CHEM330

Physical chemistry of polymers

Credit hours: 1 h course + 1 h Laboratory

College of Science
Chemistry department

1443H-2022
 Grades
•1rst Midterm Exam :15 points
•2nd Midterm Exam :15 points
* lab: 30 points
*Final Exam :40 points
 References and books
 Ger Challa “Polymer chemistry: an
introduction: Ellis Horwood, 1993

 Polymer Synthesis and Characterization,

Basic laboratory course, Edited by Florian
Paulus, Dirk Steinhilber, Tobias Becherer
2011/2012

 Industrial Polymers, Specialty Polymers, and

Their Applications, 1rt Edition, Manas
Chanda, Salil K. Roy, 2008.
 Course Objectives
1-Definition and classification of polymers
2-Polymers and copolymers Nomenclature
3- Structure and microstructure of polymers
4- Polymerization reactions
5- Techniques of polymerization
6- Techniques used to determine the average
molecular weights
7- Thermal properties of polymers
1. Generalities
1.1Definition and classification of polymers
A polymer is one or several sequences of several molecules of the
same type called “monomeric units” linked by covalent or
coordination bonds.
“All polymers are macromolecules but not all macromolecules are
polymers, because a macromolecule does not necessarily include
repetitive units”
There are two types of polymer, depending on the nature of the monomeric
units.
❑ Homogeneous also called “homopolymer” in which all the monomeric units
are similar

❑ Heterogeneous called “copolymer” in which the monomeric units are different

Examples: Homogeneous polymers

Polyethylene (PE), Poly(methyl methacrylate)(PMMA), poly(dimethyl

siloxane)(PDMS), polystyrene (PS)…

The parenthesis (…): We must put the name of the monomer in

parentheses only if is composed of two or more words
For example:
Polyethylene: “ethylene” is only in one word
Poly(methyl methacrylate): “methyl methacrylate” is composed of two words
methyl and methacrylate

Examples: Heterogeneous polymers

Poly(ethylene-co-terephtalate) (PET), Poly(styrene-co-butadiene)(PSB)
The symbol “co” indicates the two first letters of the word “copolymer” and
indicates that the two units coexist in the same polymer chain.
1.2 Nature of polymer
According to its origin, a polymer can be natural or synthetic
1.2.1 Natural polymers: These polymers are of animal origin such as
Chitosan (shrimp shell), or plant like cellulose, natural rubber
(vegetable plants)

Shrimp Vegetable plants rubber tree

1.2.2 Synthetic polymers:
These polymers are obtained from the polymerization of monomers
containing vinylic, acetylenic, di or more functional active groups and
ring opening monomers containing heteroatoms.

Examples:
▪ Polymerization of vinylic monomers leads to obtain polystyrene,
poly(vinyl chloride), poly(vinyl alcohol)…. etc.
▪ Polymerization of acetylenic monomers leads to obtain
polyacetylene, poly(phenyl acetylene), poly(alkyl acetylene)… etc.
▪ Polymerization of monomers having di functional active groups
leads to obtain poly(ethylene oxide), poly(dimethyl siloxane) oil,
polyester, polyurethane … etc.
▪ Polymerization of monomers having tri functional active groups
leads to obtain poly(dimethyl siloxane) rubber
▪ Polymerization by ring opening of monomers leads to obtain poly
(caprolactone), ethylene oxide… etc.
 Exercises
Exercise1: Which among the following molecules are polymers

Exercise2: Which Among the following polymers, classify the

homogeneous polymers and the heterogeneous polymers
 Answers
Exercise 1
Polymers are:

Exercise 2
Homopolymers are:
 Answers

Exercise 2
Heteropolymers (copolymers)
 Exercises

Exercises 3. Give two examples of natural

vegetal polymer

Exercises 4. Give four examples of natural

animal polymer

Exercises 5. Give three examples of

synthetic polymer
 Answers

Exercise 3.
▪ Amylopectine,
▪ Lignin

Exercise 4.
• Albumin,
• Collagen,
• Gelatin,
• Chondroitin

Exercise 5.
• Poly(methyl methacrylate) (Plexiglass)
• Nylon
• Acid polyacrylic
2. Structure and microstructure
2. 1 Chemical structure and microstructure
A polymer is represented by a structure well defined which is
based on that of the corresponding monomer, but a polymer can
have several microstructures which play a determining role in its
properties.

Chemical structure of polymer

Examples:
Polystyrene its molecule is symbolized by the following structure:

styrene: polystyrene:
❑ Triple bonds such as acethylene and alkylacetylene

nCH≡CH ─ polymerization → -[CH=CH]n-

n R-C≡CH - polymerization → -[C(R)=CH]n-

❑Two or more functional groups such as ethylene glycol

Example:
2. 3 Naming the polymers and copolymers
2.3Naming the polymers and copolymers
 Exercise 1: What is the nomenclature and the structure of the
each polymer synthesized from the following monomers?

A) Acrylononitrile (CH2=CH-CN)
B) Acrylic acid (CH2=CH-COOH
C) Acrylamide (CH2=CH-CO-NH2)
D) Vinylalcohol (CH2=CH-OH)
E) Vinylacetate (CH2=CH-O-CO-CH3)

Exercise 2: What is the nomenclature and the structure of the

each monomer used in the synthesis of the following polymers?

A) poly(methyl methacrylate)
B) Poly(vinylpyridine)
C) Poly(2-hydroxyethylmethacrylate)
D) Poly(ethylene glycol)
E) Poly(vinylnaphtalene)
 CORRECTION 1

A) Nomenclature: Polyacrylonitrile structure: -[CH2-CH(CN)]n-

B) Nomenclature: Poly(acrylic acid) structure: -[CH2-CH(COOH)]n-

C) Nomenclature: Polyacrylamide) structure: -[CH2-CH(CO-NH2)]n-

D) Nomenclature: Poly( vinyl alcohol) structure: -[CH2-CH(OH)]n-

A) Nomenclature: Poly(vinyl acetate) structure: -[CH2-CH(O-CO-CH3)]n-

 CORRECTION 2
A) Nomenclature: methyl methacrylate
Structure: CH2=C(CH3)(COOCH3)
B) Nomenclature: vinylpyridine
Structure: CH2=CH(C5H4N)
C) Nomenclature: 2-hydroxyethylmethacrylate
Structure: CH2=C(CH3)(COO-(CH2)2-OH)]n-
D) Nomenclature: ethylene glycol
Structure: HO-CH2-CH2-OH
E) Nomenclature: vinylnaphtalene
Structure: CH2=CH-C10H8
Inorganic polymer

-[PH – NH]n- Poly(phosphazene)

 2.4 Polymer microstructure (tacticity, cis/trans)

A-Tacticity of Polymers
A polymer can be present three distinct microstructures

1) Isotactic or

2) Syndiotactic

3) Atactic
B- Isomery Cis/Trans

A polyconjugated polymer can be present two microstructures cis

or trans with respect to the double bonds

Example

Microstructure Cis:

Microstructure Trans:
 EXERCISES
Exercise 1
Among the following polymers Indicate those have a tacticity.
-[CH2-CH(COOH)]n-; -[CH2-CH(C6H5)]n-; -[CH2-CH2]n-; -[CH2-
CH2-O-]n-; -[O-C6H4-]n-

Exercise 2
What is the tacticity of the following molecule.

Exercise 3
Write the miscrostructure syndiotactic for the following
molecules. – Poly(vinyl chloride); Poly( sodium acrylate)
 Correction 1

The molecules that have tacticities are:

-[CH2-CH(COOH)]n-; -[CH2-CH(C6H5)]n-

Because these molecules have substituent : in the

first one presence of carboxylic group and in the
second one presence of benzyl group
 Correction 2
The tacticity of this molecule is syndiotactic. Because
the substitutents are distributed alternativement on
both sides of the polymer chain (backbone)
Correction 3
Copolymer structure

A copolymer also called heterogen polymer contains

two or more monomeric units in its chain.
If A and B are its monomer units we can write Its
structure as follow:
 Examples
Nomenclature: The polymerization of ethylene with
vinyl alcohol give a copolymer called poly(ethylene-co-
vinyl alcohol) or copoly(ethylene/vinylalcohol)
Structure: -[CH2-CH2]n-[CH2-CH(OH)]m-

▪ If this copolymer is alternative: poly(ethylene-alt-vinyl

alcohol)
▪ If this copolymer is sequenced: poly(ethylene-block-vinyl
alcohol)
▪ If this copolymer is rundom: poly(ethylene-rand-vinyl
alcohol)
▪ If this copolymer is grafted: poly(ethylene-graf-vinyl
alcohol)
 Exercises

Exercise1: Indicate the name and the formula of a grafted

copolymer prepared from styrene and acrylic acid
Exercise2: Indicate the name and the formula of a block
copolymer prepared from acrylonitrile and acrylamide
Exercise3: Indicate the name and the formula of a grafted
copolymer prepared from acrylonitrile and styrene

Exercise4: Indicate the name and the formula of a random copolymer

prepared from acrylonitrile and styrene

Exercise5: Indicate the name and the formula of a random terpolymer

prepared from acrylonitrile, styrene and methyl methacrylate
Corrections
3. Polymer crystallinity
 3. Polymer crystalline and polymer amorphous
The principle of crystallinity in polymers is different from that of small
molecules. Because a crystalline system in small molecules is
characterized by a well-defined geometry of crystals in the crystal
lattice eg NaCl the crystals have cubic shapes. But in polymers, only
parts of the chain is in orderly condition with other parts of other chains.
In this case the crystallinity in the polymers means that some parts of
the chains are in an certain ordered state as shown in the figure above. A
state is said to be amorphous when the chains are randomly arranged in
the polymer matrix and do not obey any defined order.

The crystallinity of polymers can be compared to hair that is neither smooth

nor crisp. There is no such thing as a 100% crystalline polymer , polymer has
a semi -crystalline structure, the most crystalline does not exceed 80% and
varies according to the nature and the structure and microstructure of the
polymer.
 3.Polymer crystalline and polymer amorphous
The more linear polymer chains, the higher their degrees of crystallinity.

For example the maximum degree of crystallinity (~ 80 %) is found in

polyethylene because polyethylene does not have substituents.

Poly(methylmethacrylate) (PMMA) is amorphous, because this polymer

has bulky substitutents.

Most polymers are amorphous due to the presence of very crowded

substitutes. Most amorphous polymers do not have melting temperatures.
3. Polymer crystalline and polymer amorphous

Properties

A- Amorphous polymers:

1- clear
2- high elongation
3-Non specific melting
temperature
4- low-moderate chemical
resistance
3. Polymer crystalline polymer and polymer amorphous

Properties

B- Semi-crystalline polymers

1- cloudy opaque
2- low elongation
3- specific melting temperature
4- good-to high chemical resistance
3. Polymer crystalline polymer and polymer amorphous

crystalline polymers
1-opaque
2- low elongation
3- specific melting temperature
4- good-to high chemical resistance
5- Strength
6-Higher density
7-Less Soluble
8-Less Permeable
3. Polymer crystalline polymer and polymer amorphous

Factors affected on the crystallinity

Crystalline (rigid, soluble)…… amorphous(Soft, rubbery material)

1- Rate of cooling during solidification

2-monmer complexity
3-side group

4-Copolymerization

*alternating and block can crystallize more easily as compared to

random and graft
3. Polymer crystalline polymer and polymer amorphous

5-Chain flexibility
Ether, imine, double bonds in cis form, C-O and C-N
3. Polymer crystalline polymer and polymer amorphous

6- chine structure
 Linear polymers crystallize relatively easily

 Branches inhibit crystallization,

 Network polymers almost completely amorphous

 Crosslinked polymers can be both crystalline and amorphous

3. Polymer crystalline polymer and polymer amorphous

7- Isomerism
*Isotactic and syndiotactic polymers crystallize relatively easily
*atactic difficult to crystallize
3. Polymer crystalline polymer and polymer amorphous

Measuring Crystallinity

A-Density measurements

B-X-ray diffraction e.g. powder (XRD)

C-Differential scanning calorimeter (DSC)

 4. Polymerization and
copolymerization monomers
Principal polymerization reactions

Polyaddition Polycondensation Ring opening

Vinylic, ethylenic Monomers having Monomers cyclic

and acetylenic two or more
monomers functional groups heteroatomic
 4.1 Polyaddition reactions

Polyadditions

Free radical Ionic Coordination

polymerization polymerization polymerization

Chemical Anionic Ziegler-Natta

polymerization polymerization polymerization

Physical Cationic Metathesis

polymerization polymerization polymerization
4.1.1 Free radical Polymerization

Monomer used: Vinylic monomers having as substituent an

attractor atom or group of atoms such as : CH2=CH-X with X =
Halogene, carboxylic, amine, amide, phenyl, …etc.

Chemical initiator used: Chemical substance capable to generate

free radical such as: peroxide, azoisobutyronitrile (AIBN),
potassium persulfate (KPS)… etc.

Physical initiator used: heat and radiation (UV, Gamma, Alpha,

…etc.)
A-Steps of polymerization

Steps of polymerization

Initiation Propagation Termination

Progression of
Formation of the Maturation of the
chains or chains
active center polymer chains
growth

A-M✽ A-M-M-M-M✽ A-M-M-M-M-M

A-1.Initiators and free radical formation

CN
CN CN 60oC
H3C C N N C CH3 2 H3C C + N2

CH3 CH3 CH3

Azo bis isobutyronitrile
(AIBN)
❑ Initiation ( formation of the active center):
Initiators and free radical formation

If A2 is the chemical initiator and M the monomer

For example:
A2 : diacyl peroxid : C6H5-CO-O-O-CO-C6H5
M: Acid acrylic: CH2=CH-COOH

C6H5-CO-O-O-CO-C6H5 → 2 C6H5-CO-O*

C6H5-CO-O* + CH2=CH-COOH → C6H5-CO-O -CH2-CH*(COOH)

(Active center)
❑Propagation (Chains progression)

(Macroradical formation)

C6H5-CO-O -CH2-CH*(COOH) + n (CH2=CHCOOH)

C6H5-CO-O –[CH2-CH*COOH]n- CH2-CH*COOH

(Macroradical)
❑Termination

This step can be achieved by different reactions

A- Transfer to the impurity according to the following

reactions:

presence of impurity (I) in the reaction mixture

C6H5-CO-O –[CH2-CH*COOH]n- CH2-CH*COOH + I

(Macroradical)

C6H5-CO-O –[CH2-CH*COOH]n- CH2-CHCOOH + I*

I* + m (CH2=CH-COOH) → I-CH2-CH*COOH]n- CH2-CH*COOH

B) Transfer to the solvent (S)

C6H5-CO-O –[CH2-CH*COOH]n- CH2-CH*COOH + S

(Macroradical)

C6H5-CO-O –[CH2-CH*COOH]n- CH2-CHCOOH + S*

(Mature chain)

S* + m (CH2=CH-COOH) → S-CH2-CH*COOH]n- CH2-CH*COOH

(Macroradical)

This termination type can occur in the hologened solvent

such as chloroform.
 C) Transfer to the Monomer (M)

C6H5-CO-O –[CH2-CHCOOH]n- CH2-CH*COOH + M

(Macroradical)

C6H5-CO-O –[CH2-CHCOOH]n- CH2-CHCOOH + M*

(Mature chain)

M* + m (CH2=CH-COOH) → M-CH2-CH*COOH]n- CH2-CH*COOH

D) Termination by combination of two macroradical

C6H5-CO-O –[CH2-CHCOOH]n- CH2-CH*COOH

(Macroradical)
+
C6H5-CO-O –[CH2-CHCOOH]n- CH2-CH*COOH
(Macroradical)

C6H5-CO-O –[CH2-CH*COOH]n- CH2-CHCOOH

C6H5-CO-O –[CH2-CH*COOH]n- CH2-CHCOOH

Usually this type of termination leads to long polymer chains

4.1.2 Anionic polymerization
Initiators: Strong base such as : NaOH, KOH, KNH2,
Carbanion such as Butyl lithium (Li+C4H9-), sodium
ethanolate (NaOC2H5) …etc.

Monomers: vinylic monomers having attractor atoms or group

of atoms and other molecules such as ethylene epoxide.

Vinylic monomers
❑ Initiation ( Active center formation)

Example:
Initiator= KNH2 (Potassium amide)

Monomer = H2C=CH-CN (Acrylonitrile)

❑ Propagation ( Chain growth)

❑ Termination (Chain maturation)

In most cases the termination is achieved by adding small amounts

of mineral acid such as HCl, HNO3, … etc.
 4.1.3 Cationic polymerization

Initiators: Strong acid such as: HCl, H2SO4, HNO3, Carbocation

(Iodate tertiobutylate(CH3)3I), Lewis acids, … etc.

Monomers: Vinyl monomers, epoxide, two conjugated double bonds

❑ Initiation (active center formation)

For example : BF3 as initiator and traces of H2O or ROH as co-initiator
CH2=C(CH3)2 as monomer
❑ Initiation

❑ Propagation (chain growth)

❑ Termination (chain maturation)

In most cases the termination is achieved by adding small amounts
of mineral base
 Factors affecting the rate of ionic polymerization
(anionic and cationic)

A- Effect of the temperature of polymerization

B- Effect of the solvent

C- Effect of the counter ion of the catalyst

D- Effect of the monomer structure

HW1:Compare between ionic and cationic polymerization

 4.1.4 Coordination polymerization

Initiators = complex formed from a catalyst + co-catalyst system

Catalyst: Transition element + halogen ligand

Examples: TiCl4, TiCl3, VCl3, CoCl2, … etc

Co-catalyst: Aluminum chloride (AlCl3), Alkyl Aluminum

Al(Butyl)3, Aluminum chloride (AlCl3)… etc.

Monomers:
All vinylic, ethylenic and acetylenic monomers do not weigh
attracting atoms such as oxygen, nitrogen, sulfur, phosphate.
Monomers with fully carbon aromatic rings polymerize by these
catalysts such as styrene and phenyl acetylene.
Complex formation

❑ Initiation (active center formation)

(Active center)
❑ Propagation ( chain growth)

❑ Termination (Chain maturation)

In most cases the termination is achieved by adding small
amounts of mineral base of minral acid
 Polyaddition/Exercises

Exercise 1: Among the following initiators, which of them can

polymerize acrylic acid through radical polymerization route.
NaOH; HCl; AlCl4; Ph-CO-O-CO-Ph; Et-ONa; TiCl4
Exercise 2: Among the following initiators, which of them can
polymerize acrylic acid through anionic polymerization route.

NaOH; HCl; AlCl4; Ph-CO-O-CO-Ph; Et-ONa; TiCl4

Exercise3: Among the following initiators, which of them can
polymerize acrylic acid through cationic polymerization
route.
NaOH; HCl; AlCl4; Ph-CO-O-CO-Ph; Et-ONa; TiCl4
Exercise 4: Among the following initiators, which of them can
polymerize propylene through coordination polymerization
(Ziegler-Natta) route.
NaOH; HCl; AlCl4; Ph-CO-O-CO-Ph; Et-ONa; TiCl4; TiCl4/AlCl3;
NaCl/AlCl3; Et-Na/AlCl4
 Polyaddition/Exercises
Exercise5: Among the following monomers indicate which of
them can be polymerized through a radical polymerization
way?

Exercise6: Among the following monomers indicate which of

them can be polymerized through a anionic polymerization
way?
 Polyaddition/Exercises

Exercise 9. In general, the increase in the

temperature of the polymerization leads to:
A) Increase the polymerization rate
B) decrease the polymerization rate
C) Increase the molecular weight of resulted polymer
C) decrease the molecular weight of resulted polymer
D) Increase the yield of polymerization
E) decrease the yield of polymerization
 Polyaddition/Exercises

Exercise 10- What is the effect of polar solvent

on the polymerization of styrene
Exercise 11- What is the effect of non-polar
solvent on the polymerization of acrylic acid
Exercise 12- What is the effect of the contre ion
on the cationic polymerization of styrene
Exercise 13- What is the effect of the monomer
structure on the polymerization of styrene
 Polyaddition/Exercises
Exercise7: Among the following monomers indicate which of
them can be polymerized through a ziegler-Natta (coordination)
polymerization way?

Exercise8: Among the following monomers indicate which of them

can be polymerized through a cationic polymerization way?
 4.2 Ring Opening Polymerization

Ring Opening Polymerization can be realized by anionic

or cationic catalysts

Anionic catalysts:
Exemples: Sodium ethanolate; sodium amide; NaOH;
carbanion.
Monomers:
Examples: Cycle heteroatomic such as: ethylene
epoxide, caprolacton, valerolactone.
 Cationic catalysts: Terbutyl iodate [(CH3)3I]
Monomer: ethylene glycol
❑ Initiation

❑ Propagation

❑ Termination
Living polymer
Cationic catalyst:
H2SO4
Monomer: ℇ-caprolactone

❑ Initiation

❑ Propagation

❑ Termination: leads to living polymers

 Exercise 1: Write a ring polymerization of L-lactide

Exercise 2: Write the structure of the monomer that used to obtain

the following polymer
 4.3. Polycondensation reaction

Monomers: Molecules having two or more functional

active groups.

Homogen such as:

Ethylene glycol (HO-(CH2)2-OH); dicarboxylic acid
(HOOC-(CH2)n-COOH; dialkylamine (H2N-(CH2)n-NH2)

Heterogen such as: HO-(CH2)2-COOH; HO-(CH2)n-NH2;

HCO2-(CH2)n-NH2

Catalysts:
Strong acid: H2SO4; HCl; HNO3
Strong base: NaOH, NaOC2H5; NH2Na,
 4.3 Polycondensation/Reactions

Step-growth Polymerization): Polymerization of monomers containing two

functional groups propagates from both of the advancing chain to give a linear
polymer and elimination of small molecules such as water, HCl...
On the other hand, the monomers containing three or four functional groups
propagates on the three or four ends of the chain in progression giving a
crosslinked polymer with elimination of small molecules such as water or HCl.

Example of linear polymer:

HO O
n HO R OH + n C R' C H O R O C R' C OH + (2n+1) H2O
O OH n
O O
O
n HO R'' C H O R'' C OH + (n-1) H2O
OH O n

Produces Linear and Cross linked Polymers

Thermoplastic Thermoset
Example of polycondensation leading to a crosslinked polymer

Monomer: methyltriolsiloxane

Catalyst: H2SO4

(Silicone rubber) (PDMS)

 4.3 Polycondensation /properties

Kevlar

Properties
very strong material
used for reinforcing car tyres
Used to make ropes
20 times as strong as steel ropes of the same weight
Used for making reinforced aircraft wings and bullet-proof vests
 4.2 Polycondensation/properties

Dacron
is the DuPont trade mark for the polyester, Polyethylene
terephthalate
(PET, PETE, PETP) Sometimes called Terylene

Polymer chains are held together by strong dipole-dipole

interaction.
 4.3 Polycondensation/properties

Dacron

Strong
Tough
Smooth
Resistant to water and chemicals
4.4. Copolymerization of vinylic monomers and
reactivity ratio

The polymerization reaction of vinyl monomers proceeds

exactly like the homopolymerization of a monomer but it
involves two or more different monomers.

Among the interests of copolymerization reaction

are:
1- to improve the properties of a polymer
2- to obtain the properties of two or more
homopolymers in one
3- to obtains new properties in the resulted hybrid
polymer
4.4.1 Copolymerization reaction
Example:

Acrylic acid + styrene → poly(acrylic acid-co-styrene)

In a general way: nA + mB → poly(A-co-B)

In the copolymerization reaction not all A monomers always react with
B monomers. This depends on the reactivity of each monomer with
respect to the other.

For example: if we start from a mixture containing 50 mol% of A and

50 mol % of B, this does not necessarily give a copolymer containing 50
of A and 50 of B.

To have an idea of the composition of the copolymer resulting from a

copolymerization reaction between two monomers A and B, it is then
necessary to know the reactivity ratio of these two monomeric
entities.
4.4.2 Reactivity ratio
The reactivity ratio is determined from the kinetic
reactions of A and B during the copolymerization reaction
The kinetics of copolymerization of monomer A with B in the
presence of the initiator radical Am✽ are written as follows:

kAA
A → Am-A-A✽

Am✽ + A → Am-A✽
kAB
B → Am-A-B✽
kBA
A → Am-B-A✽

Am✽ + B → Am-B✽
kBB
B → Am-B-B✽
In this case two kinetics reactions can be generated:

𝑑𝐴
= kAA(Am-A✽)(A) + kAB(Am-A✽)(B)
𝑑𝑡

𝑑𝐵
= kBB(Am-B✽)(B) + kBA(Am-B✽)(A)
𝑑𝑡

Dividing the first equation by the second

𝑑𝐴 𝑘𝐴𝐴 𝐴𝑚 − 𝐴∗ 𝐴 + 𝑘𝐴𝐵 𝐴𝑚 − 𝐴∗ 𝐵
=
𝑑𝐵 𝐾𝐵𝐵 𝐴𝑚 − 𝐵∗ 𝐵 + 𝑘𝐵𝐴 𝐴𝑚 − 𝐵∗ 𝐴

𝑘𝐴𝐴 𝐾𝐵𝐵
By replacing by RA, by RB , the mole fraction of A in the feed
𝑘𝐴𝐵 𝐾𝐵𝐴
𝐴 𝐝𝐀
by fA and the mole fraction of A in the copolymer by FA
𝐴+𝐵 𝐝 𝐀 +𝐝 𝐁
fA + fB =1 and FA+FB=1
The reactivity ratio equation

𝑑𝐴 𝑘𝐴𝐴 𝐴𝑚 − 𝐴∗ 𝐴 + 𝑘𝐴𝐵 𝐴𝑚 − 𝐴∗ 𝐵
=
𝑑𝐵 𝐾𝐵𝐵 𝐴𝑚 − 𝐵 ∗ 𝐵 + 𝑘𝐵𝐴 𝐴𝑚 − 𝐵 ∗ 𝐴

can be written as follows:

𝑅𝐴 × 𝑓𝐴2 + 𝑓𝐴 𝑓𝐵
𝐹𝐴 =
𝑅𝐴 𝑓𝐴2 + 2𝑓𝐴 𝑓𝐵 + 𝑅𝐵 𝑓𝐵2

5 cases can arise:

If RA ~ RB > 1 → Block copolymer

If RA ~ RB = 1 → Random copolymer
If RA = RB = 0 → Alternating copolymer
If RA ~ RB >> 1 → Mixture of two homopolymers

If RA < 1 and RB < 1 → Azeotrope system ( feed composition =

copolymer composition)
From this equation, knowing the reactivity ratios RA and RB, we can
evaluate the composition of co-monomers in the copolymer.

In general the reactivation ratios are given in the tables.

For examples

Monomer A Monomer B RA RB
Styrene Butadiene 1.0 1.0
Styrene Vinyl acetate 0.55 0.35
butadiene Methyl methacrylate 0.98 1.05
Acrylonitrile Butadiene 0.02 0.05
Vinyl acetate Methylacrylate 0.71 0. 34
Vinyl chloride Vinylidene chloride 2. 30 3.56
Exercises

Exercise 1. Using the data of the previous table indicate

the dstribution in co-comonomers in poly(Styrene-co-
butadiene).

Exercise 2. Using the data of the previous table indicate

the dstribution in co-comonomers in poly(Sthyrene-co-vinyl
acetate).

Exercise 3. Using the data of the previous table indicate

the dstribution in co-comonomers in poly( Butadiene-co-
methyl methacrylate).
Exercise 4. Using the data of the previous table indicate the
dstribution in co-comonomers in poly( Acrylonitrile-co-butadiene).
Exercise 5. Using the data of the previous table indicate the
dstribution in co-comonomers in poly( Vinyl acetate-co-methyl
acrylate).
Exercise 6. Using the data of the previous table indicate the
dstribution in co-comonomers in poly( Vinyl chloride-co- vinylidene
chloride).
Corrections

Answer 1. Randum copolymer

Answer 2. Azeotropic system

Answer 3. Randum copolymer

Answer 4. Alternating copolymer

Answer 5. Azeotropic system

Answer 6. Block copolymer
5. Polymerization techniques
There are 6 ways to polymerize a monomer

1. Bulk polymerization
2. Polymerization in solution
3. Polymerization by precipitation
4. Polymerization in suspension
5. Polymerization in emulsion
6. Polymerization in Interface
5.1 Bulk polymerization

*need initiator and monomer only

*do not require a solvent, so the monomer must be in a liquid
state, such as styrene

The polymer resulted is pure dissolved in the residual

monomer (non reacted). The polymer is isolation by
precipitation or by solvent evaporation.
 5.2 Polymerization in Solution
*This polymerization requires the presence of a solvent that dissolves
the monomer, initiator, and the resulting polymer.
*The resulting polymer is obtained by precipitating in non solvent or
by solvent evaporation.
Advantages/desadvantages
Advantages
*easy way
*don't need complicated devices
*High yield and molecular mass
Desadvantages
*None economic( need solvent)
 5.3 Polymerization by precipitation
*This polymerization requires the presence of a solvent
that dissolves the monomer and initiator but the resulting
polymer does not dissolve and is therefore easy to
remove.
Advantages/desadvantages
Advantages
* Easy way
* Obtaining low molecular mass
* Don't need complicated devices
Desadvantages
None economic (need solvent)
 7.4 Polymerization in suspension
- This process need monomer, initiator and water
Initiator must be soluble in monomer, however both are
insoluble in water.
-Initiator dissolved in monomer is in the form of a droplet in
suspended in water.
-The resulting polymer is solid and insoluble in water.
5.4 Polymerization in suspension
Advantages/desadvantages
Advantages
1- The presence of water, which leads to the absorption of heat
2- The size of the polymer particles can be controlled by the suspension
factor
Desadvantages
The resulting polymer is impure due to the presence of a suspension
agent and is therefore not used in food applications
 5.4 Polymerization in emulsion

This process needs monomer, initiator, water and surfactant

(soap)
There are two types of emulsion : microemulsion rich in water
(W/O) and emulsion rich in organic (O/W).

Conditions:
-This process only applies when the monomer is organic
insoluble in water.
- The emulsion must be rich in water (W/O).

Micelles formation
In this case, the monomer and initiator will be surrounded by water
molecules. The polymerization reaction will take place in the center of
the micelle and when the polymer reaches maturity it precipitates
immediately by difference in density (polymer / water).
 5.4 Polymerization in interface

This process needs two monomers and water

*Two monomers, one soluble in an organic solvent and the other in water
*The polymer is formed at the interface
Such as nylon 6.6
6. Determination of molecular wights of
polymers and copolymers
 6. 1 Notion of molecular weight in the polymers (statistical calculation)

In a same polymer, the chains do not have the same lengths (the same
masses) and this comes from the step of termination , in particular the
transfer reactions. For this reason we use the term " average molecular
mass" noted M X

, so there is a distribution of molecular weights. There are several ways

based on statistical formula used to define an average molecular
weight.
6.1Polydispersity index
Importance of the molecular weight in the polymer

 1- increase tensile strength

 2- increase viscosity
 3- increase chemical resistance
 4- increase impact resistance
 5- increase strength
 6- decrease elongation
 7- decrease creep
 8-decrease melt flow
 Exercises
Exercise 1: A polymer sample contains 9 moles of chains have
molecular of 30,000 g/mol and 5 moles of chains have molecular weight
of 50,000 g/mol. calculate

Exercise 2: A polymer sample contains 105 moles of chains have

molecular weight 104 g/mol and 106 moles of chains have molecular
weight 103 g/mol. Calculate the viscosimetric average molecular weight.
given that a = 1.34.

Exercise 3: A polymer sample, synthesized by radical polymerization

route, contains 105 moles of chains with molecular weight 104 g/mol and
106 moles of chains with molecular weight 103 g/mol. Calculate the
number average molecular weight , the weight average molecular weight
and the polydispersity index. What do you think about the distribution of
molecular weight of this sample ( polydisperse or monodisperse).
Exercise 4: A sample of polystyrene has the following information:
2 chain (DP= 1000), 3 chain (DP= 100), 6 chain (DP = 20) and 7 chain (
DP= 40), Calculate
 Exercises/Solutions

Exercise 1:


M i Ni
(9  30,000) + (5  50,000)
M n = i =1

= = 37,000 g/mol
(9 + 5)
N i =1
i

9(30,000) 2 + 5(50,000) 2
Mw = = 40,000 g/mol
9(30,000) + 5(50,000)

9(30,000)3 + 5(50,000)3
Mz = = 42,136 g/mol
9(30,000) + 5(50,000)
2 2
6. 2 Experimental methods used to determine the molecular
masses of polymers
6. 2.1 Determination of molecular weight by freezing point
depression
This method is used when the polymeric solution is infinitely
diluted according to the Raoult’s Law and only for polymers
having low molecular mass
∆𝑻𝒇 𝑹𝑻𝟐
= + 𝑨𝟐 C
𝑪 𝝆×∆𝑯𝒇 ×𝑴𝒏

∆Tf : freezing-point depression,

C : the concentration
R : gas constant
T : freezing point
∆Hf: the latent heats of fusion
A2 is called second coficient of Virial and measures the
interaction between polymer and solvent.
6. 2.2 Determination of molecular weight by boiling point elevation

This method is used when the polymeric solution is infinitely

diluted according to the Raoult’s Law and only for polymers having
low molecular mass

∆𝑻𝒃 𝑹𝑻𝟐
= + 𝑨𝟐 C
𝑪 𝝆×∆𝑯𝒗 ×𝑴𝒏

∆Tb : Boiling point depression,

C : the concentration
R : gas constant
T : freezing point
∆Hv: vaporization heats
A2 is called second coficient of Virial and measures the
interaction between polymer and solvent.
6. 2.3 Determination of molecular weight by Osmometry method
This method is used when the polymeric solution is infinitely
diluted according to the Raoult’s Law and only for polymers having
low molecular mass

According to van't Hoff equation

Example: calculation of molecular mass by osmometry method

The osmotic pressures of solutions of poly(vinylchloride), PVC, in

cyclohexanone at 298K are given below. The pressures are expressed in
terms of the heights of solution (of mass density ῥ = 0.980 g.cm-3) in balance
with the osmotic pressure. The concentration of this polymeric solution is 1.0
g/dm3 and the height of the solution in the capillary tube is 0.21 cm. If the
concentration of the polymeric solution is considered as infinitely diluted
Determine the molar mass of the polymer.

RT 1
M= 
  g 0.21cmg −1dm3

(8.3145 JK −1mol −1 )
= 1.2 10 2 kg.mol −1
298 K
M= 
(980 kgm −1 )  (9.81ms −2 ) 2.110 −3 m 4 kg −1

M = 1200000 g/mol = 1.2 106 g/mol

6.2.4. Determination of molecular weights of polymers by Light
scattering method
This method is used to determine any molecular weights,
but very sensitive to solid impurities. the solution must be
clean and filtered carefully.

Precautions
1- The polymer solution should be completely free of impurities
2- There should be a difference between the refractive index of the
solvent and the polymer

Rayleigh Equation:
Ʈ= turbidity
C : concentration
no: refractive index of the solvent
λ : wavelength of the incident light
No : Avogadro's number
dn/dc : specific refractive increment
P( ) : function of the angle,θ
A2 : second virial coefficient
 6.2.5 Determination of molecular weights of polymers by
viscosimetry method
This technique is very sensitive to solid impurities. Any solid imurity in the
capillary tube reduces the flow rate. Therefore prepared solution must be devoid
of any solid impurities. Filtration of the solution is necessary.

Ubbelohde viscosimetry
tube
6.2.6 Determination of molecular weights of polymers by
viscosimetry method

Example: What is the average molecular weight of polystyrene is its intrinsic

viscosity is 1.42 g/dm3 and the constants “a” and “k” are 0.88 and 1.5 10-3,
respectively.
6.2.7 Determination of molecular weights of polymers by size
exclusion Chromatography (SEC)
This technique is also called gel permeation chromatography (GPC)

HW2:What is the difference between separating organic materials

and polymers by column chromatography?
Determination of average molecular weight by size exclusion
chromatography (SEC) or gel permeation chromatography (GPC)

Example: Determine the average molecular weight of poly(methyl methacrylate)

by SEC technique. Given that the retention volume (Vm) is 15 mL and the
standard polystyrene has an average molecular weight equal to 105 g/mol gives a
retention volume of 14.32 mL.

Solution:

The molecular mass of a polymer is inversely proportional to its volume of

retention
7. Degree of polymerization
 Dp

Example:
If the molecular mass of a polytetrafluoroethylene is
120,000 g/mol and the molar mass of its monomer is 100
g/mol its degree of polymerization is:
120,000/100 = 1200 units
 EXERCISES
Exercise 1: Calculate the degree of polymerization of
nylon 6,6 if the mass of its repeated unit is: 226.32
g/mol.
and the molecular mass of this polymer is 23,000 g/mol
Exercise 2: Calculate the average molecular weight of
a poly(dimethylsiloxane) if the molar mass of its
monomer is 74 g/mol and the polymerization degree
is 2367.
Exercise 3: What is the molar mass of the monomer
used to obtain a polymer with an average molar
mass of 105 g/mol and a polymerization degree of 232.
 Correction1

With a molar mass of polymer= 23,000 g/mol

And molar mass of monomer = 226.32 g/mol
Correction 2
Correction 3
 Degree of polymerization

High degree of polymerization are known as

polymers having high number of monomeric units
,while those having comparatively low degree of
polymerization (low number of monomeric units)
are known as oligomers (Dimers, trimers, and
tetramers ( several thousands.
Examples:
Dimers: -[O-CH2-CH2]2- ; -[CH2-CH-Cl]2-; -[Si(CH3)2O]2-
Polymerization degree is 2 ( polymer having 2 monomeric units)
Trimers: -[O-CH2-CH2]3- ; -[CH2-CH-Cl]3-; -[Si(CH3)2O]3-
Polymerization degree is 3 ( polymer having 3 monomeric units)
Tetramers: -[O-CH2-CH2]4- ; -[CH2-CH-Cl]4-; -[Si(CH3)2O]4-
Polymerization degree is 4 ( polymer having 4 monomeric units)
Suplementary informations on the polymers
8. Thermal properties of polymers
The thermal properties of polymers are different from those of small
molecules. Polymers have neither vaporization temperature nor heat
of vaporization as in the case of small organic molecules. Sometimes
do not have fusion nor crystallization temperature as in the case of
poly(vinyl chloride) because this polymer burns before its fusion.

By heating the small molecules, their state changes from

fusion towards vaporization and this transition is called
“First order transition”

By heating the polymers, their state changes from the

solid state called “glassy state” to the soft state and
this transition is called the “second order transition”.
8.1 Glass transition temperature (Tg)

The glass transition temperature in the polymer is the limit

temperature called “Tg” localized between its glass state
and its soft state.
When the chains of the polymer absorb a certain energy (second
transition energy) the chains begin to slide against each other due to
the breaking of certain physical bonds such as van der Waals,
hydrogen bond, newton etc.

8.2 Melting temperature (Tm)

When the chains of the polymer absorb a certain energy (first
transition energy) all the chains slide against each other due to
the breaking of physical bonds such as van der Waals,
hydrogen bond, newton etc.
8.3 Crystallization temperature Tc
During the cooling of the polymer from the fusion state to a certain
temperature called crystallization temperature the polymer releases
the energy which it absorbed during the fusion causing the
immobility of the chains due to the development of the interchain
forces again.
8.4 Temperature of degradation Td
At temperatures higher than that of fusion, the polymer degrades
according to a radical mechanism. The products that generate the
degradation are:
1- Radical reactions between related chains giving cross-linking
polymer.
2- Radical reactions accompanied by chain scission resulting in the
formation of chain fragments.
3- Elimination reactions leading to the evaporation of small molecules
such as H2O, CO2, ethylene, benzene, etc.
4- Sometimes among the products of thermal decomposition of the
polymer we find the regeneration of the monomer.
8.5 Transition phenomenon

Structure- thermal properties relationship

Factors affecting Tg
There are 7 factors affect on Tg value

1-chain flexibility
2- interchain attractive forces
3- side group
4- Cross linking
5-crystallinity
6- plasctization
7- molecular weight
 1-chain flexibility
1- Long chain aliphatic
2- Ether and ester linkage

Flexibility Tg

2- interchain attractive forces

With increasing increases Tg Tg of PVC (87) > Tg of PE (-120)

3- side group
With increasing size of side group increases Tg

Tg of PS (100) > PE (-120)

4-Crosslinking

Crosslinking leads to increasing of Tg (HW such as)

5- Crystallinity

With increasing crystallinity % decrease Tg

 6- Plasctization

Decrease Tg

7- Molecular weight

Increase Tg

Tg of PP (0) > Tg of PE (-120)

8.6 Determination of the thermal parameters
There are different techniques used to determine the
differents thermal parameters.

1- The differential scanning calorimetry (DSC)

2- The thermogravimetry analysis (TGA)
3- The inverse gas chromatography (IGC)

4- The thermal dynamic mechanical Analysis (TDMA)

We mention in this program only the most commonly techniques used

such as the DSC and theTGA.
1- DSC Analysis
This technique is based on the measurement of the heat released
or absorbed by the polymer during its heating. Since the heat
capacity (Cp (glass)) of the glass state is different from that of the
soft state (Cp(solft)), during the transition from one state to
another the materials keep the temperature constant. during this
time they absorb or release energy called transition energy.
Before the glass transition the heating enthalpy is:
∆H1 = Cp(glass)(Tg-T1)

After the glass transition the heating enthalpy is:

∆H2 = Cp(soft)(T2-Tg)

During the glass transition the enthalpy absorbed is the latent

heat of glass transition (Lg) and during fusion the enthalpy
absorbed is the latent heat of fusion (Lf). These two
parameters are practically independent of temperature.

The total heat (∆HT ) required to heat the polymer from start
to finish is equal to:

∆HT = Cp(glass)(Tg-T1) + Lg +Cp(soft)(T2-Tg) + Lf

The variation of the heating enthalpy as a function of temperature is

represented by as following curbe called “DSC thermogram”:
 DSC Thermogram (Heating mode)

Heat Flow
Exothermic Heating

ΔH(Glass) ΔH(Soft)

Tg
Lg

Tm
Endothermic Lf

-20 0 20 40 60 80 100
Temperature (OC)
During the cooling, the polymer passes from the liquid state where
it is at high temperature through the crystalline state, then through
the soft state and finally it will end up in the glass state (solid).

During this step, the polymer first releases the heat that was
absorbed during fusion which is called the heat of crystallization
(ΔH (crystallization) then the soft state and puts back the heat of
the glass transition to pass to the glass state as shown in the DSC
diagram below. Noting in this case all energy are exothermic.
Thermogram DSC ( Cooling mode)

Heat flow
Cooling
Exothermic Tc

ΔH(Soft)

ΔH(Glass)

Lg Lc

Endothermic

-20 0 20 40 60 80 100
Temperature (OC)
2-Thermogravimetry Analysis (TGA)

This technique measures the weight loss of the polymer

sample during the period of its thermal degradation using a
microbalance incorporated into the analysis system.

This analysis generates a curve indicating the weight loss of

the polymer sample versus temperature called “TGA
thermogram”.

The first break in this thermogram indicates the limit of the

thermal stability of the polymer. In the Figure, different TGA
thermograms attributed to the degradation of poly(vinyl
chloride) (PVC), poly(methyl methacrylate) (PMMA), low
density polyethylene (LDPE), poly(ethylene terephthalate)
(PTFE) and polyisoprene (PI).
These thermograms shows the thermal stability (TS) of each
polymer. TS(PVC) = 220 oC; TS(PMMA) = 260oC; TS(LDPE)=
340oC; TS(PTFE) = 450 oC and TS(PI) = 520oC.
 9-Solubility of polymer

Solution(solvent +polymer)

types of solvents:
1- good solvent

2- bad solvent

3- Edge solvent(theta solvent)

The factors affecting on the solubility of polymers

1- polarity 2- Mwt Solubility

3- Cross linking S 4- Crystalinity