Subject Code: CH301 Course Title: Polymeric Materials

Objective of the Course: To impart knowledge of polymerization processes and

properties of polymer
 Polymeric Materials: CH 301
What we learn in this course
Polymer Synthesis Structure Properties

How can I make What are its molecular

polymeric materials? or macromolecular
structure? What are its
properties?

How can I change

the chemistry or What aspects of the
structure to affect chemistry and
the properties in a structure affect the
desirable way properties
 Polymeric Materials: CH 301: Syllabus
S. No. Contents Contact Hours
1 General introduction to polymer structure: Classification, monomer and 9
functionality, polymerization and degree of polymerization, Classification of
polymerization mechanism, step polymerization, radical chain (addition)
polymerization,
2 Coordination polymerization, ring opening polymerization, Copolymer and their 8
types, methods of copolymerization, techniques of polymerization: Bulk, Solution,
Suspension & Emulsion, Industrial methods of polymerization
3 Polymer molecular weight, and its distribution, method of determination of 8
different molecular weights, Polymer Structure analysis, configuration,
conformation of polymers, structure, and properties of amorphous, semi crystalline,
and cross-linked polymers
4 Thermal properties of polymers, concept of glass transition temperature, melting 9
and softening temperature, thermal analysis of polymers by TGA, DSC, DMTA.
Polymer Crystallization and Methods of determination of crystallinity. Viscoelastic
properties of Polymer, creep, stress relaxation, mechanical models
5 Mechanical properties of polymers strength (creep, fatigue, stress relaxation tensile, 8
flexural and compressive), hardness, resilience, impact properties, factors affecting
these properties, methods of determination of these properties. Electrical and
Optical properties of polymers
 Polymeric Materials: CH 301: Syllabus
Books

Rs.450/- Rs. 2010/- Rs. 3720/-

 Polymeric Materials
Course Outcomes (CO)
CO-1 Identify monomer and its functionality, polymerization mechanism and type
of polymers.

CO-2 Design and develop polymers and copolymers using various polymerization
techniques

CO-3 Describe the need of average molecular weights for polymers and identify the
molecular weight by different techniques.

CO-4 Understand the structure and properties correlation for thermal, viscoelastic,
mechanical, electrical, and optical properties of polymer.

CO-5 Analyze the thermal, viscoelastic, mechanical, electrical and optical properties of
polymers with modern testing equipments.
 Assessment Plan
CWS (15) PRS (25) MTE (20) ETE (40)
Unit-1 Unit-1
Class Work (10) Practical File: 15
Unit-2 Unit-2 10
(Continuous (Continuous
Assessment) Assessment) Unit-3 Unit-3
Unit-4
Assignment (5) Practical Exam:10 30
Unit-5
 Evolution of Polymeric Materials
Macromolecules: Available in nature: Cotton, Wool, Silk, DNA, Protein, Carbohydrate,
natural rubber

replacement of
manufactured Polymers conventional materials with
improved or cheaper
substitutes

Transition from entirely natural materials to either substitutes or modified macromolecules

Synthetic polymers: raw materials: coal or oil

 Evolution of Polymeric Materials

Billiard Ball made out Ivory from elephant tusks

John Wesley Hyatt patented the Billiard Ball in

1865 coated with nitrocellulose

In 1889, Eastman Kodak used nitrocellulose

to formulate a flexible film. This film was
used mostly for x-rays. Celluloids: closed
1933.
 Evolution of Polymeric Materials
Bakelite –invented by Leo Baekeland (1909), which is the first
example of a truly synthetic polymer

Bakelite, formed from the condensation

reaction of phenol with formaldehyde

Nylons were developed in the 1930s by a research

team headed by an American chemist, Wallace H.
Carothers, working for E.I. du Pont de Nemours &
Company.
 Scientific Understanding towards Polymers
People used to think that polymer materials were actually colloids – they described the
material properties they observed by saying that there were “lots of small molecules
that were interacting strongly with each other

Hermann Staudinger was the first to suggest in 1920 that

a polymer is actually a very large molecule, a
macromolecule, where the atoms in the molecule were
held together by covalent bonds.

It took over a decade for Staudinger’s ideas to fully catch on, and he received the Nobel
Prize for his contributions in 1953.
 Scientific Understanding towards Polymers

The Nobel Prize in Chemistry 1963 was awarded jointly

to Karl Ziegler and Giulio Natta "for their discoveries in
the field of the chemistry and technology of high
polymers

Professor Paul John Flory received the 1974 Nobel Prize in

Chemistry "for his fundamental achievements, both
theoretical and experimental, in the physical chemistry of
the macromolecules."
Paul John Flory
 Scientific Understanding towards Polymers

The Nobel Prize in Chemistry 2000 was awarded

jointly to Alan J. Heeger, Alan G. MacDiarmid
and Hideki Shirakawa "for the discovery and
development of conductive polymers".
 Few Recent Research Topics
✓ Self-healable functional polymers

✓ Polymer-based triboelectric nanogenerators

✓ Polymers for Organic Photovoltaics: Solar Cells and Photodetectors

✓ Polymers for flexible energy storage devices

✓ Design and synthesis of biodegradable polymer

✓ Biobased polymers

✓ Recycling of polymers
 Unit-1

General introduction to polymer structure: Classification, monomer and

functionality, polymerization and degree of polymerization, Classification of
polymerization mechanism, stepwise polymerization, radical chain (addition)
polymerization

✓ Textbook of Polymer Science/ F.W. Billmeyer/ John Wiley

✓ Polymer Science/ V.R. Gowarikar/ New Age International
✓ Polymer Science and Technology/ P Ghosh/McGraw Hill
✓ Principle of Polymerization/ G Odian/ Wiley
 Introduction
Big molecule or macromolecule made up of small molecules
Poly (many) mer (part)

Example:
Repeating unit
Ethylene + ethylene molecules

(4000 to 5000)

Gas Solid

The small molecules , which combine to form a big molecule, can be of one or more
chemical compound
Introduction
 Classification of Polymers (Based on source)
Natural Synthetic Regenerated

Isolated from Synthesized from low Modification and

natural material molecular weight regenerated with
compounds natural polymers
Cotton (cellulose) Polyvinyl chloride (PVC) Nitrocellulose
Natural rubber Polymethyl methacrylate Cellulose acetate

PVC
Cellobiose

Polyisoprene
 Classification of Polymers (Based on backbone structure)
Organic Polymer Inorganic Polymer
Made by carbon atoms No carbon atom contain in chain backbone

PVC

Polymethyl siloxane
 Classification of Polymers
(Based on Chain Structure)

Linear Branched Crosslinked

If the monomers are linked the monomers are Formed when the
together in a linear manner, joined together in a monomer units are linked
the resulting structure is branched manner in multiple chains and
called a linear polymer have interconnections
between chains.
Classification of Polymers
(Based on Chain Structure)

Branched Polymers
Classification of Polymers
(Based on Chain Structure)
Crosslinked Polymers

IPN structures
 Classification of Polymers
(based on mechanical properties, physical form and applications)

Plastics Elastomers Fibers Liquid resins

Classification of Polymers (based on mechanical properties)
Plastics Fibers Elastomers
 Classification of Polymers (action on heat)

Thermoplastic Thermosetting
Polymer, that soften on heating and stiffer Polymers that become an infusible and
on cooling are known as “Thermoplastic” insoluble mass on heating are known as
“Thermosetting”
Classification of Polymers (action on heat)

Heat

Degradation
 Basic Terminology
Degree of Polymerization
Defined as the number of monomer units in the polymer.
Calculated as the ratio of molecular weight of a polymer and molecular weight of the
repeat unit.
𝑴𝒂𝒔𝒔 𝒐𝒇 𝑷𝒐𝒍𝒚𝒎𝒆𝒓 (𝑴)
Degree of Polymerization (𝐃𝐏, 𝑿𝒏)=
𝑴𝒂𝒔𝒔 𝒐𝒇 𝒎𝒐𝒏𝒐𝒎𝒆𝒓𝒊𝒄 𝒖𝒏𝒊𝒕(𝒎)

Example:1 Calculate the degree of polymerization of a sample of polyethylene [ (CH2-

CH2)n], which has a molecular weight of 150,000 g/mol.
Answer: The molecular weight of a repeating unit, m= (12 x 2 + 1 x 4) g/ mol = 28 g/mol

𝟏𝟓𝟎𝟎𝟎𝟎 𝒈𝒎/𝒎𝒐𝒍
Dp or Xn= = approx. 5357
𝟐𝟖 𝒈𝒎/𝒎𝒐𝒍
 Example-2
What is the degree of polymerization (DP) of each of the following polymers with
molecular weight 254,000 g/mol?

Mass of repeating
C6H11O1N1
a unit = 113 g/mol

Dp= 2247.78
Nylon 6

b C10H8O4

Mass of repeating
Polyethylene terephthalate unit = 192 g/mol

Dp=1322.91
 Class Work
Q-1: What is the degree of polymerization (DP) of each of the following polymers
with molecular weight 254,000 g/mol?

C2H2Cl2 Mass of repeating

C Dp= 2645.83
unit = 96 g/mol

Polyvinylidene Chloride

C16H14O3
d
Mass of repeating unit = 254 g/mol

Dp=1000
Polycarbonate
 Introduction to Polymer Structure
Functionality of a Monomer
The number of bonding sites (or) reactive sites or functional groups present in the
molecule.
A bifunctional monomer, i.e., monomer with functionality two, can link to two other
molecules under suitable polymerization conditions

Examples:
The double bond in vinyl monomers (CH2 = CHX) can be considered as a site for two free
valences

When the double bond is broken, two single bonds become available for combination

Bifunctional monomers form linear chain structure

 Introduction to Polymer Structure
Monomers
Polyethylene
Ethylene

Polypropylene
Propylene

Polyacrylonitrile
Acrylonitrile

Vinyl chloride Polyvinyl chloride

 Introduction to Polymer Structure

Polyamide (Nylon 66)

Polyester (Polyethylene
terephthalate)
 Introduction to Polymer Structure

Polyurethane

Polysiloxane
 Introduction to Polymer Structure

Phenol formaldehyde (Resole resin thermosetting resin)

Phenol Formaldehyde

Reactive sites = 3 Reactive site=1

Molar Ratio: Phenol: formaldehyde:: 1:1.5 under alkaline condition

 Synthesis principle of thermosetting phenolic resin (resol)

The ortho and para positions on

the phenol nucleus are activated
by the phenolic hydroxyl group,
producing ortho- or para- phenol-
hydroxymethyl when reacted with
formaldehyde.

The methylol phenol can continue

to react with formaldehyde to
form dimethylol phenol and
trimethylol phenol

Functionality =3
 Synthesis principle of thermosetting phenolic resin (resol)

2. Polycondensation reaction.

The phenol-hydroxymethyl obtained react with

each other or undergo a polycondensation
reaction with each other.

When the functionality of monomer is

three (tri- functional), three-dimensional
net work polymer is formed.
Polymerization Mechanisms
 Classification of Polymerization Mechanisms
Carothers (1929): Classification: (i)Addition polymerization (ii) condensation polymerization
H. F Mark (1950): Classification : (i) Chain Polymerization (ii) Step Polymerization
Polymerization Mechanisms

Chain Polymerization Step Polymerization

Free Radical Ionic Coordination

Polymerization polymerization Polymerization

Polycondensation Polyaddition Ring opening

Polymerization Polymerization polymerization
 Free Radical Chain Polymerization
✓ Characterized by a self addition of the monomer molecules , to each other, very
rapidly through a chain reaction
✓ No by product formed
✓ The product has the same elemental composition as that of the monomer
✓ Compound containing reactive double bonds can undergo chain polymerization reaction

Examples: Vinyl Compound ( CH2=CHX)

CH2=CHCONH2 CH2=CHCOOH CH2=CHCN CH2=C(CH3)COOCH3

Acrylamide Acrylic acid Acrylonitrile Methyl methacrylate

CH2=CHOCOCH3 CH2=CHCl CH2=CCl2

CH2=CHC6H5
Vinyl acetate Vinyl chloride Vinylidene chloride
Styrene
 Free Radical Chain Polymerization
Examples: Allyl Compounds (CH2=CHCH2X)

CH2=CHCH2OCOCH3 CH2=CHCH2OH CH2=CHCH2Cl

Allyl acetate Allyl alcohol Allyl Chloride

Olefines (CH2=CHR)

CH2=CH2 CH2=CHCH3 CH2=C (CH2)2

ethylene Propylene Isobutylene

Dienes (CH2=CR-CH=CH2)

CH2=CH-CH=CH2 CH2=CH-CCl=CH2 CH2=CCH3-CH=CH2

1,3 Butadiene Chloroprene Isoprene
 Chain Polymerization

Steps of Polymerization

(i) Initiation (ii) Propagation (iii) Termination

 Free Radical Chain Polymerization Steps of Polymerization

(i) Initiation

Involves the creation of the radical, i.e., creation of the active center.

Special molecule called an initiator are added to reaction to generate radicals in

the first place
Initiator homolytically decompose into fragments containing radicals that can be
used to initiate polymerization with the help of heat or light or catalyst

Endothermic process

Not all radicals generated during initiation actually get transferred to the monomer. Some molecules with radicals
may further decompose, and the radicals recombine, before they ever get a chance to react with the monomer
 Free Radical Chain Polymerization Steps of Polymerization
(i) Initiation
Once radical generate: transferred to a monomer to create an active center
a radical can add to the double bond of a monomer in two ways
The two carbons involved in the double bond may not be equivalent (i.e., they may
have different substituents).
Steric effects
Mode 1, the only substituents on the reacting
carbon are hydrogens (since it is a methylene
group), which are small, so there's really not much
steric hindrance.
Mode 2 Bulky substituent groups (i.e., bulky, large
"X" groups) prevent the radical from being able to
approach the other molecule closely enough to
react.
The radical in Mode 1 ends up on the carbon with more substituents, which can help to make that radical more
stable than the radical on the methylene group.
 Chain Polymerization Steps of Polymerization
(i) Initiation

The monomer unit is linked to the free radical unit through sigma bond forming
single molecule

The free radical site shifted from initiator fragment to the monomer unit

The process of electron pair coming down from its  energy level to sigma level
associated with energy release of approx. 20 Kcal

The free radical attack on the monomer initiating polymerization is an exothermic

process
 Chain Polymerization Steps of Polymerization

(ii) Propagation
Propagation involves the growth of the polymer chains, where monomers are
sequentially added to the active center
 Chain Polymerization Steps of Polymerization
(iii)Termination

Termination involves destruction of the radical active centers, thus preventing any
further propagation.
Termination occurs via combination of radicals

Polymer has a final degree of polymerization of x+y, and there are two initiator fragments
on each end.
 Chain Polymerization Steps of Polymerization

(iii)Termination

Termination by disproportionation
H atom is extracted from the end of a growing chain and the left over electron
combines with another radical generating a terminal π bond

In termination by disproportionation, two polymers chains created, one with an

unsaturated end, and both have one end with an initiator fragment.
Polymerization Kinetics: Free radical chain polymerization
✓ Speed of reaction under set of condition
✓ How these conditions influence the polymer molecular weight and
extent of polymer conversion
 Polymerization Kinetics: Free radical chain polymerization
Rate of polymerization: defined as the rate at which monomer M is consumed
−𝒅[𝑴] negative sign, defining the rate as the
𝑹𝒑 = disappearance or consumption of monomer
𝒅𝒕
Rate of initiation there are two parts to initiation:
1) the formation of the radical from decomposition of the initiator
2) transfer of the radical to a monomer.

The first step of initiation, generation of the

radicals, is generally much slower than transfer
of the active center to the monomer.

✓ the first step of initiation is the rate determining step

✓ rate of initiation is only a function of the slow step, formation of radicals
 Polymerization Kinetics: Free radical chain polymerization
the rate of initiation as the rate of formation of radicals:
monomer concentration is not used in rate of initiation. Because we
𝒅[𝑹 ∙] consume so little monomer during initiation, we neglect any changes in
𝑹𝒊 =
𝒅𝒕 monomer concentration here

two radicals generate per initiator molecule

The rate of initiation
𝒅[𝑹 ∙] I= initiator concentration
𝑹𝒊 = = 𝟐𝑲𝒅 [𝑰] Kd= initiator decomposition rate constant
𝒅𝒕

Not all the radicals that are produced actually get transferred to monomer.

Radicals may combine or react with solvent, To account for the fact that not all radicals produced are actually used, a
concept of initiator efficiency, f. introduced

For example, If half of radicals produced actually get used and transferred to monomer, then f =0.5.
 Polymerization Kinetics: Free radical chain polymerization
Rate of initiation
𝑹𝒊 = 𝟐𝒇𝑲𝒅 [𝑰]

Arrhenius equation
The rate constant is related to temperature
𝑬
−𝑹𝑻 A= constant :frequency factor
K𝒅 = 𝑨 𝒆 E= activation energy
R= gas constant
T= temperature
𝑬
−
𝑹𝒊 = 𝟐𝒇[𝑰]𝑨 𝒆 𝑹𝑻

Rate of initiation or rate of decomposition of an initiator increases with temperature

and concentration of the initiator
 Polymerization Kinetics: Free radical chain polymerization
Rate of propagation
Propagation involves the transfer of the radical from one monomer to another monomer,
or to polymer.

Monomer consumed in this step.

The rate of disappearance of monomer is a function of the propagation rate constant (Kp),
the monomer concentration (M), and concentration of active centers (M·)

−𝒅[𝑴]
𝑹𝒑𝒓𝒐𝒑 = = 𝑲𝒑 𝑴 [𝑴 ∙]
𝒅𝒕
 Polymerization Kinetics: Free radical chain polymerization
Rate of termination
two different pathways for termination: combination and disproportionation.

rate equations for these two termination pathways

−𝒅[𝑴 ∙] Ktc= termination rate constant

𝑹𝒕𝒄 = = 𝟐𝑲𝒕𝒄 𝑴 ∙ [𝑴 ∙]
𝒅𝒕 by combination
−𝒅[𝑴 ∙] Ktd= termination rate constant
𝑹𝒕𝒅 = = 𝟐𝑲𝒕𝒅 𝑴 ∙ [𝑴 ∙] by disproportionation
𝒅𝒕
The coefficient of two results from the fact that
−𝒅[𝑴 ∙]
two growing polymers are consumed by either 𝑹𝒕 = = 𝟐𝑲𝒕 𝑴 ∙ 𝟐

pathway. 𝒅𝒕
 Polymerization Kinetics: Free radical chain polymerization
At steady state
The rate of production of radicals is the same as the consumption of radicals
𝑹𝒊 = 𝑹𝒕
𝑹𝒊 = 𝟐𝑲𝒕 𝑴 ∙ 𝟐
Rearrange to solve for the steady state concentration of radicals:
𝑹𝒊 1/2
𝑴∙ =
𝟐𝑲𝒕

rate of polymerization: defined as rate of consumption of monomer

−𝒅[𝑴] 𝑹𝒊 1/2
𝑹𝒑 = 𝑹𝒑𝒓𝒐𝒑 = = 𝑲𝒑 𝑴 𝑴 ∙ = 𝑲𝒑 𝑴
𝒅𝒕 𝟐𝑲𝒕

𝑹𝒊
𝑹𝒑 = 𝑲𝒑 𝑴 𝑹𝒊 = 𝟐𝒇𝑲𝒅 [𝑰]
𝟐𝑲𝒕
 Polymerization Kinetics: Free radical chain polymerization
𝟐𝒇𝑲𝒅[𝑰]
𝑹 𝒑 = 𝑲𝒑 𝑴
𝟐𝑲𝒕

𝒇𝑲𝒅[𝑰]
𝑹 𝒑 = 𝑲𝒑 𝑴
𝑲𝒕

𝒇𝑲𝒅
𝑹 𝒑 = 𝑲𝒑 𝑴 [𝑰]
𝑲𝒕

Polymer formation is proportional to the first power of monomer concentration

and also the square root of the initiator concentration
The extent of conversion (the amount of monomer converted into polymer or yield
of polymerization ) increases with an increase of (i) temperature (ii) polymerization
time (iii) initiator and monomer concentration
 Polymerization Kinetics: Free radical chain polymerization
Kinetic Chain length ()

Defined as the average number of monomer molecules consumed by each

effective free radical generated by initiator
𝒓𝒂𝒕𝒆 𝒐𝒇 𝒑𝒓𝒐𝒑𝒂𝒈𝒂𝒕𝒊𝒐𝒏 𝒓𝒂𝒕𝒆 𝒐𝒇 𝒑𝒓𝒐𝒑𝒂𝒈𝒂𝒕𝒊𝒐𝒏
𝒗= =
𝒓𝒂𝒕𝒆 𝒐𝒇 𝒊𝒏𝒊𝒕𝒊𝒂𝒕𝒊𝒐𝒏 𝒓𝒂𝒕𝒆 𝒐𝒇 𝒕𝒆𝒓𝒎𝒊𝒏𝒂𝒕𝒊𝒐𝒏

𝑹𝒑 𝑲𝒑[𝑴]
𝒗= =
𝑹𝒊 𝟐 (𝑲𝒅 𝑲𝒕 𝒇 [𝑰]

Kinetic chain length gives the average number of monomer molecules present in
a growing chain at the time of termination
 Polymerization Kinetics: Free radical chain polymerization

Average Degree of Polymerization (Dp)

Dp= 2v=, when termination occurs by coupling

Dp=v= when termination occur by disproportionation

The degree of polymerization decrease with an increase of temperature and of

initiator concentration and with decrease of monomer concentration
 Problems
Q. 3 Vinyl acetate polymerized at 50ᵒC, the value of the ratio kp2/kt is 0.0138 l/mol-
s. What is the value of chain length, when monomer concentration is 6.53 mol/l
and rate of polymerization is 2.0*10-4mol/ls?
𝑹𝒑
Chain Length 𝒗=
𝑹𝒊

𝑹𝒊
𝑹𝒑 = 𝑲𝒑 𝑴
𝟐𝑲𝒕

𝑹𝒑 𝑲𝒑𝟐 𝑴𝟐
=𝒗=
𝑹𝒊 𝟐𝑲𝒕 𝑹𝒑

Chain length= 1471.1

 Problems
Q.4 What are the relative chain lengths of vinyl chloride and styrene, polymerized at
60ᵒC, having the values of ratio kp2/kt as 0.126 l/mol-s and 0.0034 l/mol-s, respectively?
Assume the rate of polymerization and monomer concentration same for both the
cases.
𝑲𝒑 𝟐 𝑴 𝟐
𝒗=
𝟐𝑲𝒕 𝑹𝒑

Chain length of vinyl 𝑲𝒑𝟐 𝑴 𝟐 𝑴𝟐

𝒗𝑽𝑨 = = 𝟎. 𝟏𝟐𝟔
acetate 𝑲𝒕 𝟐𝑹𝒑 𝟐𝑹𝒑

Chain length of 𝑲𝒑𝟐 𝑴 𝟐 𝑴𝟐

𝒗𝒔 = = 𝟎.0034
𝑲𝒕 𝟐𝑹𝒑 𝟐𝑹𝒑
styrene
𝒗𝑽𝑨
= 𝟑𝟕. 𝟎𝟓
𝒗𝑺
 Problems
Q.5 For styrene polymerized at 70ᵒC, monomer concentration is 7.85mol/l and the
value of the ratio (kp2/kt) is 0.0015 l/mol-s. What is the rate of polymerization
reaction, if the chain length is 300?
𝑲𝒑 𝟐 𝑴𝟐
𝒗=
𝟐𝑲𝒕 𝑹𝒑

𝑲𝒑𝟐 𝑴 𝟐
𝑹𝒑 =
𝟐𝑲𝒕 𝒗

Rp= 1.54*10-4 mol/ls

 Free radical Polymerization
Initiator
Thermally unstable compounds and decompose into products call free radicals
Supply energy
-
R R
R:R
in the form of heat
2R.
Molecule break onto two
symmetrical components

In order to function as a useful source of radicals an initiator system should be

✓ Readily available
✓ Stable under ambient or refrigerated conditions
✓ Posses a practical rate of radical generation at temperatures which are not
excessive (<150°C)
 Initiators
The decomposition of the initiator to form free radicals can be induced by
✓ Heat energy (thermal initiators)
✓ Light energy ( Photo initiator)
✓ Catalyst ( Redox initiator)

Thermal decomposition of initiator

Most widely used mode for generating radicals to initiate polymerization
Polymerization is known as thermal initiated polymerization

Compounds having bond dissociation energies in the range of 100-170 KJ per mole

Compounds having O-O, S-S, N=N bond posses desire range of dissociation energy
Low molecular weight compounds mainly azo compound, peroxides, hydroperoxide,
peracids and peresters are useful initiators
 Initiators
Benzoyl peroxide (BPO)

Cumyl peroxide
 Initiators
Azo-bis-isobutyronitrile (AIBN)

t-butyl hydroperoxide

t-butyl per benzoate

 Initiators
The various initiators are used at different temperatures depending on their rates of
decomposition

S. No. Name of initiator Decomposition

temperature (°C)
1 Azo bis iso butyronitrile (AIBN) 50-70
2. Acetyl peroxide 70-90
3. Benzoyl peroxide 80-95
4. Dicumyl peroxide 120-140
5. Di t-butyl peroxide 120-140

Decomposition rate constant (Kd) : 10-4 to 10-9 per second

Most initiator are used at temperature where Kd is usually 10-4 to 10-6 s-1.
 Initiators
Initiator half life, t1/2 : the difference in the decomposition rate of initiator expressed in
terms of initiator half life and defined as the time for the concentration of initiator to
decrease to one half its original value

Thermal decomposition
R:R 2R.

−𝒅 [𝑰] I= concentration of initiator

= 𝒌𝒅 [𝑰]
𝒅𝒕
Kd= decomposition rate constant
Integration yield
Io = initial concentration of initiator
𝑰 = 𝑰 𝒐𝒆−𝒌𝒅𝒕
at the start of polymerization
At I= Io/2
𝟎.𝟔𝟗𝟑
𝒕½= 𝒌𝒅
Half lives of Initiators
Initiators
Effect of Temperature

Initiator Solvent Half life (hours)

40°C 50°C 60°C 70°C
Azo bis Benzene 354 73 17 5
isobutyronitrile
Benzoyl peroxide Acetone - 86 - 7
Lauryl Peroxide Carbon tetra 662 167 41 10
chloride
 Initiators
Half lives of Initiators
Effect of solvent
Initiator temperature Half life (hours)
benzene Toluene Carbon Ethyl
tetra acetate
chloride
Azo bis 40°C 354 - 895 410
isobutyronitrile
Benzoyl peroxide 70°C 13 - - -
Tert. Butyl peroxide 120°C 14 14 21 -
Lauryl Peroxide 40°C 392 - 662 319
Redox Initiation
Initiators
Many oxidation-reduction reactions produce radicals that can be used to initiate
polymerization
✓ Advantage
Radical production occurs at reasonable rates over a very wide range of
temperatures, depending on the particular redox system (temperature range 0-50°C
or lower)
✓ Greater freedom of choice of the polymerization temperature

✓ A lower energy of activation (40– 80 kJ /mol ) allows the redox polymerization

to be carried out under milder conditions than thermal

✓ This lowers the possibility of side chain reactions giving high molecular weight
polymers with a high yield
 Initiators
Types of Redox Initiators
I: Peroxides in combination with reducing agents
Ex: Reaction of hydrogen peroxide with ferrous ion

II. A. Persulphate
Ex: Ferrous ion reacts with disulfides or persulphates

R-S-S-R + Fe2+ Fe3+ + RS. + RS-

-O S-O-O-SO - + Fe2+ Fe3+ + -OSO . + SO42-

3 3 3

-OSO . + Fe2+ Fe3+ + SO42-

3
 Initiators
II.B Oxyacid of Sulphur with sulphite, bisulphite, thiosulphate, metasulphite and
dithionate form efficient redox system with persulphates
S2O82- + SxOyn- SO4.- + SO42- + .SxOy(n-1)-

Ex: persulphate and thiosulphate redox pair

S2O82- + S2O32- SO4.- + SO42- + .S2O3-

Reductant such as Cr2+, Ti3+, V2+, CO2+ and Cu+ can be used in place of Fe2+
 Initiators
Photochemical or Photo initiator
Photo initiated polymerization occurs when radicals are produced by ultraviolet and
visible light irradiation of a reaction system

The free radicals formed by the photodecomposition of an initiator are the same as
those formed by its thermal decomposition

Azo-bis-isobutyronitrile (AIBN)

h

The rate of decomposition depends mainly on the intensity and wavelength of radiation.
 Initiators
Use of photo initiators

✓ Surface and thin layer application in the printing and coating industries

✓ Ultrafast drying of varnishes, printing inks, coating for metals, paper, wood
and plastics

✓ Photolithography for producing integrated and printed circuits

✓ Curing of dental restoration, bone cement and adhesive formulations

 Initiators
Ultraviolet light/ Gamma rays can also produce free radicals by the direct excitation of
the monomer molecules
Chain transfer
Chain Polymerization
In many Polymerization system,
experimentally, the polymer molecular weight is observed to be lower

This effect is due to premature termination of growing chain by transfer of

hydrogen or other atom or species

Compound may be
Monomer

Initiator
Solvent
Chain transfer agents
 Chain Polymerization
Chain Transfer
Chain transfer is a process that occurs during polymerization in which the active
center is transferred from one species to another

T-A can be initiator, monomer, polymer, solvent, or something added purposefully

transfer the radical (i.e., a transfer agent).

Often , T is a hydrogen atom or halogen atom

Breakage of the single bond in TA happens by homolytic cleavage, such that the radical
has been transferred from one species to another.
 Chain Polymerization
Chain Transfer
Chain transfer through initiator: not very significant due to low concentration of initiator
Chain transfer to monomer: in some cases it is significant

Chain transfer to solvent: Highly significant

Chain transfer constant: defined as the ratio of rate constant Ktr for the chain transfer
of propagating radical with that substance to the rate constant Kp for propagation of
radical
𝑲𝒕𝒓 C= chain transfer constant
C =𝑲 Ktr= rate constant for transfer reaction
𝒑
Kp= rate constant for propagation reaction

The chain transfer constant depends on: Temperature

Nature of growing polymer chain radical
 Chain Polymerization
Chain Transfer

𝑲𝒕𝒓𝑴
The chain transfer constant for monomer C M= 𝑲𝒑

𝑲𝒕𝒓𝑺
The Chain transfer constant for solvent Cs= 𝑲𝒑

𝑲𝒕𝒓𝒊
The Chain transfer constant for initiator CI= 𝑲𝒑
 Chain Polymerization
Chain Transfer

Initiator Chain transfer constant (styrene) Monomer Chain Transfer Constants

Initiator CI Monomer CMx 104

Azobisisobutyronitrile 0.091-0.14 Acrylamide 0.6
(AIBN) Acrylonitrile 0.26-0.3
Benzoyl peroxide 0.048-0.10 Ethylene 4.2
Cumyl hydroperoxide 0.063 Methyl methacrylate 0.07-0.10
Vinyl acetate 1.75-2.8
Vinyl chloride 10.8-12.8
 Chain Polymerization
Chain transfer to polymer
Chain transfer to polymer means that the radical is transferred to somewhere in or on a
polymer

it can be the same polymer where the radical was initially (intramolecular chain transfer,
or backbiting)
 Chain Polymerization
Chain transfer to polymer
the active center can be transferred to a different polymer chain (intermolecular chain
transfer).

The extent of branching is greater in polymers such as poly (vinyl acetate), poly (vinyl
chloride) and polyethylene, which have very high reactive propagating radicals.
 Chain Polymerization Chain Transfer

Example: Chain transfer through solvent

Solvent Chain transfer constant (Styrene)
Carbon tetra chloride (CCl4)
Solvent CSX 104
Acetone 4.1
Chloroform 3.4
Di-n –butyl disulfide 24
Carbon tetrachloride 110
 Chain Polymerization Chain Transfer

Solvents with very high chain transfer ability are used to producing low molecular
weight liquid polymers.

A solvent having a chemical structure similar to that of the monomer is selected so

that terminal end groups formed by the solvent molecules do not alter the chemical
structure of the polymer formed.

The method of polymerization which utilize the solvent of a high chain transfer ability
and having chemical structure similarity to the monomer and formed liquid polymer
are known as “ Telomerization”

The solvent used in this case are known as “telogen”

 Chain Polymerization Chain Transfer

Example: Polymerization of bromo trifluoro ethylene using bromo trifluoro

methane as telogen
 Chain Polymerization Chain Transfer

Chan Transfer Agents or Chain Modifier

In Industrial polymerization , specific chain transfer agents to control the molecular
weight of the polymer
Examples Diisoproyl xanthate disulfide is used as chain modifier for industrial
production of styrene butadiene rubber

mercaptan
Dodecyl mercaptan
 Chain Polymerization Kinetics of Chain Transfer

Chain Transfer Reaction

Ktr
Mn . + X-A Mn-X + A .

The rate of chain transfer reaction

Rtr = Ktr [M.] [XA] Ktr= chain transfer rate constant

Chain transfer results in the production of a new radical A . , which then initiate
polymerization
Ka
A.+ M M.

Chain transfer is chain breaking reaction.

Decrease in the size of the propagating chain
 Chain Polymerization Kinetics of Chain Transfer

The effect of chain transfer on the polymerization rate is dependent on whether the
rate of re-initiation is comparable to that of original propagating radical

Case Relative rate constants for Type of Effect Effect on Rp Effect on Dp

Transfer, propagation and
re-initiation
1 Kp >> Ktr Ka  Kp Normal chain None Decrease
transfer
2 Kp << Ktr Ka  Kp Telomerization None Large
decrease
3 Kp >> Ktr Ka < Kp Retardation Decrease Decrease
4 Kp << Ktr Ka< Kp Degradative chain Large decrease Large
Transfer decrease
 Chain Polymerization Kinetics of Chain Transfer
𝑹𝒑 𝑹𝒑 𝑲𝒑 𝑴 [𝑴.]
Dp = v = = =
𝑹𝒊 𝑹𝒕𝒓 𝑲𝒕𝒓 𝑴. [𝑿𝑨]
𝟏 𝐊𝐭𝐫[𝐗𝐀]
=
𝐃𝐩 𝐊𝐩[𝐌] CXA= Chain transfer constant for
𝟏 [𝐗𝐀] compound (Chain transferring
= 𝐂𝐗𝐀
𝐃𝐩 [𝐌] agent)
If the chain transfer takes place by chain transfer reaction of solvent, monomer,
initiator, chain modifier in addition to coupling and disproportionation
𝟏 [𝐗𝐀] [𝒔] [𝑰] [𝑴] 𝑹𝒊
= 𝐂𝐗𝐀 + 𝑪𝒔 + 𝑪𝑰 + 𝑪𝐌 +𝑵
𝐃𝐩 [𝐌] [𝑴] [𝑴] [𝑴] 𝑹𝒑

𝟏 [𝐗𝐀] [𝒔] [𝑰] 𝑹𝒊

= 𝐂𝐗𝐀 + 𝑪𝒔 + 𝑪𝑰 + 𝑪𝐌 + 𝑵
𝐃𝐩 [𝐌] [𝑴] [𝑴] 𝑹𝒑
Mayo equation
 Free radical Chain Polymerization
Polymerization suppressor The addition of certain substances suppresses the
polymerization of monomers
These substances react with the initiating and propagating radicals
Convert them to either nonradical species or radicals of reactivity too low to undergo
propagation
Classification of Suppressor Depends on the effectiveness of the substance
Inhibitor ✓ Stop every radical formation
✓ Polymerization is completely halted until they are consumed

Retarder ✓ Less efficient and stop only a portion of the radicals

✓ Polymerization occurs but at a slower rate
✓ Low molecular weight polymer obtained
 Free radical Chain Polymerization Polymerization suppressor

No inhibitor 0.1% benzoquinone

Inhibitor
0.5% nitrobenzene
Retarder

0.2% nitrosobenzene
Combined effect of
inhibitor and retarder

Inhibition and retardation in the thermal, self initiated polymerization of styrene

 Free radical Chain Polymerization

Examples
Hydroquinone Benzoquinone Chloranil Benzothiazine

Nitrobenzene Diphenylpicrylhydrazyl (DPPH)

Dinitrobenzene
 Free radical Chain Polymerization

Examples
 Ceiling Temperature
Propagation reaction is considered as reversible reaction

RM. + M RMM. Depropagation reaction

At polymerization temperature
Rate of propagation >> rate of depropagation
As temperature increases
Rate of depropagation increase

Temperature at which
Rate of propagation = rate of depropagation Ceiling temperature

No polymerization
 Step Polymerization
Different chemical reactions are used to synthesized polymeric materials by step
polymerization
Chemical reactions: esterification, amidation, formation of urethanes, aromatic
substitutions
Polymerization proceeds by the reaction between two functional groups

Depending on the type monomer

Involve two different bifunction and /or

Involves single monomer
polyfunctional monomers in which each
containing both type of
monomer possesses only one type of
functional groups
functional group
n H2N-R-NH2 + n HOOC-R’-COOH n H2N-R-COOH

H-(NH-R-NHCO-R’-CO-)n-OH +(2n-1) H2O H-(NH-R-CO-)n-OH + (n-1) H2O

 Step Polymerization
General representation
n A-A + n B-B -(A-AB-B)n- n A-B -(A-B)n-

Where, A and B are the two different types of functional groups

The characteristics of these two polymerization reactions are similar

The successful synthesis of high molecular weight polymer using any step polymerization
reaction generally is more difficult than the corresponding small molecule reaction

High conversion synthesis need:

✓ A and B functional groups to be present at very close to stoichiometric amounts
✓ favorable equilibrium
✓ Absence of cyclization and side reactions
 Kinetics of Step Polymerization
Step polymerization: relatively slow increase in molecular weight of the polymer
Example: consider synthesis of polyester from diol and diacid Esterification reaction
catalyzed by acid
First step: reaction of diol and diacid monomers
HO-R-OH + HOOC-R’-COOH HO- R-OCO-R’-COOH + H2O
The dimer then form trimer by reaction with diol monomer and also with diacid monomer
HO-R-OH + HO- R-OCO-R’-COOH HO- R-OCO-R’-COO-R-OH+ H2O

HOOC-R’-COOH + HO- R-OCO-R’-COOH HOOC-R’COO- R-OCO-R’-COO-R-OH+ H2O

Dimer reacts with itself to form tetramer
2 HO- R-OCO-R’-COOH HO-R-OCO-R’-COO-R-OCO-R’- COOH + H2O

Tetramer and trimer procced to react with themselves, with each other and with monomer
 Kinetics of Step Polymerization
Polymerization proceeds in stepwise manner and molecular weight of polymer
continuously increasing with time (Conversion)
characterized by the disappearance of monomer early in the reaction far before
the production of any polymer of sufficient Molecular weight (> 5000-10000)

Less than 1% of original monomer remain at a point where average polymer chain
contains  10 monomer units

The rate of step polymerization is the sum of the rates of reaction between molecules of
various sizes

Monomer + monomer = dimer Trimer+ monomer = tetramer

n-mer +m-mer =
Dimer +monomer= trimer Trimer+ dimer = pentamer
(n+m) mer
Dimer + dimer = tetramer Trimer + trimer = hexamer
 Kinetics of Step Polymerization
The reaction mixture at any instance consists of various sized diol, diacid, hydroxy acid
molecules
Any -OH containing molecule can react with any –COOH containing molecule

Flory Assumption: the reactivity of the functional group is independent of the size of
the molecule to which it is attached (independent of the values of n and m)

Case-1 non catalyzed polycondensation

When no strong acid added to catalyzed esterification reaction, dicarboxylic acid has
dual function : as a reactant and as a catalyst
The polyesterification reaction rate will be proportional to the square of the concentration
of the carboxylic acid group and to the first power of the hydroxyl group concentration

−𝒅[𝑶𝑯]
= 𝒌 𝑪𝑶𝑶𝑯 𝟐[ 𝑶𝑯] K= esterification rate constant
𝒅𝒕
 Kinetics of Step Polymerization
When the concentration –OH and –COOH groups are equal : (Stoichiometric
quantities of the functional group (FG))
At give time t 𝑪𝑶𝑶𝑯 = 𝑶𝑯 = [𝑭𝑮]

−𝒅[𝑶𝑯]
= 𝒌 𝑭𝑮 𝟐 𝑭𝑮 = 𝒌 𝑭𝑮 𝟑
𝒅𝒕
Integrating and rearranging the terms
𝟏 𝟏 [FG]0 represents the initial
𝟐𝒌𝒕 = 𝟐
−
𝑭𝑮 𝑭𝑮 𝟎𝟐 concentration of –COOH or -OH
If p represents the fraction of the functional groups which has undergone the esterification
reaction at a time t, then [FG] could be related to [FG]0 by

𝑭𝑮 𝟎 − [𝑭𝑮] [𝑭𝑮]
=𝒑 = (𝟏 − 𝒑) 𝑭𝑮 = 𝑭𝑮 𝟎(𝟏 − 𝒑)
𝑭𝑮 𝟎 𝑭𝑮 𝟎
 Kinetics of Step Polymerization
𝟏 𝟏
𝟐𝒌𝒕 = 𝟐 𝟐
− 𝟐
𝟏−𝒑 𝑭𝑮 𝟎 𝑭𝑮 𝟎

𝟐𝒕
𝟏
𝟐𝒌 𝑭𝑮 𝟎 = 𝟐
−𝟏 Condensation
𝟏−𝒑
reaction of
adipic acid with
𝟏 𝟐𝒕 Y = mX+C diethylene
𝟐
= 𝟐𝒌 𝑭𝑮 𝟎 +𝟏
𝟏−𝒑 glycol at 166°C

For simple esterification reaction, which proceeds without any side reaction, the
degree of polymerization related to “p” the fraction of the functional groups which has
undergone the esterification at a time t

𝟏 𝑭𝑮 𝟎
𝑫𝒑 = = or 𝑫𝟐𝒑 = 𝟐𝒌 𝑭𝑮 𝟎
𝟐𝒕 +𝟏
𝟏−𝒑 [𝑭𝑮]
 Kinetics of Step Polymerization
Case-2: Acid catalyzed polycondensation
The condensation reactions are enhanced by the presence of strong acids.
The acid catalyzed polycondensation reaction Where, Kx =esterification
−𝒅[𝑭𝑮] rate constant,
= 𝒌𝒙 𝑪𝑶𝑶𝑯 [ 𝑶𝑯] k[X]: [X] concentration of
𝒅𝒕
catalyst
Catalyst concentration remain same throughout the reaction
The pattern of the reaction remains same, similarly equation can derive for acid
catalyzed polycondensation
𝟏
𝒌𝒙 𝑭𝑮 𝟎𝒕 = −𝟏
𝟏−𝒑
𝑫𝒑 = 𝒌𝒙 𝑭𝑮 𝟎𝒕 + 𝟏
 Kinetics of Step Polymerization
Case-2: Acid catalyzed polycondensation

Condensation reaction of adipic acid with diethylene glycol (0.4 mole % of toluene
sulphonic acid) at 109°C
 Step Polymerization
Extent of reaction and Degree of Polymerization

𝟏 p the fraction of the functional groups

𝑫𝒑 =
𝟏−𝒑 which has undergone the
esterification at a time t
 Step Polymerization
Stoichiometry of reactants and Degree of polymerization

Assume that Na moles of reactant A-A are reacted with Nb moles of reactant B-B and
that Na< Nb
The stoichiometric ratio of A-A and B-B will be less than 1
𝑵𝒂
=𝒓
𝑵𝒃
Number of reactive groups A to start with = 2Na
Number of reactive groups B to start with = 2Nb
𝟏
Total number of reactive groups to start with = 2Na+ 2 Nb= 2Na [1+ ]
𝐫

When extent of conversion is p, the fraction of group A consumed will be p

Fraction of group B consumed = rp
 Step Polymerization
Stoichiometry of reactants and Degree of polymerization

Fraction of group A remaining unreacted= 1-p

Fraction of group b remaining unreacted = (1-rp)
Total number of groups remaining unreacted = 2 Na (1-p) + 2 Nb (1-rp)

The degree of polymerization is given by

𝟏
𝑭𝑮 𝟎 𝟐𝑵𝒂 𝟏+ 𝒓+𝟏
𝒓
𝑫𝒑 = = =
[𝑭𝑮] 𝟐 𝑵𝒂 𝟏−𝒑 +𝟐 𝑵𝒃(𝟏−𝒓𝒑) 𝒓+𝟏−𝟐𝒓𝒑

𝟏
When there is no stoichiometric imbalance i.e r=1 𝑫𝒑 = 𝟏−𝒑

𝟏+𝒓
When the extent of conversion is 1 i.e. p=1 𝑫𝒑 = 𝟏−𝒓
 Problems
Q.6 Calculate the degree of polymerization of an equimolar mixture of adipic acid
and hexamethylene diamine for extent of reaction 0.80 & 0.90

𝟏
𝑫𝒑 =
𝟏−𝒑

For 0.80 Dp= 5

For 0.90 Dp= 10

 Problems
Q.7 Calculate the feed ratio of adipic acid and hexamethylene diamine that should be
employed to obtain a polyamide of approximately 15,000 molecular weight at 99.5%
conversion. What is the identity of the end group.

Dp= 15000/226 = 66.37

𝒓+𝟏
𝑫𝒑 = 𝒓+𝟏−𝟐𝒓𝒑

𝒓+𝟏
𝟔𝟔. 𝟑𝟕 = 𝒓+𝟏−𝟐𝒓(𝟎.𝟗𝟗𝟓)

Feed ratio r= 0.979

The polymerization is carried out with either COOH/NH2 or NH2/ COOH =0.979