POLYURETHANE FOAMS

CONTAINING RENEWABLE CASTOR OIL REPLACEMENT

A Thesis

Presented to

The Faculty of the Graduate School

At the University of Missouri-Columbia

________________________________________________________________

In Partial Fulfillment

Of the Requirements for the Degree

Master of Science

________________________________________________________________

By

RUI XING

Fu-hung Hsieh, Thesis Supervisor

May 2014
 The undersigned, appointed by the dean of the Graduate School,
have examined the thesis entitled

POLYURETHANE FOAMS

CONTAINING RENEWABLE CASTOR OIL REPLACEMENT

Presented by Rui Xing

A candidate for the degree of
Master of Science
And hereby certify that, in their opinion, it is worthy of acceptance.

Fu-hung Hsieh

Galen J. Suppes

Kattesh V. Katti
 ACKNOWLEDGEMENTS

I am willing to dedicate the most lofty respect and gratitude to my mentor,

Prof. Fu-hung Hsieh, for his full guidance, unremitting support, and critical spur. It

is Prof. Hsieh that make it possible for me to complete this thesis. What is more

important, Prof. Hsieh’s knowledge, wisdom, principles and personality charm

are always encouraging me, and I believe all this will benefit me through my life.

I also deeply appreciate my committee members Profs. Galen J. Suppes

and Kattesh V. Katti for their valuable time, nice patience, helpful suggestions

and critical reviews of my thesis.

My appreciation especially goes to our lab’s technician, Mr. Harold Huff, for

his unique skills on equipment and irreplaceable contribution to this research.

My special thanks goes to Dr. Hongyu Fan, who guided me into the

fantastic world of foams, and Ms. Carla Roberts, who offered me precious and

practical advice on thesis writing.

My thanks also goes to my lab colleagues, Alif Razi, Chih-Ying Lin, Fei

Cheng, and Yun Wang, for their helpful suggestions and contributions to this

research.

My final appreciation goes to my parents: Yahui Lin and Haibin Xing, for

their full trust, financial support, unconditional encouragement and the most

significant love. This appreciation also goes to my dear beloved, Yuanyuan Xue.

ii
 TABLE OF CONTENTS

ACKNOWLEDGEMENTS ......................................................................................ii

LIST OF TABLES ................................................................................................. v

LIST OF FIGURES ...............................................................................................vi

ABSTRACT ........................................................................................................ viii

CHAPTER 1. INTRODUCTION ............................................................................ 1

1.1 Background ................................................................................................ 1
1.2 Chemistry ................................................................................................... 2
1.3 Chemicals .................................................................................................. 2
1.3.1 Isocyanates ......................................................................................... 3
1.3.2 Polyols ................................................................................................ 6
1.3.3 Blowing agents .................................................................................... 7
1.3.4 Other chemicals .................................................................................. 8
1.4 Biobased content replacement ................................................................... 9
1.4.1 Biobased polyols ................................................................................. 9
1.4.2 Biobased isocyanates ....................................................................... 11

CHAPTER 2. LITERATURE REVIEW ................................................................ 13

2.1 Introduction of castor oil ........................................................................... 13
2.2 Uses of castor oil ...................................................................................... 16
2.2.1 Uses of castor oil in food processing................................................. 16
2.2.2 Uses of castor oil in medicine ........................................................... 17
2.2.3 Castor oil as a biodiesel .................................................................... 17
2.3 Uses of castor oil in chemical industry ..................................................... 19
2.3.1 Castor oil for cosmetics ..................................................................... 19
2.3.2 Castor oil for lubrication .................................................................... 19
2.3.3 Castor oil for inks, paints, and adhesives .......................................... 20
2.3.4 Undecylenic acid, nylons, and other derivatives of castor oil ............ 20
2.4 Uses of castor oil in polyurethane ............................................................ 23
2.4.1 Interpenetrating polymer network with castor-oil-based polyurethane
................................................................................................................... 23
2.4.2 Polyurethane nanoparticles based on castor oil................................ 24
2.4.3 Polyurethane foams based on castor oil ........................................... 24
2.5 Limitations of existing literature ................................................................ 26

iii
CHAPTER 3. WATER-BLOWN RIGID POLYURETHANE FOAMS WITH
CASTOR OIL REPLACEMENT .......................................................................... 27
3.1 Background .............................................................................................. 27
3.2 Materials and methods ............................................................................. 29
3.2.1 Raw materials ................................................................................... 29
3.2.2 Experimental design and foaming formulations ................................ 30
3.2.3 Foam preparation .............................................................................. 33
3.2.4 Foam property measurements .......................................................... 35
3.3 Results and discussion ............................................................................. 36
3.3.1 Influence of castor oil replacement ................................................... 36
3.3.2 Influence of blowing agent content .................................................... 42
3.3.3 Influence of hydroxyl number ............................................................ 45
3.4 Conclusion ............................................................................................... 54

CHAPTER 4. WATER-BLOWN FLEXIBLE POLYURETHANE FOAMS WITH

CASTOR OIL REPLACEMENT .......................................................................... 55
4.1 Background .............................................................................................. 55
4.2 Materials and methods ............................................................................. 58
4.2.1 Raw materials ................................................................................... 58
4.2.2 Experimental design and foaming formulations ................................ 59
4.2.3 Foam preparation .............................................................................. 61
4.2.4 Foam property measurements .......................................................... 62
4.3 Results and discussion ............................................................................. 64
4.3.1 Influence of different temperature conditions .................................... 64
4.3.2 Influence of cross-linker content ....................................................... 73
4.3.3 Influence of Isocyanate Index with different castor oil replacements 81
4.4 Conclusion ............................................................................................... 89

REFERENCES ................................................................................................... 90

iv
 LIST OF TABLES

Table 3.1 Properties of raw materials. ................................................................ 29

Table 3.2 Foaming formulation of rigid polyurethane foams with different castor
oil replacement percentages............................................................................... 31
Table 3.3 Foaming formulation of rigid polyurethane foams with different water
content percentages. .......................................................................................... 32
Table 3.4 Foaming formulation of castor-oil-based rigid polyurethane foams with
different glycerol contents. .................................................................................. 33
Table 4.1 Properties of raw materials. ................................................................ 59
Table 4.2 Foaming formulation of flexible polyurethane foams with different
temperature conditions. ...................................................................................... 60
Table 4.3 Foaming formulation of flexible polyurethane foams with different
cross-linker contents. .......................................................................................... 60
Table 4.4 Foaming formulation of flexible polyurethane foams with different
castor oil replacements and isocyanate indices.................................................. 61

v
 LIST OF FIGURES

Figure 1.1 Chemical structures of TDI .................................................................. 4

Figure 1.2 Chemical structures of MDI ................................................................. 5
Figure 1.3 Structure of ricinoleic triglyceride ......................................................... 9
Figure 3.1 Procedures to make polyurethane foams. ......................................... 34
Figure 3.2 Effect of castor oil replacement on density of rigid polyurethane foams.
........................................................................................................................... 36
Figure 3.3 Effect of castor oil replacement on compressive strength of rigid
polyurethane foams. ........................................................................................... 38
Figure 3.4 Effect of castor oil replacement on thermal conductivity of rigid
polyurethane foams. ........................................................................................... 40
Figure 3.5 Effect of castor oil replacement on density of rigid polyurethane foams
with different water content. ................................................................................ 42
Figure 3.6 Effect of castor oil replacement on compressive strength of rigid
polyurethane foams with different water content. ............................................... 43
Figure 3.7 Effect of castor oil replacement on thermal conductivity of rigid
polyurethane foams with different water content. ............................................... 44
Figure 3.8 Effect of hydroxyl number on density of rigid polyurethane foams with
castor oil and glycerol or Voranol 490. ............................................................... 46
Figure 3.9 Effect of hydroxyl number on compressive strength of rigid
polyurethane foams with castor oil and glycerol or Voranol 490. ........................ 49
Figure 3.10 Effect of hydroxyl number on thermal conductivity of rigid
polyurethane foams with castor oil and glycerol or Voranol 490. ........................ 51
Figure 4.1 Collapse of the flexible polyurethane foam with no cross-linker content
but 100% castor oil replacement. ....................................................................... 57
Figure 4.3 Surface temperature history of flexible polyurethane foams with
different polyols and mold temperatures ............................................................ 65
Figure 4.4 Height of flexible foams with different foaming conditions. ................ 67
Figure 4.5 Density of flexible foams with different foaming conditions. ............... 68
Figure 4.6 Compression force deflection of flexible foams with different foaming
conditions. .......................................................................................................... 70
Figure 4.7 50% Constant deflection compression of flexible foams with different
foaming conditions.............................................................................................. 72
Figure 4.9 CFD of flexible foams with different cross-linker content percentages.
........................................................................................................................... 76

vi
Figure 4.10 50% CDC of flexible foams with different cross-linker content. ....... 77
Figure 4.11 Tear resistance of flexible foams with different cross-linker content 78
Figure 4.12 Resilience of flexible foams with different cross-linker content. ...... 79
Figure 4.13 Density of flexible foams with different isocyanate indices. ............. 81
Figure 4.14 CFD of flexible foams with different isocyanate indices. .................. 83
Figure 4.15 50% CDC of flexible foams with different isocyanate indices. ......... 84
Figure 4.16 Tear resistance of flexible foams with different isocyanate indices.. 86
Figure 4.17 Resilience of flexible foams with different isocyanate indices. ......... 87

vii
 ABSTRACT

Polyurethane foams have a wide variety of commercial applications in daily

life due to their unique advantages. Traditionally, polyurethane foams are made

from petroleum-based polyols and isocyanates. Due to the shortage of fossil

resources, renewable biobased materials are studied as alternatives to

petroleum. In this project, castor oil was chosen as a renewable biobased polyol

in order to replace the nonrenewable petroleum-based polyols. Water-blown rigid

foams were made from polyols with different levels of castor oil replacement. For

foams without castor oil and with 25% castor oil replacement, the effects of water

added content were studied. Another group of foams made from a castor oil/

glycerol mixture were also prepared to investigate the effects of hydroxyl number.

With the help of glycerol, rigid polyurethane foams with 80%-95% castor oil

replacement were successfully prepared and showed competitive physical

properties. Water-blown flexible foams were made from polyols using different

levels of castor oil replacement. At the same time, the influence of cross-linker

contents and isocyanate index on flexible foam was studied. Considering the low

reaction rate of castor oil during the synthesis of polyurethane, a specific “heated

mold” method was applied. Density, compression force deflection (CFD), 50%

constant deflection compression (CDC), tear resistance (TR) and resilience were

tested to identify the physical properties of flexible polyurethane foams. Results

show that castor oil replacement often leads to a high cross-linking density. With

0.5% necessary cross-linker and low isocyanate index, flexible polyurethane

viii
foams with 100% castor oil replacement showed a good recovery property and

proved to be a suitable alternative to nonrenewable petroleum-based polyols.

ix
 CHAPTER 1. INTRODUCTION

1.1 Background

Polyurethane is a kind of polymer formed by urethane linkage. It was first

studied and developed by Dr. Otto Bayer and his colleagues in 1937. In the

1950s, with the introduction of blowing reaction, polyurethane foams were

developed and soon became one of the most popular polymers.

As a widely applied material, polyurethane has many unique advantages.

Due to different recipes and multiple production processes, the physical

properties of polyurethane can be adjusted in a wide range. Due to the

hardness, polyurethane products can be classified as flexible foams, semi-rigid

foams, rigid foams, fibers, and hard plastics. Gas bubbles inside foams also give

products more advantages such as low density, good heat insulation, excellent

strength and weight ratio, and mechanical wave absorbing properties. Therefore,

polyurethane foams can be easily found in both daily life and industry (Herrington

and Hock, 1997). They are in shoes, packing materials, refrigerators, furniture,

vehicles, water vessels, building materials , and even in the new iPad® Smart

Covers.

1
1.2 Chemistry

Basically, polyurethane is produced by the synthesis of polyols and

isocyanates. A bond of urethane is formed when the isocyanate group reacts

with the hydroxyl group as shown below (Herrington and Hock, 1997).

For polyols with two or more hydroxyl groups, the same reaction may repeat

and thus form the polyurethane structure.

For water-blown polyurethane foams, due to the reactive –OH group in the

molecule, water can also react with isocyanate and produce carbon dioxide. The

blowing reaction in water-blown polyurethane preparation is shown as:

The product amine of blowing reaction can also react with isocyanate again

to produce another urea linkage (Herrington and Hock, 1997).

1.3 Chemicals

Isocyanates and polyols are the two main parts of the chemical content in

the synthesis of polyurethane foams. Blowing agents, catalysts, surfactant and

other chemicals are also required to modify the processes and properties.

2
1.3.1 Isocyanates

Isocyanates are the most reactive components due to the “N=C=O” (NCO)

groups in their chemistry structures and are usually kept separately as “A-side.”

These NCO groups are the key to reactions within the hydroxyl groups in “B-

sides” referred to the polyols. The major two types of isocyanates used to

produce polyurethane are methylene diphenyl diisocyanate (MDI) and toluene

diisocyanate (TDI).

Commercially, TDI contains two major isomers, which are 2,4-TDI and 2,6-

TDI as shown in Figure 1.1. The raw material of TDI is toluene, a product of

petroleum. Toluene reacts first with nitric acid to get two nitro groups in the

position of 2,4 or 2,6. The next step is to transform the nitro groups into amino

groups with the participation of hydrogen. The product of this step is called

diaminomethylbenzene or diaminotoluene (TDA). The final step is to react TDA

with phosgene (COCl2) to produce TDI and HCl (Six and Richter, 2000). TDI is

very reactive but also volatile and dangerous. The permissible exposure limit

(PEL) of TDI is 0.02 ppm (0.14 mg/m3), according to the documents from the

Occupational Safety and Health Administration (OSHA) in the United States. It is

also defined as very toxic (T+) according to EU classification.

3
Figure 1.1 Chemical structures of TDI. (Left: 2,4-TDI; Right: 2,6-TDI)

The raw material of MDI is aniline. Before the amino groups are

transformed into isocyanate, aniline first reacts with formaldehyde to produce

diphenylmethane diamine. Then the diphenylmethane diamine is transformed

into diisocyanate through a similar path as the production of TDI (Randall and

Lee, 2003). Due to the structures of diamines, pure MDI mixture contains three

major isomers: 4,4’-MDI, 2,4’-MDI, and 2,2’-MDI. During the distillation of the

MDI, polymeric MDI can also be formed as a kind of polyisocyanate. Since the

polymeric MDI mixture has lower vapor pressure and is less hazardous

compared with other diisocyanates (such as TDI), polymeric MDI is more

commonly used in the polyurethane industry.

4
Figure 1.2 Chemical structures of MDI (from upper to lower: 2,2'-MDI; 2,4'-MDI;
4,4'-MDI; polymeric MDI)

Isocyanate index is a significant parameter that affects the properties of

polyurethane foams directly. It is usually defined as the actual amount of

isocyanate consumed relative to the amount that is theoretically required. Usually

5
higher isocyanate index leads to more hardness. For rigid polyurethane foams,

the isocyanate index is usually over 100. But there is still a limitation to the

isocyanate index over which the stiffness of foams can hardly increase;

Herrington and Hock (1997) claimed that value should be 140. To produce

flexible polyurethane foams, the isocyanate index is usually less than 100

(Klempner and Senijarevic 2004).

1.3.2 Polyols

In polymer chemistry, polyols are usually defined as compounds containing

multiple hydroxyl groups. Hydroxyl groups are the functional groups that react

with isocyanate to produce polyurethane. Functionality of a polyol is defined by

the number of reactive hydroxyl groups on a single polyol molecule. Equivalent

weight is based on the molecular weight of the polyol and its functionality as

follows (Herrington and Hock, 1997):

Eq. 1.1

The hydroxyl number is also a parameter to characterize a polyol. It is

defined as the equivalent amount in milligrams of KOH per gram of the polyol

(mg KOH/g). Hydroxyl number can be tested through the methods according to

ASTM Designation E222-10 and the relation of the hydroxyl number and the

equivalent weight of the same polyol can be described as follows:

6
 Eq. 1.2

Besides the –OH amount of a polyol, the types of hydroxyl groups are also

very important. According to Herrington and Hock (1997), primary hydroxyl

groups are very reactive in the synthesis of polyurethane and almost 3.3 times

faster than secondary hydroxyl groups in polyurethane reaction rate, while the

tertiary hydroxyl groups can hardly react with isocyanate. Most of the petroleum-

based polyols such as polyester polyols and polyether polyols contain primary

hydroxyl groups. But most of the biobased polyols have only secondary hydroxyl

groups.

1.3.3 Blowing agents

Blowing agents are another significant content of product polyurethane

foams, which can produce gas bubble inside the structure. Water is a widely

used blowing agent because it costs little and it is environmental friendly. The

carbon dioxide produced from water is also nontoxic and can contribute to the

improvement of many properties such as density and thermal conductivity.

Besides water, there are also other types of blowing agents, such as

chlorofluorocarbons, which are liquid in standard state and then vaporize after

absorbing enough heat produced from the synthesis of polyurethane. However,

since chlorofluorocarbons are considered a major cause of stratospheric ozone

7
depletion (Drake, 1995), the application and production of chlorofluorocarbons

have been strictly limited.

1.3.4 Other chemicals

Catalysts, mainly including gelling catalysts and blowing catalysts, are vital

to the foaming reaction. The ratio between the gelling catalysts and blowing

catalysts directly affects the chemical balance needed to form a stable foam

structure.

Surfactant is also needed in the system, which plays two important roles: 1)

A surfactant can help mix the raw chemicals uniformly, and 2) a surfactant can

help control the size of gas bubbles in the foam and adjust the status of these

gas cells. For rigid foams, the surfactant is selected to strengthen the cell walls

and protect the cells from breaking, which is beneficial to secure a low thermal

conductivity. For flexible foams, which is just the opposite, the surfactant is

designed to break the cell by dissolving the urea in silicone oil.

To reduce the consumption of petroleum resources, researchers have been

experimenting with renewable biobased materials to replace petro-based

chemicals since Rheineck and others started making urethane coatings from

biobased aldehyde oils (1969). Since isocyanates and polyols are two main

components of the polyurethane synthesis system, biobased isocyanates and

polyols have been widely studied and developed.

8
1.4 Biobased content replacement

1.4.1 Biobased polyols

Many biobased products, such as animal fat or vegetable oil, have fatty acid

glyceride. Most of the fatty acids have or have the potential to add/replace at

least 1 hydroxyl group on its carbon chain. This means biobased triglyceride can

be considered as a wonderful alternative to replace the current petroleum-based

polyols.

1.4.1.1 Castor oil

Castor oil is a renewable bio-based resource. The hydroxyl group on the

12th carbon atom of ricinoleic acid, the main fatty acid in castor oil, reacts with

isocyanates to form a crosslinking structure (Figure 1.3). Therefore, it is possible

for castor oil to form polyurethane without any pretreatment.

Figure 1.3 Structure of ricinoleic triglyceride

Long fatty chains on the ricinoleic acid make castor oil fit for preparing

flexible polyurethane foams, which is supported by Beneš and others (2012).

9
 However, castor oil cannot be used in rigid polyurethane foams. With the

help of the cross-linker, a small molecule with three or more hydroxyl groups,

foams can be modified with properties near to the control (Veronese, 2012).

Also,. Ristić and others (2012) tried to introduce Ti nanoparticles into the system

and found that these novel castor-oil-based polyurethane foams have excellent

damping properties, which have the potential to create a new type of vehicle

body that can lessen damage on impact during accidents.

1.4.1.2 Soybean oil

Soybean oil does not have any natural hydroxyl group on its structure.

However, it contains many functional or active groups, including double bonds,

allylic compounds, and ester groups. These help to introduce the hydroxyl groups

through chemical methods. Through using organic peroxy acid, the double bonds

on the triglyceride can be epoxidized and the epoxy groups can then be

transformed into s hydroxyl group that react with organic acid (Casper and

Newbold, 2006). Lubguban and others in Dr. Suppes’ lab from the University of

Missouri-Columbia developed a novel polyol called soy-phosphate polyol (2009).

Fully epoxidized soy-bean oil is prepared and phosphoric acid is added to

decompose and then recollect the polyols. Soy-bean-based polyols can now

replace as much as 50% of petroleum-based polyols in rigid polyurethane foams

without obvious property changes (Tu and others, 2008).

10
1.4.1.3 Other biobased polyols

There are also other research groups focusing on many other biobased

polyols. Due to the multiple hydroxyl groups on starch molecules, corn stover

can also be prepared as liquid polyols after microwave and heat treatment (Wu.

and others, 2009). Fish-oil-based polyols also have the potential to make rigid

polyurethane foam, which perform well in compressive strength. Molasses, a by-

product from the sugar industry, can also take part in polyols and adjust the

properties of polyurethane foams together with castor oil (Hatakeyama and

others, 2012). In a word, almost all biobased triglyceride and starch products

have the potential to prepare polyols for synthesis polyurethane. But researchers

still need to consider the cost of raw material and pretreatment, and also the

effect of the replacement.

1.4.2 Biobased isocyanates

Isocyanates are very active chemicals, which cannot be easily found or

collected directly from biological products. Chemical methods are used to add Br

on the double bond of oil and then AgNCO are introduced to the triglycerides with

Br replacing the functional groups to produce biobased isocyanates. Although

AgNCO is costly, the byproduct, AgBr, can be easily recycled to reproduce

AgNCO again. (Çayli and Küsefoǧlu, 2008)

According to the literature above, both isocyanates and polyols can be

prepared by biobased materials, theoretically making it possible to produce

polyurethane with both biobased polyols and renewable isocyanates. However,

products with almost totally biobased content do not have the mechanical
11
properties needed to perform well. In this study, raw castor oil was applied to

synthesize both flexible and rigid polyurethane foams. Their physical and thermal

properties were also tested and studied. Many foam samples produced in this

research contained nearly 100% biobased polyols, which is a new product not

previously considered possible in previous research.

12
 CHAPTER 2. LITERATURE REVIEW

2.1 Introduction of castor oil

Castor oil is a kind of plant seed oil refined or pressed from the seed of

castor plant. Castor plant exists widely and mostly in tropical regions, such as

Southern Asia, South America and Africa (Phillips and Rix, 2002). The seed of

castor plant is useful but toxic. The main toxin in castor seed is ricin, a toxic

protein which can be effectively denatured and inactivated when the temperature

is over 80 centigrade degrees (Audi and others, 2005).

13
Figure 2.1 The annual worldwide production of castor oil seeds from 1965 to
2012 according to faostat.fao.org.

14
Figure 2.2 The production of castor oil seeds among major countries in 2012
according to faostat.fao.org.

Castor oil is a biological based oil refined from the castor oil seeds. It is a

light yellow liquid with a unique smell. Its density is 961 kg/m3. The boiling point

of castor oil is 313°C, and its melting point is between -10 to -18°C (according to

National Institute for Occupational Safety and Health). The chemical formulation

of castor oil is a triglyceride containing three fatty acids and 90% of its fatty acids

are ricinoleic acid, a hydroxyl fatty acid with a hydroxyl group on its 12th carbon

atom. Therefore, castor oil is highly valued in industry processing.

15
2.2 Uses of castor oil

Castor oil is commonly used in the food processing, medicine, fuels and

chemical industry.

2.2.1 Uses of castor oil in food processing

Although castor oil seed contains toxic ricin proteins, food-grade castor oil is

still available due to the development of methods to detoxify castor seed. The

half-life of ricin at 80 °C is 9 minutes (Wang, 2010). So heating or steaming is

very effective to detoxify ricin.

Food-grade castor oil is commonly applied as food additives. In South Asia,

castor oil is directly used to coat on grains, such as rice and wheat, to keep them

from rotting (Gana and others, 2013). Another successful example is the use of

polyglycerol polyricinoleate (PGPR). PGPR is prepared through the esterification

of ricinoleic acids with polyglycerol. It is a good water-in-oil emulsifying agent,

and it proved to be safely edible when used in tin-greasing emulsions and in

chocolate couverture. (Wilson R and others, 1998) In addition, castor cake, the

byproduct of castor oil extraction, is also widely used as cattle feed after fully

steamed (Ogunniyi, 2005).

16
Figure 2.3 The derivative of castor oil (PGPR) applied in candy bars.

2.2.2 Uses of castor oil in medicine

According to the United States Food and Drug Administration (FDA), castor

oil is generally recognized as safe and effective (GRASE) as a stimulant laxative.

When in the small intestine, castor oil can be digested into ricinoleic acid and

stimulate the small intestine. Castor oil is also used for external application as a

skin protectant or wart remover (FDA OTC Ingredient List, 2006).

Castor oil is used to produce polyethoxylated castor oil, which is also known

as Kolliphor EL or Cremophor EL. Kolliphor EL is a nonionic surfactant commonly

applied in both liquid drugs and capsules (Zhang and others, 2001).

2.2.3 Castor oil as a biodiesel

Castor oil contains medium length (C18) fatty acids and is possible to be

regarded as a biodiesel. Compared with other vegetable oil, castor oil can show

a distinguish cold flow property. The 10% castor methyl ester blend with petro

diesel can achieve all the standard limits in ASTM D6751 and D7467, while
17
100% castor methyl esters failed only two of the properties (Berman and others,

2011), which shows a considerable potential as alternative fuel.

18
2.3 Uses of castor oil in chemical industry

Castor oil has multiple applications in chemical industry, such as soap

manufactory, lubrication, paints, adhesives, inks, nylon, and many other useful

derivatives.

2.3.1 Castor oil for cosmetics

As a non-comedogenic bio-based oil, castor oil is a most vital ingredient in

cosmetics. For soap manufactory, castor oil can be a wonderful bubble booster.

Due to the unique hydroxyl group on ricinoleic acid, castor oil can also act as a

humectant in soaps, washing powders, shampoos, and hair waxes. Cosmetics

with castor oil can provide a special silky, but not oily feel on skin or hair.

(Nagaraj, 2009)

One of the distinguished castor oil product is known as Turkey red oil.

Turkey red oil is actually sulfated castor oil, which is prepared from castor oil and

concentrated sulfuric acid. The product is then neutralized with sodium hydroxide

solution. Sulfated castor oil is a powerful moistening agent and helps pigments

and dyes. Therefore, turkey red oil is often used in hair coloring. (Ogunniyi, 2005)

2.3.2 Castor oil for lubrication

Castor oil has not only a wonderful cold flow property, but also high

temperature lubrication. At 10°C, the viscosity of castor oil is 2420 centipoise.

(Brady G and others, 1986) Some lubricants companies, such as Castrol,

developed castor oil as an attractive vegetable-based alternative to petroleum-

19
based lubricants in jet, diesel, and race car engines. Unlike ordinary chemical oils,

castor oil will not dissolve natural rubbers. Thus, castor oil is also considered as

a wonderful lubricant for bicycle (Older, 2000).

2.3.3 Castor oil for inks, paints, and adhesives

As a fatty alcohol, castor oil has specific pigment-wetting properties and is a

significant component in printing or duplicating inks (Abraham T, 2012). For

paints and adhesives, castor oil and ricinoleate are also used to adjust the

viscosity. In non-polar solvent, the long carbon chains in castor oil will wind each

other to form thixotropic structures and contribute to a higher viscosity, which

prevents dyes from precipitating. When shear force happens, thixotropic

structures are unwound to offer less viscosity, which helps dyes disperse

uniformly. (Shareef and others, 1985)

Castor oil is non-drying liquid. However, dehydrated castor oil is commonly

used in semi-drying or drying paints and adhesives. By removing the hydroxyl

group on the ricinoleic acid, dehydrated castor oil contains conjugated double

bonds. Therefore, dehydrated castor oil is converted into a drying oil (Ogunniyi,

2005).

2.3.4 Undecylenic acid, nylons, and other derivatives of castor oil

Undecylenic acid is prepared through the pyrolysis of ricinoleiceate (Ereaux

and Craig, 1949). According to FDA, undecylenic acid is approved to use for skin

infections (FDA OTC Ingredient List, 2006). It is also a wonderful antifungal

20
ingredient for skin care product. In addition, some perfume contains undecylenic

acid as well (Kula J and others, 1994).

Figure 2.4 Production of undecylenic acid from castor oil (Ogunniyi, 2005)

Sebacic acid is another pyrolysis product of castor oil. It can be applied in

plasticizers and lubricants. Plastic made from sebacic acid is approved with good

thermo stability and low toxic. (Daintith, 2008)

Figure 2.5 Production of sebacic acid from castor oil (Ogunniyi, 2005)
21
 Sebacic acid and undecylenic acid are the raw material for making nylon-11.

(Kovaly K, 1982) Nylon-11 is a castor-oil-based polyamide with good molding

properties and resilient. It is widely applied as flexible fiber, powder coating, and

engineering plastic. (Nagaraj, 2009)

22
2.4 Uses of castor oil in polyurethane

Castor oil is a triglyceride with multiple hydroxyl groups. Such a structure

enables castor oil to make polyurethane through the reaction with isocyanate.

Castor-oil-based polyurethane have been widely researched to produce plastics,

elastomers, nanoparticles, and foams.

2.4.1 Interpenetrating polymer network with castor-oil-based polyurethane

Yenwo and others (1977) were the first to set up interpenetrating polymer

network with castor-oil-based polyurethane and polystyrene. Devia and others

(1979) developed the similar systems and produced tougher plastics, and

elastomers. The elastomers can be extended to 125% at maximum. Later,

Kumar V and others (1987) found out a marginal increase in tensile strength and

crosslink density from pure castor oil polyurethane to 60% polyurethane with

40% polystyrene. Further studies indicated the effects of polyurethane and

polystyrene in tensile modulus (Siddaramaiah and others, 2003), percentage

elongation (Bai and others, 1997), and other morphological and mechanical

properties (Suthar and others, 1994; Siddaramaiah and others, 2003).

Besides polystyrene, researchers also developed polyurethane

interpenetrating polymer network with other polymers, such as polymethacrylate

(Patel and Suthar, 1989), polyethyl-methacrylate (Patel and Suthar, 1990), and

acrylonitrile (Xie and Guo, 2002). Especially , Guo and others (2011) have

successfully introduced the Eucalyptus globulus cellulose nanocrystals into

waterborne polyurethane based on castor oil/polyethylene glycol, which shows

23
promising potential of interpenetrating polymer network containing castor oil

replacement.

2.4.2 Polyurethane nanoparticles based on castor oil

In recent years, polyurethane nanoparticles were widely developed and

studied because of their good stability, biocompatibility, and mechanical

properties (Page and others, 2012). So they are suitable for drug coating and

delivery. Since Cremophor, the hydrogenated castor oil, has been commonly

applied in medicine, it becomes an ideal material to form polyurethane

nanoparticles. Morral-Ruiz’s research (2014) indicated polyurethane network can

help minimize the risk of acute hypersensitivity reactions and improve the

biocompatibility of some drugs. Also, castor-oil based polyurethane can be

applied on tissue engineering without a strong inflammatory reaction (Laschke,

2009).

2.4.3 Polyurethane foams based on castor oil

The functionality of raw castor oil is 2.7, thus, castor oil is commonly applied

to produce rigid polyurethane foams. Lyon, Garrett and Frankel have already

developed rigid urethane foams from hydroxymethylated castor oil with large

amount (20–65%) of crosslinkers to strengthen the structure and prevent foams

from shrinking (1974). The thermal properties of rigid polyurethane foams

containing castor oil have been tested in roof systems (Cardoso and others,

2008). Recently, Zhang and others (2013) have developed epoxidized

glycerolysis castor oil based flame-retardant polyols and introduced them into

24
rigid polyurethane foams. Such foams showed a high close-cell content and

appear to be promising.

However, compared to rigid foams, castor-oil-based flexible polyurethane

foams are much less studied. Directly using castor oil for flexible polyurethane

foams leads to a low resiliency and a temperature dependent modulus (Nozawa

and others, 2005). For flexible foam polyols, the range of two hydroxyl groups in

castor oil is too short. Still, flexible polyurethane foams is a main part in

polyurethane production (Zhang and others, 2007). Therefore, the study of

castor-oil-based flexible polyurethane foams is meaningful.

25
2.5 Limitations of existing literature

Castor oil is a natural polyol which can be directly used in polyurethane

foaming. Many researchers have developed their castor-oil-based polyurethane

products in order to select a biological resource as an alternative to petroleum. In

most of the research, they used multiple petroleum-based chemicals to modify

castor oil, and some of those treatments were not environmental friendly. In this

study, raw castor oil was chosen as the only bio-based polyol to investigate its

influence on both rigid and flexible polyurethane foams. Besides, other critical

factors, such as average hydroxyl number, water content, and isocyanate index,

were also adjusted to study their effects on physical and thermal properties of

foams containing castor oil.

26
 CHAPTER 3. WATER-BLOWN RIGID POLYURETHANE FOAMS
WITH CASTOR OIL REPLACEMENT

3.1 Background

Rigid polyurethane foams are very widely used in both industry and daily life

due to their unique advantages which include low density and good heat

insulation as well as excellent strength and weight ratio. Therefore, thermal

insulation foam and structural foam are two of the main applications of

polyurethane rigid foams.

The two main raw materials of polyurethane, polyol and isocyanate, are

usually prepared from petroleum resources. Considering non-renewability of

petroleum, researchers are studying bio-based resources such as corn stover

and vegetable-based oils as alternatives for polyols. As one of the few vegetable

resources which contain natural hydroxyl groups, castor oil can be directly

applied to form polyurethane without any chemical modification . Narine and

others (2007) produced polyurethane foams with different seed oils, and their

results showed foams made with castor oil had the highest compressive strength

over those foams made with soybean oil or canola seed oil.

Castor oil is a triglyceride containing three fatty acids and 90% of its fatty

acids are ricinoleic acid, which has a hydroxyl group on the 12th carbon atom.

Therefore, castor oil could be considered as a natural polyol with a functionality

of 2.7 (= 0.9 x 3) and be used to prepare rigid polyurethane foams. The long fatty

acid chains in castor oil, however, reduce the density of the hydroxyl group, and

27
also limit the degree of cross-linkage in polyurethane foams. Considering the

application of the rigid polyurethane foams, more cross-linkages per volume are

preferred to form a firmer and more stable structure (Seo and others, 2004), and

also to trap the thermal-insulation gas more effectively (Klempner and Frisch,

1991).

Due to the active –OH group in the water molecule, it can react with

isocyanate and produce carbon dioxide. So water can be used as the blowing

agent making this isocyanate/castor oil/water combination a water-blown

polyurethane system. The thermal conductivity of carbon dioxide is very low

(0.0146 W/(m.K)), almost 50% lower than air (0.024 W/(m.K)). Therefore, water

content can affect the thermal conductivity of the rigid foam product. Also, gas

from the blowing agent will influence the shapes of the cells and the size of the

whole foam (Tu, 2008 and Fan, 2011); hence, the blowing agent content also

contributes to the density and some mechanical properties.

The aim of this study was to investigate the potential of castor oil to replace

petroleum-based polyols in rigid polyurethane foams and study the effect of the

blowing agent (water) in rigid foams containing castor oil.

28
3.2 Materials and methods

3.2.1 Raw materials

Raw materials of polyurethane foams are usually divided into two sides: A-

side (referring to isocyanate) and B-side (referring to the polyol). In this research,

PAPI® 27 from Dow Chemical Co. (Midland, MI) was used as the isocyanate in

the A-side. VORANOL® 490 was used as the petroleum-based polyether polyol,

which was also obtained from Dow Chemical Co. (Midland, MI). Castor oil was

the bio-based polyol and it was obtained from Alnor Oil Company, Inc (Valley

Stream, NY). Glycerol was obtained from Fisher Scientific (Fair Lawn, NJ).

Distilled water was used as the blowing agent. Table 3.1 lists the properties of

these chemicals.

Table 3.1 Properties of Raw Materials.

Average
Raw Water Hydroxyl Equivalent
Molecular Functionality
Materials Content Number Weight
Weight
Castor oil 0 900 2.7 168 333.93
Voranol
0.007 460 4.3 485 115.72
490®
Glycerol 0 92.09 3 1828 30.7
Water - 18.02 2 6233 9.01
Isocyanate 0 340 2.7 - 134

POLYCAT® 5 and POLYCAT® 8 were used as the blowing catalyst and

gelling catalyst respectively. DABCO® DC-5357 was chosen as the surfactant.

POLYCAT® 5, POLYCAT® 8, and DABCO® DC-5357 were obtained from Air

Products & Chemicals (Allentown, PA).

29
3.2.2 Experimental design and foaming formulations

There were two main parts in this study. Firstly, the influence of castor oil

replacement (0, 25, 50 and 75%) was tested at a fixed water content of 3%. In

addition, another group of foams made from castor oil and glycerol mixtures

(80:20, 85:15, 90:10, and 95:5) were also prepared to investigate the effects of

hydroxyl number. Secondly, according to the results from the first part, rigid

foams with 25% castor oil replacement were chosen and the effect of blowing

agent was investigated at different water contents (2, 3, 4 and 5%). Foams

without castor oil replacement were also tested as controls at the same level of

water content.

The isocyanate index for all rigid foams was fixed at 110%. Tables 3.2, 3.3,

and 3.4 list the recipes of each test.

30
Table 3.2 Foaming formulation of rigid polyurethane foams with different castor
oil replacement percentages.
Parts by Weight of Total Polyol
Ingredients
Control Foams Castor Oil Foams
VORANOL® 490
100 75 50 25
Castor Oil
0 25 50 75
Distilled Water
3.0 3.0
B-side
POLYCAT® 5
1.26 1.26
POLYCAT® 8
0.84 0.84
DABCO® DC-5357
2.5 2.5
PAPI® 27
A-side 176.6 155.8 134.9 114.1
Index =110

31
Table 3.3 Foaming formulation of rigid polyurethane foams with different water
content percentages.
Parts by Weight of Total Polyol
Ingredients
Control Foams Castor Oil Foams
VORANOL®
100 75
490
Castor Oil 0 25
Distilled
2.0 3.0 4.0 5.0 2.0 3.0 4.0 5.0
Water
B-
side POLYCAT®
1.26 1.26
5
POLYCAT®
0.84 0.84
8
DABCO®
2.5 2.5
DC-5357
A- PAPI® 27
160.2 176.6 193.0 209.4 139.4 155.8 172.2 188.5
side Index =110

32
Table 3.4 Foaming formulation of castor-oil-based rigid polyurethane foams with
different glycerol contents.
Ingredients Parts by Weight of Total Polyol
Glycerol 5 10 15 20
Castor Oil 95 90 85 80
Distilled Water 3.0
B-side
POLYCAT® 5 1.26
POLYCAT® 8 0.84
DABCO® DC-5357 2.5
PAPI® 27
A-side 115.1 136.9 158.7 180.5
Index =110

3.2.3 Foam preparation

For B-side, both petroleum-based polyol (Voranol® 490), glycerol, and

castor oil were weighed and mixed in a plastic container. Distilled water and two

catalysts (POLYCAT® 5 & 8) followed. Finally, after surfactant (DABCO® DC-

5357) was weighed and added, the mixture was taken to the electric mixer and

mixed at 3450 rpm for 40 s. Then the mixture was set at quiescence and

degased for 2 min. For A-side, the isocyanate was weighed in another plastic

container. After adding to the B-side container, the whole mixture was mixed at

3450 rpm for 10 s. Then the mixture was put into a wooden mold covered with

aluminum foil at once. The size of the mold was 11.4 × 11.4 × 21.6 cm. The

reacting mixture in the mold grew freely and the foam would conform to the

mold’s shape in one to three minutes.

After foaming, the foams were cured at ambient conditions (around 298 K)

for seven days, while their thermal conductivity was tested within 24 to 48 hours.

33
Figure 3.1 shows the procedures of the molded polyurethane foam’s preparation

in lab scale.

Figure 3.1 Procedures to make polyurethane foams.

34
3.2.4 Foam property measurements

Thermal conductivity of foams were determined according to ASTM

Designation C518–10 with modifications. Each foam sample was cut into 4

pieces (10.2 × 10.2 × 3.8 cm) within 24-48 h after foaming. They were assembled

together to give a total size of 20.3 × 20.3 × 3.8 cm and tested using a Fox 200

heat flow meter instrument (LaserComp, Wakefield, MA).

For foam density, samples were cut to the size of 6.4 × 6.4 × 3.8 cm 7 days

after preparation. Density was calculated by dividing sample mass by sample

volume. There were four replicates from each treatment. The mean value was

reported.

Compressive strength was determined after the density test using the same

samples following ASTM Designation D1621–10 with modifications. A TA.HDi

Texture Analyzer (Texture Technologies Corp., Scarsdale, NY) with XTRA

Dimension software was used. The value obtained was shown as force.

Compressive strength was then calculated as the force divided by the area of

compression surface.

35
3.3 Results and discussion

3.3.1 Influence of castor oil replacement

3.3.1.1 Density

Density is a basic property of polyurethane foams. Usually a low density is

preferred for saving ingredients.. Figure 3.2 illustrates the result of densities of

foams with different levels of castor oil replacement.

Figure 3.2 Effect of castor oil replacement on density of rigid polyurethane foams.

The density of the rigid foams decreased with the increase of castor oil

replacement from 0 to 50%. This is mainly because of the molecular structure of

the castor oil. One of the most significant characteristics of polyols is their

hydroxyl number. It directly influences the equivalent weight and the amount of

36
the isocyanate for reaction. The hydroxyl number of castor oil (168) is much

lower than that of VORANOL® 490 (490). Due to the lower hydroxyl number,

castor oil requires less isocyanate. So the mass of the foam decreases with the

increase of castor oil. Because the blowing agent was fixed at 3% and the

isocyanate index was fixed at 110, which means there should be enough

isocyanate to react with both polyols and blowing agent, the amount of carbon

dioxide produced was similar among the foams with castor oil percentage from 0

to 50%. Because the CO2 gas volume was the main factor of the foam volume,

these foams had a similar volume. A linear relationship can be found between

the density (y in kg/m3) and the castor oil percentage (x) as shown by:

y = -19.25x + 44.071 Eq. 3.1

However, the density of foam with 75% castor oil replacement was higher

than that of foam containing 50% castor oil. This may have been due to the

breakdown of the structure. A sample with 75% castor oil replacement and 3%

blowing agent content challenged the foam’s cross-linking structure and the cell

walls inside the foams with 75% castor oil replacement were too fragile to

maintain a volume as big as those of foams with 50% or less castor oil

replacement. The reduction in volume with 75% castor oil replacement could be

clearly observed during foaming.

3.3.1.2 Compressive strength

Compressive strength reflects the hardness and compression behavior of

rigid polyurethane foams. Rigid foams with higher compressive strength and

37
lower density are usually preferred. The compressive strength results of foams

with different castor oil replacement are shown in Figure 3.3.

Figure 3.3 Effect of castor oil replacement on compressive strength of rigid

polyurethane foams.

The compressive strength of foams decreased with an increased castor oil

percentage. The rate of the decrease was higher at larger castor oil percentages.

This may due to the density of foam and the inner structure, especially cross-

linkage in the foam. The density of foam decreased as shown in Figure 3.2 when

the castor oil replacement increased, except for the foam with 75% castor oil.

Due to the lower hydroxyl value of castor oil, when more castor oil was used, less

isocyanate was involved in the gelling reaction, which led to the reduction of

38
cross-linkage in the foam. For rigid foams, a higher cross-linking degree was

necessary to keep the strength of the structure. Therefore foams with 75% castor

oil replacement in the test were too fragile to satisfy the hardness requirement.

3.3.1.3 Thermal conductivity

Thermal conductivity is one of the most vital properties for rigid

polyurethane foams. Higher thermal conductivity means the material can conduct

heat more easily. Rigid polyurethane foams are often used for heat insulation.

Therefore lower thermal conductivity is preferred. The result of thermal

conductivity of foams with different castor oil replacement levels is shown in

Figure 3.4.

39
Figure 3.4 Effect of castor oil replacement on thermal conductivity of rigid
polyurethane foams.

When the castor oil replacement was lower than 25%, the thermal

conductivity remained at a lower level. When it was higher than 25%, the thermal

conductivity rose rapidly. Thermal conductivity depends on the inner structure of

the foams and the amount of carbon dioxide inside the foam.

According to its chemical structure, all hydroxyl groups in the castor oil

triglyceride structure are secondary, while most of the hydroxyl groups in

VORANOL® 490 are primary. Because the gelling reaction in polyurethane

preparation is s nucleophilic addition, primary hydroxyl groups, as nucleophile,

40
are more active than secondary hydroxyl groups due to the steric effects. Thus

the gelling reaction would be slower when the castor oil percentage was higher.

Considering the speed of the blowing reaction, slower gelling reaction led to a

weaker inner structure that cannot burden the pressure of the gas generated

from the blowing reaction, which increased the thermal conductivity of foams.

The carbon dioxide in foams contributes a lot to the decrease of thermal

conductivity. At 25% castor oil replacement, the structure of PU foams was not

obviously affected and the thermal conductivity remained low. However, when

castor oil replacement was over 50%, the density of cross-linkage in the foams

became too low to maintain the structure. When the structure traps less carbon

dioxide, more CO2 escaped from the foam and increased the thermal

conductivity.

41
3.3.2 Influence of blowing agent content

3.3.2.1 Density

Figure 3.5 Effect of castor oil replacement on density of rigid polyurethane foams
with different water content.

As shown in Figure 3.5, the density of foams with 25% castor oil was lower

than control at 2-5% water (blowing agent) content, which is consistent with

previous discussion. Furthermore, with the increase of water, the densities of

foams decreased. More water in the foam formulation consumes more

isocyanate which produces more carbon dioxide and more gas cells, which then

42
enlarged the volume of the foams. Because there was little change in foam

weight the density of foam with higher water content was lower.

3.3.2.2 Compressive strength

Figure 3.6 Effect of castor oil replacement on compressive strength of rigid

polyurethane foams with different water content.

As shown in Figure 3.6, the compressive strength of foams with 25% castor

oil was also lower than control at the same water content, respectively. For each

43
series, using more water (blowing agent) in the foam formulation reduced the

compressive strength of polyurethane foams. In addition to the effect of water

content on density, a higher water content boosted the blowing reaction and

challenged the newly formed and unstable cross-linking structure. Therefore, the

compressive strength of foams has the same order as the density of foams.

3.3.2.3 Thermal conductivity

Figure 3.7 Effect of castor oil replacement on thermal conductivity of rigid

polyurethane foams with different water content.

44
 As shown in Figure 3.7, no obvious difference in thermal conductivity

occurred due to increasing the water (blowing agent) content from 2~4%. But it

became much higher at 5% water content. Principally, water helps produce

carbon dioxide. However, the thermal conductivity did not decrease with

increasing water content. In fact, it significantly increased at 5% water. This may

be due to the weakening of the foam as the water content was increased. More

water produced more carbon dioxide gas, and cell walls became thinner. More

cells inside the foam were broken due to the high pressure from gas when

foaming. Although the polyurethane structure at this point might be still stable, it

cannot stop the gas flow from one cell to another or from inner structure to the

outside. Although more CO2 was produced, less was kept inside the foam. Then

the space in the foam was overtaken by air in the environment, and thus the

thermal conductivity increased (thermal conductivity of air, which was 0.0243

W/m.K at 0⁰C while CO2 was 0.0105 W/m.K at 0⁰C).

3.3.3 Influence of hydroxyl number

To investigate the effect of the hydroxyl number on the properties of rigid

polyurethane foam, glycerol was introduced into the polyols’ side to modify the

overall hydroxyl number.

45
3.3.3.1 Density

Figure 3.8 Effect of hydroxyl number on density of rigid polyurethane foams with
castor oil and glycerol or Voranol 490.

Assuming that all the chemicals could be reacted to build the structure of

polyurethane foams, water was the only blowing agent that defined the final

volume of the product. Thus, due to the increasing hydroxyl number together with

the isocyanate content, the total weight of the foams should also increase. Then

the density would also increase with the increasing of hydroxyl number.

However, this did not happen when the castor oil was added into the system. As

46
shown in Figure 3.8, when the hydroxyl number of polyol mixture was lower than

300, the density of foam was higher than that with a hydroxyl number of around

330. There are at least two factors resulting in the high density with a lower

hydroxyl number. Firstly, too low a hydroxyl number contributed to a low cross-

linking density foam. Foam structures with too low cross-linking density could not

maintain their volumes, which led to the loss of volume. Also, foams with a lower

hydroxyl number contained more castor oil. The hydroxyl groups of castor oil are

all secondary, and their reaction rate with isocyanate was only 1/3 of the primary

hydroxyl groups. During foaming, a fraction of gas produced from the blowing

agent might have escaped from the system if the structure of castor oil had not

been strengthened enough. Since the hydroxyl number of glycerol (1827.56) is

much higher than that of Voranol 490, in order to achieve a similar average

hydroxyl number level, the castor oil content with glycerol should be much higher

than that with Voranol 490. Besides castor oil, glycerol also contains one

secondary hydroxyl group out of the total three hydroxyl groups on each

molecule. Thus even when the hydroxyl number is similar, foams with castor oil

and glycerol combination contain more secondary hydroxyl groups than foams

with castor oil and Voranol 490 combination. Therefore, when the hydroxyl

number was lower than 350, the density of foam with castor oil and glycerol was

higher than that with castor oil and Voranol 490. However, it is interesting to note

that when the hydroxyl number was higher than 400, the density of foams with

Voranol 490 was even higher than that with glycerol. One possibility for this

phenomenon is that when the hydroxyl number was over 400, the main polyol in

47
the group of castor oil and Voranol 490 was Voranol 490 (with the percentage of

75 and 100). The structure was already finished and almost fixed when carbon

dioxide was still involved in the blowing reaction. Such cases would not happen

in foams with castor oil and glycerol because even when the hydroxyl number is

over 400, castor oil remained as the main polyol (with the percentage of 85 and

80). With the help of glycerol as the cross-linker, the structure of polyurethane

with castor oil could be pushed to its maximum possible volume during foaming.

Therefore, the total volume of foams with castor oil and glycerol was larger than

that with Voranol 490.

3.3.3.2 Compressive strength

Figure 3.9 shows the relationship between the compressive strength and the

overall hydroxyl number.

48
Figure 3.9 Effect of hydroxyl number on compressive strength of rigid
polyurethane foams with castor oil and glycerol or Voranol 490.

The compressive strength increased with the increase of the overall

hydroxyl number. With a fixed total polyol content, foams with a higher hydroxyl

number consumed more isocyanate to form denser cross-linkage inside the

structure, and it also contributed to higher compressive strength. The figure also

shows that the line of the glycerol series was always lower than that of the

Voranol 490 series. The results reflect that the structure of foams with castor oil

49
and glycerol is not as firm as that with Voranol 490. As stated previously, foams

with castor oil and glycerol contain much more secondary hydroxyl group content

than that of Voranol 490. Thus the distribution of cross-linkage in the foams with

castor oil and glycerol was not as uniform as that with Voranol 490, which could

have contributed to the instability of the structure. In addition, Dr. Tu’s (2008) and

Dr. Fan’s (2011) research also mentioned that the density of the foam had a

positive influence on its compressive strength.

50
3.3.3.3 Thermal conductivity

Figure 3.10 Effect of hydroxyl number on thermal conductivity of rigid

polyurethane foams with castor oil and glycerol or Voranol 490.

As shown in Figure 3.10, the hydroxyl number itself is not a direct factor

affecting the thermal conductivity of polyurethane foams. However, the huge

difference between two series indicates that the type of hydroxyl groups is the

main factor to the thermal insulation property. When the polyols have more

secondary hydroxyl group (glycerol series and foams with 75% castor oil and

25% Voranol 490), the thermal conductivity is always above 0.034 W/m.K. While

51
the polyols have more primary hydroxyl group (75% or 100% Voranol 490

content), the thermal conductivity remains at a very low level. Due to the faster

reaction rate, primary hydroxyl groups can help strengthen the foams’ structure

more effectively and trap more carbon dioxide. Also the series of foams with

castor oil and glycerol have less uniform structures, which might also lead to the

escape of carbon dioxide.

In summary, castor oil replacement influenced the physical and thermal

properties of polyurethane foams. The product with more castor oil replacement

tends to be lighter (from the changes in density) and more fragile (from

compressive strength) due to the lower hydroxyl number. At the same time, the

thermal conductivity increased when the castor oil percentage was over 50% due

to the lack of cross-linkage. Therefore, the replacement of the castor oil should

be limited.

The blowing agent also affects the properties of PU foams. Water helps

produce more gas and enlarge the foam volume, which is reflected by the

decreasing density. Water also weakens the foam structure. The decrease of the

compressive strength shows water makes foams more fragile. Too much water

will break cell walls, weaken the foam structure and increase the thermal

conductivity of polyurethane foams.

Hydroxyl number is a key factor affecting many properties of polyurethane

foams. It directly affects the cross-linking density. With the help of the cross-

linker, glycerol, the overall hydroxyl number can be increased and part of the

52
mechanical properties can be modified. However, the type of hydroxyl group is

still a limitation of castor-oil-based polyurethane foams.

53
3.4 Conclusion

In this study, water-blown rigid polyurethane foams were prepared using

four levels (0, 25, 50, and 75%) of castor oil to replace petroleum-based polyol

and four levels (2, 3, 4, and 5%) of water content. The results indicate that both

the castor oil replacement and the water content can affect the physical and

thermal properties of rigid foam. Too much castor oil replacement makes foams

light but fragile, and product can conduct heat more easily. Water has a similar

effect on physical properties and has a complex influence on thermal

conductivity. The overall hydroxyl number of castor-oil-based polyurethane foams

can be modified by adding glycerol as a cross-linker and have potential to

increase castor oil replacement level. Still the secondary hydroxyl group in castor

oil is a limitation leading to foams with a higher thermal conductivity.

54
 CHAPTER 4. WATER-BLOWN FLEXIBLE POLYURETHANE
FOAMS WITH CASTOR OIL REPLACEMENT

4.1 Background

Flexible polyurethane foams are polymers with low hardness but good

properties in recovery and flexibility. The study of flexible polyurethane foams

can be dated from the early research of polyurethane around World War II

(Seymour and Kauffman, 1992). Usually, flexible polyurethane foams are applied

as upholstery material in bedding, toys, footwear, packaging, and vehicles. In

1952, the global consumption of flexible foams was 1000 tons. In 2011, the

consumption reached 5 million tons, representing an increase 5000 times of the

1952 estimate (Engels and others, 2013).

Flexible polyurethane foams, like other popular polymers, relied on

petroleum resources as the major feedstock. Petroleum is a nonrenewable

resource and the consumption of petroleum usually accompanies damage to the

environment. Also, the cost of petroleum-based polyurethane is increasing

annually along with the increase of petroleum prices. Therefore, both economic

and environmental considerations mandate developing novel, renewable

resources to take the place of petroleum resources (Molero and others, 2008).

Vegetable-based chemicals are regarded as the most significant renewable

substitute for petroleum. Many plant-based raw materials contain unsaturated

bonds and hydroxyl groups, which enable them to be used as or modified into

polyols. Cinelli and others (2013) recently developed a method to prepare flexible

55
polyurethane foams from liquefied lignin. Meier and others (2007) investigated

the properties of polyurethane foams with modified canola oil, sunflower oil,

linseed oil and corn oil replacement. Tu (2008) and Fan (2011) have increased

the soybean-oil-based polyols replacement ratio by as much as 50% and have

investigated the influences of biobased polyol contents. Among those vegetable

oils, castor oil is one of the most promising alternatives. Castor oil contains

natural reactive hydroxyl groups on its ricinoleic acid branches, which is

significant in the production of polyurethane structure. Also, castor oil plants can

be cultivated in both acid and basic soil types. Thus, they are widely planted in

southern Asia, South America and some areas in southern Africa. According to

the Food and Agriculture Organization of the United Nations (FAO:

http://faostat.fao.org/), India is the main producer of castor oil seeds. In 2012, the

production of castor oil seeds in India was 5.05 million tons, which was about

90% of the global production. Large production and excellent adaptation ensure

that castor oil can be a competitive renewable substitute for fuel oil or chemical

feedstock.

Compared to rigid foams, flexible polyurethane foams usually have a lower

degree of cross-linking. Thus, they require a lower Isocyanate index for foaming

and polyols with lower hydroxyl value. However, as our preliminary tests showed

- if we simply replace polyols by castor oil without any cross-linker, foams would

soon fail due to serious collapse (Figure 4.1). The objective of this study is to

investigate the potential and effect of castor oil replacement in flexible

polyurethane foams.

56
 .
Figure 4.1 Collapse of the flexible polyurethane foam with no cross-linker content
but 100% castor oil replacement.

57
4.2 Materials and methods

4.2.1 Raw materials

Castor oil used in this study was obtained from Alnor Oil Company, Inc. (Valley

Stream, NY) with a hydroxyl number of 168. Voranol® 4701, a petroleum-based

polyol with a hydroxyl number of 34, was supplied by Dow Chemical Co.

(Midland, MI). PAPI® 27 came from Dow Chemical Co. (Midland, MI) and is a

polymeric diphenylmethane diisocyanate (MDI). Distilled water was the blowing

agent. Diethanolamine was the cross-linker and supplied by Fisher Scientific

(Hanover Park, IL). DABCO® 33-LV and DABCO® 8154 were the gelling

catalysts and DABCO® BL-17, the blowing catalyst. Stannous octoate and

DABCO® DC 2585 were a tin-catalyst and a surfactant, respectively. DABCO®

33-LV, DABCO® 8154, DABCO® BL-17, and DABCO® DC 2585 were supplied by

Air Products & Chemicals (Allentown, PA). Table 4.1 lists the properties related

to the chemicals used in this research.

58
Table 4.1 Properties of raw materials.
Average
Water Hydroxyl Equivalent
Raw Materials Molecular Functionality
Content Number Weight
Weight
Castor oil 0 900 2.7 168 333.93
Voranol 4701 0.06 4900 2.97 34 1650
Not Not
DABCO 33-LV 0 560 100.18
applicable applicable
Not Not
DABCO 8154 0 548 102.37
applicable applicable
Not Not
DABCO BL-17 0 476 117.86
applicable applicable
Not Not
DABCO 2585 0 60 935
applicable applicable
Water - 18.02 2 6233 9.01
Diethanolamine 0 105.14 3.00 1602 35.02
Isocyanate 0 340 2.7 - 134

4.2.2 Experimental design and foaming formulations

This study was divided into three sections. Section 1 focused on the

influence of different temperature conditions. Foaming formulations are shown in

Table 4.2. Foams were prepared through three different treatments. The first

group of polyurethane mixtures were allowed to foam in molds unheated, that is,

at room temperature, and the foams were also cured at room temperature.

Foams in the second group were prepared in molds that were preheated in the

oven to 102⁰C and also cured at room temperature. The surface temperatures

were recorded by a laser sensor during the foaming process. This method was

called “hot-mold cold-cure” and it was applied for all the samples in Sections 2

and 3. Foams in the third group were prepared in preheated molds but cured in

the 102⁰C oven for 1 hour. Tables 4.3 and 4.4 show foaming formulations for

Section 1 and 2, respectively. The sample’s total height, foaming temperature,

59
density, compression force deflection (CFD), and constant deflection

compression (CDC) were tested.

Table 4.2 Foaming formulation of flexible polyurethane foams with different

temperature conditions.
Parts by Weight of total Polyol
Ingredients
Control Foams Castor oil Foams
VORANOL® 4701 100 0
Castor Oil 0 100
Distilled Water 5.0
Diethanolamine 0.5
®
B-side DABCO BL-17 0.05
DABCO® 33-LV 0.3
®
DABCO 8154 0.3
Stannous Octoate 0.4
DABCO® DC-2585 3
PAPI® 27
A-side 55.43 74.10
Index =60

Table 4.3 Foaming formulation of flexible polyurethane foams with different

cross-linker contents.
Parts by Weight of Total Polyol
Ingredients
Control Foams Castor Oil Foams
®
VORANOL 4701 100 0
Castor Oil 0 100
Distilled Water 5.0
Diethanolamine 0.25, 0.5, 1.0, 2.0
B-side DABCO® BL-17 0.05
®
DABCO 33-LV 0.3
DABCO® 8154 0.3
Stannous Octoate 0.4
®
DABCO DC-2585 3
A-side PAPI® 27 Isocyanate Index = 60

60
Table 4.4 Foaming formulation of flexible polyurethane foams with different
castor oil replacements and isocyanate indices.
Parts by Weight of Total Polyol
Ingredients Control Castor Oil Half Castor Oil
Foams Foams Replacement
®
VORANOL 4701 100 0 50
Castor Oil 0 100 50
Distilled Water 5.0
Diethanolamine 0.5
B-side DABCO® BL-17 0.05
®
DABCO 33-LV 0.3
DABCO® 8154 0.3
Stannous Octoate 0.4
®
DABCO DC-2585 3
A-side PAPI 27 Isocyanate Index = 50, 60, 70, 80

4.2.3 Foam preparation

The process of flexible foam preparation in this study was similar to the

procedures shown in Figure 3.1. Polyols, blowing agent (water), catalysts, cross-

linker and surfactant were weighed and placed in a plastic container as B-side.

The mixture was taken to the electric mixer and mixed uniformly at 3450 rpm for

40 s. Then the mixture was set at quiescence and degased for 2 min. For A-side,

the isocyanate was weighed, placed in another plastic container, and then taken

to the same electric mixer. After the isocyanate was added, the whole mixture

was mixed at 3450 rpm for an additional 10 s. Then the mixture was poured into

a wooden mold.

The wooden mold was preheated to 102⁰C except for foams in the first

section. After foaming, foams were cured at either room temperature (Sections 1

and 2 foams) or at 102⁰C (Section 3 foams) for one hour. Then, they were

pressed to their half thickness by an aluminum plate rapidly and relaxed. This

61
was repeated twice in order to break the inner gas cells and prevent foams from

shrinking. All tests were conducted seven days after the foams were cured and

pressed.

4.2.4 Foam property measurements

The properties of flexible foams were measured according to the ASTM

D3574-11 (2011) with modifications, including density, compression force

deflection, constant deflection compression, tear resistance, and resilience.

Density: Samples were cut according to a dimension of 5.08 × 5.08 × 2.54

cm3. Density was obtained through the mass and volume. There were at least 3

replicates for each set.

Compression force deflection (CFD): Samples were cut into 5.08 × 5.08 ×

2.54 cm3 blocks and tested using a TA.HDi Texture Analyzer. After placed on the

TA machine’s plate, each sample was pressed to 25% of its original height

(about 0.7 cm and then released to assume its normal state, which is called

“preflex”. The preflex procedure was done twice before force measurement. After

the second preflex the sample was allowed to relax for about 6 min. The sample

was then compressed to 50% of its thickness and the final force was obtained 60

s after the maximum force occurred. The pressure value was reported as the

final force divided by the sample area.

62
 Figure 4.2 Procedures of compression force deflection test.

Constant deflection compression (CDC): Samples were cut into 5.08 × 5.08

× 2.54 cm3 squares and placed on the aluminum plate apparatus which was

placed in an oven for the constant deflection process. The samples were

compressed by two parallel aluminum plates. The distance of two plates was

adjusted and fixed by bolts. The ratio of deflection was set as 50%. Constant

deflection process was conducted in a 70⁰C oven for 22 h, and then the samples

were taken out of the oven, removed from apparatus and recovered at room

temperature for 30 min. Then the final thickness was obtained. The constant

deflection compression set point was calculated as the difference between the

original thickness and the final thickness divided by the original thickness.

Tear resistance test: Samples were cut into bars with a thickness of 2.54

cm and an incision of 10.16 cm length. Two parts from the incision were bonded

63
in the TA machine separately. Then the machine tore the sample with a speed of

8.5 mm/s. The tear resistance was reported as the maximum resistance force

divided by the thickness.

Resilience test: Samples were cut into 10.16 × 10.16 × 5.08 cm 3 squares. A

transparent open tube (510 mm in length and 44.35 mm in diameter) was

prepared marked from 0% to 100% from one side to the other along its length.

The tube was placed vertically with its lower end 1.6 cm above the center of the

sample. A steel ball with a diameter of 1.6 cm was released freely from the top

inside the tube. The maximum rebound height was recorded by percentage as its

resilience.

4.3 Results and discussion

4.3.1 Influence of different temperature conditions

Figure 4.3 describes the surface temperature history of the polyurethane

foams during foaming. The treatments included the effect of composition (castor

oil based or petroleum polyol based) and mold temperature (room temperature or

heated to 102⁰C).

64
Figure 4.3 Surface temperature history of flexible polyurethane foams with
different polyols (castor-oil based or petroleum-based foam) and mold
temperatures (heated or unheated).

Due to the limitation of electronic laser sensor, the temperature of samples

foaming in the oven could not be recorded and are not shown in Figure 4.3. We

assume the temperatures of these foams were kept at 102⁰C. As shown in

Figure 4.3, for petroleum-based polyurethane foams, the wooden mold

65
temperature did not influence the rapid temperature rise in the beginning of

foaming. The only difference between the two methods was the peak value of

surface temperature of petroleum-based foams in the heated mold was slightly

higher than that of foams in unheated molds. The temperature rise of castor-oil-

based polyurethane foams was much slower than that of petroleum-based

polyurethane foams, which was due to the lower reaction rate of the secondary

hydroxyl groups in castor oil molecules. The synthesis of polyurethane is an

exothermic process. Lower reaction rate leads to slower heat generated. It

required a longer time for castor-oil-based polyurethane mixtures to reach the

maximum temperature. Under this testing method, the effect of a heated mold

can be shown in the temperature curves. With higher initial mold temperature,

castor-oil-based polyurethane was able to react faster at the beginning and

accumulate more reaction heat from the synthesis of polyurethane to accelerate

the foaming process. The peak foam surface temperature was about the same

as the petroleum-based foam with heated mold.

4.3.1.1 Density and height of foams

Figures 4.4 and 4.5 show the height and density of flexible foams.

66
Figure 4.4 Height of flexible foams with different foaming conditions.

67
Figure 4.5 Density of flexible foams with different foaming conditions.

As shown, mold temperature did not have any significant effect on the

height and density of petroleum-based polyurethane foams (p = 0.522 for height

and 0.696 for density according to single-factor ANOVA). However, the castor-

oil-based flexible foams were higher and had lower density when mold was

heated (p= 0.006 for height and 0.045 for density). For castor-oil-based foams in

unheated molds, the gelling reaction rate was too slow to fit the blowing reaction

rate, even though the blowing catalyst BL-17, a delayed-action blowing catalyst,

was applied. A large mass of carbon dioxide produced from blowing reaction

68
might have escaped from the mixture and could not contribute to the final

volume. Therefore, the castor-oil-based foams in unheated molds had lower

height and higher density. It was interesting that the castor-oil foams foaming in

the oven had a higher density than those foams in unheated molds, but their

actual height was still higher than the unheated foams. It was observed that

these foams were not uniform in cell size and some spots showed signs of

collapse which led to an increase in density. Due to the higher hydroxyl number,

castor-oil-based foams required more isocyanate, but their volumes were limited

due to the blowing agent content and their slower reaction rate. Therefore, the

density of castor-oil-based foams were always higher than the density of

petroleum-based foams.

69
4.3.1.2 Compression force deflection

Figure 4.6 shows the compression force deflection of foams at different

foaming conditions.

Figure 4.6 Compression force deflection of flexible foams with different foaming
conditions.

For petroleum-based foams, the CFD of foams was affected by the mold

temperature (p = 0.112). Literature shows that the two main factors of CFD are

the overall density and the cross-linking rate (Fan, 2011 and Tu, 2008). Since

these foams had a similar density, there may have been a potential for high

70
temperature that reduced the cross-linking rate of polyurethane foams. Results of

CFD for castor-oil-based foams verify this influence (p = 0.029). The castor-oil

foams foamed in the oven and the foams prepared in unheated molds had similar

density but the latter samples had a larger value in CFD, which suggests the

cross-linking rate of foams in unheated-molds was higher. The low CFD value of

foams in heated molds can also be explained in the same manner. Under the

same foaming conditions, the values of CFD for castor-oil-based foams were

always higher than that for petroleum-based foams due to their higher density.

4.3.1.3 Constant deflection compression

Figure 4.7 shows the 50% constant deflection compression values of these

foams.

71
Figure 4.7 50% Constant deflection compression of flexible foams with different
foaming conditions.

As shown, foaming conditions did not influence the properties of CDC (p =

0.888 for petroleum-based foams and 0.961 for castor-oil-based foams). The

value of 50% CDC reflects the flexibility of a foam. The lower the value is, the

better its recovery to its original thickness. The difference in 50% CDC between

castor-oil-based foams and petroleum-based foams was still evident. The key to

a low CDC value and excellent recovery property lies in the soft segments of the

foam. Usually longer polymer chains between the nearby reactive hydroxyl

72
groups can lead to more flexible foams. The hydroxyl number of Voranol 4701,

the petroleum-based polyol in this study, is only 34 while castor oil has the

hydroxyl number of 168, which means the degree of hydroxyl groups’ density of

castor oil is much higher than that of Voranol 4701. Thus, the distance between

two hydroxyl groups in castor oil’s structure is much shorter than that in Voranol

4701.Therefore, castor-oil-based foams had a higher value of 50% CDC than

petroleum-based foams.

In summary, the foaming temperature basically did not affect the properties

of foams produced by petroleum based polyols. However, a higher mold

temperature can boost the reaction between castor oil and isocyanate and help

the polyurethane foams to grow faster and higher. However, higher temperature

may also lead to the collapse of foams. Therefore a “hot-mold cold-cure” method

is recommended in flexible polyurethane foams containing castor oil

replacement.

4.3.2 Influence of cross-linker content

4.3.2.1 Density

Figure 4.8 shows the effect of cross-linker content on the density of flexible

polyurethane foams.

73
Figure 4.8 Density of flexible foams with different cross-linker content.

For both castor-oil-based flexible foams and petroleum-based foams, the

density of foams generally increased with the increase of cross-linker content.

Diethanolamine was the cross-linker applied in this study, which has a hydroxyl

number as high as 1602. Thus more cross-linker content required more

isocyanate to be added into the system, which led to an increase of total weight.

Also, diethanolamine contains reactive primary hydroxyl groups on each of the

two ends of its molecular structure, and its secondary amine structure can also

74
boost its reactivity 200-500 times higher than the reactivity of water (Herrington

and Hock, 1997). Since the isocyanate index was set at 60, the cross-linker had

the ability to capture the isocyanate from water and castor oil and less gas was

produced in the foams. The increase of cross-linker content led to the decrease

of foam volume. Thus the density of foams increased with the increase of the

cross-linker content. However, the density of castor-oil-based foams with 0.25%

cross-linker was higher than that of foams with 0.5% cross-linker content. This

might be due to the partial structure collapse assuming that 0.25% cross-linker

content was not enough to form the stable matrix before castor oil and

isocyanate were reacted to produce polyurethane segments, which might lead to

a loss of volume. On the other hand, the density of castor-oil-based foams had a

higher density than that of petroleum-based foams due to the higher hydroxyl

number as discussed previously.

4.3.2.2 Compression force deflection

Figure 4.9 represents the effect of cross-linker content on compression

force deflection (CFD).

75
Figure 4.9 CFD of flexible foams with different cross-linker content percentages.

When the cross-linker content was higher than 0.5%, the value of CFD for

castor-oil-based foams increased with the increase of cross-linker content while

the value of CFD for petroleum-based foams only increased slightly following the

same trend of density curves (Figure 4.8). Because of the reactive hydroxyl

groups in the diethanolamine, the cross-linker generated hard urea segments

rapidly. As the reactivity of primary hydroxyl groups on the molecular structure of

Voranol 4701 was higher than that of secondary hydroxyl groups in the castor oil,

the influence of cross-linker content on castor-oil-based polyurethane foams was

much more profound than on petroleum-based foams.

76
4.3.2.3 Constant deflection compression

Figure 4.10 demonstrates the influence of cross-linker content on the values

of 50% constant deflection compression tests.

Figure 4.10 50% CDC of flexible foams with different cross-linker content.

As shown, petroleum-based foams had lower values of 50% CDC and

better flexibility than the castor-oil-based foams because Voranol has a lower

hydroxyl number and a longer carbon chains. For each series, the values of 50%

CDC increased with the increase of the cross-linker content. This was because

77
more hard segments were produced from the cross-linker and less soft

polyurethane segments were generated from polyols and isocyanate.

4.3.2.4 Tear resistance

Figure 4.11 represents the influence of cross-linker content on tear

resistance of flexible foams.

Figure 4.11 Tear resistance of flexible foams with different cross-linker content.

The test of tear resistance reflects the strength of the cross-linkage inside

polyurethane foams. Several factors may contribute to the results of tear

resistance tests, such as the degree of cross-linking, the contents of hard and
78
soft segments, and the structure of polyols. In Figure 4.11, the cross-linker

content did not influence the tear resistance of petroleum-based foams.

However, it increased the tear resistance of foams made from castor-oil-based

polyols, similar to the trends shown in Figures 4.8 and 4.9. The results suggest

that the cross-linker content might affect the tear resistance of flexible

polyurethane foams through its influence on cross-linking density.

4.3.2.5 Resilience

Figure 4.12 displays the effect of cross-linker content on resilience of

polyurethane foams.

Figure 4.12 Resilience of flexible foams with different cross-linker content. \

79
 Resilience mainly relies on the properties of soft polyurethane segments in

flexible foams. Due to the disadvantage of the molecular structure of castor oil

polyol, foams containing castor oil performed worse in resilience than foams

made from petroleum based polyol. As shown in Figure 4.12, the effect of cross-

linker content on resilience was not significant.

80
4.3.3 Influence of Isocyanate Index with different castor oil replacements

4.3.3.1 Density

As shown in Figure 4.13, the density of each group of foams decreased with

the increase of isocyanate index.

Figure 4.13 Density of flexible foams with different isocyanate indices.

Since the isocyanate index varied from 50 to 80 or less than 100 in this

study, one may assume that part of the polyols did not react. Although the

81
increase of isocyanate index means more isocyanate was added and the total

weight was increased, the added isocyanate could soon be consumed along with

the rest of the polyols and water to form a larger volume of polyurethane foam.

Compared with the increase of volume, the increase of weight was less

significant. Therefore the increase of isocyanate index from 50 to 80 resulted in a

decrease in foam density.

Additionally, the replacement of petroleum based polyol with castor oil

based polyol contributed to the increase of density. This was because of the high

hydroxyl number and low equivalent weight of castor oil. Therefore, compared

with petroleum-based Voranol 4701, the same amount of castor oil required a

larger amount of isocyanate to reach the same isocyanate index. Also as

discussed above, the reactivity of secondary hydroxyl groups in castor oil was

much lower than that of primary hydroxyl groups in petroleum-based polyols.

During the process of foam blowing, castor oil cannot generate stable

polyurethane matrix to trap carbon dioxide, which led to a smaller volume.

4.3.2.2 Compression force deflection

Figure 4.14 illustrates the effect of isocyanate index on compression force

deflection with different levels of castor oil replacement.

82
Figure 4.14 CFD of flexible foams with different isocyanate indices.

With the increase of isocyanate index, the compression force deflection of

foams increased even though the foam density decreased at the same time

(Figure 4.13). This was because a higher isocyanate index led to a higher cross-

linking density which was beneficial to the increase of compression force

deflection. Since the carbon chains of castor oil were much shorter compared to

the petroleum-based Voranol 4701, the cross-linking density of castor oil was

much higher and the influence of isocyanate index on CFD was much more

significant for castor-oil-based foams.

83
4.3.2.3 Constant deflection compression

Figure 4.15 demonstrates the influence of isocyanate index on 50%

constant deflection compression.

Figure 4.15 50% CDC of flexible foams with different isocyanate indices.

For petroleum-based polyurethane foams, Isocyanate index had no

significant effect on the foam’s CDC value. However, for the foams with 50 and

100% castor oil replacements, the value of CDC increased with the increase of

84
isocyanate index. Especially for foams with 100% castor oil replacement, the

influence of isocyanate index was significant. Fifty percent CDC tests reflected

the flexibility of a polyurethane foams, which depended on the polyurethane soft

segments. Not all ricinoleic acid in castor oil was used after the depletion of

isocyanate. The unreacted ricinoleic acid could form a part of soft segments.

Increasing isocyanate index gradually consumed the unreacted hydroxyl groups

from castor oil to form the cross-linkage structure. Thus, the flexibility of castor-

oil-based foams was less leading to a higher value of 50% CDC. Due to the long

carbon chains in the molecular structure of V4701, such influence was not

present.

4.3.2.4 Tear Resistance

Figure 4.16 displays the positive relationship between tear resistance and

isocyanate index.

85
Figure 4.16 Tear resistance of flexible foams with different isocyanate indices.

As stated above, a higher isocyanate index resulted in a higher degree of

cross-linkage. A larger force was then required to tear the foam into two pieces.

For the same reason, the castor-oil-based foams with higher isocyanate index

contained a denser cross-linking network and had a much higher tear resistance.

4.3.2.5 Resilience

Figure 4.17 shows the relationship between resilience and the isocyanate

index.

86
Figure 4.17 Resilience of flexible foams with different isocyanate indices.

For both petroleum-based foams and foams with 50% castor oil

replacement, the resilience decreased with the increase of the isocyanate index.

Tthe increase of isocyanate index contributed to firmer cross-linking structures

and thus increased the damping effect resulting in a low resilience.

However, foams with 100% castor oil replacement showed the opposite

trend. The value of resilience test rose along with the isocyanate index.

87
According to the 50% CDC results in Figure 4.15, the flexibility of castor-oil-

based foams decreased with the increase of the isocyanate index. Castor oil

based foams with an isocyanate index of 80 could hardly recover after constant

compression in the CDC test. It was not the property of foam resilience to

rebound the iron ball, but the property of foam hardness. Just as when releasing

a ball from above a rigid plate, the harder the plate is, the higher the ball would

rebound. Therefore, in this instance, the ball rebound test did not reflect the

resilience of these foams.

88
4.4 Conclusion

In this study, water-blown flexible polyurethane foams containing 50% and

100% castor oil replacement was prepared. The effect of foaming temperature

was investigated and the “hot-mold cold-cure” method was applied in castor-oil-

based flexible polyurethane foams. The effects of castor oil replacement, cross-

linker content and isocyanate index were studied. Flexible foams with castor oil

replacement had a higher density and higher cross-linking degree. Cross-linkers

were necessary for foams with castor oil replacement to protect the structure

from collapse. However, the cross-linker content also had a negative influence on

density and flexibility. Isocyanate index influenced the density of cross-linking

networks and hardness. Castor oil based foams with a lower isocyanate index

had better flexibility properties, but improvement in the resilience of foams with

100% castor oil replacement needs further investigation.

89
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