective. For this reason stent surface
modifications have been proposed to prevent bacterial and inorganic molecule adhesion.
Various strategies have been conceived, using silver-coated surfaces (Leung et al. 1992;
Multanen et al. 2000), surface modification towards hydrophobicity (Jansen et al. 1993) or
functional groups creation with intrinsic antimicrobial activity. Heparin is a good candidate
for solving these problems. In previous in vitro and in vivo studies, heparinization of medical
devices showed a reduction of microbial colonization (Appelgren et al. 1996; Cauda et al.
2008; Ruggieri et al. 1987). Heparin is a highly sulfated, anionic polysaccharide known for its
anti-coagulant and anti-thrombogenic properties (Piper 1946). It has a strong negative
electrical charge able to prevent cells adhesion since bacterial' cell membrane surface is also
negatively charged. Coating stents with heparin can be practical and low-cost. Over the last
three decades several studies, especially in vascular medicine, were indeed reported,
showing that this approach is effective (Appelgren, Ransjo, Bindslev et al. 1996; Hildebrandt
et al. 1999; Ruggieri, Hanno and Levin 1987).

Another successful approach preventing biofilm formation comprises the use of Diamond-
Like Carbon (DLC) coatings on the ureteral stent. DLC is a thermodynamically meta-stable
state of carbon where diamond-like (sp3-hybridized) and graphite-like (sp2-hybridized)
bonding coexist with a large fraction of sp3 bonds. Coatings can be prepared by
miscellaneous deposition methods, e.g. ion deposition, sputtering, pulsed laser deposition
and plasma-enhanced chemical vapor deposition, using accelerated hydrocarbon ions as
film forming particles (Grill 1999). In general, they are characterized by high mechanical
hardness and chemical inertness. Depending on the deposition conditions, the properties of
DLC films can be adjusted depending on the applications, e.g. allowing enhancement of the
wear and corrosion resistance of precision cutting and machining tools. These films are
already used as protective coatings on magnetic hard disks and optical glasses. They
showed excellent tribological and mechanical properties, corrosion resistance,
biocompatibility, and hemocompatibility (Anne Thomson et al. 1991; Roy and Lee 2007;
Voevodin and Donley 1996). Recent studies have been focused on their ability to decrease
the formation of crystalline bacterial biofilm as well as stent related side effects and
discomfort (Laube et al. 2006; Laube et al. 2007).

The evaluation of the in vivo efficacy of both heparin and plasma deposited DLC-coated
ureteral stent have been reported. Recent works show the superiority of both coated stents
for preventing biofilm adhesion and encrustation compared to uncoated PU catheters
(Cauda et al. 2009).
126 Polyurethane

Despite these recent advances, oral administration of antibiotics (e.g. ciproflaxin) cannot be
avoided. Papers in this respect report that bacteria proliferation has been addressed with a
local release of antibiotics or antiseptics (Cormio et al. 2001; John et al. 2007; Leung et al. 2001;
Raad et al. 1997). Drug-Eluting Stent (DES) has the advantage of maximizing the local tissue
levels of therapeutic agents while minimizing systemic toxicity. The problem has been faced
with antibiotics incorporation (Gorman and Woolfson 2002) using novel biomimetic and
bioactive silicones. For example, with a gentamicin-releasing urethral catheter, encrustation
inhibition in a rabbit model has been shown in the short term (Cho et al. 2001). Other authors
(Cadieux et al. 2006) reported on a triclosan-loaded ureteral stent implanted in rabbit bladders
with bacterial infection. The study showed a significant decrease of urinary tract infection rate.
However, a very high control on the delivery kinetics has been not achieved yet.

Another important problem with stents is that they require an additional cytoscopic
procedure for their removal. Stents removal may be uncomfortable for the patient, in
particular when these are encrusted, therefore requiring hospitalization and anaesthesia.
Considering this big concern, the development of time bio-degradable stent materials has
become a major keypoint. In principle, bio-adsorbable stents shall be designed to maintain
their integrity for a given period of time, and undergo a dissolution process followed by
spontaneous expulsion by the patient at the same time.

So far, the bio-degradable stents degrade very fast (typically 48h) or leave fragments
removable by lithotripsy and ureteroscopy (Lingeman et al. 2003). Some tests on pigs with
degradable poly-L-lactic-L-glycolic acid (PLGA) devices showed fragments embedded in
the ureteral walls within cystic sacs, normally leading to fibrosis, inflammation and a
large foreign body giant cell reaction (Olweny et al. 2002). These results show that further
enhancement on their degradable characteristics is highly required. It is straightforward
that the future of ureteral stents will head towards this direction, i.e. to chemically
controlled biodegradation, combined to a concomitant release of biologically active
molecules on target sites and with minimally invasive surgical procedures. Moreover,
highly engineered stents can possibly work as a “scaffolds” for tissue regeneration via cell
attachment and proliferation, finally controlling the local inflammation and healing
(Zdrahala and Zdrahala 1999).

This chapter focuses in details on the use of PU catheters for endourological applications,
providing new insights on the in vivo performances of PU stent. Given to our past expertise,
we report on the influence of the PU surface treatments in preventing the encrustation and
the formation of bacterial biofilm when implanted into the ureter.

2. Application
As an application of PU in biomedical devices, in this paragraph we present our clinical
experience with ureteral stents. In particular the focus is driven on the in vivo efficacy of PU
stents and their surface modification with heparin or with diamond-like carbon. Parameters
 Polyurethane in Urological Practice 127

like biofilm formation, inorganic encrustation extent, stiffness, brittleness or failure of the
PU material depending on the indwelling time will be examined. The surface chemistry and
morphology characterization of the indwelled stents will also be evaluated according to the
surface coating and biofilm formation. The characterization techniques used in this work
included Field Emission Scanning Electron Microscopy (FESEM), Energy Dispersive
Spectroscopy (EDS), and Infrared (IR) spectroscopy.

2.1. Experimental part: Patients, stents and characterization methods

We review here the results collected from 2006 to 2010, concerning the characterization
studies on uncoated, heparin- and DLC-coated PU double-J ureteral stents (all provided by
Cook Ireland LTD) after indwelling. We enrolled 59 patients (from 45 to 75 years old). 49
patients showed unilateral ureteral obstruction, thus requiring ureteral stenting in the
affected ureter. The patients with unilateral obstruction received an heparin-coated, DLC-
coated or an uncoated PU stent in the ureter to be treated.
10 patients suffered from bilateral obstruction, therefore the coated and uncoated PU stents
were indwelled at the same time in both ureters, respectively. Each patient with bilateral
obstruction received randomly both the coated stent (with heparin or with a diamond-like
carbon coating) in one ureter, and the uncoated one, thus the pure PU stent, in the other ureter.
Stents indwelling was also studied for different periods of time. The stent types and
indwelling times are reported in Table 1.

Number of Type of
Coating Indwelling time
stents indwelling

14 Heparin 1-3 months Unilateral

9 Heparin > 3 months Unilateral

19 Nonea 1-3 months Unilateral

3 None > 3 months Unilateral

4 DLC 1 month Unilateral

5b None 1 month Bilateral

5b Heparin 1 month Bilateral

5b None 1 month Bilateral

5b DLC 1 month Bilateral
aNone indicates that the stent surface is of pure PU.
bThese stents were implanted bilaterally, thus inserting both the uncoated and the coated stents into both ureters
respectively of the same patient.

Table 1. Stents types and indwelling periods of the PU, heparin-coated and diamond-like carbon
coated PU stents.
128 Polyurethane

The criteria used for patient selection for indwelling time of 1 month were mainly post–
endoscopic stone treatment, ureteropelvic junction (UPJ) obstruction (awaiting surgery). In
the long term indwelling (thus 3 or more months) stenting was performed in case of
hydronephrosis due to extrinsic compression in patients with multi-cystic disease (no
surgical indications) and UPJ obstruction after failure of endoscopic and surgical treatments
(patient refused re-intervention). Pregnant women, patients with dermatitis or a burn over
the insertion site were excluded. All patients enrolled in this study gave their informed
consent.

In all cases, double-J stents were placed using a retrograde uretero-pielography approach
during cystoscopy, as suggested by the stent producer, to evaluate the excretory system.

Ciprofloxacin (500 mg twice a day) was administered for prophylaxis for the first 4 days
after the procedure. Any occurrence of technical problems and violations of aseptic
conditions during the procedures were recorded. The antibiotic therapy administrations,
other therapeutic interventions administered during the period of indwelling, the presence
of fever, infections or urinary symptoms were also recorded. After the procedure, the
follow-up check included urine analysis and culture on day 15 and afterwards every three
months. In addition, a complete blood count, serum creatinine levels, and ultrasonography
were performed on day 30, and every 3 months thereafter. All patients received instructions
to present themselves at the institution in the event of experiencing side pain, fever, dysuria,
hematuria, or vomiting.

The stents were removed after different times (see Table 1) during cystoscopy.
Characterization of the stents after the indwelling period was carried out using
morphological and compositional analysis and the results obtained were compared with the
reference stent before use. In particular they were cut both perpendicularly and parallel to
the stent axis in order to obtain cross sections or plan views of the inner and outer surfaces
(Figure 1). The samples were then characterized by three different techniques:

a. FESEM (JEOL JSM 6500F) for the morphological characterization of the stent surface
and the formed encrustations;
b. EDS (INCA) to collect data about the chemical composition of the stent material and the
deposited encrustation at the inner and outer surface of the samples;
c. IR spectroscopy on Attenuated Total Reflectance mode (ATR, Bruker Equinox 55) for
the identification of the chemical compounds deposited on the inner and outer surface
of the samples.

Measurements (a) and (b) were carried out at the same time. Since the stent are made of a
polymeric material (polyurethane), i.e. constituted by carbon, oxygen, hydrogen, and
nitrogen, these elements are excluded from the elemental analysis on the encrustation.
Moreover, the specimen is fixed to the sample holder for the FESEM and EDS
characterizations by a carbon sticker, the composition of which also interferes with the
elemental analysis of the stent itself. For these reasons, the detection of bacterial biofilm is
not possible with the EDS technique and therefore IR spectroscopy is required.
 Polyurethane in Urological Practice 129

IR spectroscopy was carried out directly on the inner and outer surfaces of the cut stent in
Attenuated Total Reflectance (ATR) mode by means of a diamond immersion probe (as
shown in Figure 1, scheme a).

All the described measurements were also performed on reference stents without in-vivo
indwelling.

Figure 1. Scheme of the analyzed surfaces for the polyurethane ureteral stents for the characterization
with FESEM and IR spectroscopy IR. (a) For the plan view analysis, a cut along the stent axis was
carried out for characterizing the outer (left) and inner (right) surface; (b) Cross-sections were obtained
by cutting the stent perpendicular to its axis.

2.2. Clinical results

No technical problems or violations of aseptic conditions during endoscopic procedures
were recorded. In all cases retrograde uretero-pielography, performed at the start of the
procedure, showed unilateral or bilateral ureteral obstruction with various degrees of
excretory system dilatation.
130 Polyurethane

None of the patients reported fever, side pain or voiding symptoms during the period of
study. Urine culture was negative in all cases. In three patients, groups frequency/urgency
symptoms were recorded. Until stents removal, these patients were successfully treated
with antimuscarinics. Follow-up examination revealed no diferences in blood count, serum
creatinine and ultrasonographic features of kidney and ureter with respect to the baseline
values. During indwelling, all the stents were well tolerated.

Stents were removed without technical difficulties in all cases. No technical problems
occurred during the endoscopic procedures on ten patients showing chronic unilateral
obstruction. In these cases, uretero-pielography showed ureteral obstruction with severe
excretory system dilatation.

2.3. Characterization results on starting stents surfaces

The starting stent surfaces were analyzed prior to indwelling, in order to evaluate the
differences between the pure PU surface, the heparin- and DLC-coatings.

To understand the performances of both coatings in preventing bacterial adhesion and

encrustation with respect to the PU material, the stents were also characterized after
different indwelling times (see Table 1 for details). These results will be discussed in the
next paragraphs.

Here we report on the results from the different characterization techniques concerning the
stents before patient’s indwelling (hereafter “reference-stents”). It is intended that all the
results and comments presented in the Paragraph 2.4 are based on the comparison with
these reference stents.

Figure 2 shows the surface morphology (measured by FESEM) of the PU (uncoated),

heparin-coated and DLC-coated stents. The internal and external surfaces of the PU stent
(Figure 2.a and 2.b) presented several irregularities, attributed to the polyurethane particles
(of about 0,5 – 1 μm) or undispersed barium sulfate particles, used to impart radiopacity to
the stent. The elemental analysis by means of EDS showed no additional results, since
carbon, oxygen and nitrogen are excluded due to the reasons mentioned in the Paragraph
2.1. For this reason the results of the EDS analysis are not shown.

At the edge of heparin-coated reference-stent it was possible to observe the smooth heparin
layer on the polyurethane substrate (Figure 2.d), with a thickness of about 5 μm.

The EDS shows the presence of sulphur, an element present in the heparin chemical formula
together with C, O and N. Barium was present in the black paint line, used as fluoroscopic
marker, at the outer surface of the catheter.

Figure 2.e shows the external surface, close to a lateral drainage hole, of the DLC-coated
reference-stent. At the internal surface of this stent (Figure 2.f) several grains and thin cracks
were observed, possibly attributed to the carbon coating. The elemental analysis on DLC-
coated stent surface detected carbon, oxygen and nitrogen, attributed to PU.
 Polyurethane in Urological Practice 131

Figure 2. FESEM results of the stents surfaces of PU, Heparin-coated PU and carbon-coated PU.

The IR spectra of the reference-stents are shown in Figure 3 and were recorded at the
internal surface, showing the functional groups of PU, heparin and DLC.
132 Polyurethane

Figure 3. IR of the stents surface: comparison between PU stents without coating and with heparin and
diamond-like carbon coatings.

The PU spectrum (in black) in the 3800-1200 cm-1 region reflected the vibration modes of its
functional groups. Hydroxyl groups (-OH) and physisorbed hydration water were
responsible for the bands from 3700 to 3100 cm-1. The stretching vibration of the –NH group
was associated to the band at 3300 cm-1, while peaks at 2900 and 2860 cm-1 are the stretching
vibrations of alkyl –CH2 and –CH3 groups. The peak at 1690 cm-1 represents another
vibration mode (bending) of clustered water. The band at 1740 cm-1 indicated the carboxyl
group C=O vibration mode, at 1450 cm-1 the mode of the aromatic ring (C6H6) and at 1400
cm-1 the bending modes of alkyl –CH2 and –CH3 groups. In the spectral zone below 1200 cm-
1 only collective vibrations of the single bonds were observed since the bands in this range

are typical of the polymer chain and constitute its “fingerprint”.

In the DLC-coated stent spectrum (in blue), no significant differences were appreciable with
respect to the previous PU spectrum, however several changes in the peak intensities were
observed. In particular, the band from 3400 to 3250 cm-1, representing water, –OH groups
and amine group (-NH) were more intense. A similar increase was observed for to the
bending peak of water at 1690 cm-1, concluding that the DLC-coated stent surface was more
hydrophilic than the untreated polyurethane catheter. Stretching peaks at 2940 and 2850 cm-
1, representing alkyl –CH2 and –CH3 groups, also showed an increased intensity, due to the

plasma treatment implanting hydrocarbon ions. For the same reason, similar changes in
intensity were observed at 1400 cm-1 for the peak related to –CH2 and –CH3 bending
vibrations and an additional peak at 1597 cm-1 attributed to the C=C group. The IR light
beam penetrated under the thin DLC-modified surface and also detected the polyurethane
surface. For example, the aromatic ring belonging to PU was also slightly observed in the
range between 1430 and 1290 cm-1.
 Polyurethane in Urological Practice 133

The spectrum of the heparin-coated PU surface (in red) shows some new features with
respect to the PU reference-stent (in black). In particular, the broad band from 3700 to 3100
cm-1, representing water and –OH groups, showed a lower intensity. A similar decrease was
observed for the bending peak of water at 1690 cm-1. It was than concluded that the heparin
coated stent surface showed lower hydration than the uncoated one. In contrast, stretching
peaks at 3300 cm-1, belonging to –NH groups, and peaks at 2900 and 2860 cm-1, representing
alkyl –CH2 and –CH3 groups, increased, since both functional groups were also present in
the heparin chemical formula. For the same reason, similar changes in intensity were
detected at 1400 cm-1 for the peak related to –CH2 and –CH3 bending vibrations. Additional
peaks appeared in the range from 1650 to 1600 cm-1, due to the presence of carboxylate
(-COOH) and sulphate (-SO4) groups belonging to heparin. The other peaks of the red
spectrum are no longer discussed, since they belonged to the PU substrate.

2.4. Characterization results on the indwelled stents

In the following sections, the results on the indwelled stents are reported and divided
according to the indwelling time (from 1 to 3 months, more than 3 months) and the adopted
approach (unilateral or bilateral indwelling). In addition, some example will be given in order
to show how the patient pathology, such as recidivist calculosis, would affect the stent surface.

2.4.1. Stents indwelled unilaterally for 1 - 3 months

In this section we will examine the surface characterization of stents indwelled unilaterally
and for a period ranging from 1 to 3 months. We have examined (see also Table 1):

i. 19 PU stents;
ii. 14 heparin-coated stents;
iii. 4 DLC-coated stents.
The samples were analyzed by means of the three techniques described above. The
characterization aimed to evaluate the presence of bacterial biofilm and inorganic
encrustations, such as calcium oxalate (CaC2O4), sodium chloride (NaCl), brushite
(CaHPO4∙2H2O) and other salts, such as silica (SiO2) and compounds of magnesium (Mg)
and potassium (K). The obtained data were used to evaluate the behavior of PU ureteral
stent in vivo according to the indwelling time and the surface treatment.

Figure 4 shows the comparison between the surfaces of PU, heparin-coated and DLC-coated
stents, indwelled unilaterally into three different patients. They were all indwelled into the
patient’s ureter after the stone removal from the kidney by endoscopic lithotripsy with
holmium laser. In the cases of both heparin-coated and DLC-coated stents almost clean and
encrustation-free surfaces were observed (Figures 4.e-4.l). In contrast, higher levels of
encrustation were detected at both the inner and outer surfaces of the PU stent (Figures 4.a-4.d).

The elements found at both inner and outer stent surfaces by means of Energy Dispersive
Spectroscopy (EDS) are reported in Table 2. Some inorganic salts were detected at all the stent
surfaces, such as sodium chloride (NaCl, evidenced by the presence of both Na and Cl, Table
134 Polyurethane

2). In addition, oxides of calcium (evidenced only from the presence of Ca, whereas oxygen
and carbon were both not taken into account by EDS analysis), silica (revealed by Si element),
phosphorous (P) and potassium (K) were collected. In the case of the heparin-coated stent,
the sulphur (S) element present at both inner and outer surfaces clearly derived from the
heparin layer.

Figure 4. FESEM results of PU, heparin-coated and DLC-coated polyurethane stents surfaces after
unilateral indwelling for a period ranging from 1 to 3 months.
 Polyurethane in Urological Practice 135

PU stent Heparin-coated stent DLC-coated stent

Inner Surface Outer Surface Inner Surface Outer Surface Inner Surface Outer Surface
Atom Atom Atom Atom Atom Atom
Element Element Element Element Element Element
% % % % % %
Na K 29.17 Na K 37.71 Na K 22.79 Na K 0.00 Na K 0.00 Na K 10.70
Mg K 0.00 Mg K 0.00 Mg K 0.00 Mg K 0.00 Mg K 0.00 Mg K 0.00
Si K 3.55 Si K 0.00 Si K 0.00 Si K 0.00 Si K 0.00 Si K 0.62
PK 2.14 PK 2.48 PK 0.00 PK 0.00 PK 0.00 PK 0.00
SK 1.89 SK 0.00 SK 38.40 SK 61.01 SK 0.00 SK 0.00
100.0
Cl K 20.45 Cl K 38.09 Cl K 10.07 Cl K 0.00 Cl K Cl K 88.78
0
KK 2.46 KK 2.06 KK 0.00 KK 0.00 KK 0.00 KK 0.00
Ca K 34.99 Ca K 0.00 Ca K 2.61 Ca K 0.00 Ca K 0.00 Ca K 0.00
Bi K 5.35 Bi K 19.66 Ba L 26.13 Ba L 38.99 Ba L 0.00 Ba L 0.00
Table 2. EDS analysis on PU, heparin-coated and DLC-coated stent surfaces after 1-3 months of
unilateral indwelling.

IR spectroscopy (here only the spectra carried out at the internal surfaces are shown, see
Figure 5) confirmed the previous findings (a higher content of water was observed in the
case of DLC-coated stent, blue spectrum). It was therefore concluded that the stent surfaces
were clean and the bacterial biofilm was not detected.

Figure 5. IR of the internal stent surfaces.

By combining the results of the three characterization techniques, the following

considerations can be drawn: (i) the inner surface of the stents, independently from the
surface treatment, was more encrusted than the outer one; (ii) the PU stent showed higher
level of inorganic encrustation with respect to both surface-modified stents.
136 Polyurethane

To see how the patient’s pathology and conditions affected the ureteral stents, in Figure 6
we compare the surfaces of three PU, heparin-coated and DLC-coated stents respectively,
indwelled into stone-former patients. All the catheter surfaces were heavily encrusted;
however lower level of depositions were observed at both the coated stent surfaces (Figures
6.d-6.i) with respect to the PU stent (Figures 6.a-6.c).

Figure 6. FESEM images of PU, heparin-coated and DLC-coated stents after indwelling of 1-3 months
into stone-forming patients.
 Polyurethane in Urological Practice 137

The encrustation of the three stents was mainly composed of calcium oxalate, as clearly
detected by the IR spectroscopy (Figure 7) and the EDS analysis (here not shown). In
particular, IR spectrum of the oxalate crystals was very well defined, with the characteristic
peaks at 1706 and 1313 cm-1 representing the vibration modes of C=O and C-O groups,
respectively. These spectra showed the high purity of the isolated bio-mineral on the stent
surfaces. In addition, the vibration modes of the polymeric substrate (heparin, DLC and
polyurethane) were no longer recognizable. One can then conclude that the encrustation
was thicker than the depth of the analysis (about 1 μm using the Attenuated Total Reflection
(ATR) detection mode).

These findings do not allow to conclude which stent is more or less encrusted with respect
to the surface treatment. Indeed, in stone former patients with recidivist calculosis, whatever
stent is applied, the urologist has to plan frequent stent exchange (the suggested indwelling
time by the producer is one month indeed), due to the ease of stent encrustation.

Figure 7. IR spectra of the three stents surfaces, also depicted in Figure 6, clearly showing the vibration
modes of calcium oxalate.

2.4.2. Stents unilaterally indwelled longer than 3 months

In this paragraph we present the results obtained from the surface characterization of both
heparin-coated and unmodified PU stents, indwelled longer than three months. This
indwelling time actually exceed the recommendation of the stent producer, and the results
are therefore quite interesting. All these patients refused the stent substitution after 3
months, thus the stents were substituted or definitely removed once the consent of patient
was given. Again, the stent study has to be divided according to the patient’s pathology,
that is, stone-former patient or not.
138 Polyurethane

The first example shows the comparison between PU and heparin-coated stents indwelled
unilaterally into non-stone former patients after calculus removal by lithotripsy.

Despite the long indwelling time and the producer recommendation, both stents were quite
free from encrustation (Figure 8 shows FESEM characterization). The encrustation thickness
was measured 2.5 μm at the PU stent, whereas it was not enough compact to form a layer on
the heparin-coated surfaces. The results obtained by EDS and IR spectroscopy confirmed the
absence of bacterial biofilm on both stent surfaces. In addition, the PU surface showed a
higher percentage of sodium chloride and silica with respect to the heparin-coated one.
From these findings, one can conclude that the encrustation levels of the surface-treated
stent were lower than the PU one.

Figure 8. Surface morphology of PU and heparin-coated stents inserted unilaterally for more than 3
months.

The second example referred to the stents indwelled into stone-former patients for long-
term periods (more than 3 months).
 Polyurethane in Urological Practice 139

In contrast to the previous results, the heparin-coated stent showed higher degree of
encrustations at both inner and outer surfaces with respect to the PU stent (Figure 9.a, b, c).
In particular, needle-like crystals were observed a higher magnification at the internal stent
surface (Figure 9.e and f). This morphology corresponded to the calcium oxalate crystals,
and was confirmed by both EDS spectroscopy (due to the presence of calcium in high
percentages in Table 3), and IR spectroscopy (Figure 10.b). Indeed both spectra collected at
the inner and outer surfaces indicated a thick layer of pure calcium oxalate.

Figure 9. FESEM images of PU and heparin-coated stents indwelled unilaterally for more than 3
months in stone former patients.

In this example no general conclusion can be drawn concerning the comparison of the two
stents, since the surface-modified stent and PU one were indwelled into two different
patients, although both stone-formers.
140 Polyurethane

PU stent Heparin-coated stent

Inner Surface Outer Surface Inner Surface Outer Surface
Element Atom% Element Atom% Element Atom% Element Atom%
Na K 34.75 Na K 0.00 Na K 10.14 Na K 0.00
Mg K 0.00 Mg K 0.00 Mg K 0.00 Mg K 0.00
Si K 18.65 Si K 37.77 Si K 0.00 Si K 0.00
SK 4.39 SK 0.00 PK 0.00 PK 2.56
Cl K 32.53 Cl K 37.93 SK 24.46 SK 0.00
KK 0.00 KK 0.00 Cl K 3.42 Cl K 0.00
Ca K 0.00 Ca K 0.00 KK 0.00 KK 0.00
Br L 0.00 Br L 0.00 Ca K 43.82 Ca K 97.44
Bi M 9.69 Bi M 0.00 Ba L 18.17 Ba L 0.00
Table 3. Results of the EDS analysis carried out at both the inner and outer surfaces of PU and heparin-
coated stents after prolonged unilateral indwelling into stone-former patients.

Figure 10. IR spectroscopy of the internal and external surfaces of (a) PU stent and (b) heparin-coated
stent, unilaterally indwelled into stone-former patient for a period longer than 3 months.

2.4.3. Stents bilaterally indwelled for 1 month

The bilateral indwelling is the ideal condition to compare the effectiveness of the surface
treatment in preventing encrustation, since both stents are exposed to the same patient’s
conditions.

Here we report on two examples of surface-modified and PU stents, bilaterally indwelled

for one month into a non-stone former patient and, in a second case, into a stone-former one.

In the first example, shown in Figure 11 by FESEM, heparin-coated and PU untreated stents
were indwelled bilaterally after calculus removal by lithotripsy with holmium laser. Both
the treated and untreated surfaces showed low levels of encrustation. The EDS and IR
 Polyurethane in Urological Practice 141

spectroscopic characterizations (not shown here) revealed phosphorous, potassium and

sodium chloride salts at both stents surfaces, with higher percentages of bacterial biofilm at
the inner surface of the PU stent.

Figure 11. The surface morphology of PU and heparin-coated stents indwelled bilaterally into the same
patient for one month.

In the second case, we examined the stents after bilateral indwelling into a patient
presenting a recidivist calculosis into both her kidneys. In particular the patient had
multiple lithiasis (3 calculus) at the lower calyx of the left kidney. Stenting into both the
ureters was carried out after removal of stones by endoscopic lithotripsy with holmium
laser; however residual lithiasis was still present. The DLC-treated stent was positioned into
the left ureter, to verify its performance after calculus removal. The PU stent was indwelled
at the same time into the right ureter. After one month both stents were removed, due to
patient low tolerance. This patient underwent two repetitive stents indwelling, always
having pain and very low tolerance towards every catheter.
142 Polyurethane

Figure 12 shows the high degree of encrustation, in particular concerning the PU stent. In
particular, the encrustation was thicker than 40 μm and was composed of bacterial biofilm
and inorganic salts, such as brushite (CaHPO4·2H2O ) and sodium chloride.
In contrast, the encrustation level of the DLC-coated stent was not so compact and uniform
as in the untreated PU stent. It was therefore assumed that the presence of the DLC surface
modification prevented partially the encrustation deposition and the bacterial adhesion,
despite the pathology of the patient. In particular the DLC-coating seemed to guarantee the
stent lumen free for urine drainage (Figure 12.c).
From EDS analysis, no particular inorganic compounds were identified on the surface of the
DLC-coated stent (data not shown).
For the overall 20 stents indwelled bilaterally for one month (see Table 1) it was concluded
that both surface treatments effectively prevented or at least decreased the levels of
encrustation by both bacterial biofilm and inorganic compounds, with respect to the pure
PU catheter. It was found that the highest incidence of encrustations took place at the inner
surface of the catheter.

Figure 12. FESEM images of PU and DLC-coated ureteral stents indwelled bilaterally for one month
into the same patient, suffering from recidivist calculosis.
 Polyurethane in Urological Practice 143

2.5. Results summary

Summarizing the results obtained upon stent indwelling into 59 patients, some statistical
considerations can be drawn. Considering only the surface-treated stents, the level of
bacterial biofilm stabilized after three months of indwelling (incidence of the encrustation
on the total amount of heparin-coated stents analyzed: 81.3%), remaining almost constant
for longer indwelling time (78.6%). The incidence of sodium chloride, silica and salts of
magnesium and potassium increased with the indwelling time or due to the recidivist
calculosis of the patient. Interestingly, the highest levels of calcium oxalate and brushite
were found at the surface-modified stents indwelled for 3 months into stone-former patients
(75% for both compounds). For indwelling times longer than 3 months, the levels of calcium
oxalate and brushite decreased (42.9 % for calcium oxalate and 57.1% for brushite).
Concerning the PU stents, high contents of sodium chloride and other salts were generally
observed in high percentages (up to 100%), despite the indwelling time and the patient
pathology. The highest percentages of both bacterial biofilm and calcium oxalate were
observed after already 3 months of indwelling time (85% of biofilm , 50% of calcium oxalate,
43% of brushite).

3. Conclusion
In the present chapter we have summarized the results from the characterization of
uncoated PU, heparin- and DLC-coated PU ureteral stents after indwelling into 59 patients.
Field Emission Scanning Electron Microscopy, Energy Dispersive Spectroscopy, Infrared
Spectroscopy were used to characterize both inner and outer catheter surfaces.

With these techniques two kinds of deposits were detected at the stent surfaces:

1. inorganic compounds, like calcium oxalate, sodium chloride, brushite and salts of
potassium, magnesium and phosphorous;
2. bacterial biofilm;

In addition, the thickness of the encrustations was estimated at the stent cross sections.

We have divided the obtained data according to their indwelling time, the unilateral or
bilateral indwelling and the patient’s tendency to form calculus (stone-former or not).

Concerning the non-stone former patients, the encrustation levels were lower in the surface-
treated stents with respect to the untreated PU surfaces. In particular, concerning the
bilaterally indwelled stents, a direct comparison between the surface properties of the stent
in preventing encrustation was clearly observed. It was indeed assessed that the formation
of bacterial biofilm was lower at the surface-treated catheters, whereas the precipitation of
inorganic compounds were not completely inhibited. We attributed reduction of the biofilm
to the presence of the surface treatments (heparin- or DLC-coatings) on the polyurethane
surface. No relevant differences were found between the two surface modifications in
preventing the stent encrustation upon indwelling. It was also observed that both treated
and untreated PU stents did not degrade in this kind of patients.
144 Polyurethane

These considerations were no more valid when the patient was a stone-former. Indeed, the
recidivist calculosis induced a continuous deposition of biofilm and salts at the stent surface,
thus strongly reducing the effect of the surface modification in preventing encrustation. In
addition, the stents were more stiff and brittle after already one month of insertion, thus
inducing patient discomfort or pain.

It was noteworthy that both the formation of biofilm and inorganic encrustation and the
success of the stent indwelling depended more significantly on the patient’s pathology (i.e.
stone former or not) than on the indwelling time. For these reasons, implanting a stent for a
period of time longer than one month was feasible. A surface-treated polyurethane stent
was also preferable with respect to the untreated PU one. However, frequent stent exchange,
regardless of the surface treatment, is a general recommendation for patients suffering from
a recidivist calculosis.

As a future outlook, new studies should expand in the direction of bio-degradable drug-
eluting polymeric stents. The preparation of such highly engineered ureteral stents should
require the following properties:

 Providing effective urine drainage without the formation of bacterial biofilm;

 Being biocompatible and preventing cytotoxicity;
 Being fully biodegradable to avoid the complications of the stent removal and the
subsequent patient hospitalization;
 Effectively incorporating a therapeutic agent;
 Showing the capability to release the drug in a time-controlled manner;
 Releasing the required amount of drug, between the minimum effective level and the
minimum toxic one;
 Preventing the patient discomfort and pain;
 Being deliverable and visible, with adequate radiopacity (or the presence of radiopaque
markers) to enable precise positioning under X-ray fluoroscopic guidance.

We envision that such a commitment will require a strong interdisciplinary background,

thus combining the fields of material science and technology to the clinical and
endourological requirements.

Author details
Valentina Cauda
Center for Space Human Robotics CSHR@Polito, Italian Institute of Technology, Turin, Italy

Furio Cauda
Urology division, Koelliker Hospital,Turin, Italy

Acknowledgement
Cook Ireland Ltd. is gratefully acknowledged for the financial support and the stent supply.
 Polyurethane in Urological Practice 145

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 Chapter 8

Polyurethane as Carriers
of Antituberculosis Drugs

Yerkesh Batyrbekov and Rinat Iskakov

Additional information is available at the end of the chapter

[Link]

1. Introduction
Polyurethanes (PU) are an important class of polymers that have found many applications
as biomaterials due to their excellent physical properties and relatively good
biocompatibility. Basically, PU may be produced by two chemical processes: by
polycondensation of a diamine with bischloroformates or by reaction between a diol and a
diisocyanate. Many biomedical devices are made from segmented PU such as catheters,
blood pumps, prosthetic heart valves and insulation for pacemakers (Lelah & Cooper, 1986,
Lamba et al., 1997). A promising approach for the development of new controlled-releasing
preparations is use of PU as the carriers in drug delivery systems.

Drug delivery systems have been progressively developed in the field of therapeutic
administration owing to their advantages: providing drug concentration over a period of
prolonged action, decreasing the total therapeutic dose and reducing the undesirable side
effects, and, hence, improving the pharmaceutical efficiencies. These are achieved by the use
of the controlled-release drug delivery systems (Hsien, 1988). Controlled release dosage
forms are consist of the pharmacological agent and the polymer carrier that regulate its
release. In general two types of drug delivery systems have been used: diffusion-controlled
systems and dissolution-controlled systems. In the first cause the drug is usually dispersed
or dissolved in the solid reservoir or membrane and the kinetics of drug release are
generally controlled by diffusion through the polymer. In the second cause the drug are
generally incorporated into a water-soluble or water-swellable polymer and the release of
drug is controlled by swelling and dissolution of polymer. In both the causes polymer
function is a principal component which controls the transport and the release rate of drug
molecule. To be a useful drug carrier, a polymer needs to possess certain features. The
polymeric carrier has to be non-toxic, non-immunogenic and biocompatible; the carrier must
contain an effective dose of active agent; the material of system must be biodegradable and

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([Link] which permits
which permits unrestricted use,
unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.
distribution, and reproduction in any medium, provided the original work is properly cited.
148 Polyurethane

form biologically acceptable degradation products; the rate of drug release from the carrier
must occur at an acceptable rate; the carrier must be able to be easily sterilized.

The design of the PU controlled-release forms for therapeutic drug administration is the
subject of intense interest. Such systems are being used for sustained and controlled delivery
of various pharmaceutical agents such as prednisolon (Sharma et al., 1988), morphine,
caffeine (Graham et al., 1988), prostaglandin (Embrey et al., 1986) and theophylline (Reddy
et al., 2006). The PU carrier is utilized to deliver iodine-containing drugs (Touitou &
Friedman, 1984). Urethane-based hydrogels were prepared based on the reaction of
diisocyanates with amphilic ethylene oxide and triol crosslinker to deliver propranolol
hydrochloride, an antihypertensive drug (Van Bos & Schacht, 1987). Drug delivery systems
on a PU base with various antitumorous drugs, such as cyclophosphane, thiophosphamide
and vincristine, have been prepared (Iskakov et al., 1998, 2000). An in vitro technique was
used to determine the release characteristics of the drugs into model biological media. It was
shown the drug release occurs in accordance with first-order kinetics.

PU-based drug delivery systems have considerable potential for treatment of tuberculosis.
Tuberculosis is widely spread disease in most developing countries. The main method of
tuberculosis treatment is chemotherapy. Although current chemotherapeutic agents for
tuberculosis treatment are therapeutically effective and well tolerated, a number of
problems remain. The chemotherapy is burden some, extends over long periods and
requires continuous and repeated administration of large drug doses. Thus, traditional drug
chemotherapy has serious limitations because of increasing microbial drug resistance and
toxico-allergic side effects. One of the ultimate problems in effective treatment of
tuberculosis is patient compliance. These problems of increasing drug resistance, toxico-
allergic side effects, patient compliance can be approached by the use of long-acting
polymeric drug delivery systems (Sosnik et al., 2010). The design of implantable systems
containing the antituberculosis drugs in combination with biocompatible polymers would
make possible to achieve the significant progress in treatment of this global debilitating
disease (Shegokar et al., 2011).

Biodegradable microsphere drug delivery systems have shown application for oral and
parenteral administration. Administration of microparticles to the lungs (alveolar region)
may provide the opportunity for the prolonged delivery active agent to tuberculosis
infected macrophages. Microspheres can be produced to meet certain morphological
requirements such as size, shape and porosity by varying the process parameters. However,
the morphology of the lung is such that to achieve effective drug deposition it is necessary
to control the particle size of microparticles.

The objective of the chapter is to develop an effective polymeric drug delivery systems
based on PU for the treatment of tuberculosis. Polyurethane materials are investigated as
carriers for sustained and controlled release of antituberculosis drugs. The synthesis and
characterization of PU microcapsules are studied making use various molecular weight
polyethylene glycol and tolylene-2,4-diisocyanate. Antituberculosis drug isoniazid (Is),
rifampicin, ethionamide and florimicin were incorporated into the PU microcapsules and
 Polyurethane as Carriers of Antituberculosis Drugs 149

foams. The effects of nature and concentration of drugs and diols, molecular weight (Mw),
morphology of polyurethanes on release behavior from polymeric systems were studied.
The possibility of application of the polymeric drug delivery systems based on polyurethane
for tuberculosis treatment was shown by some medical and biological tests.

2. Polymeric microparticles for tuberculosis treatment

Recent trends in polymeric controlled drug delivery have seen microencapsulation of
pharmaceutical substances in biodegradable polymers as an emerging technology. Extensive
progressive efforts have been made to develop various polymeric drug delivery systems to
either target the site of tuberculosis infection or reduce the dosing frequency (Toit et al.,
2006). Carriers as microspheres have been developed for the sustained delivery of
antituberculosis drugs and have demonstrated better chemotherapeutic efficacy when
investigated in animal models. Antituberculosis drugs have been successfully entrapped in
microparticles of natural and synthetic polymers such as alginate (ALG), ALG-chitosan,
poly-lactide-co-glycolide and poly-butyl cyanoacrylate (Gelperina et al., 2005, Pandey &
Khuller, 2006).
ALG, a natural polymer, has attracted researchers owing to its ease of availability,
compatibility with hydrophobic as well as hydrophilic molecules, biodegradability under
physiological conditions, lack of toxicity and the ability to confer sustained release potential.
The ability of ALG to co-encapsulate multiple antitubercular drugs and offer a controlled
release profile is likely to have a major impact in enhancing patient compliance for better
management of tuberculosis (Ahmad & Khuller, 2008).
Spherical microspheres able to prolong the release of Is were produced by a modified
emulsification method, using sodium ALG as the hydrophilic carrier (Rastogi et al., 2007).
The particles were heterogeneous with the maximum particles of an average size of 3.719
μm. Results indicated that the mean particle size of the microspheres increased with an
increase in the concentration of polymer and the cross-linker as well as the cross-linking
time. The entrapment efficiency was found to be in the range of 40-91%. Concentration of
the cross-linker up to 7.5% caused increase in the entrapment efficiency and the extent of
drug release. Optimized Is-ALG microspheres were found to possess good bioadhesion. The
bioadhesive property of the particles resulted in prolonged retention in the small intestine.
Microspheres could be observed in the intestinal lumen at 4h and were detectable in the
intestine 24h post-oral administration. Increased drug loading (91%) was observed for the
optimized formulation suggesting the efficiency of the method. Nearly 26% of Is was
released in simulated gastric fluid pH 1.2 in 6h and 71.25% in simulated intestinal fluid pH
7.4 in 30h.

ALG microparticles were developed as oral sustained delivery carriers for antituberculosis
drugs in order to improve patient compliance (Qurrat-ul-Ain et al., 2003). Pharmacokinetics
and therapeutic effects of ALG microparticle encapsulated Is, rifampicin and pyrazinamide
were examined in guinea pigs. ALG microparticles containing antituberculosis drugs were
evaluated for in vitro and in vivo release profiles. These microparticles exhibited sustained
150 Polyurethane

release of Is, rifampicin and pyrazinamide for 3-5 days in plasma and up to 9 days in organs.
Peak plasma concentration, elimination half-life and infinity of ALG drugs were
significantly higher than those of free drugs. The encapsulation of drug in ALG
microparticles resulted in up to a nine-fold increase in relative bioavailability compared
with free drugs. Chemotherapeutic efficacy of ALG drug microspheres against experimental
tuberculosis not detectable at 1:100 and 1:1000 dilutions of spleen and lung homogenates.
Histopathological studies further substantiated these observations, thus suggesting that
application of ALG-encapsulated drugs could be useful in the effective treatment of
tuberculosis.

Pharmacokinetics and tissue distribution of free and ALG-encapsulated antituberculosis

drugs were evaluated in mice at different doses (Ahmad et al., 2006). ALG nanoparticles
encapsulating Is, rifampicin, pyrazinamide and ethambutol were prepared by controlled
cation-induced gelification of ALG. The formulation was orally administered to mice at two
dose levels. A comparison was made in mice receiving free drugs at equivalent doses. The
relative bioavailabilities of all drugs encapsulated in ALG nanoparticles were significantly
higher compared with free drugs. Drug levels were maintained at or above the minimum
inhibitory concentration until 15 days in organs after administration of encapsulated drugs,
whilst free drugs stayed at or above 1 day only irrespective of dose. The levels of drugs in
various organs remained above the minimum inhibitory concentration at both doses for
equal periods, demonstrating their equiefficiency.

Chemotherapeutic potential of ALG nanoparticle-encapsulated econazole and

antituberculosis drugs were studied against murine tuberculosis (Ahmad et al., 2007).
Econazole (free or encapsulated) could replace rifampicin and Is during chemotherapy.
Eight doses of ALG nanoparticle-encapsulated econazole or 112 doses of free econazole
reduced bacterial burden by more than 90% in the lungs and spleen of mice infected with
Mycobacterium tuberculosis. ALG nanoparticles reduced the dosing frequency of azoles
and antitubercular drugs by 15-fold.

Is was encapsulated into microspheres of ALG-chitosan by means of a complex coacervation

method in an emulsion system (Lucinda-Silva & Evangelista, 2003). The particles were
prepared in three steps: preparation of a emulsion phase and adsorption of the drug. The
results showed that microspheres of ALG-chitosan obtained were of spherical shape. The
emulsion used for microparticle formation allows the preparation of particles with a narrow
size distribution. The adsorption observed is probably of chemical nature, i.e. there is an
ionic interaction between the drug and the surface of the particles.

ALG-chitosan microspheres encapsulating rifampicin, Is and pyrazinamide, were

formulated (Pandey & Khuller, 2004). A therapeutic dose and a half-therapeutic dose of the
microsphere-encapsulated were orally administered to guinea pigs for pharmacokinetic and
chemotherapeutic evaluations. The drug encapsulation efficiency ranged from 65% to 85%
with a loading of 220-280 mg of drug per gram microspheres. Administration of a single oral
dose of the microspheres to guinea pigs resulted in sustained drug levels in the plasma for 7
days and in the organs for 9 days. In Mycobacterium tuberculosis H37Rv-infected guinea
 Polyurethane as Carriers of Antituberculosis Drugs 151

pigs, administration of a therapeutic dose of microspheres spaced 10 days apart produced a

clearance of bacilli equivalent to conventional treatment for 6 weeks.

Polylactide-co-glycolide (PLG) polymers are biodegradable and biocompatible, they have

been the most commonly used as carriers for microparticle formulations. Monodispersed
poly-lactic-co-glycolic acid (PLGA) microspheres containing rifampicin have been prepared
by solvent evaporation method (Makino et al., 2004, Yoshida et al., 2006). The microspheres
were spherical and their average diameter was about 2 μm. The loading efficiency of
rifampicin was dependent on the molecular weight of PLGA. The higher loading efficiency
was obtained by the usage of PLGA with the lower Mw, which may be caused by the
interaction of the amino groups of rifampicin with the terminal carboxyl groups of PLGA.
PLGA with the monomer compositions of 50/50 and 75/25, of lactic acid/glycolic acid, were
used in this study. From rifampicin-loaded PLGA microspheres formulated using PLGA
with the Mw of 20,000, rifampicin was released with almost constant rate for 20 days after
the lag phase was observed for the initial 7 days at pH 7.4. On the other hand, from
rifampicin-loaded PLGA microspheres formulated using PLGA with the molecular weight
of 5000 or 10,000, almost 90% of rifampicin-loaded in the microspheres was released in the
initial 10 days. Highly effective delivery of rifampicin to alveolar macrophages was
observed by the usage of rifampicin-loaded PLGA microspheres. Almost 19 times higher
concentration of rifampicin was found to be incorporated in alveolar macrophages when
rifampicin-loaded PLGA microspheres were added to the cell culture medium than when
rifampicin solution was added.

Controlled release rifampicin-loaded microspheres were evaluated in nonhuman primates

(Quenelle et al., 2004). These microsheres were prepared by using biocompatible polymeric
excipients of lactide and glycolide copolymers. Animals received either 2.0 g of a large
formulation (10–150 mcm, 23 wt% rifampicin) injected subcutaneously at Day 0 (118–139 mg
rifampin/kg), 4.0 g of a small formulation (1–10 mcm, 5.8 wt% rifampicin) administered
intravenously in 2.0 g doses on Day 0 and 7 (62.7–72.5 mg rifampicin/kg), or a combination
of small and large microspheres (169–210 mg rifampin/kg). Extended rifampicin release was
observed up to 48 days. Average rifampicin concentrations remaining in the liver, lung, and
spleen at 30 days were 14.03, 4.09, and 1.98 μg/g tissue, respectively.

PLG nanoparticles encapsulating streptomycin were prepared by the multiple emulsion

technique and administered orally to mice for biodistribution and chemotherapeutic studies
(Pandey & Khuller, 2007). The mean particle size was 153.12 nm with 32.12±4.08% drug
encapsulation and 14.28±2.83% drug loading. Streptomycin levels were maintained for 4
days in the plasma and for 7 days in the organs following a single oral administration of
PLG nanoparticles. There was a 21-fold increase in the relative bioavailability of PLG-
encapsulated streptomycin compared with intramuscular free drug. In Mycobacterium
tuberculosis ([Link]) H37Rv infected mice, eight doses of the oral streptomycin
formulation administered weekly were comparable to 24 intramuscular injections of free
streptomycin.
152 Polyurethane

PLG nanoparticle-encapsulated econazole and moxifloxacin have been evaluated against

murine tuberculosis (drug susceptible) in order to develop a more potent regimen for
tuberculosis (Ahmad et al., 2008). PLG nanoparticles were prepared by the multiple
emulsion and solvent evaporation technique and were administered orally to mice. A single
oral dose of PLG nanoparticles resulted in therapeutic drug concentrations in plasma for up
to 5 days (econazole) or 4 days (moxifloxacin), whilst in the organs (lungs, liver and spleen)
it was up to 6 days. In comparison, free drugs were cleared from the same organs within 12-
24h. In M. tuberculosis-infected mice, eight oral doses of the formulation administered
weekly were found to be equipotent to 56 doses (moxifloxacin administered daily) or 112
doses (econazole administered twice daily) of free drugs. Furthermore, the combination of
moxifloxacin+econazole proved to be significantly efficacious compared with individual
drugs. Addition of rifampicin to this combination resulted in total bacterial clearance from
the organs of mice in 8 weeks. PLG nanoparticles appear to have the potential for
intermittent therapy of tuberculosis, and combination of moxifloxacin, econazole and
rifampicin is the most potent.

Antituberculosis drugs Is, rifampicin, streptomycin and moxifloxacin have been

encapsulated in poly(butyl cyanoacrylate) nanoparticles (Anisimova et al., 2000, Kisich et al,
2007). Incorporation of drugs in polymeric nanoparticles not only increased the intracellular
accumulation of these drugs in the cultivated human blood monocytes but also produced
enhanced antimicrobial activity of these agents against intracellular M. tuberculosis
compared with their activity in extracellular fluid. Encapsulated moxifloxacin accumulated
in macrophages approximately three-fold times more efficiently than the free drug, and was
detected in the cells for at least six times longer than free moxifloxacin at the same
extracellular concentration.

This brief review suggested that micro- and nanoparticles based delivery systems have a
considerable potential for treatment of tuberculosis. Their major advantages, such as
improvement of drug bioavailability and reduction of the dosing frequency, may create a
sound basis for better management of the disease, making directly observed treatment more
practical and affordable.

3. Polyurethane microparticles as carriers of drug

PU microspheres can be prepared by interfacial polycondensation in emulsions. These
techniques include polycondensation of two or more complimentary monomers at the
interface of two-phase system, carefully emulsified for obtaining little drop-lets in emulsion
phase. Usually, the interfacial polycondensation carried out by two steps: emulsification
step (emulsion formation using a mechanical stirring during few minutes and one of the
monomers is dissolved in the emulsion drops; polycondensation step (the second
complementary monomer is added to the external phase of the emulsion and the
polycondensation reaction takes place at the liquid-liquid emulsion interface). Interest in the
PU microparticles in each day has being increased since products presents numerous
advantages in biomedical, pharmaceutical and cosmetic applications.
 Polyurethane as Carriers of Antituberculosis Drugs 153

PU microparticles could be interesting matrices for controlled drug delivery. Aliphatic PU

Tecoflex was evaluated as microsphere matrix for the controlled release of theophylline
(Subhaga et al., 1995). PU microspheres were prepared using solvent evaporation technique
from a dichloromethane solution of the polymer containing the drug. A dilute solution of
poly(vinyl alcohol) served as the dispersion medium. Microspheres of good spherical
geometry having theophylline content of 35% could be prepared by the technique. The
release of the drug from the microspheres was examined in simulated gastric and intestinal
fluids. While a large burst effect was observed in gastric fluid, in the intestinal fluid a close
to zero-order release was seen.

Microencapsulation of theophylline in PU was developed with 4, 4'-methylene-

diphenylisocyanate, castor oil and ethylene diamine as chain extender (Rafienia et al., 2006).
PU microspheres were prepared in two steps pre-polymer preparation and microspheres
formation. Particle size investigation with optical microscopy revealed size distribution of
27–128 μm. Controlled release experiment of theophylline was performed in phosphate
buffered saline at pH 7.4 with UV-spectrometer at 274 nm. Drug release profiles showed
initial release of 2–40% and further release for more than 10 days.

The effect of chain-extending agent on the porosity and release behavior of biologically
active agent diazinon from PU microspheres were studied (Jabbari & Khakpour, 2000).
Microsphere was prepared using a two-step suspension polycondensation method with
methylene diphenyl diisocyanate, polyethylene glycol 400 and 1,4-butanediol as the chain-
extending agent. Chain-extending agent was used to increase the ratio of hard to soft
segments of the PU network, and its effect on microsphere morphology was studied with
SEM. According to the results, porosity was significantly affected by the amount of chain-
extending agent. The pore size decreased as the concentration of chain-extending agent
increased from zero to 50 mole%. With further increase of chain-extending agent to 60 and
67%, PU chains became stiffer and formation of pores was inhibited. Therefore, pore
morphology was significantly affected by variations in the amount of chain-extending agent.
The release behavior of microspheres was investigated with diazinon as the active agent.
After an initial burst, corresponding to 3% of the incorporated amount of active agent, the
release rate was zero order.

PU polymers and poly(ether urethane) copolymers were chosen as drug carriers for alpha-
tocopherol (Bouchemal et al., 2004). This active ingredient is widely used as a strong
antioxidant in many medical and cosmetic applications, but is rapidly degraded, because of
its light, heat and oxygen sensitivity. PU and poly(ether urethane)-based nanocapsules were
synthesized by interfacial reaction between two monomers. Interfacial polycondensation
combined with spontaneous emulsification is a new technique for nanoparticles formation.
Nanocapsules were characterized by studying particle size (150-500 nm), pH, yield of
encapsulation and morphologies. Polyurethanes were obtained from the condensation of
isophorone diisocyanate and 1,2-ethanediol, 1,4-butanediol , 1,6-hexanediol. Poly(ether
urethane) copolymers were obtained by replacing diols by polyethylene glycol oligomers
Mw 200, 300, 400 and 600. Mw of di- and polyols have a considerable influence on
154 Polyurethane

nanocapsules characteristics cited above. The increase of Mw of polyols tends to increase the
mean size of nanocapsules from 232±3 nm using ethanediol to 615± 39 nm using PEG 600,
and led to the agglomeration of particles. We also noted that the yield of encapsulation
increases with the increase of polyol length. After 6 months of storage, polyurethanes
nanocapsules possess good stability against aggregation at 4 and 25o C. Comparing results
obtained using different monomers, it reveals that the PU based on hexanediol offers good
protection of alpha-tocopherol against damaging caused by the temperature and UV
irradiation (Bouchemal et al., 2006).

Ovalbumin (OVA)-containing PU microcapsules were successfully prepared by a reaction

between toluene diisocyanate and different polyols such as glycerol, ethane diol, and
propylene glycol (Hong & Park, 2000). The structural and thermal properties of the resultant
microcapsules and the release profile of the OVA from the wall membranes were studied. In
conclusion, the microcapsules from the glycerol showed the highest thermal stability, with
the formation of many hydrogen bonds. From the data of release profiles, it was confirmed
that the particle size distribution and morphologies of microcapsules determined the release
profiles of the OVA from the wall membranes.

Bi-soft segmented poly(ester urethane urea) microparticles were prepared and characterized
aiming biomedical application (Campos et al., 2011). Two different formulations were
developed, using poly(propylene glycol), tolylene 2,4-diisocyanate terminated pre-polymer
and poly(propylene oxide)-based tri-isocyanated terminated pre-polymer (TI). A second soft
segment was included due to poly(ε-caprolactone) diol. Infrared spectroscopy, used to
study the polymeric structure, namely its H-bonding properties, revealed a slightly higher
degree of phase separation in TDI-microparticles. TI-microparticles presented slower rate of
hydrolytic degradation, and, accordingly, fairly low toxic effect against macrophages. These
new formulations are good candidates as non-biodegradable biomedical systems.

The synthesis of PU microsphere-gold nanoparticle "core-shell" structures and their use in

the immobilization of the enzyme endoglucanase are described (Phadtare et al., 2004).
Assembly of gold nanoparticles on the surface of polymer microspheres occurs through
interaction of the nitrogens in the polymer with the nanoparticles, thereby precluding the
need for modifying the polymer microspheres to enable such nanoparticle binding.
Endoglucanase could thereafter be bound to the gold nanoparticles decorating the PU
microspheres, leading to a highly stable biocatalyst with excellent reuse characteristics. The
immobilized enzyme retains its biocatalytic activity and exhibits improved thermal stability
relative to free enzyme in solution.

Microencapsulation of the water soluble pesticide monocrotophos (MCR), using PU as the

carrier polymer, has been developed using two types of steric stabilizers polymethyllauril
acrylate (PLMA) macrodiol and PLMA-g-PEO graft copolymer (Shukla et al., 2002). The
microencapsulation process is carried out in non-aqueous medium and at a moderate
temperature to avoid any chemical degradation of monocrotophos during the encapsulation
process. Microcapsules were characterized by optical microscopy and SEM for particle size
and morphology, respectively. The effects of loading of MCR, crosslinking density of PU,
 Polyurethane as Carriers of Antituberculosis Drugs 155

and nature of steric stabilizer on the release of MCR from PU microcapsules have been
studied.

Poly(urea-urethane) microcapsules containing oil-soluble dye dioctyl phthalate as core

material were prepared by the interfacial polymerization with using mixtures of tri- and di-
isocyanate monomers as wall forming materials (Chang et al., 2003, 2005). The time course
of the dye release in dispersing tetrahydrofuran was measured as a function of the weight
fraction of tri-isocyanate monomer in the total monomer weight and the core/wall material-
weight ratio. The dye release curves were well represented by an exponential function
C=Ceq(1-e-t/tau), where C is the concentration of the dye in the dispersing medium, Ceq
that at equilibrium state, t the elution time and tau is a time constant. tau increased linearly
against weight at high contentration, suggesting controllability of the release rate of
microcapsules by varying tri-isocyanate/di-isocyanate ratio

4. Polyurethane microparticle as carrier of antituberculosis drug

New polyurethane microcapsules incorporated with antituberculosis drug Is have been
synthesized by interfacial polyaddition between toluene-2,4-diisocyanate (TDI) and various
poly(ethylene glycol)s (PEG). Drug Is is hydrophilic water-soluble compound, and it is
insoluble in toluene. Thus Is could be capsulated by interfacial polycondensation technique
using water-in-toluene emulsion, which prevents transferring of Is to the external phase.
And drug encapsulation is possible during the process of the polymer wall formation
(Batyrbekov et al., 2009; Iskakov et al., 2004).

Isocyanate groups react with hydroxyl groups of PEG to form polyurethane chains
according to the Scheme (Fig.1 a). TDI can also reacts with molecules of water at the border
of reaction to form unstable NH-COOH group, which dissociates into amine and carbon
dioxide (Fig.1 b). Chains with amine end-group reacts with the isocyanate groups of
growing polymer with urea segments formation.

Polycondensation was carried out in a 1 L double-neck flask fitted with a stirrer.

Polyethylene glycol with 4 various molecular weights 400, 600, 1000 and 1450 (Sigma, USA)
- PEG 400, PEG 600, PEG 1000 and PEG 1450 respectively were used as diol monomers. TDI
(Sigma, USA) was applied as a bifunctional monomer for the polycondensation. Three
solutions were prepared separately. Solution A: 10 mg surfactant Tween 40 was dissolved in
100 ml of toluene; solution B: x mmol diol and Is were added in y ml of water; amount of Is
was 10, 20, and 30 mol % from PEG; solution C: 2.5 x mmol TDI was dissolved in 10 ml of
solution A. Water/oil ratio was 1:10 vol.%. Solution B was poured into the reaction flask,
contaning 90 ml of solution A under the stirring at 1000 rpm during 15 minutes. After the
formation of microemulsion, solution C was added dropwise. After 180 min the
polymerization was stopped. Microparticles were filtered, carefully washed with distillated
water and dried at ambient conditions. Yield of polymers was estimated from the total
amount of introduced monomers compared to the weight of polycondensation products.
156 Polyurethane

a OCN NCO
m HO(CH2CH2O)nH + m
CH3

[-O(CH2CH2O)n-C(O)-NH NH-C(O)-]m

CH3

b
N=C=O + H2O NH-COOH NH2 + CO2

Figure 1. Scheme of reaction between PEG and TDI with polyurethane formation.

The completion of polycondensation process was estimated by IR-spectra from decreasing

of the absorption band at 2270-2320 cm-1, which correspond to -N=C=O isocyanate group. IR
spectra were obtained by a Nicolet 5700 FT-IR (USA) infrared spectrophotometer in KBr.
In the IR-spectra of microparticles the N-H stretching vibration were observed at 3450–3300
cm-1, absorption bands at 1740–1700 cm-1 for the C=O stretching of urethane and at 1690–
1650 cm-1 for urethane-urea formation were also present (Fig.2). Absorption bands are
present at 1100 cm-1 for C-O-C ether group and at 2850 -2950 cm-1 for C-H. In FT-IR spectra
of microparticles containing Is, the new stretching vibrations band appeared at 1350 cm-1,
1000 cm-1 and 690 cm-1, which were also present in FT-IR spectra of pure Is that indicates the
physical mechanism of Is capsulation.
In the process of interfacial polycondensation, two PU products of reaction were detected:
the main product - microparticles, and the secondary product - linear precipitated
polyurethane. The increase of PEG content in water phase resulted in increased amount of
the secondary product, and as the PEG content in water phase reached 60 vol.%, maximum
of the secondary product was observed (about 40%).
Decreasing PEG concentration in water phase leads to increased yield of polyurethane
microparticles. Maximum of yield was reached at PEG concentration 22 - 27 vol.% and in
that condition whole olygomer reacted at surface of emulsion drops with microparticles
formation. Reduction of microparticle yield after the maximum is due mainly to increasing
contribution of the hydrolysis process of isocyanate groups.
Appearance of the secondary product and increase of its yield, probably, can be attributed
to the increase of PEG concentration and results in PEG partially transfer from the water
phase to the internal phase of toluene and the process of polycondensation between PEG
and TDI takes place with linear polyurethane formation. At the end of reaction rate of PEG
diffusion to surface, namely at the reaction region, seems to be a limit stage of the process.
Reducing of PEG concentration causes to decrease of system viscosity. Effectiveness of Is
capsulation in PU microparticles ranged from 3.4 to 41.7 % and significantly depended on
water/PEG ratio in the water phase of emulsion.
 Polyurethane as Carriers of Antituberculosis Drugs 157

Figure 2. FT-IR-spectra of polyurethane microparticles containing isoniazid (a), polyurethane

microparticles (b) and isoniazid (c).

Fig. 3 shows that composition of the water phase influences upon effectiveness of capsulation.
Increase of PEG concentration results in decreasing effectiveness of capsulation and decrease
of Is loading correspondingly. The high PEG concentration promotes miscibility of Is in the
internal oil phase - toluene. Morphology of the surface of microparticles is very important
factor, which affects release behavior of active agent. The wall structure depends on the
conditions of interfacial polycondensation process, such as Mw and chemical structure of diol,
the concentration of the monomers and other. The effect of water/PEG ratio in aqueous phase
on morphology of microparticle was investigated. Microparticles prepared from PEG solutions
of higher concentration have dense surface so that Is diffused much slower. At the high
concentration of PEG reaction between PEG and TDI is significantly limited on the interface of
the drops. Furthermore excessive PEG transfers to the external surface of microparticles and
reacts with TDI and less penetrable wall was formed.

Fig.4 shows SEM photos of interfacial polycondensation products prepared by reaction

between TDI and PEG 400 at water/PEG ratio 11,8 : 88,2 vol.% in water phase. According to
Figs. 4a and 4b two products of polycondensation with different structure were formed. PU
microparticles have spherical shape and size about 5 - 10 μm (Fig. 4a). The secondary
product has fibril structure with diameter less then 500 nm (Fig 4b). The effect of water/PEG
ratio on morphology of microparticle walls is shown in Figs. 4c and 4d. PU microparticles
prepared at water/PEG ratio 82,4 :17,6 (Fig. 4c) have rough surface. On the contrary the
surface of PU microparticles prepared at water/PEG ratio 11,8 : 88,2 (Fig 4d) were dense and
smooth.
158 Polyurethane

Figure 3. The effect of PEG content in water phase on effectiveness of encapsulation () and Is loading
in PU microparticles ().

Figure 4. SEM photographs of products of interfacial polycondensation . between TDI and PEG 400 at
60oC. PU microparticles (a) and PU secondary product (b)synthesized at water/PEG ratio 11.8 : 88.2 in
water phase. Surface of PU microparticles prepared at water/PEG ratio 82.4 :17.6 (c) and 11.8 : 88.2 (d)
in water phase.
 Polyurethane as Carriers of Antituberculosis Drugs 159

The release behavior of Is from PU microparticles was carried out and different conditions
of synthesis such as water/PEG ratio, molecular weight of PEG and isoniazid concentration
was investigated. The release behavior of microparticles loaded with isoniazid was studied
with ultraviolet (UV) spectroscopy. For calibration, physiological solutions of isoniazid with
concentration ranging from 0.004 to 0.05 mg/ml were prepared and their absorption was
measured at 263.5 nm with Jasco UV/VIS 7850 spectrophotometer (Japan). 10 mg of
isoniazid-loaded microparticles were dispersed in 10 ml of physiological solution under
light stirring at constant temperature 37oC. After fixed time interval 2 ml of solution was
taken out by the squirt equipped with the special filter. The efficiency of capsulation was
calculated as ratio of introduced isoniazid to solution B compared with amount of delivered
isoniazid into water during 3 weeks. Isoniazid loading was weight of isoniazid (mg)
contained in 1 g of microparticles.

Fig. 5 shows the release behavior of Is from PU microparticles, synthesized at different

water/PEG ratio. The most part of the drug delivered during the first three hours, then slow
release of the residual Is was observed during the next two weeks. Microparticles prepared
with less concentration of PEG in the water phase demonstrated faster diffusion of Is
through walls of microparticles. The increased PEG content in water phase of reaction,
results in decreasing Is diffusion, due to formation of PU microparticles with denser
polymer wall. Microparticles prepared with PEG concentration 17.6, 29.4 and 41.2 vol.%
showed the release 58 - 66 % of Is during 3 h. However, due to denser wall of microparticles
prepared with PEG 64.7 и 88.2 vol. % demonstrated the release no more 35% of the drug
within the same time.

100
Release of isoniazid (%)

80

60

40

20

0
0 2 4 6 8
time (h)
Figure 5. Release of Is from PU microparticles synthesized at various water/PEG ratio: ● - 82.4:17.6, o -
70.6:29,  - 58.8:41.2,  - 35.3:64.7 and  - 11.8:88.2.

The effect of molecular weight of PEG on release of Is from PU microparticles was

investigated (Fig 6). Microparticles were prepared by using PEG with Mw 400, 600, 1000 and
1450. Increasing molecular weight of soft segments (PEG) results in the increase of diffusion
160 Polyurethane

rate of Is into solution. This phenomenon can be attributed to increasing Mw of PEG which
leads to accelerating diffusion of water-soluble Is through hydrophilic PEG chains.

100

Release of isoniasid (%) 80

60

40

20

0
0 2 4 6 8
time (h)
Figure 6. Release of Is from PU microparticles synthesized at various Mw of PEG. MW = 400 (o), 600 (●),
1000 () and 1450 ().

Microparticles with different Is loading, namely 18.4, 35.3 and 65.6 mg/g were produced. In
Fig 7 release behavior of Is is shown.

100
Release of isoniazid (%)

80

60

40

20

0
0 2 4 6 8
time (h)

Figure 7. Release of Is from PU microparticles with different Is loading: 18.4 (), 35.3 () and 65.6
mg/g (●).

Microparticles with higher Is loading demonstrate faster release rate of the drug due to
increased gradient of concentrations between the external solution and core of
microparticles.
 Polyurethane as Carriers of Antituberculosis Drugs 161

PU microparticles were administrated subcutaneously to mice BL/6. Histologic analyses of

the underskin tissue was carried out at a different period of microparticles administration in
the mice by using electron microscope LEO F360, equipped with X-ray analyzer EDS Oxford
ISI 300.
Fig 8 shows histologic analyses of tissue under skin. Within 5 days of the microparticles
deposition, the thickening of the surrounding tissue due to primary macrophage reaction
and fibrillar tissue formation were detected as shown in Fig. 8b. On day 21, some enzymatic
lysis of polyurethane – С(О)–NH – group probably took place (Fig. 8c) and partial
biodegradation of PU microparticles was observed. For all experimental animals no casting-
off or necrosis of tissue were observed.

a b c

Figure 8. Histological slices of tissue under mice skin 1 (а), 5 (b), and 21 (c) days after deposition of is-
containing PU microparticles to BL/6 mice provided by transparent electron microscope with 400x
magnification.

Thus, the data obtained in the present work have demonstrated the possibility of using PU
microparticles as a carrier for the controlled delivery of antituberculosis drug Is. PU
microparticles were prepared by interfacial reaction between PEG and TDI in water in
toluene emulsion. The effect of water/PEG ratio on the morphology of microparticles and
release behavior was shown. The low PEG content in aqueous phase results in the formation
of microparticles with rough surface, which demonstrate faster diffusion of Is in comparison
to PU microparticles produced from more concentrated PEG solutions, they have smooth
surface and less penetrable walls for Is. Increased Mw of PEG and Is loading leads to
increased diffusion rate of isoniazid from polyurethane microparticles. For PU
microparticles administered in mice BL/6 subcutaneously, biodegradation was observed due
to enzymatic lysis of polyurethane group. Preliminary data indicate that PU microparticles
could be perspective carriers for controlled delivery and respirable administration of
antituberculosis drug Is.

5. Polyurethane foams as carriers of antituberculosis drugs

The use of soft PU foams as carriers of antituberculosis drugs is of considerable interest. In
such systems pharmaceutical agents are dispersed or dissolved in the PU carrier and the
162 Polyurethane

kinetics of drug release are generally controlled by diffusion phenomena through the
polymer. Such systems are being used for treatment of tuberculosis-infected cavities
(wounds, pleural empyema, bronchial fistula). It is the purpose of this chapter to show the
possibility of using polyurethane foams as carriers of some antituberculosis agents for tuber-
culosis treatment.
PU foams were synthesized by reaction of pre-polymer with isocyanate terminal groups
with a small amount of branching agent and water. Other ingredients, such as catalyst and
chain extenders, were not used in order to preserve medical purity. The scheme of synthesis
is presented below in Fig.9.

- 2 O=C=N-R-N=C=O + HO-R’-OH  OCN-R-NH-COO-R’-OCO-NH-R-NCO

diisocyanate macrodiol prepolymer (R*)

- ~ R*-NCO + H2O  ~ R*-NH2 + CO2

- ~ R*-NH2 + OCN-R*~  ~R*- NH-CO-NH- R*~

Figure 9. Scheme of PU foams synthesis.

Antituberculosis drugs Is, ethionamide (Eth), florimicin (Fl) and rifampicin (Rfp) were
incorporated as fine crystals in the polymeric matrix at the stage of PU synthesis. The PU
contained 100-300 mg of heterogeneously dispersed antituberculosis drugs.
The release of drugs from PU was examined by immersing polymeric samples in a model
biological medium (physiological solution, phosphate buffer pH 7.4 and Ringer-Locke
solution) at 37°C. The amount of drug released was determined UV-spectrophotometrically
by measuring the absorbance maximum characteristic for each drug.

100
90
Ethionamide released, %.

80
70

60

50
40
30
20

10
0
0 1 2 3 4 5 6

Time, days
Figure 10. Release of Eth from polyurethane foam into Ringer-Locke solution at 37oC. Drug loadings
(mg/g PU): 100(), 200(), 300().
 Polyurethane as Carriers of Antituberculosis Drugs 163

All the release data show the typical pattern for a matrix-controlled mechanism. The
cumulative amount of drugs released from the PU was linearly related to the square root of
time and the release rate decreased with time. The process is controlled by the dissolution of
the drug and by its diffusion through the polymer. The release is described by Fick's law
and proceeds by first-order kinetics (Philip & Peppas, 1987). The structure of the drugs and
their solubility influences the rate of release: the total amount of Is is released in 3-4 days,
Eth in 5-6 days (Fig.10), Fl and Rfp in 14-16 days (Fig.11). The release time for 50% of Is is 22-
26 h, for Eth 28-30 h, for Fl and Rfp 72-76 h, respectively. The rapid release of Is and Eth in
comparison with Fl and Rfp is due to the higher solubility of these drugs in the dissolution
medium. Increasing the drug loading from 100 to 300 mg/g resulted in an increase in the
release rate.

200
Florimicine released,mg

150

100

50

0
0 2 4 6 8 10 12 14 16 20
Time,days
Figure 11. Release of Fl from PU foam into Ringer-Locke solution at 37oC. Drug loadings (mg/g PU):
100(), 200(), 300().

Table 1 presents the values of the diffusion coefficients for drug release into different media,
calculated for the initial release stage by a modified Higuchi equation (Higuchi, 1963). With
increase of drug loading, the diffusion coefficient is not significantly decreased. This is
connected with the plasticizing action of the drug, resulting in the deterioration of the
mechanical properties of the polymeric matrix. The medium into which the drugs are
released has no significant effect upon the diffusion coefficient.

The release results show that the use of PU as a carrier of antituberculosis drugs provides a
controlled release of drugs suitable for use in practical medicine, i.e. it allows prolonged
action of drugs over some days.

The tuberculostatic activity of drugs released from the PU was determined by diffusion into
dense Levenshtein-Iensen nutrient medium compared with a museum strain of M.
tuberculosis.

It has been shown that drugs introduced into a polymeric matrix have tuberculostatic
activity on the level of free drugs. Is formed a microorganism growth delay zone of 41 mm,
Eth 35 mm and Fl 29 mm.
164 Polyurethane

107 x D (cm2 s-1 )

Loading
Drug Physiological Ringer-Locke Phosphate
(mg/g PU)
solution solution Buffer
100 7,482 7,926 7,346
Is 200 7,026 7,150 7,158
300 6,845 6,890 6,804
100 6,433 6,228 6,248
Eth 200 6,237 5,928 6,142
300 5,972 5,768 5,636
100 2,124 2,430 2,315
Fl 200 1,980 2,068 2,112
300 1,642 1,786 1,720
100 1,116 1,224 1,226
Rfp 200 0,984 1,082 1,068
300 0,922 0,944 0,896
Table 1. Diffusion coefficient (D) values for drug release from polyurethane foams into different media
at 37oC for initial stage of release.

The efficiency of tuberculosis treatment by PU containing drugs was studied in experiments

on guinea pigs (Batyrbekov et al., 1998). Several groups of animals, consisting of 20-25
guinea pigs, were infected with a 6-week culture of a laboratory strain of M. tuberculosis.
Treatment was started 2 weeks after infection. Animals were treated by weekly
administration of PU containing 5-day doses of the drugs (PU-Is, PU-Eth or PU-Fl), or by
daily administration of a day's dose of Is, Eth or Fl. Animals of the control group were not
treated (C). The weights of the guinea pigs and the dimensions of ulcers at the site of
infection were periodically determined during the experiment. All untreated animals died
1.5-2 months after infection. The animals of the other groups were killed with 2.5 months
after the beginning of the treatment. Guinea pigs were dissected and damage to lungs,
livers, spleens and lymphatic ganglions was determined. The efficiency of the applied
therapy is presented in Table 2.

Index of damage, %
Group Lymphatic
Lung Liver Spleen Summary
ganglion
С 36.6 25,8 22,0 6,0 90,4
Is 5,0 12,2 12,2 2,5 31,9
PU-Is 4,0 11,4 12,0 2,5 29,9
Eth 8,0 13,6 14,6 3,5 39,7
PU-Eth 7,2 13,0 14,2 3,5 37,9
Fl 20,2 14,4 16,8 4,8 56,2
PU-Fl 18,8 13,0 16,6 4,4 52,0
Table 2. Macroscopic evaluation of damage to inner organs of guinea pigs.
 Polyurethane as Carriers of Antituberculosis Drugs 165

The experimental observations show that the treatment of tuberculosis in the animals by the
polymeric systems gave the same therapeutic effect as daily treatment with single doses of
the drugs. The most effective action was displayed by PU containing Is. This is related to its
greater tuberculostatic activity in comparison with Eth and Fl. The animals of the PU-Is and
Is groups had the dissemination nidi in their inner organs practically cured: guinea pigs lost
weight slightly (4.6% and 1.2%, cf. untreated 30.6%) and had small ulcers in the place of
infection (3.0 mm and 3.2 mm in diameter, cf. untreated 11.2 mm) (Batyrbekov et al., 1997)
The values of weight loss and ulcer dimensions in the place of infection in animals of the
another groups are following: 8.6% and 4.4 mm (PU-Eth); 9.0% and 4.8 mm (Eth); 11.4% and
5.2 mm (PU-F1); 11.0% and 5.0 mm (Fl). The treatment of experimental tuberculosis by the
polymeric systems was analogous to daily treatment with free drugs. The use of a PU carrier
provides a stable bacteriostatic concentration of chemotherapeutic agents for 5-7 days.
Clinical observations have shown the efficiency of PU drug delivery systems for treatment
of tuberculosis-infected cavities (wounds,pleural empyema, bronchial fistula).

The results obtained in the present work have shown the possibility of using PU foams as a
matrix for drug delivery systems for prolonging the action of chemotherapeutic agents in
tuberculosis treatment.

6. Conclusion
PU microparticles containing antituberculosis drugs were prepared by interfacial reaction
between PEG and TDI in water in toluene emulsion. Two products of polycondensation
were detected: the main product is spherical microparticles with size about 5-10 μm and the
second product is fibrils of linear PU, which precipitate in toluene. The increase of PEG
content in water phase results in increased amount of the secondary product, and as the
PEG content in water phase reaches 60 vol.%, maximum of the secondary product was
observed (about 40%). Decreasing PEG concentration in water phase leads to increased yield
of PU microparticles. Maximum of yield was reached at PEG concentration 22 - 27 vol.% and
in that conditions whole oligomer reacted at surface of emulsion drops with microparticles
formation.
The release behavior of drugs from microparticles was carried out and different conditions
of synthesis such as water/PEG ratio, molecular weight of PEG and drug concentration was
investigated. The increase PEG content in water phase of reaction, results in decreasing drug
diffusion, due to formation of PU microparticles with densere polymer wall. Increasing
molecular weight of soft segments (PEG) results in the increase of diffusion rate of drug into
solution. This phenomenon can be attributed to increasing molecular weight of PEG which
leads to accelerating diffusion of water-soluble drug through hydrophilic PEG chains. It was
shown that microparticles with higher drug loading demonstrate faster release rate of the
drug due to increased gradient of concentrations between the external solution and core of
microparticles.

The tuberculostatic activity of drugs released from the PU show that drugs introduced into
PU have antimicrobial activity identical of low molecular drugs. The efficiency of the
166 Polyurethane

tuberculosis treatment by polyurethane drug delivery systems was shown in experiments

on animals. The use of PU carrier provides a stable bacteriostatic concentration of the
chemotherapeutical agents for 5-7 days. The treatment of animals infected with tuberculosis
by PU systems was more effective than the treatment by free drugs. It was shown that is
released from PU systems was 1.5-2 times less toxic in comparison with the low molecular
drug. Minimal toxic action of PU on the native organism tissue was established
hystologically. Medical-biological tests show that PU ensures sustained release of
antituberculosis drugs and maintains effective drug concentration for long time.

The results obtained in the present chapter have shown the possibility and outlook of PU as
carriers of antituberculosis drugs for the delivery systems for prolonging the action of
chemotherapeutical agents in tuberculosis treatment.

Author details
Yerkesh Batyrbekov and Rinat Iskakov
Institute of Chemical Sciences,
Kazakh-British Technical University, Kazakhstan

Acknowledgement
This research was financially supported by a grant from the Ministry for Education and
Science of Republic of Kazakhstan. The authors thank Dr. Mariya Kim for her assistance in
carrying experimental studies.

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 Chapter 9

Use of Polyurethane Foam in Orthopaedic

Biomechanical Experimentation and Simulation

V. Shim, J. Boheme, C. Josten and I. Anderson

Additional information is available at the end of the chapter

[Link]

1. Introduction
Biomechanical experimentation and computer simulation have been the major tool for
orthopaedic biomechanics research community for the past few decades. In validation
experimentations of computer models as well as in vitro experimentations for joint
biomechanics and implant testing, human cadaver bones have been the material of choice
due to their close resemblance to the in vivo characteristics of bones. However, the
challenges in using cadaveric bones such as availability, storage requirements, high cost and
possibility of infection have made synthetic bone analogs an attractive alternative.

There are a variety of synthetic bone materials available but polyurethane foam has been
used more extensively in orthopaedic experiments, especially in fracture fixation testing.
The foams are produced by a polymerization reaction with a simultaneous generation of
carbon dioxide by the reaction of water and isocyanate. The resultant product is a closed cell
structure, which is different from the open porosity of cancellous bone. However the
uniformity and consistency in their material properties make rigid polyurethane ideal for
comparative testing of various medical devices and implants.

Therefore we have extensively used synthetic bones made of polyurethane foam in various
orthopaedic biomechanical researches from optimization of bone graft harvester design to
acetabular fractures and the stability of osteosynthesis. We identified important design
parameters in developing bone graft harvester by performing orthogonal cutting
experiment with polyurethane foam materials. We also validated the fracture prediction
capability of our finite element (FE) model of the pelvis with a validation experiment with
polyurethane foam pelvis. We also performed in vitro experimentation to compare the
stability of different types of osteosynthesis in acetabular fractures and used this result again
to validate our fracture fixed pelvis model. These results as well as reports from others that

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172 Polyurethane

highlight the use of polyurethane in orthopaedic biomechanical experiment will be included

in this chapter.

Specifically, there will be three sections in this chapter. The first section will describe the
basic material properties of rigid polyurethane foam. We will especially highlight the
similarities and differences between the foam and human bone. The second section will then
present the review of the literature focusing on the use of polyurethane foam in
biomechanical experimentations. We will conclude the chapter with our use of polyurethane
foam in bone grafting harvester design, fracture predictions and stability testing of
osteosynthesis.

2. Basic material properties of rigid polyurethane foam

Polyurethanes are characterized the urethane linkage (-NH-C(=O)-O-) which is formed by
the reaction of organic isocyanate groups with hydroxyl groups as shown below

R-NCO+R-OH=R-NH-C(=O)-O-R

Polyurethanes can be turned into foam by means of blowing agents such as water. The cells
created during the mixing process are filled and expanded with carbon dioxide gas, which is
generated when water reacts with isocyanate group. The result is a closed foam structure,
which is a cellular solid structure made up of interconnected network of solid struts or
plates which form the edges and faces of cells. Thanks to its desirable material properties
that give versatility and durability to the material, polyurethane has become one of the most
adaptable materials that it is found everywhere such as carpet, sofa, beds, cars to name a
few.
One unlikely place, however, is inside human body, that is human cancellous or spongy
bone. The macroscopic structure of cancellous bone consists of a network of interconnecting
rods and plates that forms complex struts and columns. Although this structure has strictly
speaking open porosity structure, the overall macroscopic structure shows close
resemblance to the closed foam structure of polyurethane foam (Figure 1)

Polyurethane foam microscopic structure Cancellous bone microscopic structure

Figure 1. Microstructures of cancellous bone and polyurethane foam.

 Use of Polyurethane Foam in Orthopaedic Biomechanical Experimentation and Simulation 173

The stress-strain curve of polyurethane foam exhibits similar pattern as cancellous bone.
Figure 2 shows a schematic compressive stress-strain curve for polyurethane foams which
shows three regions; firstly they show linear elasticity at low stresses followed by a long
plateau, truncated by a regime of densification at which the stress rises steeply (Gibson and
Ashby, 1988). Linear elasticity is controlled by cell wall bending while the plateau is
associated with collapse of the cells by either elastic buckling or brittle crushing. When the
cells have almost completely collapsed opposing cell walls touch and further strain
compresses the solid itself, giving the final region of rapidly increasing stress.

Figure 2. Typical compressive stress-strain curve of polyurethane foam

The compressive stress-strain curve of cancellous bone has the similar three regimes of
behaviour (Figure 3). Firstly the small strain, linear elastic region appears which is mainly
from the elastic bending of the cell walls. Then the linear-elastic region ends when the cells
begin to collapse and progressive compressive collapse gives the long horizontal plateau of
the stress-strain curve which continues until opposing cell walls meat and touch, causing
the stress rise steeply.

Such similarities have made polyurethane (PU) foams as popular testing substitutes for
human cancellous bones and many researchers have quantitatively characterized material
properties of polyurethane foam to investigate the suitability and usefulness of PU foams
as bone analog. Szivek, Thomas and Benjamin (Szivek et al., 1993)conducted the first
study on mechanical properties of PU foams with different microstructures. Compression
testing was done to identify elastic modulus and compressive strength. The same group
conducted further studies with three compositions of PU foams and evaluated their
properties as well(Szivek et al., 1995). Thompson and co-workers(Thompson et al., 2003)
analyzed compressive and shear properties of commercially available PU foams. They
tested samples of four grades of rigid cellular foam materials and found out that elastic
174 Polyurethane

behaviour was similar to cancellous bones and an appropriate density of PU foams can be
determined for a particular modulus value. However the shear response showed some
discrepancy and concluded that caution is required when simulating other behaviours
than elastic behaviour with these foams. Calvert and coworkers (Calvert et al.) evaluated
cyclic compressive properties of PU foams and examined the mechanical properties in
terms of microstructural features. They found that microstructural properties such as cell
size and volume were uniform and increased with decreasing density. And their cyclic
testing revealed hysteresis in the low density foams but consistent modulus up to 10
cycles.

Figure 3. Compressive stress-strain curves for several relative densities (ρ*/ρs)of wet cancellous bone
(modified from Figure 11-5 in Gibson and Ashyby, 1997)

As the use of PU foams in orthopaedic implant testing and their use as bone analogs
increased, the American Society for Testing and Materials (ASTM) developed ASTM F1839-
97, “Rigid polyurethane foam for use as a standard material for testing orthopaedic devices
and instruments.” The aim of this standard is to provide a method for classifying foams as
graded or ungraded based on the physical and mechanical behaviour with a given density.
This standard has been revised twice since 1997 when it was originally introduced in order
to include a wide range of properties and nominal densities(American Society for Testing
and Materials, 2008a). As such the number of studies that used PU-foam in testing implant
materials and function has increased dramatically after the introduction of the standard. The
next section will give review of those studies.
 Use of Polyurethane Foam in Orthopaedic Biomechanical Experimentation and Simulation 175

3. The use of PU foams in orthopaedic implant testing

The number and variety of implants for osteosynthesis and joint replacement has increased
dramatically over the past few decades along with the use of biomechanical testing of these
implants to evaluate their performance. The most obvious material of choice will be fresh or
embalmed cadaveric human or animal bones as they have the unique viscoelastic properties
and internal structures of real bone. However such studies are often beset with a number of
other problems such as issues in handling biological samples and huge variety in size, shape
and material properties even in matched pairs to name a few. If reproducibility of
experiments is important and comparable not absolute results are required, synthetic bones
made from PU-foam can provide a great alternative to the real bones (Figure 4).

(a) plastic cortical (b) rigid PU-foam (c) transparaent (d) Solid PU-foam
shell with cellular cortical shell with plastic cortical shell throughout
PU-foam inside cellular PU-foam with cellular PU-
inside foam inside

Figure 4. Various synthetic bone material combinations with different types of PU foams and plastics
(from [Link])

The major use of PU foam blocks is comparatives studies for quantitatively measuring some
important functional parameters of orthopaedic implants such as pull out strength, stability
and stiffness. Bredbenner et al. (Bredbenner and Haug, 2000) investigate the suitableness of
synthetic bone made of PU-foam in testing rigidity of fracture fixations by comparing pull
out strength from cadaveric bones, epoxy red oak and PU foams. They found out that PU-
foam bone substitutes generated comparable results to cadaveric bones, concluding that PU-
foams can be used in mechanical investigation of human bones.
Indeed many researchers have used PU-foam in comparative studies measuring pullout
strength of fixation screws. Calgar et al.(Caglar et al., 2005) performed biomechanical
comparative studies of different types of screws and cables using Sawbone models and
found out that the load to failure of screws was significantly greater than that of the cables.
Farshad et al. (Farshad et al., 2011)used PU foam blocks to test bone tunnels drilled during
anterior cruciate ligament reconstruction. They found that screw embossed grafts achieved
higher pull out strengths. Krenn et al. (Krenn et al., 2008)investigated the influence of thread
design on screw fixation using PU-foam blocks with different densities.
176 Polyurethane

PU-foams are also extensively used in biomechanical studies for finding optimal surgical
parameters in orthopaedic surgeries. For example, osteotomy is a surgical procedure where
a bone is cut to shorten or lengthen to rectify abnormal alignment. One variation of that
technique is Weil osteotomy where the knuckle bone in the foot is cut to realign the bones
and relieve pain. There are two separate independent studies on Weil osteotomy involving
PU-foams and cadaver bones. Melamed et al. (Melamed et al., 2002) used 40 PU-foams to
find the optimal angle for the osteotomy and found that an angle of 25° to the metatarsal
shaft give the best result. This result was confirmed a year later by Trnka et al. (Trnka et al.,
2001)who performed the similar study on fresh frozen cadaver feet. They also found that the
range between 25°-35° give the optimal results, confirming that the use of PU-foams in such
studies. Nyska et al. (Nyska et al., 2002) analyzed osteotomy for Bunion deformity using 30
PU-foams and found that displacement osteotomies provided good correction for middle
and intermediate deformity. Acevedo et al. (Acevedo et al., 2002) compared five different
first metatarsal shaft osteotomies by analyzing the relative fatigue endurance. They used 74
polyurethane foam synthetic bones to determine the two strongest of the five osteotomy
techniques and they found that Chevron and Ludloff osteotomies showed superior
endurance than the other techniques.

Nasson and coworkers (Nasson et al., 2001)used eight foam specimens for tibia and talus to
evaluate the stiffness and rigidity of two different arthrodesis techniques where artificial
joint ossification is induced between two bones either with bone graft or synthetic bone
substitutes. They performed arthrodesis on these artificial bones made up of PU-foams and
tested rotation and bending strength and recommended that the use of crossed screws for
the strength, simplicity , speed and minimal tissue dissection.

Another interesting development in the use of PU foam in orthopaedic biomechanics is the

development of so called composite bones. Since PU foam closely resembles cancellous bone
structure and properties, a composite material made up of epoxy resin with fibre glass along
with PU foam was used to create a synthetic bone where cortical and cancellous bone
materials are simulated with epoxy resin and PU foam respectively (Figure 5). Zdero et al
(Zdero et al., 2007, Zdero et al., 2008) tested the performance of these composite bones by
measuring bone screw pullout forces in such composite bones and comparing them with
cadaver data from previous literature. They found out that composite bones provide a
satisfactory biomechanical analog to human bone at the screw-bone interface.

When such composite bone material is shaped according to the actual bony shapes of
human bones such as femur and tibia, they can be a great alternative for cadaver bones in
research and experiment. Since they closely mimic both geometry and material properties of
actual bones and yet have consistency that is lacking in cadaver bones, they can lower
variability significantly, offering a more reliable testing bed. Composite replicates of femur
and tibia were first introduced in 1987 and then have undergone a number of design
changes over the years. The currently available composite bones are fourth-generation
composite bones where a solid rigid PU-foam is used as cancellous core material while a
 Use of Polyurethane Foam in Orthopaedic Biomechanical Experimentation and Simulation 177

mixture of glass fibres and epoxy resin was pressure injected around the foam to mimic
cortical bone. Chong et al. (Chong et al., 2007a, Chong et al., 2007b) performed extensive
mechanical testing with these synthetic bones and found out that the fourth-generation
material has better fatigue behavior and modulus, strength and toughness behaviours a lot
closer to literature values for fresh-frozen human bones than previous composite bones.
Heiner (Heiner, 2008) tested stiffness of the composite femurs and tibias under bending,
axial and torsional loading as well as measuring longitudinal strain distribution along the
proximal-medial diaphysis of the femur. She found out that the fourth-generation composite
bones average stiffness and strains that were close to values for natural bones (Table 1).
Papini et al.(Papini et al., 2007) performed an interesting study where they compared the
biomechanics of human cadaveric femurs, synthetic composite femurs and FE femur models
by measuring axial and torsional stiffness. They found that composite femurs represents
mechanical behaviours of healthy rather than diseased femur (e.g. osteoporosis), hence
caution is required in interpreting the data from experiment with composite bones.

(a) Femur (b) Humerus (c) Tibia

Figure 5. Various composite bones made up of PU-foam core covered with a cortical shell of short fiber
filled epoxy (from [Link])

Property Bone Type Value

Natural 317
Anterior flexural rigidity (N m2)
Composite 241
Natural 290
Lateral flexural rigidity (N m2)
Composite 273
Natural 2.48
Axial stiffness (N/μm)
Composite 1.86
Natural 4.41
Torsional rigidity (N m2/deg)
Composite 3.21
Table 1. Structural properties of natural human and 4th generation femurs (modified from Table 2 of
(Heiner, 2008))
178 Polyurethane

The advert of such biomechanically compatible bone analog greatly widened the use of PU-
foam in orthopaedic biomechanics experiments as more mechanically meaningful
parameters such as strength and surface strains were possible to be introduced in the design
of the experiment.

Agneskirchner et al. (Agneskirchner et al., 2006) investigated primary stability of four

different implants for high tibial osteotomy with composite bones and found that the length
and thickness as well as the rigidity of the material strongly influence the load to failure of
tibial osteotomy. Gulsen et al. (Gulsen et al.) used composite bone in testing biomechanical
function of different fixation methods for periprosthetic femur fractures and compared the
yield points of these techniques. Cristofolini et al. (Cristofolini et al., 2003) performed in
vitro mechanical testing with composite femurs to investigate difference between good
design and bad design in total hip replacement femoral stems. They placed two different
implants (one good design and the other bad design) to synthetic femurs and applied one
million stair climbing loading cycles and measured interface shear between the stem and
cement mantle to see the result of long term performances. Their set-up involving composite
bones was sensitive enough to detect the result of design difference and was able to predict
long term effects of different implant designs. Simoes et al. (Simoes et al., 2000) investigated
the influence of muscle action on the strain distribution on the femur. They measured strain
distributions for three loading conditions that involve no muscle force, abductor muscle
force only and then 3 major muscle forces in the hip. They placed 20 strain gauges on the
composite femur and applied muscle and joint forces accordingly. They found out that
strain levels were lower when muscle forces were applied than when only joint reaction
force was used, indicating that the need to constrain the femoral head to reproduce
physiological loading conditions with joint reaction force only.

As discussed up till now, the use of PU-foam based material is almost limitless and the list
discussed here is by no means an exhaustive survey of the use of PU-foam based materials
in orthopaedic experiment. However, our group has also been working with the PU-foam
materials in our orthopaedic biomechanics extensively. The following chapters give
summary of these works.

4. Use of PU-foams in device and implant testing for bone grafting and
acetabular fractures
4.1. Identification of optimal design parameters in bone grafting tools with PU-
foams
Bone grafting is a reconstructive orthopaedic procedure in which a bone substitute is used
to fuse broken bones and to repair skeletal defects (Arrington et al., 1996, Lewandrowski et
al., 2000). Bone grafting is performed worldwide around 2.2 million times per year, with
approximately 450 000 procedures in the United States alone (Russell and Block, 2000). Most
popular method is autograft where the graft material is extracted from the patient itself. The
graft can be harvested from the patient’s femur, tibia, ribs and the iliac crest of the
 Use of Polyurethane Foam in Orthopaedic Biomechanical Experimentation and Simulation 179

pelvis(Betz, 2002). Autograft has the advantages of being histocompatible and non-
immunogenic, it eliminates the risk of transferring infectious diseases and has
osteoinductive and osteoconductive properties (Arrington et al., 1996). However, the
harvesting procedure often requires a second incision to extract the graft from the donor
site, which can extend operation time by up to 20 min (Russell and Block, 2000). The ensuing
donor site morbidity is regarded as “a serious postoperative concern for both patient and
surgeon” (Silber et al., 2003). Ross et al. (Ross et al., 2000) reported an overall complication
rate of 3.4–49%, of which 28% suffered persistent pain, which can last as long as 2 years and
often exceeds the pain from the primary operation.

The reason for donor site pain remains unclear, however, it might be proportional to the
amount of dissection needed to obtain the graft (Kurz et al., 1989). Conventional bone
grafting tools usually require great exposure of the donor site with accompanied trauma to
nerves and muscles. Damage to nerves and muscles may be reduced by using minimally
invasive bone grafting techniques (Russell and Block, 2000), which shorten the incision
length by approximately 60%, reduce the amount of dissection and are roughly two times
faster than conventional methods (Burstein et al., 2000). Minimally invasive tools are usually
rotational cutting tools, which include trephines, bone grinders (Burstein et al., 2000) and
bone graft harvesters as depicted in Figure 6 A.

Figure 6. Bone graft harvester and its major parameters

The harvester collects the graft, i.e. bone chips consisting of cancellous bone fragments and
bone marrow, in its barrel as it turns and penetrates deeper into the bone. Despite the
advantages of using minimally invasive tools such as the bone graft harvester, cell morbidity is
yet unavoidable, because both fracturing of the bone architecture and heat generation
accompany every bone cutting process. However, mechanical and thermal damage could be
reduced by improving tool geometry and by applying appropriate cutting parameters.

Many researchers have studied various cutting operations, such as orthogonal cutting
(Jacobs et al., 1974), drilling (Saha et al., 1982, Natali et al., 1996) milling (Shin and Yoon,
2006) and sawing (Krause et al., 1982), in order to identify some of the critical parameters
that influence heat generation and to gain an overall understanding of bone cutting
180 Polyurethane

mechanisms. For a bone graft harvester, these parameters are the rake and point angles of
tool, the rotational speed and the feed rate (Figure 6 B).

The influence of such parameters can be measured by characterizing chip types formed
when cutting the bone. Smaller chips imply more fracturing per volume of bone material
collected and due to the linkage between fracturing of the bone architecture and cell
morbidity, and larger chips are believed to act as “life rafts” for the bone cells and will
increase the rate of survival for embedded living cells. We have conducted two-part study
where we identified various chip types during orthogonal cutting process(Malak and
Anderson, 2008, Malak and Anderson, 2005).

In Part I (Malak and Anderson, 2005), we used polyurethane foams of various densities and
cell sizes to investigate chip formation and surface finish. An optical arrangement made up
of dynamometer, microscope and camera system (Figure 7) was used to visually record the
cutting process, while horizontal and vertical cutting forces were measured. A total of 239
measurement were performed using rake angles of 23°, 45° and 60° with depths of cut from
0.1 to 3 mm (increments of 0.1 and 0.2 mm). Cutting events were observed on the video and
then linked to simultaneous force events by merging both sets of data into a combined video
stream, generating force plot images.

Figure 7. Experimental set-up for measuring chip formation during orthogonal cutting procedure

Three types of cutting response were identified and categorized as 1) surface fragmentation;
2) continuous chip formation; 3) discontinuous chip formation depending on tool rake
angle, depth of cut, foam density and cell size (Figure 8). Surface fragmentation was
associated with cutting depth less than the PU-foam cell size. By cutting an order of
magnitude of the cell size deeper, continuous chips were produced, which is a desirable
feature whenever good surface finish after cutting is desired as in the case of bone harvester.
A large rake angle (60°) was also inductive of continuous chip formation. Discontinuous
chip formation was associated with 1) foam compaction followed by chevron shaped chip;
2) crack propagation in front of the tool. Compaction of the foam could be minimized by
using a tool with a large rake angle and normal cut depth.
 Use of Polyurethane Foam in Orthopaedic Biomechanical Experimentation and Simulation 181

Figure 8. Various chip types formed during orthogonal cutting of polyurethane foams of various
densities

The same experiment was repeated with bovine fresh cancellous bone(Malak and Anderson,
2008) from the patella, the femur and the iliac crest. Similar orthogonal cutting experiments
were conducted using the same device used in Part I to identify major parameters that
influence the formation of chips after cutting. Three groups of experiments were done where
the effect of the depth of the cut, rake angle and cutting speed. Similar chip types as the
experiment with PU-foams in Part I were observed which were found to be dependent on
rake angle and depth of cut (Figure 9).

Figure 9. Chip foramtion during orthogonal cut of cancellous bone.

182 Polyurethane

When the results from cancellous bone were compared with those from PU-foams, both
showed surface fragmentation, continuous and discontinuous chip formations. During
polyurethane foam cutting, chip types were influenced by rake angle and depth of cut. Bone
cutting showed similar trend, however, resulting chip type were mainly influenced by the
tool rake angle. We also identified the depth of cut that marked the transition from surface
fragmentation to continuous or discontinuous chip types. In PU-foams, such a transition is
indicated by a change in cutting forces. A similar trend was observed in bone; a depth of cut
of 0.5 mm ~ 0.8 mm led to continuous or discontinuous chips. These values approximately
correspond to the trabecular separation values. This is in accordance with our findings
during the cutting of polyurethane foam, where depths of cut had to reach values of the
foam cell size diameter in order to be either continuous or discontinuous.

Therefore polyurethane foam was successfully used in identifying optimal parameters for
designing minimally invasive bone graft harvester. The next section will describe how PU-
foam based synthetic bone was used in FE modeling of hip fracture.

4.2. Development and validation of finite element fracture predictions with PU-
foam based synthetic bones
Acetabular fractures are one of the big challenges that trauma surgeons face today. Despite
the great stride made in treating this fracture in the past few decades, one medical text book
states that “fractures of the acetabulum remains an enigma to the orthopaedic surgeon(Tile
et al., 2003).” The main reason for this difficulty lies on the complexity of acetabular
fractures. Acetabular fractures are usually a result of indirect trauma where the major
impact is transmitted via the femur after a blow to the greater trochanter, to the flexed knee
or to the foot with the knee extended (Ruedi et al., 2007). Moreover acetabular fractures are
dependent on a number of variables such as the type of force that caused the fracture, the
direction of displacement, the damage to the articular surface as well as the anatomical
types of the fracture (i.e. the shapes of the fragments). The relative rareness of acetabular
fractures makes matters worse since general orthopaedic surgeons may not gain wide
experience with them.
The past researches on acetabular fracture can be broadly divided into two categories. The
first is experimental studies where the stability of different acetabular fracture fixation
techniques was investigated with in-vitro mechanical experiments (Goulet et al., 1994,
Konrath et al., 1998a, Konrath et al., 1998b, Olson et al., 2007). There are also clinical studies
that examined the effectiveness and longer-term results of different fracture fixation
techniques (Borrelli et al., 2005, Cole and Bolhofner, 1994, Giannoudis et al., 2005). Finite
element (FE) models can enhance greatly the body of knowledge obtained from such
experimental and clinical studies. FE models can overcome the limitations of in-vitro
experimental studies because they can be used to simulate the behaviour of the fractured
acetabulum under physiological loading conditions that include muscle forces. FE models
can also elevate the results from clinical studies into a new dimension as they can be used to
predict the outcome of particular fixation techniques after the surgery. If the model
performance in fracture prediction is validated, it can be used to evaluate various fixation
 Use of Polyurethane Foam in Orthopaedic Biomechanical Experimentation and Simulation 183

techniques depending on their fracture types. The problem is how to validate the model. If
cadaver bone is to be used, the issue of sample variability and the requirement of ethics
approval, special storage and high cost need to be resolved first. Therefore the aim of this
study is to develop a finite element model of the pelvis that can accurately predict the
fracture load and locations of acetabular fractures and validate its performance with
synthetic PU-foam based bones(Shim et al., 2010).

4.2.1. Fracture experiment with PU-foam synthetic pelvic bones

Ten synthetic male pelves made with polyurethane foam cortical shell and cellular rigid
cancellous bone (Full Male Pelvis 1301-1, Sawbones, Pacific Research Laboratories, INC,
Washington, WA, USA) were used for fracture experiment. A similar set-up as (Shim et al.,
2008) was used where the pelvis was placed upside down in a mounting pane filled with
acrylic cement. Two different loading conditions – seating (or dashboard) fracture and fall
from standing fracture – were tested. When the angle (α) between the vertical line and the
line formed by joining the pubic tubercle and the anterior superior point of the sacrum
(Figure 10) was 30 °, the whole set-up mimicked the standing position, hence simulating
standing fracture. When the angle α was raised to 45°, the set-up mimicked the position of
the pelvis when seated, hence simulating seating fracture. Force was exerted from the
femoral head attached to the crosshead of the Instron machine (Instron 5800 series,
Norwood, MA, USA). The femoral head was also from a matching Sawbone femur (Large
Left femur 1130, Sawbones, Pacific Research Laboratories, INC, Washington, WA, USA) to
the pelvis used. The femur was first chopped at the neck region and then attached to a
custom made holding device connected to the crosshead of the Instron machine (Figure 10).
The femoral head was dipped into liquid latex to ensure a complete and stable seating of the
femoral head to the acetabulum. The force was applied from the femoral head to the
acetabulum at a constant speed of 40N/s until failure. Total ten pelves were used for testing.
Five were tested for standing fracture and the rest was tested for seating fracture. The
fracture loads and patterns were recorded for comparison with finite element simulations

Figure 10. Photos of the experiment: The photo on the left shows the angle alpha that determined
seating or standing positions; the center photo shows the close-up of the chopped femoral head
attached to the holding device that goes into the crosshead of the Instron machine; the photo on the
right shows the overall set-up.
184 Polyurethane

4.2.2. Finite element analysis of PU-foam based synthetic pelvis

The Sawbone pelvis used in the experiment was CT scanned (Philips Brilliance 64, Philips).
Each CT image was manually segmented and a finite element model of the hemi pelvis was
generated using the previously validated procedure (Shim et al., 2007, Shim et al.,
2008)(Figure 11). Our model is both geometrically and materially non-linear. Geometric non-
linearity was achieved by using finite elasticity governing equations rather than linear
elasticity approximations (Shim et al., 2008). Material non-linearity was incorporated in a
similar manner as in (Keyak, 2001). In our model, the material behaviour of the synthetic
PU-foam based pelvis was divided into two regions – 1) an elastic region with a modulus E;
2) perfectly plastic regions with a plastic strain εAB (Figure 11) according to the material
behaviour of polyurethane materials(Thompson et al., 2003). The value for εAB was
obtained from the specifications provided by the manufacturer (Pacific Research
Laboratories, INC, Washington, WA, USA).

Figure 11. FE model and it nonlinear material behaviour. The polyurethane foam material behavior
was represented by an elastic region with modulus E until stress S, followed by a perfectly plastic
region with plastic strain εAB.

Two materials were incorporated in our model – 1) solid polyurethane foam that mimicked
the cortical bone property; 2) cellular rigid polyurethane foam for cancellous bone. The
material properties for the two polyurethane foams are given in Table 2.

Density (g/cc) Strength (MPa) Modulus (MPa)

Solid polyurethane foam 0.32 8.8 260
Cellular polyurethane foam 0.16 2.3 23
Table 2. Material properties of solid and cellular polyurethane foam

The previously developed algorithm that determines cortical thickness was used to distinguish
between solid polyurethane and cellular polyurethane foam regions from CT scans. We used
Gauss points inside the mesh to assign material properties and those points placed in the solid
region was given the solid polyurethane foam material properties while those in the cellular
region was assigned with the cellular polyurethane foam material property(Shim et al., 2008).
This allowed our model to have location dependent cortical thickness.
 Use of Polyurethane Foam in Orthopaedic Biomechanical Experimentation and Simulation 185

The contact between the femoral head and the acetabulum was modeled as frictional contact
(μ = 0.3) and the boundary conditions used in FE simulation were the same as the experiment.
The nodes on the superior region of the iliac crest were fixed and two different loading
conditions used in the experiment were used as the boundary condition. As in the experiment,
the standing and seating positions were differentiated by varying the angle α defined in Figure
10. A vertically directed force was exerted on the femoral head mesh until failure.
The failure behaviour was characterized using the distortion energy (DE) theory of failure
(Keyak et al., 1997). The DE theory is a simplified form of the Hoffman failure theory which
was proposed for brittle fracture of orthotropic materials (Hoffman, 1967). Assuming
isotropy, the fracture condition is reduced to the following (Lotz et al., 1991)

2 2 2
C1  2   3   C2  3   1   C3  1   2   C4 1  C5 2  C6 3 
1 (1)

where
1
C
1 C
2 C
3
2StSc
1 1
C
4 C
5 C
6 
St Sc

In this equation, σi is the principal stresses and St is the tensile strength and Sc is the
compressive strength. If St and Sc are equal, Equation (1) becomes the distortion energy (DE)
theory of failure, which was used in our study as a failure criterion. Since we used Gauss
points in assigning material properties, we calculated a factor of safety (FOS) for every
Gauss point (Equation 2) and if the FOS value was predicted to be less than one the Gauss
point was regarded as in failure (Keyak et al., 1997). The fracture load and location were
recorded for each loading condition and compared with the experimental results.

Gauss point strength (from CT and material property)

FOS= (2)
Gauss point von Mises stress (from FE simulation)

4.2.3. Finite element model sensitivity analysis

Sensitivity analysis was performed to find out which material parameters affect the strength
of the pelvic bone most. The parameters of interest for sensitivity analysis were: 1) cortical
thickness; 2) cortical modulus; 3) trabecular modulus. Since we used synthetic bones made
of polyurethane foam, the three corresponding material parameters for the Sawbone FE
model were 1) solid polyurethane foam thickness; 2) solid polyurethane modulus; 3) cellular
polyurethane modulus. The values for the parameters were varied to see their effects on the
predicted fracture load. The following equation (Equation 3) was used to measure the
sensitivity of the chosen parameters.

% Change in predicted fracture load

S (3)
% Change in input parameter
186 Polyurethane

The range of simulated variation in the input parameters is given in Table 3. Since we used
Gauss points in assigning material properties, the number of Gauss points in the transverse
direction was varied from 4 to 6, which had the equivalent effect of varying the solid
polyurethane thickness by -40% to +50% (Shim et al., 2008). As for the modulus values, the
values were varied by ±25%, which was the next available value in the manufacturer’s
specification for material properties (Table 3). Multiple FE simulations were run with these
values and the change in the predicted fracture load was recorded.

Simulated of variation
Solid polyurethane foam -40% and +50% from the original thickness
thickness obtained from CT scans
Solid polyurethane foam
±25 % from the original density value of 0.32g/cc
modulus
Cellular polyurethane foam
±25% from the original density 0.16 g/cc
modulus
Table 3. Sensitivity analysis of polyurethane foam thickness and modulus

4.2.4. Fracture experiment with PU-foam pelvis and corresponding FE model predictions
The fracture behaviour of Sawbone pelves was linear elastic fracture of brittle material
(Figure 12 (a)), which coincides with other studies involving fractures of polyurethane
(Mcintyre and Anderston, 1979)
The fracture loads from the mechanical experiments are given in Figure 12 (b). The standing
case has a slightly higher fracture load (mean 3400N) than the seating case (mean 2600N).
Our FE model predicted the fracture load for both cases with a good accuracy as the
predicted values are within the standard deviation of the experimental values for both case
(Figure 12). The predicted fracture loads from the FE model are 3200N and 2300N for
standing and seating cases respectively.
The predicted and actual fracture locations were consistent for both experiments and FE
simulations and the fractures occurred mainly in the posterior region of the acetabulum.
Different fracture patterns were obtained from two different loading conditions. For the fall
from standing experiment, the fracture pattern resembled posterior column fracture
according to the Letournel’s classification (Letournel, 1980) while the dashboard experiment
produced posterior wall fractures. Since the main cause of posterior wall fracture is car
accidents (Spagnolo et al., 2009), our experimental set-up was able to capture the main
features present in this fracture. The fracture locations predicted by the FE model were
similar to the actual fracture patterns from the experiment. For the fall from heights fracture
case, the failed Gauss points were concentrated at the region that extends from the dome of
the acetabulum to the posterior superior region and then to the posterior column of the
pelvis. This resembled the posterior column fracture that was observed from the
experiment. For the seating case, on the other hand, the failed Gauss points were more or
less limited in the posterior wall region of the acetabular rim, resembling the posterior wall
fracture (Figure 12 (a)).
 Use of Polyurethane Foam in Orthopaedic Biomechanical Experimentation and Simulation 187

(a) Fracture location prediction results (b) Fracture load prediction results
Figure 12. Fracture location (a) and load (b) predictions from FE models

Once the fracture prediction was done, the sensitivity analysis was performed. Three input
parameters (solid polyurethane thickness and modulus, cellular polyurethane modulus)
were varied to examine the effect of their variation on the predicted fracture load. Among
the three input parameters solid polyurethane foam modulus had the greatest impact on the
resulting fracture load. Solid polyurethane foam thickness also had some effect on the
predicted fracture load, but the sensitivity of this parameter was not as high as the modulus.
Cellular polyurethane foam modulus, on the other hand, did not have any significant
impact on the predicted fracture load as can be seen in Table 4. Since the pelvis has a
sandwich structure where the outer cortical shell bears most of the load, our results indicate
that this structural characteristic is also preserved even when the pelvis undergoes fracture.

Type of input Amount of variations Predicted fracture

Sensitivity
parameters in input parameters load
Solid polyurethane 0.6 3200 0.395
foam thickness 1.4 4500 0.461
Solid polyurethane 153 2200 0.858
foam Modulus 400 5000 0.874
Cellular 12.4 3200 0.128
polyurethane foam
47.5 3500 0.028
Modulus
Table 4. Results of sensitivity analysis

4.2.5. Feasibility of the use of synthetic PU-based bone in validating FE fracture

predictions
FE models have been extensively used in predicting fracture load. Our approach to fracture
mechanics was based on the work by Keyak and co-workers (Keyak et al., 1997, Korn et al.,
188 Polyurethane

2001) which used the DE theory of fracture as well as material non-linearity. However, our
approach differs from their work in that we simulated acetabular fractures not fractures of
the proximal femur which are generally more complicated than fractures of the proximal
femur. Moreover, rather than applying force directly to the bone of interest as done in
majority of the FE fracture studies, we employed a contact mechanics approach where the
force was applied to the acetabulum via the femoral head. Another novel approach of our
study is that we incorporated geometric non-linearity to the model by using full finite
elasticity governing equations, which has been found to enhance the fracture prediction
capabilities of FE models (Stˆlken and Kinney, 2003).

However the most notable feature of our approach is the use of PU-based synthetic bone in
validating FE fracture predictions. At present, it is not known whether our model can
predict human bone fractures with the same degree of accuracy as the synthetic bones.
Therefore caution is required when interpreting the data. However we are confident that
our result will translate into human bones due to the following reasons. Firstly our
experimental results with PU-foam pelves showed similar results as other human cadaver
results as the fracture patterns generated in seating and standing cases correspond well with
clinical results. Moreover the sensitivity analysis revealed that our model behaves in a
similar manner as the cadaver bones despite the apparent difference in absolute magnitudes
in modulus values between PU-foams and bones.

In fact, PU-foam based synthetic bone served our purpose of model validation very well due
to their uniformity and consistency (Nabavi et al., 2009). As such, the ASTM standard states
that it is “an ideal material for comparative testing” of various orthopaedic devices
(American Society for Testing and Materials, 2008b). Although the fracture load is expected
to be different from the fracture load of human pelvis, the material behaviour is expected to
be comparable to human bones, both of which exhibit brittle fracture (Schileo et al., 2008,
Thompson et al., 2003). Therefore the model’s ability to predict fracture load and location of
the synthetic bone can be regarded as a positive indication that it will also be applicable to
human cases. Therefore we continued to use this approach in developing and validating FE
model predictions for fracture stability with PU-foam based synthetic bones, which will be
described in the next section(Shim et al., 2011).

4.3. Development and validation of finite element predictions of the stability of

fracture fixation with PU-foam based synthetic bones
The posterior wall fracture is the most common fracture type of the
acetabulum(Baumgaertner, 1999). Depending on the fragment size, open reduction and
internal fixation (ORIF) is performed especially when the fracture involves more than 50%
of the posterior wall. But ORIF requires considerable exposure that often leads to major
blood loss and significant complications(Shuler et al., 1995). Percutaneous screw fixations,
on the other hand, have become an attractive treatment option as they minimize exposure,
blood loss and risk of infection. As such, they have been advocated by some authors
 Use of Polyurethane Foam in Orthopaedic Biomechanical Experimentation and Simulation 189

(Parker and Copeland, 1997) for the treatment of minimally displaced acetabular fractures
without comminution or free fragment in the joint. However the biomechanical stability
of percutaneous fixation has not been studied thoroughly, especially in terms of
interfragmentary movement. In particular, the stability of percutaneous fixation in
acetabular fractures has not been compared with the more conventional ORIF involving a
plate with screws. There have been previous biomechanical studies that compared
different types of stabilization in posterior wall fractures (Goulet et al., 1994, Zoys et al.,
1999). But the main focus of such studies was to compare the strength of several types of
osteosynthesis. However it is interfragmentary movement that exerts major influences on
the primary stability and fracture healing (Klein et al., 2003, Wehner et al., 2010). As
discussed in Section 3, PU-foam based synthetic bones have been used extensively in
testing stability of various osteosynthesis techniques. Therefore we have further
developed our FE model capable of prediction acetabular fractures to simulate stability in
osteosynthesis. Specifically, we have developed a fast and efficient way of predicting the
interfragmentary movement in percutaneous fixation of posterior wall fractures of the
acetabulum and validated with a matching biomechanical experiment using PU-foam
based synthetic pelves.

4.3.1. Mechanical experiment with PU-foam based synthetic pelvis

Seven synthetic pelves (Full Male Pelvis 1301-1, Pacific Research Laboratories Inc) were
loaded until failure with the loading condition that resembled seating fracture[10], creating
posterior wall fractures[11]. The fractures were then reduced and fixed with two fixation
methods –with two screws (3.5mm Titan Screws, Synthes) and then with a 10-12 hole plates
(3.5mm Titan Reconstruction- or LCDC-Plates, Synthes) by an experienced surgeon (JB)
(Figure 13 A and B). The maximum remaining crack was 0.7 mm.

(a) Screw fixation (b) Plate fixation

Figure 13. Two fixation methods performed on the fractured acetabulum

190 Polyurethane

The pelves were then loaded in the Instron Machine (Instron 5800 series) with a cyclic load
that oscillated between 0N to 900N at 40N/s. The force was applied using a synthetic
femoral head (Large Left Femur, 1129, Pacific Research Laboratories Inc) attached to the
crosshead of the Instron Machine (Figure 14). At the multiple of 300N the loading was
paused for 3 seconds to measure the displacement between the fragment and the bone by
taking photographs of the crack opening (Figure 14 (a)). A digital SLR camera (Nikon D70)
with a 50mm macro lens (NIKKOR dental lens) was used to accurately measure the amount
of crack openings (resolution of 10 μm (Figure 14 (b))). A resolution of 10μm was achieved
(Figure 15).

(a) Measurement set-up (b) Optical set-up with macro

Figure 14. Interfragmentary movement measuring set-up with a digital single-lens reflex camera and
an Instron machine

Figure 15. A photo taken with the macro lens. The magnified view shown in the box left has the
resolution of 10μm
 Use of Polyurethane Foam in Orthopaedic Biomechanical Experimentation and Simulation 191

The displacement was measured in two different positions – front and side - to obtain the
fragment movement in three directions – frontal, vertical and lateral directions (Figure 16).
10 photographs were taken at each angle and load and the mean value was taken.

Figure 16. Getting fragment movements in three directions – horizontal, vertical and lateral – using
photos taken at two different views. The actual movement of the fragment is from P1 to P2 from no load
to full load conditions. The front view photo gives the triangle P1P4P3, allowing us to calculate
horizontal and vertical movement. The side view photo gives the triangle P4P2P3 which allows us to
calculate the lateral movement.

4.3.2. Finite element simulation

The stability of screw fixation was analyzed with finite element models. We developed
the models of the fractured pelvis, fragment and femoral head in order to perform
the mechanical testing that we did in silico. Firstly, one of the PU-foam based synthetic
fractured pelves that had been fixed with two screws was dismantled. The resulting
fractured pelvis and its fragment were scanned separately with a Faro Arm (Siler Series
Faro Arm) and a laser scanner (Model Maker H40 Laser Scanner). Two sets of data point
192 Polyurethane

clouds, which accurately described the shapes of the fragment and the fractured pelvis,
were obtained (Figure 17). The fractured pelvis model was developed from our previous
FE model of the pelvis, which was generated from CT scans of the synthetic pelvis used in
the experiment (Shim et al., 2010) . Our elements had inhomogeneous location dependent
material properties despite large element size and different material properties were
assigned to solid and cellular polyurethane foams which mimic cortical and cancellous
bone properties separately. The loading and boundary condition that mimics
the mechanical experiment setup were employed. The FE models of the screws were not
generated explicitly. Instead tied contact was used to model the bond between the
fractured pelvis and the fragment from the screws. The locations of the screws on the
fragment FE model were identified first from the laser scanned data. Then, the tied
contact condition that ensures a perfect bond between slave and master faces was
imposed on the identified faces to simulate the bond that screws provide when connecting
the fragment with the bone. The rest of fragment faces were modeled with frictional
contact (μ=0.4)(Gordon et al., 1989). The predicted interfragmentary movements from
the FE model under the same loading and boundary conditions as the experiment
were then compared with the experimental value to test our hypothesis. Once tested,
then, the screw positions were varied by changing tied contact faces to simulate all
possible screw positions in order to identify the positions that achieved the most stable
fixation.

Data clouds obtained Model generated from data Model for fracture
from laser scanning PU- points by geometric fitting reduced pelvis
foam pelvis

Figure 17. The far left column shows clouds of data points obtained from laser scanning. The center
column shows the meshes for the fragment and fractured pelvis that were generated by geometric
fitting to laser scanned data points. The red faces on the fragment mesh indicate where tied contact
conditions were imposed in order to simulate the support provided by the screws. The final mesh is
shown on the far right column.
 Use of Polyurethane Foam in Orthopaedic Biomechanical Experimentation and Simulation 193

4.3.3. Interfragmentary movement in acetabular fracture osteosynthesis measured with

PU- foam based synthetic bones
The overall amount of displacement between the pelvis and the fragment was relatively small
and the main direction of the fragment movement was in the lateral posterior direction (in
body directions). The average displacement was around 0.4 – 0.9 mm for both screw and plate
fixations. The plates gave higher stability especially in the horizontal and lateral directions
(Figure 18). However, screw fixations also gave good stability of less than 1mm on average in
all directions. Therefore, considering the fact that the maximum load of our experiment was
higher than normally allowed weight bearing (around 20kg after the surgery for 3 months),
the stability of screw fixation was sufficient for the cyclic loading condition used.

1.4
1.2 Plate fixation Screw fixation
1
0.8
0.6
0.4
0.2
0
horizontal vertical lateral

Figure 18. Comparison of interfragmentary movement between plate and screw fixation

4.3.4. Accuracy of FE model interfragmentary movement predictions validated with PU-

foam based synthetic bones
The FE model predicted the movement of the fragment in screw fixations with a good
accuracy. The values predicted by the FE simulation were within one standard deviation of the
experimental measurements (Figure 19) in the horizontal and lateral directions. The predicted
vertical direction movement was a little bit greater than the upper limit of the experimental
measurement (mean + 1 SD) but still very close to it as the difference was 0.05 mm.

The optimized screw positions were found to be on the two diagonal corners of the
fragment. When the virtual screws were placed in this manner, the stability of screw
fixations improved dramatically to the level that is comparable to plate fixation (Figure 20).
The fragment movements in the horizontal and lateral directions were smaller than the
average movements in the plate fixation in these directions. Although the movement in the
vertical direction was bigger than the upper limit of the experimental measurement, the
difference was small 0.1mm.
194 Polyurethane

1.4
Screw fixation FE prediction
1.2
1
0.8
0.6
0.4
0.2
0
horizontal vertical lateral

Figure 19. Comparison between FE prediction and experimental measurement

1.4

1.2 Plate fixation Optimized FE prediction

1

0.8

0.6

0.4

0.2

0
horizontal vertical lateral

Figure 20. Comparison between plate fixation and optimized screw fixation predicted from FE model

4.3.5. Feasibility of the use of synthetic PU-foam based bone in validating FE predictions of
fracture stability
We have developed a new and efficient way of simulating interfragmentary movement in
acetabular fractures using a FE model. We validated our method with a biomechanical
experiment involving PU-foam based synthetic bones. There are numerous studies that
employed PU-foam based synthetic bones in measuring fracture stability as discussed in
Section 3. However this data has not been used in validating FE model predictions of
fracture stability. The use of FE models in fracture analysis is not new. However, the major
focus has been to analyze the stress distribution on the implant or the overall stiffness of
bone/implant composite after fracture fixation (Eberle et al., 2009, Stoffel et al., 2003).
 Use of Polyurethane Foam in Orthopaedic Biomechanical Experimentation and Simulation 195

Therefore we have performed a biomechanical experiment with PU-foam based synthetic

bones to measure interfragmentary movements in 3D and used the result to validate our FE
model.

The mechanical experiment with synthetic pelves showed that the displacement between
fragment and bone was relatively small for both plate and screw fixations, indicating that
screw fixations in single fragment fractures may be a good alternative to the current gold
standard of plate fixation. In particular the excellent stability displayed by the screw FE
model with the optimized screw positions indicate that screw fixations along with computer
navigation should be an option considered by trauma surgeons if available.

The FE model showed a great potential for use in analyzing fracture fixation techniques.
Our model was able to predict the movement of the fragment with a reasonable accuracy.
Although we have not modeled screws explicitly, our modeling approach was able to
accurately predict the fragment movement, which was the main aim of the model. Moreover
the computational efficiency of the approach allowed us to perform a parametric study for
optimization of screw positions.

Since we have used PU-foam based synthetic pelves in our study it is not known if our
model predictions will be as accurate when cadaver bones are used. However the use of
synthetic bones has some advantages due to their uniformity and consistency (Nabavi et al.,
2009). Moreover the main aim was to make comparisons between different osteosynthesis
techniques and between experimental and FE simulations and the ASTM standard states
that it is “an ideal material for comparative testing (American Society for Testing and
Materials, 2008a).” In this regard, the use of PU-foam based synthetic bones in comparative
studies in orthopaedic biomechanics can provide useful data for FE model validation as well
as testing hypothesis.

5. Concluding remarks
In this chapter we discussed the use of polyurethane in orthopaedic biomechanical
experiments. Due to the similarity of polyurethane foam with cancellous bone in terms of
microstructure and material properties, polyurethane has found a unique and important
position in orthopaedic biomechanics studies. The main use of PU-foams was in
experimental studies to find optimum values in various surgical procedures and to test
stability of fracture or joint replacement implants. Due to the uniformity and consistency in
material properties, PU-foam based synthetic bones are capable of generating reproducible
results that are so difficult to obtain when using human cadaver bones. Therefore we used
PU-foam materials in designing bone graft harvesters and obtaining validation data for FE
model predictions in fracture load and stability. Although material properties of PU-foams
are not identical to natural bone, they are able to generate comparable results that can
provide important insight into surgical procedures or function of implants or devices.
Moreover thanks to the advent of new composite bones made up of PU-foams and other
relevant materials that mimic the geometry, structure and material properties of human
196 Polyurethane

bone, only the imagination of biomechanical engineers is the limit in ways that PU-foam
based materials can be used in orthopaedic biomechanical studies in the future.

Author details
V. Shim and I. Anderson
Auckland Bioengineering Institute, University of Auckland, New Zealand

J. Boheme and C. Josten

University of Leipzig, Germany

Acknowledgement
This work was supported in part by Faculty Development Research Fund (FRDF) from the
University of Auckland awarded to V. Shim and Federal Ministry of Education and
Research (BMBF) grant awarded to J. Böhme. The authors would like to thank Mr. Sharif
Malak for his work in orthogonal cutting of PU-foams.

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 Chapter 10

Biocompatibility and Biological

Performance of the Improved Polyurethane
Membranes for Medical Applications

Maria Butnaru, Ovidiu Bredetean, Doina Macocinschi,

Cristina Daniela Dimitriu, Laura Knieling and Valeria Harabagiu

Additional information is available at the end of the chapter

[Link]

1. Introduction
Polyurethanes (PUs) are one of the most “pluripotent” synthetic polymer classes used in
medical applications. Due to their structural versatility, they have been widely discussed as
materials appropriate for biomedical applications (Abd El-Rehim & El-Amaouty, 2004;
Guelcher et. al., 2007; Guelcher, 2008; Kavlock et. al, 2007; J.S. Lee et. al., 2001; Lelah &
Cooper, 1987; Siepe et. al., 2007). Up to now, new PUs have been synthesized that possess
good mechanical properties. Most of them are considered biocompatible on account of in
vitro cytotoxicity evaluation.
However, it is well known that structural and mechanical adaptability of PUs is not always
accompanied by cell and tissue biocompatibility. Therefore, numerous data in the literature
are focused on biocompatibilization or functionalization of PUs (Yao, 2008; Sartori, 2008,
Huang & Xu, 2010). Some promising methods for the improvement of biological response of
PUs are conjugation, blending or coating with natural polymers. Thus, polysaccharides as
chitosan, cellulose and their derivatives (Raschip, 2009; Zia, 2009; Zuo, 2009), proteins and
glycoproteins as collagen, fibrin, fibronectin (R. Chen et. al., 2010; Sartori et. al., 2008),
proteoglycans and glycosaminoglycans (Gong et. al., 2010) and other molecules (Hwang &
Meyerhoff, 2008; Hsu et. al., 2004; Makala et. al., 2006; Song et. al., 2005; Verma & Marsden,
2005) are employed successfully for PUs modification. Owing its specific properties,
hydroxypropylcellulose (HPC) is already used as binder, thickener, lubricating material
(artificial tears) and emulsion stabilizer in pharmaceutical and food industry. Moreover,
HPC may provide interactions through its hydroxyl radicals, being an excellent compound
for copolymerization in scaffolds for tissue engineering and in drug delivery systems
(Berthier et. al., 2011; D. Chen & Sun, 2000; Gutowska et. al., 2001; Raschip et. al., 2009;

©©2012
2012Butnaru
Butnaruetetal.,al.,
licensee InTech.
licensee ThisThis
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an open under the
access chapter terms of the
distributed Creative
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License ([Link] which use,
which permits unrestricted permits
unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.
distribution, and reproduction in any medium, provided the original work is properly cited.
202 Polyurethane

Valenta & Auner, 2004). In previous studies we found that when added to PU structure,
HPC improves hydrophilicity and mechanical properties of PUs by increasing the elasticity
of the resulted materials (Macocinschi et. al., 2009).
Considering the reviewed concept of biocompatibility as “the ability to exist in contact with
tissues of the human body without causing an unacceptable degree of harm to the body”
(Williams, 2008), our interdisciplinary work was focused on the synthesis of PU-based
materials with improved ability to long-time functional integration. PU/HPC membranes
were prepared by blending method. HPC was chosen due to its physical-chemical
properties, its demonstrated biocompatibility and accessibility. The aim of the chapter is to
highlight the most important criteria, able to predict the behaviour of material-tissue
interfaces and the long-term material-tissue integration, in order to select most suitable
compositions and morphologies for specific medical application. Thus, surface zeta (ζ)
potential, wettability (as contact angle measurement and water uptake), pH modification
after long time hydration and autoclaving, protein adsorption at protein physiological
concentration and some relevant elements of bulk and surface morphology are treated as
screening criteria for suitable membrane choice in the first part of the chapter. Biological
performance evaluation, such as oxidative stress action, thrombogenicity and in vivo
behaviour of PU/HPC membranes are further discussed.

2. Materials and methods

2.1. Preparation of polymer samples
Preparation of PU/HPC samples was performed according to Fig. 1 as previously reported
(Macocinschi et. al. 2009; Vlad et. al, 2010).

Figure 1. Scheme of chemical structure and synthesis way of PUs/HPC

 Biocompatibility and Biological Performance
of the Improved Polyurethane Membranes for Medical Applications 203

Briefly, isocyanate terminated urethane prepolymers were first synthesized by the

polyaddition reactions between 4',4’-diphenylmethane diisocyanate (MDI) and macrodiols in
N,N-dimethylformamide (DMF) as solvent. Poly(ethylene adipate)diol (PEGA, Mn = 2000
g/mol), polytetrahydrofuran (PTHF, Mn = 2000 g/mol) or poly(propylene)glycol (PPG, Mn =
2000 g/mol) were used as macrodiols. The urethane prepolymers were treated in a subsequent
step with ethylene glycol (EG) as chain extender. Finally, HPC (average weight molecular
weight Mw = 95 000 g/mol) was added to PU solutions to obtain the following compositions
for all PU/HPC samples: macrodiol/MDI/EG/HPC = 52.24 /36.57/7.27/3.92 (weight ratios). As
the molar ratio between isocyanate groups in MDI and the sum of hydroxylic groups in
macrodiol and EG was 1.02, the excess of isocyanate groups linked to PU prepolymers were
available to bind a part of HPC chains. Membranes with about 1 mm thickness were prepared
by pouring PU/HPC DMF solutions in distilled water, at 40 oC. The formed films were then
dried under vacuum for several days and kept in distilled water for solvent removing.

To half of PUs with PEGA macrodiol in the soft segment no HPC was added to obtain PU-
PEGA reference sample. HPC containing samples based on PEGA, PTHF and PPG
macrodiols were codified as PU-PEGA/HPC; PU-PTHF/HPC and PU-PPG/HPC,
respectively.

2.2. ζ potential determination

ζ potential of the PU membranes was measured by streaming potential method using a
commercial electrokinetic analyzer SurPASS, (Anton Paar GmbH, Graz, Austria). For each
sample, ζ potential has been measured in 0.1 M NaCl solution at physiological 7.4 pH value,
a 300 mbar electrolyte pressure and a 80 ml/min flow rate. For statistical reasons, four
streaming potentials were measured. The mean value of these data was used for potential
calculation by Fairbrother–Mastin equation, considering also the effect of surface
conductivity (Luxbacher, 2006)

2.3. Wettability
Wettability of the PU membranes was determined by measuring the surface contact angle
and water uptake. For surface contact angle, uniform drops of the tested liquid (double-
distilled water) with a volume of 2 μl were deposited on the film surface and the contact
angles were measured after 30 s, using a video-based optical contact angle measuring device
equipped with a Hamilton syringe in a temperature-controlled environmental chamber. All
measurements were performed at room temperature of 25 C. Repeated measurements of a
given contact angle were all within the range of ± 3 degrees. Water uptake was calculated as
the ratio between fully hydrated and dried sample weights.

2.4. Material extraction in a simulated biological microenvironment

Material extraction in a simulated biological microenvironment was done for long period of
time (over 2 months) in Hank’s Balanced Salt Solution (HBSS) without Ca2+ and Mg2+, with
204 Polyurethane

glucose, and phenol red as pH indicator. For extraction experiments, 0.2 g of each
membrane, cut in very small pieces (see Fig. 2), were incubated in 2 ml of HBSS solution at
37oC. pH variation was monitored daily, based on phenol red indicator colour and
measured after 1, 2, 3, 30 and 60 days of incubation using Mettler Toledo SevenGo SG2ELK
pH-meter.

2.5. Scanning Electron Microscopy (SEM)

SEM analysis of PU/HPC membrane cross-sections was performed using a VEGA TESCAN
microscope, in high vacuum mode, at an acceleration voltage of 30 kV.

2.6. Protein adsorption

Amount of protein adsorption on membrane surfaces was measured in three different
conditions: (a) on individual protein solutions of fibrinogen (FB) at 3 mg/ml (95% clotable
from Sigma-Aldrich) and serum albumin (SA) at 45 mg/ml (bovine SA (BSA) from Sigma-
Aldrich); (b) FB and BSA mixed solutions of physiological concentrations (3 mg/ml for BSA
and 45 mg/ml for FB); (c) complex protein conditions (platelet poor blood plasma (PPP)).
Prior adsorption experiment, the PU/HPC films were brought to equilibrium with
phosphate buffer saline (PBS) up to reaching maximum hydration, for about 72 h. Briefly,
PU/HPC hydrated membranes with 0.5 cm x 0.5 cm surface area were covered with 0.25 ml
of one of the protein solutions or with blood plasma and kept at 37 oC for 30 min. FB and
BSA concentration in incubated medium was determined before and after incubation. A
turbidimetric method based on the formation of an insoluble complex with Na2SO4 was
used for FB determination. The method based on antigen–antibody reaction was performed
for SA measuring, using a Dialab kit, Austria. FB and SA reaction products were assessed on
a Piccos 05 UV–VIS spectrophotometer at λ = 530 nm for FB and λ = 340 nm for SA. The
adsorbed amount of proteins was calculated with the following relation:

(Co  Ce )  V
Adsorbed proetin(mg/cm 2 )  (1)
S

where Co and Ce are the initial and post-incubation concentrations of protein solution
(mg/ml), V is the incubated volume of the protein solution (ml) and S is the surface of the
incubated PU/HPC sample

2.7. Total Antioxidant Status (TAS)

TAS was measured in blood plasma obtained by human blood centrifugation at 1000 G for
20 min. PU samples were incubated in blood plasma for 1, 2 and 3 days at 37 oC and mild
orbital shacking. The TAS measurement was made by standard protocol provided by
Randox TAS kit. Thus, 2,2’-azino-di-[3-ethylbenzthiazoline sulphonate] (ABTS)® was
incubated with a peroxidase (metmyoglobine) and H2O2 to produce the ABTS®+ radical
cations having a stable blue-green colour that was measured at 600 nm on a
 Biocompatibility and Biological Performance
of the Improved Polyurethane Membranes for Medical Applications 205

spectrophotometer mentioned in the previous section. By adding blood plasma containing

antioxidants a suppression of this colour to a degree which is proportional to their
concentration is observed. Control serum (“standard” provided by the determination kit)
was used for data validation. TAS values were calculated based on the measured
absorbance in the standard, blood plasma sample and blank (buffer provided by the kit)
before and after H2O2 adding. The absorbance differences (ΔA) between measurement
before and after H2O2 adding for standard, sample or blank solutions were used for
calculation of TAS concentration according to relations 2 and 3:

concentration of standard
Factor  (2)
 A blank - A standard

TASmMol/L= Factor  ΔA blank-ΔAsample (3)

2.8. Haemocompatibility testing

Haemocompatibility of membrane surface was evaluated by haemolysis and coagulation
tests. All tests were performed on well swollen PU samples in PBS. Haemolysis was
determined using 0.25 ml of blood (human blood from healthy voluntary donors, collected
on 3.8 % sodium citrate solution as anticoagulant in 9:1 v/v ratio) that was incubated with 1
cm2 surface area PU samples for 30 min at 37 oC. Haemoglobin released from lysed
erythrocytes was measured by spectrophotometric method at λ = 545. Prothrombin time was
measured after 1 hour incubation of polymer sample in blood plasma. Standard laboratory
method was applied using PT kit (Biodevice, Italy) and ACL 100 coagulometer. Blood
plasma was obtained by blood centrifugation at 1000 G for 10 min.

Platelet adhesion on material surface was determined based on number of platelet counted in
0.1 ml platelet rich blood plasma (PRP), before and after membrane (0.5 cm x 0.5 cm)
incubation for 1 hour at 37 oC. PRP was obtained by blood centrifugation at 400 G for 20
min. Improved Neubauer haemocytometer was used for platelet counting. Clot weight test
was performed by adding 0.2 ml of human blood upon well swollen samples with 1cm2
surface area. The thrombus formation was started by adding 0.05 ml CaCl2 solution (0.025
mol/l). Each formed thrombus was weighed and compared with control. Collagen film was
used as positive pro-coagulant control and normal blood plasma without polymer sample as
negative control.

2.9. In vivo biocompatibility

Subcutaneous implantation experiment was performed on Wistar 200 g weight male rats.
Testing protocol was designed according to ISO 10993-2 (Animal Welfare Requirements)
and the guidelines of Council for International Organizations of Medical Sciences (CIOMS).
The pieces of autoclaved purified or unpurified membranes (0.5 x 0.5 cm size) were
implanted under both sites (right and left) of dorso-lateral skin. Material purification was
performed by immersion in sterile distilled water for 1 week and equilibration in
206 Polyurethane

physiological salted sterile solution for 24 hours before subcutaneous implantation. All
surgical procedures were done under thiopental anaesthesia, using a dosage of 35 mg/kg
body weight. Lots of six animals for each material were taken in each experiment. The
period of 10 or 30 days was chosen for material examination. Explanted samples together
with surrounding tissue were fixed in 10% formaldehyde solution embedded in paraffin
wax, sliced in 15 μm pieces and stained using Hematoxylin – Eosin (HE) method for cell
examination and Masson’s trichrome for collagen fibres.

3. Results and discussions

3.1. Primary screening criteria for the appropriate selection of PU/HPC
membranes for medical usage
Biocompatibility of PUs, seen in terms of specific application, is a result of a “bio-
appropriate” expression of surface and bulk properties achieved by synthesis and scaffold
fabrication methods. Thus, surface ζ potential and surface wettability are important
characteristics responsible for specific tissue-material interaction mechanisms, starting with
protein adsorption that can be influenced in turn by specific physiological/pathological
tissue environment.

3.1.1. Surface ζ potential and wettability

Surface charge plays an important and active role in tissue-material interaction and must be
considered in accordance with the targeted application. The importance of surface charge on
cell adhesion, biofilm formation or thrombogenesis was demonstrated (Cai et. al., 2006;
Colman & Schmaier, 1997; Kang et. al., 2006; Khorasani et. al., 2006). These phenomena are a
consequence of adsorptive behavior of proteins on charged surface rather than the effect of
electrostatic interactions with cells (Keselowsky et. al., 2003; Wilson et. al., 2005). Many data
refer to the effect of surface charge on biological phenomena (Jelinek et. al., 2010; Kang et.
al., 2006). However, there are not many data reporting surface charge and its clear relevance
for biocompatibility of PU-based membranes. Moreover, it is difficult to estimate the electro-
kinetic properties of such surfaces, mainly due to the complexity of the chemical
composition but also due to membrane variable porosity and swelling behavior that can
influence surface charge values (Yaroshchuk & Luxbacher, 2010). ). Surface ζ potential of
material is a property that reflects surface charge. Some reported data have shown that
poly(ether-urethane)s exhibit a very negative (– 25 mV) ζ potential, while poly(ester-
urethane)s are less negative (- 12 mV). Contradictory data were published on the beneficial
effect of positively (Khorasani et. al., 2006) or negatively charged surfaces (Sanders et. al.,
2005) on cells attachment and proliferation.

Thus, this section is aimed to predict the influence of surface potential and wettability on the
biocompatibility and biological performances of PU-based samples. Table 1 shows
hydrophilic/hydrophobic properties and ζ potential of examined PU-based samples.
 Biocompatibility and Biological Performance
of the Improved Polyurethane Membranes for Medical Applications 207

Contact angle
Material
First immersion Second immersion WU (%) ζ (mV)
samples
θ ()
adv o θ ()
rec o H(%) θ ()
adv o θ ()
rec o H(%)
PU-PEGA 85.3±1.1 54.3±0.6 36.3 51.0±0.5 54.1±0.6 5.6 141±10 - 4.31
PU-PEGA/HPC 84.8±1.1 44.2±0.5 47.9 52.6±0.5 43.7±0.5 16.9 140±4 + 3.14
PU-PTHF/HPC 77.4±1.1 42.9±0.5 44.5 31.6±0.4 42.3±0.4 25.2 167±3 + 0.78
PU-PPG/HPC 85.6±1.1 44.8±0.5 47.7 60.3±0.6 44.1±0.5 27.0 92±6 + 4.85
Table 1. Dynamic contact angle values (θ) in contact with water, hysteresis (H) resulted from advanced
(adv) and receded (rec) contact angles, water uptake (WU) (Macoconschi et. al., 2009) and ζ potential of
the PU samples

As one can see from Table 1, PU-PEGA has a slightly negative ζ potential, probably due to
the presence of carboxylic groups resulted by the hydrolysis of residual isocyanate groups
during membrane precipitation in water. After blending with HPC, the residual isocyanated
groups linked to PU prepolymer are reacted with the hydroxyl groups of HPC and all
PU/HPC membranes showed a slightly positive surface. The most hydrophilic sample (PU-
PTHF/HPC) exhibited the most neutral ζ potential. This observation is in accordance to
other data that report dependence of surface charge on water swelling capacity (Aranberri-
Askargorta et. al., 2003).

3.1.2. Extraction microenvironment

The material biocompatibility can be appreciated through its effects on the physico-chemical
properties of the physiological environment, especially on the pH. Thus, pH modification of
HBSS buffer solutions after unsterilized and sterilized membranes incubation was
measured. The results are shown in Figs 2 and 3 (1, PU-PEGA; 2- PU-PEGA/HPC; 3, PU-
PTHF/HPC; 4, PU-PPG/HPC).

Figure 2. pH variation of HBSS buffer in which unsterilized membranes were incubated: A, PU-PEGA;
B, PUs/HPC; C, pH variation curves
208 Polyurethane

Figure 3. pH variation of HBSS buffer in which autoclaved PU/HPC membranes were incubated: A, 24
h of incubation; B, 72 h of incubation; C, pH variation curves

As one can see from Figs. 2 and 3, a long-period of incubation of unsterilized and sterilized
(by autoclaving at 121 oC and 1 atm) PU/HPC membranes in simulated biological fluid did
not meaningfully modify the physiological range pH value of the incubation environment,
while a pronounced decrease of the environment pH was observed for pure PU-PEGA
sample (Fig. 2 A). Thus, one can say that HPC gives an important contribution to hydrolytic
stability of urethane and ester bonds of PU chains.
For autoclaved samples, the variation of pH values of the environment for poly(ether-
urethane)s remains in the range of the physiological value, while PU-PEGA/HPC membrane
induced a higher decrease of pH (Fig. 3), a normal result owing the higher thermal
degradability of poly(ester-urethane)s (Guelcher, 2008).
Another property that was changed by modifying PU membranes with HPC was the
floatability (see Fig. 2B). As the surface wettability and water uptake for PU-PEGA sample is
similar to HPC modified one (see Table 1), the reason of these different behavior could reside
in different morphologies, as seen from SEM images of membrane cross-sections (Fig. 4).

Figure 4. SEM image of PU-PEGA (A) and PU-PEGA/HPC (B) membrane cross-sections
 Biocompatibility and Biological Performance
of the Improved Polyurethane Membranes for Medical Applications 209

PU-PEGA sample showed important bulk microporosity, with isolated pores, while PU-
PEGA/HPC presented smaller but interconnected pores allowing water diffusion and the
decrease of the floatability.

Thus one can conclude that PU/HPC membranes are slightly positively charged and they
possess interconnected porous morphology influencing the wettability and floatability. They
also showed a less pronounced influence on the biological media as compared to the pure
PU membrane.

3.2. Protein adsorption

There are many data concerning mechanisms of protein adsorption on different surfaces
(Gray, 2004; Scott & Elbert, 2007; Van Tassel, 2006; Wilson et. al., 2005). It was clearly
demonstrated that proteins have amphoteric properties, being able to adsorb on both
negatively and positively charged surfaces (Michelsen et. al., 2000; Van Tassel, 2006). The
amount of adsorbed proteins is depending on their isoelectric points as well as on surface
chemistry and hydrophilicity (Keselowsky et. al., 2003; Wertz & Santore, 2001).
Hydrophobic surfaces manly interact with hydrophobic protein core that leads to the
modification of the protein physiological conformation and its functionality. Opposite to
hydrophobicity, superficial water maintains native protein conformation and specific
functionality (Keselowsky et. al., 2003; Noinville & Revault, 2006).
Many authors have reported protein adsorption behaviour on different surfaces using
simulated solutions and highly sensible methods in which very low protein concentrations
are detected. Thus, the adsorption of albumin solutions of different concentrations on pure
silica or on silica modified with NH2 and CH3 terminated self-assembled monolayers
(SAMs) (Noinville & Revault, 2006) and on silica-titanium surfaces (Kurrat et. al. 1997) was
studied. Other authors reported the competitive adsorption of fibrinogen on mica (Gettens
et. al., 2005; Tsapikouni & Missirlis, 2007). Surface adsorption of SA, FB, fibronectin (FN),
immunoglobulins (IGs) and lysozyme were investigated to evaluate the surface
biocompatibility (Bernsmann et. al., 2010; Pompe et. al., 2006; Rezwan et. al., 2005), each
class of these proteins providing specific surface properties for targeted application. Thus,
FN adsorption is relevant for the prediction of cell adhesion, lysozyme – for enzymatic
degradability predisposition, IGs - for immune-specific interactions, while SA and FB
adsorption have haemocompatibility predictive value.
In order to estimate protein adsorption (retention) capacity of materials at blood or tissues
contact, simulated physiological environment, close to normal blood conditions is required.
For example, Bajpai, 2005 followed SA adsorption capacity of biomaterials at SA bulk
concentration from 1 to 6 mg/ml, while Alves et. al., 2010 used mix protein conditions,
considering physiological value for each protein. The mix protein adsorption conditions are
considered to better reflect the complex interactions that occur between different proteins
(Latour, 2008).

PU/HPC membranes were previously demonstrated to possess good mechanical properties

(elongation at break for dried/hydrated PU-PEGA/HPC = 71/84; for PU-PTHF/HPC = 72/159
210 Polyurethane

and for PU-PPG/HPC = 53/55), appropriate for cardio-vascular applications (Macocinschi et.
al., 2009). The physisorption of SA and FB is further highlighted as screening criteria for
biocompatibility and, more specifically, haemocompatibility. Very short characteristics of
SA and FB, important for protein-material interaction are given below.

SA is a protein belonging to the so called “soft” class of proteins, with a molar mass of about
65 kD for BSA and 67 kD for human SA (HSA). This protein represents about 60% of the
blood proteins. Normal blood concentration of HSA is 35 – 50 mg/ml. This protein is
involved in many physiological phenomena as carrier protein for fatty acids, metals,
cholesterol, bile pigment, hormones and drugs. SA is also characterised by antioxidant
properties (Bourdon et. al. 1999; Kouoh et. al., 1999; H. Lee et. al., 2000) that is higher in
alkaline pH, up to 8 (H. Lee et. al., 2000). SA is preponderantly negatively charged, its
isoelectric point being close to 4.8 (Carter & Ho 1994; Noinville & Revault, 2006).
Approximately 67% of the secondary SA structure is represented by the α-helix. It was
demonstrated that the stability of SA secondary structure strictly depends on pH (Freeman,
2006) that influence the protein conformation. Thus, at pH = 5, SA takes almost spherical,
native, unfolded shape that forms a thick layer on the adsorptive surfaces. At pH = 7 (close
to physiological pH), due to molecular spreading, SA forms an extended contact area with
adsorptive surfaces. This behavior can be influenced by surface charge, surface functionality
and functionality distribution, surface morphology or wettability conditions (Wilson et. al.,
2005). The role of adsorbed SA on biomaterial biocompatibility is still ambiguously
described in the literature. While some authors have demonstrated biocompatibility
improvement of material with increased adsorption of SA (Eberhart [Link]. 1987; Marconi et.
al., 1996; Randrasana et. al., 1994), others demonstrated a better biocompatibility of SA-
resistant surfaces (Ostuni et. al., 2001; Wan et. al., 2006).

FB is a high molecular weight (340 kD) complex glycoprotein that has 2 molecular
domains, each of them consisting of three polypeptide chains called Aα, Bβ and γ.
Molecular updated analysis of FB can be found in recent reports (Cardinali [Link], 2010). FB
is an important factor of haemostasis. Through fibrin network formation as first cell
scaffold, FB is involved in wound healing and tissue regeneration. Its normal blood
concentration varies from 2 to 4 mg/ml. In inflammations or in other pathological statuses
- as cardiovascular diseases - FB can reach up to 7 mg/ml, therefore adsorption properties
of biomaterials for this protein should be carefully analysed, especially for those targeted
for blood contact applications.

The results obtained in adsorption experiments of SA and FB from both individual and
mixed solutions on PU/HPC membranes are presented in Fig. 5.

No significant differences between adsorption behavior of both proteins in their pure and
mixed solutions were registered, except a small tendency to decrease adsorbed BSA from
mixed solution as compared to individual solution, especially on PU-PEGA and PU-
PEGA/HPC membranes, where FB, with a higher molecular weight, showed a higher
affinity.
 Biocompatibility and Biological Performance
of the Improved Polyurethane Membranes for Medical Applications 211

Figure 5. Amount of adsorbed BSA (left) and FB (right) from individual protein solutions and in co-
adsorptive environment (mixed protein solution) of physiological concentrations, i.e., 3 mg/ml for FB
and 45 mg/ml for BSA

Figure 6 shows the ratios of adsorbed BSA and FB from mixed protein solutions and from
blood plasma. In both studied conditions and for all membranes, the amount of adsorbed
SA is higher than that of adsorbed FB, a normal result considering the lower concentration
of FB in solutions. The total amount of the adsorbed SA and FB proteins from blood plasma
is lower as compared to that adsorbed from mixed solutions due to the competitive
adsorption of some other blood plasma proteins. Moreover, the ratio between adsorbed FB
and SA is lower in blood plasma than in mixed solutions.

Figure 6. Total amount of adsorbed FB and BSA from: A – mixed protein solution at 3 mg/ml FB and 45
mg/ml BS physiological concentration; B - human blood plasma with 2.98 mg/ml initial FB
concentration and 45.3 mg/ml initial SA concentration

As conclusion, comparing PU-PEGA and PU-PEGA/HPC membranes one can observe that
small amount of polysaccharide rich in functional substituents can bio-stabilize PU
212 Polyurethane

structures and improve their resistance for autoclaving procedures as important step in
ready to use biomaterials preparation. From all the data presented in this section, one can
say that the more hydrophilic PU-PTHF/HPC membrane could be the most appropriate for
biomedical applications.

3.3. In vitro and in vivo performances of PU/HPC membranes

The biocompatibility of PUs are widely discussed and questioned, mostly in the past. In the
last two decades new generation of PUs that combine mechanical advantages with the
biological performances emerged (Gisselfa et. al., 2002; Jordan & Chaikof et. al., 2007; Jun et.
al., 2005; Kavlock et. al., 2007; Parveen et. al., 2008). For many years it has been considered
that PUs biocompatibility is spotless due to their products of degradation, e.g., aromatic
polyamines. As it is well known for the most part of biocompatible materials, the life time of
their in vitro functionality is quite short. This is a consequence of their intrinsic physico-
chemical properties, on one hand, and of the tissue action on the material, on the other hand
(Anderson, 2001; Guelcher, 2008; Shen & Horbett, 2001).

3.3.1. Oxidative in vitro behavior

Oxidative degradation of PUs caused by hydrolytic or enzymatic mechanism was
intensively discussed (Christenson et. al., 2004; Guelcher, 2008; Gary & Howard, 2002;
Sutherland et. al., 1993). First of all, PUs designed for tissue-contact devices undergo
hydrolytic degradation as a result of watering with physiological solutions. This process has
an impact especially on poly(ester-urethane)s that can generate hydroxy-acids, being
susceptible to induce reactive oxygen species (ROS) production following the material-
tissues interaction. By means of this mechanism, PUs can be implied in the sustained
oxidative degradation and a wide range of pathological states.

As it is well known, ROS can trigger subtle mechanisms responsible for diseases generation
through the peroxidation of cell membrane lipids and DNA damage (Marnett, 2002; Tribble
et. al., 1987; Yagi, 1987). The most susceptible organs to oxidative aggression are the heart,
vessels, lung, gut, liver, brain and nerves (Ames et. al., 1993; Förstermann, 2008; Paradis et.
al., 1997; Rahman et. al., 2002; Sayre et. al., 1997).

In a normal body state, ROS appear constantly as a result of some biological errors or as a
consequence of some short living reactive intermediate products generated by the cell
aerobic metabolism. Endogenous enzymatic and nonenzymatic pathways are responsible
for the formation of free radicals. These pathways are balanced by two endogenous
antioxidant pathways, which form the TAS (see fig. 7).

While some harmful material characteristics can be marked as cytotoxic or proinflammatory

by standard testing, others, such as oxidative stress (that causes long-time material failure),
are undetectable by using short period testing. Thus, well known biocompatible materials
were found to display surface alteration or cracking after long-time implantation. Adding
 Biocompatibility and Biological Performance
of the Improved Polyurethane Membranes for Medical Applications 213

antioxidant compounds to materials can improve their resistance against tissue degradation
(Oral et. al., 2006; Stachelek et. al., 2006; Wattamwar et. al., 2010).

Figure 7. Schematic representation of the oxidative/antioxidative balance with enzymatic and

nonenzymatic tissue pathways

Antioxidant defensive systems are present in both cells and extracellular environment. SA
molecules are the most important antioxidants in blood. Due to their high concentration and
polyvalent possibilities to fit with oxygen free radicals, SA molecules are considered to be
the main plasmatic components of defence that assure neutralisation of more than 70% of
ROS (Bourdon & Blache, 2001).

Assigning to SA molecules the main role in protective effect, we analysed the interaction of
PU/HPC membranes with blood plasma, following the plasma antioxidant status. To define
the importance of SA adsorption on material surface, the membranes were incubated at 37
oC in blood plasma and TAS was measured periodically. The results are shown in Fig. 8.

Two PU samples (PU-PEGA and the more hydrophobic PU-PPG/HPC) had significant
tendency to quickly decrease TAS activity in the first 48 hours. Due to the complexity of
TAS, it is difficult to speculate on the mechanism by which the decreasing phenomenon
arises and certainly more examinations are needed. However, one can suppose that PU-
PEGA alter the TAS activity as a result of plasma pH modification that leads to sustained
free radical generation in the presence of the material. The mechanisms by which TAS
activity is lowered after PU-PPG/HPC incubation could not be related directly to SA
antioxidant activity, but to some other oxidant pathways that need further investigations.
214 Polyurethane

Figure 8. TAS evolution after PU/HPC incubation in blood plasma at 37 oC

3.3.2. In vitro haemocompatibility

Haemocompatibility involves compatibility with blood cells and blood plasma in other
words, nonhaemolytic and nonthrombogenic behavior. Haemolysis is a mechanism by
which erythrocytes (red blood cells) are destroyed through cell membrane lyses. Erythrocyte
membrane lyses may occur as a result of environment pH modification or by cytotoxic
action on erythrocyte membrane. Thus, both lipid (by lipid peroxidation) and protein (by
protein modification) compounds can be affected.

Thrombogenesis is a complex phenomenon by which thrombus is formed by blood clotting.

As a physiological event, haemostasis implies the activation of the enzymatic cascades in
which three main factors are involved – vascular, cellular and plasmatic (Edmunds, 1998).

A synthetic material can induce haemostasis activation by surface charge, hydrophobicity

and/or released products of degradation. It is widely recognised that both positively and
negatively charged as well as hydrophobic surfaces can induce thrombus formation. This
can be explained by involvement of several mechanisms as presented in Fig. 9.

A positive charge can be favourable for FB adsorption, followed by its conformational

modification and adhesion of platelets and leukocytes (monocytes). Adherent cells are
activated and they release numerous molecules that lead finally to FB cleavage with fibrin
network formation (clot). Among platelet secreted factors are platelet thromboplastin, fibrin
stabilizing factor, serotonin, anti-heparin factor, and others. Adherent (activated) monocyte
releases thrombogen tissue factor (TF). Mechanism triggered by positive and hydrophobic
surfaces is mainly related to extrinsic coagulation pathway (B. Furie & B. C. Furie, 2008).
 Biocompatibility and Biological Performance
of the Improved Polyurethane Membranes for Medical Applications 215

A negative charge acts as an activator of plasmatic factor XII (Hageman factor) that involves
contact system and intrinsic coagulation pathway (Zhuo [Link]. 2006). This mechanism also
involves high molecular weight and positively charged kininogen (HMW) and plasma
thromboplastin (factor XI). Contact mechanism is tightly related to inflammatory events
because some intrinsic pathways factors are direct activators of neutrophils. Whole
mechanism of contact blood coagulation is still unclear. Some authors hypothesized that it
can also be induced by adsorbed FB (Colman & Schmaier, 1997) and hydrophobic surfaces
(Zhuo et. al., 2006). As for intrinsic coagulation mechanism of thrombus formation, this can
also be activated by negatively charged low density lipoproteins (LDL), the molecules that
adhere to the vessel walls in some pathologic conditions associated with cardiovascular
risks (Krieter et. al., 2005). This possible mechanism should be taken into account because
almost all pathological situations in which blood-assisted devices are used are accompanied
by high level of cardiovascular risk factors (high level of LDL, cholesterol, triglycerides and
modified blood pressure).

Figure 9. Contact coagulation and extrinsic (tissue factor) coagulation blood pathways

PUs are promising materials for implantable and non-implantable blood-interacting devices.
They combine an increased elasticity with good mechanical resistance. For
haemocompatibility evaluation of PU/HPC materials discussed above, the haemolytic and
thrombotic potentials were determined by standard and adapted methods (see section 2).
The obtained results are summarised in Table 2.
216 Polyurethane

All studied membranes showed a low haemolytic activity, lower for PU/HPC than for pure
PU-PEGA sample.

Haemolytic
Thrombotic potential
Material potential
samples Released Hb Adhered platelet % blood
FB (mg/ml)2 PT (s)3
(%)1 (cells x 105/mm2) clot amount4
PU-PEGA 6,7±0,2 2,79±0,04 11,06±0,4 1,40±0,08 40%
PU-PEGA/HPC 5,2±0,1 2,87±0,04 10,9±0,09 0,82±0,05 29%
PU-PTHF/HPC 4,2±0,2 2,90±0,01 10,9±0,09 0,86±0,05 15%
PU-PPG/HPC 5,5±0,1 2,77±0,07 10,9±0,07 1,25±0,09 89%
Table 2. Haemolytic and thrombotic potential of the PU/HPC samples: Hb-haemoglobin; FB-
fibrinogen; PT- prothrombin time

As for thrombotic action, a correlation between adsorbed FB, platelet adhesion and amount
of formed clot was registered, while no significant variation was recorded for PT. This latter
parameter was kept within the normal limits (see footnote 3).

The judgement strictly based on the haemocompatibility results permits to state that all
examined materials have an acceptable thrombotic potential (referring to physiological
requirements). Considering clot amount and all the other characteristics discussed above, it is
obvious that PU-PEGA and PU-PPG/HPC are not suitable for long-time functional integration.

3.3.3. In vivo biocompatibility and performance

The technological progress achieved in the last decades in apparently unrelated areas
(biomaterials, biotechnology, cell and molecular biology, tissue engineering, and polymer
science) has generated a boost in the development and use of devices for medical and/or other
type of applications (e.g. artificial organs, biosensors, catheters, heart valves) (Shastri, 2003). In
spite of real improvement of this sort of devices there are still some important problems to face
since implanted medical devices usually reveal different degree of loss of functionality over
time after insertion (Göpferich, 1996). Tissue or blood-device interface interactions or a lack of
biocompatibility resulting from the normal homeostatic response of the body to the
implantation injury, determining an inadequate in vivo functionality and longevity, remains a
serious concern (Callahan & Natale, 2008; Fujimoto et. al., 2007; Morais et. al., 2010).

In order to protect the body from the foreign object, under normal physiological conditions,
the body reacts by several nonspecific mechanisms (immune and inflammatory cells
recruitment), usually termed foreign body reaction (FBR) (Anderson, 2001). There is an
imperative call for knowing the degree to which the pathophysiological conditions are

1 Percentage of released Hb over negative control

2 FB concentration remained in blood plasma after incubation. FB control was 2,98 ± 0,04 mg/ml
3 Physiological normal value according to related laboratory are between 8,3 s and 11,3 s

4 Percentage of blood clotting over negative control (blood without incubated material)
 Biocompatibility and Biological Performance
of the Improved Polyurethane Membranes for Medical Applications 217

created, the homeostatic mechanisms are disturbed, and the resolution of the inflammatory
response (simple put, the measure of the host reaction). All of these will finally establish the
effective compatibility of a specific device. In the same time, understanding these reactions
(the implant versus the host and the host versus the implanted device) will reduce health
problems to the beneficiary of the device and device malfunction. Usually, for practical
reasons, the homeostatic mechanisms are separately assessed even if it is well known that
they are profoundly interrelated (Sieminski & Gooch, 2000).

The first event after a device/material insertion is that the body generates quickly a sort of
“interface” via nonspecific adsorption of plasma/tissue soluble proteins on the implant
surface (Shen & Horbett, 2001). There are some well identified elements that determine the
FBR strength: device material composition, surface chemistry, size and shape, porosity,
degradation, velocity as well as the place of device insertion (Ratner & Bryant, 2004)
As presented shortly below, tissue injury associated with device implantation, initiates a
complex set of events (nonspecific inflammatory reaction and wound healing responses)
that will bring about a FBR (Wahl et. al., 1989). The stages of inflammatory responses are
well studied and can be separate in acute and chronic inflammatory periods.

The initial phase, acute stage, starts quickly in matter of hours, lasts for several days (up to
14 days) and is underlined by rapid device interface generation and typical for this phase,
different degree of neutrophil leucocytes responses (Jiang et. al., 2007). The main result of
this stage is the building of temporary interface material-tissue, the cleaning-up of the injury
place and the vasodilation that bring more blood in the affected area.
The acute inflammatory reaction typically decline in maximum 14 days with a
“biocompatible” material. Some local conditions (extent of surgical injury, body reactivity)
or properties of the implanted device can trigger a chronic inflammatory evolution
(Kirkpatrick et al., 1998).
Numerous blood and tissue proteins such as cytokines (e.g. tumor necrosis factor (TNF),
interleukins (IL-6, IL-8), matrix metalloproteases (MMP-1, MMP-3), granulocyte-
macrophage growth factors (GM-CSF)) are released, and leukocytes adhere to the
endothelium of the blood vessels and infiltrate the injury site. These proteins are strong
calling factors for monocytes, cells which will migrate to the site of inflammation where they
will differentiate into macrophage. If inflammatory stimuli persist, the conditions that can
lead to chronic inflammation are created. Cell population of this stage of inflammatory
reaction is usually characterized by the presence of monocytes, macrophages, and
lymphocytes (Bhardwaj et al., 2010). Also, in this step it can be noticed that the proliferation
of blood vessels (angiogenesis), and connective tissue occurs that participate in remodelling
of the affected area. The formation of blood vessels is crucial for wound healing, supplying
necessary factors for tissues reconstruction. In the end, the granulomatous tissue is replaced
by an extracellular matrix (ECM) that acts not only as a physical scaffold but also as an
essential modulator of the biological processes, including differentiation, development,
regeneration, repair, as well as tumour progression. The end phase of the FBR draws in
wrapping the implant by a collagenic fibrous capsule that limits the implant and therefore
218 Polyurethane

prevents it from interacting with the surrounding tissue. The main tissue events of the
material-tissue interaction and wound healing are schematically presented in Fig. 10.

Morphologic aspects (light microscopy) of the acute tissue reaction to subcutaneous

implanted polyurethane (PU-PTHF/HPC) at 10 days of implantation and chronic
inflammation at 30 days of implantation are shown in Fig. 11. The study was conducted on
Wistar male rats using the protocol described in section 2.

Figure 10. Fibrosis and fibrous encapsulation. End stage healing response to biomaterials. GF – growth
factor (PD – platelet derived, T – transforming, bF – basic fibroblastic); IL – interleukin; PGL –
prostaglandin.

Figure 11. Light microscopy images of tissue response to implantation of subcutaneous non-washed
PU-PTHF/HPC (PU): A - A2, 10 days of implantation; B -B2, 30 days of implantation. All images – HE
staining. Objective magnifications are indicated in the left bottom corner
 Biocompatibility and Biological Performance
of the Improved Polyurethane Membranes for Medical Applications 219

Unwashed (unpurified) material was implanted first, to highlight the importance of the
properly prepared biomaterial for medical usage. From Fig. 11, A-A2 images, it can be easily
seen as an intense acute inflammation reaction with numerous neutrophil
polymorphonucleate leucocytes (PMN), edema and early fibrin network formation away
from implantation site. These results suggest that an inappropriately prepared material at
some stage in manufacture and/or manipulation can delay wound healing. As we expected,
at 30 days of implantation (Fig.11, B-B2 images), inflammatory chronic reaction was really
strong for related material, with the characters of neovascularised granulomatous tissue
(VNGT) and giant cells (GC).
In the end of this chapter, comparative study concerning long-time potential functionality
based on evolution of chronic inflammation of PUs/HPC discussed above was done. The
histological images of 30 days implanted, properly purified PUs/HPC are shown in Fig. 12.
There were found chronic inflammations with VNGT and FBR with GC for PU-PEGA/HPC
(A-A2 images) and PU-PPG/HPC samples (C-C2 images). Moreover, granuloma formation
(G) as result of macrophage material degradation was present at material-tissue interface of
PU-PPG/HPC (C and C1 images in Fig. 12).

Figure 12. Light microscopy images of tissue response following 30 days subcutaneous implantation of
washed PUs/HPC. A–A2, PU-PEGA/HPC; B-B2, PU-PTHF/HPC and C-C2, PU-PPG/HPC. B2, Masson’s
trchrome staining; all other images - HE staining. Objective magnifications are indicated in left bottom
corner
220 Polyurethane

The absence of GC and rich granulomatous tissue ingrowth through large material pores
was observed for PU-PTHF/HPC sample (Fig.12, B-B2 images). Morphological aspect for
PU-PTHF/HPC implant suggests a material-tissue integration and regenerative remodelling.
Moreover, the fibroblast-rich tissue ingrowth only from one side of the membrane highlights
the bifacial behavior of the implanted sample, with potentially tubular or cavity-like device
performances. Thus, considering PU-PTHF/HPC increased haemocompatibility, oxidative
and other biocompatibility advantages discussed above, we presume a cardiovascular-
device performance for this PU sample.

4. Conclusions and further perspectives

Polyester and polyether urethane structures with improved bulk and surface characteristics
by blending with small amount of biocompatible cellulose derivative, HPC, are screened for
long-time functional integration. The stability of the pH value of biological media and the
ratio of adsorbed albumin and fibrinogen from blood plasma were found to be the most
valuable screening criteria to evaluate the blood-interface functionality, but not only. These
criteria could provide information on material capacity to keep stability of the main body
balances (oxidant/antioxidant, haemostasis/haemolysis) that are responsible for material
acceptance in the early phase, followed by structural and functional integration in the later
stages. These characteristics together with other important material properties as surface
neutral charge and desired porous structure are keys points for good results expectance as
was demonstrated. Another PU characteristic highlighted in our study was washability for
potentially proinflammatory compounds removal. Due to interconnected mechanisms of
thrombosis and inflammation, even haemocompatible PU, but with chronic prolonged
inflammatory capacity (through itself or some released compound) will certainly get to fail
its haemocompatibility in vivo. From this point of view we demonstrate an acceptable
stability of some PU membrane by autoclaving and long-time watering in biological buffers.
Further studies are necessary on extended classes of polyurethanes in the aim to prepare
and keep ready to use pre-equilibrated and safe PUs for medical applications.

Author details
Maria Butnaru, Doina Macocinsch and Valeria Harabagiu
”Petru Poni” Institute of Macromolecular Chemistry, Iasi, Romania

Maria Butnaru, Ovidiu Bredetean, Cristina Daniela Dimitriu and Laura Knieling
”Grigore T. Popa “ University of Medicine and Pharmacy, Iasi, Romania

Acknowledgment
The financial support of European Social Fund – “Cristofor I. Simionescu” Posdoctoral
Fellowship Programme (ID POSTDRU/89/1.5/S/55216), Sectoral Operational Programme
Human Resources Development 2007 – 2013 is acknowledged.
 Biocompatibility and Biological Performance
of the Improved Polyurethane Membranes for Medical Applications 221

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