CAMBRIDGE INSTITUTE OF TECHNOLOGY

MODULE-4

HIGH POLYMERS

Introduction:

Polymers are the materials with large molecular masses obtained by the
covalent linkage of several small repeating units called monomers. The
repeating unit may be same or different. The word polymer is derived from
Latin words i.e. Poly= many, Mers= parts.

Staudinger Hermann (1891-1963) one of the pioneers in polymers was awarded

Nobel Prize in chemistry in 1953.These polymers play a very important role in
our daily life i.e. they provide the basic needs of our lives, namely food,
clothing, shelter. Etc. They possess a wide range of properties from soft natured
to strong natured.

Some basic definitions:

Polymers: “High polymers are macro sized molecules of high molecular mass
formed by the combination of a large number of simple molecules by covalent
bonds”.

Ex: Polyethylene, polyacetylene, polystyrene, polyvinyl chloride, natural and

synthetic rubbers etc.

Monomers: “The simple molecules which combine to give polymers are called
“Monomers” or “Repeating units” or “Building blocks of polymers”.

Ex: Ethylene, Vinyl chloride, Acetylene, Styrene. etc.

Functionality: “The total number of bonding sites or functional groups present

in a monomer is called functionality”.

Polymerization: “The process by which the monomers are converted into

polymers is called Polymerization”.

Degree of polymerization (DP): “It is the total number of repeating units (n) in
a polymer chain” .This indicates the length of the polymer chain and also helps
in determining the molecular mass of the polymers.

I.e. Molecular mass of polymer = DP × Molecular mass of monomer.

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Note: Polymers have a molecular masses ranging from 10,000 to 1, 00,000.

Classification of polymers:

Polymers are classified in different ways based on their sources, thermal

behavior, mechanism of polymerization and properties as given below.

• Natural and Synthetic polymers.

• Thermoplastics and Thermosetting polymers.
• Addition and Condensation polymers.
• Elastomers, Fibers, Resins and Plastics.
Based on the sources of availability polymers can be broadly classified as

1) Natural Polymers & 2) Synthetic Polymers

1) Natural Polymers: The polymers obtained from nature (plants & animals)
are called natural polymers.

Ex: Starch, Cellulose, Proteins, Nucleic acids, Natural rubber, Cotton, Silk,
wool, etc.

2) Synthetic polymers: The polymers which are prepared in the laboratories are
called synthetic polymers or manmade polymers.

Ex: Polyethylene (PE), Polyvinyl chloride (PVC), Nylon6, Bakelite, etc

Types of Polymerization:

Polymerization is of two types.

1) Addition polymerization (chain polymerization):

It is a process in which number of simple monomers joining together by
chain reaction without the elimination of any byproducts.

The polymer formed by the direct addition of repeated monomers is

called addition polymer.

Ex: a) Preparation of polyethylene from ethylene:

n[CH2 = CH2] [–CH2–CH2–] n

Ethylene (monomer) Polyethylene (polymer)

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b) Preparation of polyvinyl chloride (PVC) from vinyl chloride:

n[CH2=CH–Cl] [–CH2–CH–Cl–] n

Vinyl chloride (monomer) PVC (polymer)

Characteristic features of addition polymerization:

1) Only alkene compounds can undergo addition polymerization.

2) The polymer produced has the same elemental composition as that of the
monomer.
3) The molecular weight of polymer is an integral multiple of that of the
monomer.
4) Linear polymers are obtained.
5) Self addition of monomers takes place rapidly.
2) Condensation polymerization (step polymerization):
A polymerization reaction in which bi-functional monomers undergoes
condensation with continuous elimination of byproducts such as H 2O, NH3,
HCl, etc is called condensation polymerization.

Since condensation reaction is rather slow and proceeds stepwise, such

polymerization is often called step polymerization.

Ex: a) Preparation of nylon 6:6 from hexamethylene diamine & Adipic acid.

nH2N– (CH2)6–NH2 + nHOOC– (CH2)4–COOH

Hexamethylene diamine Adipic acid - 2nH2O

[–HN– (CH2)6–NH–CO– (CH2)4–CO–] n

Nylon 6:6 (Polyamide)

b) Preparation of polyester by condensation of ethylene glycol with

terphthalic acid.

nHO–(H2C) 2–OH + nHOOC–C6H4–COOH

Ethylene glycol Terphthalic acid -2nH2O

[–O–CH2–CH2–OOC–C6H4–CO–] n

Polyester

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Characteristic features of condensation polymerization:

1)Polymerization proceeds through inter molecular condensation.

2)There is a continuous elimination of byproducts.
3)Condensation polymerization is catalyzed by acids or alkalies.
4)The elemental composition of the polymer is generally different from
that of its monomers.
5) Cross linked or linear polymers are obtained.
Co-polymerization:

It is another kind of addition polymerization in which different chemical

structural monomers are combined to form a polymer.

Ex: Preparation of Buna-S from Styrene & Butadiene.

+ CH2=CH–CH=CH2 –CH–CH2–CH2–CH=CH–CH2-
CH=CH2

Styrene Butadiene Buna-S

Mechanism of polymerization:

The free radical mechanism of addition polymerization:

The free radical mechanism of polymerization of polyethylene involves

three steps

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1) Chain initiation
2) Chain propagation and
3) Chain termination
1) Chain initiation:

The polymerization is initiated by the free radicals generated from

initiators. I.e. initiators homolytically dissociated into free radicals. The free
radicals initiate the chain process by attacking the monomer molecule (ethylene)
at the double bond generating new free radicals.

R-R R• + R• or 2R•
Homolysis
Initiator Free Radicals.

R• + CH2=CH2 R – CH2–CH2•

Free radical Ethylene chain initiation species (new

free radical)

2) Chain Propagation:

The new free radical or chain initiating species capable of further

interaction with initial monomer (ethylene) molecule leading to chain
propagation.

R–CH2–CH2• + CH2=CH2 R–CH2–CH2–CH2–CH2•

3) Chain termination:

In the termination process the growing polymer chain is transformed into

a dead polymer molecule in any one of the following modes.

a) Chain termination by coupling of two new free radicals:

R–CH2–CH2• + •
CH2–CH2–R R-CH2–CH2–CH2–CH2–R

New free radical new free radical dead

polymer

b) Coupling of growing polymer with 10free radical:

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R–CH2–CH2• + R• R–CH2–CH2–R

New free radical 10 free radical Dead polymer

c) Chain termination by disproportionation:

In this process a hydrogen atom of one growing chain is transferred to

another growing chain resulting in the formation of dead polymer with a double
bond at the end.

R–CH2–CH2• + •CH2–CH2–R R–CH=CH2 + CH3–CH2–R

Unsaturated deadpolymer.Saturated
dead polymer

Note:
1) Free Radicals: Free radical is an atomic or molecular species having an
odd or unpaired electron.
2) Homolysis: Symmetrical cleavage of molecule into two equal parts is
called homolysis.

Glass Transition Temperature (Tg)

Definition: “The temperature below which an amorphous polymer is hard,

brittle, above which it becomes soft, flexible”. It is denoted by Tg.

Eg: If an ordinary rubber ball is cooled, it becomes harder and harder and
becomes so harder. When it reaches -70o C that it will break into pieces like a
glass ball. When warmed the ball regains its rubbery state.
Tg

Glassy state Rubbery state

(Hard, brittle) (Soft, flexible)

The hard brittle state of a polymer is called glassy state and soft, flexible state of
a polymer is called rubbery state.

Explanation:

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In glassy state of a polymer, there are neither segmental nor molecular

motions. When all chain motions are not possible the rigid solid results.

On heating beyond Tg the polymer passes from glassy state to rubbery

state in which there are only segmental motions while molecular motion is not
allowed.

On further heating, each polymer chain obtains sufficient energy,

molecular mobility sets in and the polymer starts flowing and behaves like a
viscous liquid. This state of a polymer is called viscous state in which both
molecular motion and segmental motions are allowed. The temperature below
which the polymers are in rubbery state, above which polymers are in viscous
state is called flowing temperature. (Tf)

Glassy state Rubbery state Viscous state

Hard, rigid, Soft, flexible and Flows like a

stiff. rubbery. liquid.

Neither Only segmental Both segmental

segmental nor motions, no molecular and molecular
molecular motion. motions.
motions.

Note: Glass transition is a second order transition.

Importance of Tg:

• Tg value is a measure of flexibility of polymers.

• The use of any polymer at any temperature is decided by its Tg value.
• Tg value along with Tm helps in choosing the right temperature of
processing the polymers by different techniques.
• Gives an idea of the thermal expansion, heat capacity, electrical and
mechanical property of polymers.

Structural parameters (factors) of a polymer which influence the Tg value

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There are several structural parameters of a polymer which influence the

Tg value. The important parameters are:

1. Crystallinity
2. Molecular Mass
3. Effect of side group
4. Inter molecular forces
5. Branching and cross linking.
6. Addition of plasticizers.
1) Crystallinity:

In crystalline polymer the polymer chains are arranged parallel to each other
and are held by strong forces like H-bonding. This leads to the high Tg value for
the polymers. Hence crystalline polymers have higher Tg value than
amorphous polymers. Higher the crystallinity, larger is the Tg value of a
polymer.

2) Molecular Mass:

Tg value of a polymer is also influenced by its molecular mass. Generally the

Tg of a polymer increases with increase in the molecular mass up to 20,000 and
beyond this there is no change.

3) Effect of side group:

Presence of effective side groups such as methyl, ethyl, -C6H5 etc increases Tg
value of a polymer by hindering free rotation at the polymer chain back bone,
and restricts the chain mobility thereby increasing Tg value.

Example: Poly (α-methyl styrene) has higher Tg value (1700c) while

Polystyrene has lower Tg value (1000c).

4) Intermolecular forces:

Presence of large number of polar groups in the molecular chain leads to strong
intermolecular cohesive forces which restrict the molecular mobility. This leads
to increase in the Tg Value.

Eg: Tg value of polypropylene (no bulky group) is -180C whereas Nylon6:6

(contain polar amide bulky group) is 57oC.

5) Branching and Cross linking:

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A small amount of branching will tend to lower the Tg. Increase in chain ends
in branched chain polymers increase free volume thus decreasing the Tg.

Cross linking of polymer chains decreases the flexibility of a polymer and

therefore as the extent of cross linking increases the Tg value decreases.

6) Presence of plasticizers:

Plasticizers are the low molecular mass, volatile substances. These plasticizers
reduce the Tg.

Eg: Addition of diisooctyl phthalate to PVC reduces its Tg from 800C to below
room temperature.

Structure – property Relationship:

The properties like crystallinity, chemical resistivity, tensile and impact

strength, elasticity, plasticity etc depends mostly on the structure of polymers.

1) Crystallinity of polymers:
A polymer is said to be crystalline if all the molecules are arranged in an orderly
manner, with symmetrical orientation, with higher force of attraction between
the two chains. The degree of crystallinity depends on how best the polymer
chains can be closely packed. The polymers invariably contain both crystalline
and amorphous regions. Crystalline regions are formed when individual chains
are linear or contain no bulky groups and are closely arranged parallel to each
other. The chains of a polymer are held together by secondary forces like
hydrogen bonding, vanderwaals forces, polar interaction etc. Such type of close
packing imparts high degree of crystallinity and exhibit high tensile and impact
strength, high density, high melting point etc.

Polymers like HDPE, PVC exhibit high crystallinity.

The randomly arranged bulky groups and branches on polymer chains

prevent close pack of chains, resulting in the formation of amorphous regions.
Intermolecular forces are weak in these polymers.

Polymers like LDPE, Polystyrene exhibit low crystallinity.

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2) Chemical Resistivity:

The resistance to chemical attack of a polymer depends on number of structural

factors such as

1. The presence of polar groups or non polar groups

2. Degree of crystallinity and Molecular mass
3. The degree of cross linking

The presence of polar groups or non polar groups:

A polymer having polar groups (-OH or -COOH group) are usually dissolved by
polar solvents such as water or alcohols. Polymers with non polar groups like –
CH3, C6H5 dissolved in non polar solvents such as benzene, CCl4, etc. Polymers
with large number of aromatic group dissolved in aromatic solvents such as
benzene toluene etc. Polymers containing ester group (polyester) undergo
hydrolysis with strong alkalies at high temperature. Polyamides like Nylon6:6
containing -NHCO- group can be hydrolyzed using strong acids/ alkalies.

Polyalkanes, PVC, Fluorocarbons are the some polymers which have a high
degree of chemical resistivity.

Degree of crystallinity and Molecular mass:

For a given polymer, the swelling character decreases with increase in the
molecular mass. For polymers having the same chemical character, the chemical
resistance increases with increase in the degree of crystallinity. This is due to
dense packing of the chain and the crystalline regions which makes the
penetration of the solvent more difficult.

The degree of cross linking:

Greater the degree of cross linking lesser is the solubility.

3) Tensile and impact strength:

The tensile strength and impact strength of a polymer are a few important
mechanical properties. These properties are directly dependent on the molecular
mass. High molecular mass polymers are tougher and more heat resistant. These
polymers accounts for high impact and tensile strength. Tensile strength and

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impact resistance increases with molecular mass up to 2000 and thereafter the
increase is negligible. The useful range is 200 to 2000.

TS and IS

200 2000

Degree of polymerization

4) Elastic deformation (Elasticity):

The elastomers are characterized by the high degree of elasticity. The elastic
deformation in polymers arises from the typical coiled structure of the polymer
chains in the normal unscratched state. The polymers chains are in a random
arrangement. When stretched the coiled chains begin to straighten out. As a
result the force of attraction between different chains increases thereby causing
stiffening of the material. When the strain is released, they return to their
original coiled form.

Natural rubber and all synthetic rubber exhibit this property.

5) Plastic Deformation (Plasticity or Rheology):

Some polymers on the application of heat and pressure initially become soft,
flexible, and rubbery and undergo deformation. On further heating beyond Tm
or Tf, they melt and flow on cooling they return to their original state. This
property of a polymer is called plasticity. This deformation property is used in
molding process. Thermoplastic are linear, stereo regular and exhibit the

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property of plastic deformation. Thermosetting plastics do not exhibit plastic

deformation.

2) Poly (methyl methacrylate): (PMMA, plexiglass)

Plexiglass is the trade name for poly (methyl methacrylate). It has the
following structure:

CH3

–CH2-C–

COOCH3 n
Synthesis: It is synthesized by bulk or suspension polymerization of methyl
methacrylate at 60-70°c in the presence of H2O2 as initiator.

CH3 CH3

60-

nCH2=C 700c
H2O – CH2 C
2

COOCH3 COOCH3 n

Methyl Methacrylate PMMA

Properties:

• It is a white transparent thermoplastic.

• It has high optical clarity.
• It is soluble in many organic solvents.
Applications:

• It is used for making lenses; sign boards chemical instruments, etc.

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• It is used for making aircraft window, artificial eyes, etc.

•
3) Polyurethanes:

These are characterized by the presence of urethane linkage (–NHCOO–)

in their repeating units. They have linear structure and are represented by the
following structure:

[–C–NH– (–R–)–NH–C–O– (–RI–)–O-]n

║ ║

O O

Synthesis: It can be synthesized by the polymerization of di-isocyanate with

glycol.

nO=C=N–R–N=C=O + nHO–R'–OH [–C–NH–(R)–NH–C–O–

(R′)–O–]n

║ ║
Diisocyanate glycol O O

Polyurethane

Properties:

• It is a spongy, transparent, polymer.

• It has high degree of flexibility.
• It is resistance to water, oil and corrosive chemicals.
Applications:

• It is used for tyre retreading and industrial wheels.

• It is used for making light weight garments, swim suits, etc.
• It is used as cushions for furniture & automobiles.
ELASTOMERS

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Elastomers are high polymers which undergo very large elongation under
stress but readily regain their original shape when the stress is removed. This
property of elastomers is called “elasticity”.

Elasticity arises from the fact that, in an unstreched condition, an

elastomer molecule is not straight chained, but it is in the form of coil.

Natural Rubber:

Natural rubber is a high polymer of isoprene (2-methyl-1,3-butadiene). It

is a hydrocarbon polymer having the molecular formula (C5H8) n

During the synthesis of natural rubber, an isoprene molecule polymerizes

to give polyisoprene.

CH3 CH3

nCH2=C-CH=CH2 [–CH2–C=CH–CH2–] n

Isoprene polyisoprene

Natural rubber has many deficiencies which include extreme softness &
stickiness. To minimize the deficiencies, raw rubber is subjected to
vulcanization. Many of the disadvantages can be overcome in synthetic rubber.

Vulcanization is a process of heating the raw rubber mixed with some

chemicals (sulphur, H2S, etc) to a high temperature (120-150°c). The added
sulphur combines chemically at the double bond of the isoprene molecules of
different springs. This sulphur cross links introduced between polymer
molecules of rubber gives more stiffness to the rubber molecule and prevents
the intermolecular movement of rubber springs.

CH3 CH3 –CH2–C=CH–CH2–CH2–C=CH–

CH2- + S
| |

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120-150oc

–CH2–C=CH–CH2–CH2–C=CH–
CH2–

| |

CH3 CH3

CH3 CH3

| |

–CH2–C–CH–CH2–CH2–C=CH–
CH2–

| |

S S

| |

-CH2-C–CH–CH2–CH2–C=CH–
CH2–

| |

CH3 CH3

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Vulcanized rubber

Deficiencies of natural rubber Advantages of synthetic rubber

1) Easily attacked by sunlight. 1) Do not easily attack by sun

2) Softens & swells in organic light.
solvents. 2) Do not swell & can hold
3) Low tensile strength. organic solvents.
4) More water absorption. 3) High tensile strength.
5) Poor electrical insulator. 4) Less water absorption.
6) Less durable. 5) Good electrical insulator.
7) Useful temperature range 10- 6) More durable
60°c. 7) Useful temperature range 40-
8) It is easily attacked by 100°c.
oxidizing agents like HNO3, 8) It is resistance to oxidizing
conc. H2SO4, chromic acid, agents.
etc.

Synthesis and applications of rubbers:

Silicon Rubber:

Silicon rubber (polymethylsiloxane) is an example for inorganic polymer. It

containing alternate silicon & oxygen atoms & each silicon atom carries two
methyl groups. The structure of the silicon is as shown below

CH3 CH3 CH3

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-O-Si-O-Si-O-Si-O-

CH3 CH3 CH3

Preparation: Silicon tetrachloride on treatment with Grignard reagent gives

dialkyldichlorosilane.

SiCl4 +2 R MgI R2SiCl2+2Mg (I) Cl2 where R=CH3

Grignard dialkyldichlorosilane

reagent

Dimethylchorosilane undergo hydrolysis & give dimethylsilanol

CH3 CH3

Cl-Si-Cl + 2H2O OH-Si-OH + 2HCl

CH3 CH3

Dimethylsilanol is unstable & immediately undergo intermolecular condensation to

give Silicones.

CH3 CH3

Polymerization

OH-Si-OH - (-O-Si-O-)-n+ n H2O

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CH3 CH3

Applications:

Silicone rubber can be extruded into tubes, strips, solid cord or custom profiles
according the size restrictions of the manufacturer. Silicone rubber can be moulded
into custom shapes and designs.

ADHESIVES

Definition: “An adhesive is a polymeric substance used to bind together two or

more materials by surface attachment”.

The surface of the materials to be joined must be properly cleaned before the
adhesives are applied. In addition to the surface cleaning the primers are often
applied to influence resistance to aging and corrosion. Care must be taken to
maintain a uniform thickness of the film. While excessive thickness reduces the
adhesive ability, thin films may cause spots.

Classification of adhesives:

Adhesives can be classified into two types:

1. Natural adhesives - Gum, glues, starch, etc.

2. Synthetic adhesives - Epoxy resins, Silicon resins, etc.
Epoxy resins: (araldite)

Epoxy resins are the condensation polymers. They are characterized by the
presence of epoxy group.

Manufacture: Epoxy resins are manufactured by the condensation polymerization

of Bisphenol-A with Epichlorohydrin in the presence of alkaline catalyst.

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CH3

n HO– | –OH

–C– + n CHO2–CH–CH2–Cl
|

CH3
CH3
CH2–CH–CH2 –O– |

O –C–

Bis-Phenol Epichlorohydrin|
CH3

–O–CH2–CH–CH2-O-

OH n

Applications:

• Used as adhesives, surface coating.

• Used as laminating materials in electrical equipments.
• Applied over cotton, rayon and bleached fabrics to impact shrinkage
control.
• Used for skid resistant surface for highways.

POLYMER COMPOSITES

The combination of two or more distinct components to form a new class of

material suitable for structural applications is referred to as composite materials.
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When one of the components is a polymer, resulting composite called as composite

material.

Materials used in polymer composites:

Polymer composites are made up of two components i) fibre ii) matrix

The fibre is embedded in the matrix in order to make matrix stronger. The matrix is
usually thermoset materials such as epoxy resin or polyamide & it holds the fibre
together. Fibre is most often glass, polyethylene or Kevlar. Fibre-reinforced
composites are strong & light.

The need to develop polymer composites based on their properties

Polymer composites shows following properties

• They are light in weight

• They have high strength to weight ratio
• They are much stronger than steel & aluminium
• They are most suitable for aerospace applications due to the inherent
characteristic properties
• They have good corrosion resistance
• Then have high temperature resistance
• They have high fatigue strength

Applications of polymer composites:

• They are used in aircraft & space industry

• They are suitable for automotive & railway applications
• Used for civil construction work

Kevlar:

Kevlar is aromatic polyamide (aramide).The composition of Kevlar is

Poly para-phenyleneterephthalamide.

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Kevlar is synthesized in solution of N-methyl-pyrrolidone & calcium chloride from

the monomers 1,4-phenylene-diamine(para-phenylenediamine) & terephthaloyl
chloride through a condensation reaction with liberation of HCl as a byproduct.

O
O
NH2
NH2
Cl
+ Cl
H2N NH
H2N

O O
n

1,4-phenylene-diamine terephthaloyl chloride kevlar

Applications of Kevlar:
It is used to make light weight boat hulls, aircraft fuselage panels, pressure vassals
, high performance race car, bullet proof vests, puncture resistance bicycle tyres
etc.

Disadvantages of Kevlar

Kevlar composites are very sensitive to environment.

CONDUCTING POLYMERS

Definition: “An organic polymer with highly delocalized pi-electron system

having electrical conductance is called conducting polymer”.

Ex: Polyacetylene, polypyrrole, polythiophene, polyphenylene, polyaniline, etc.

Conducting polymers are generally obtained by doping an oxidizing or

reducing agent into organic polymer consisting of alternating single and double

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bonds. Normally electrons in a polymer are localized and do not take part in the
conductivity, but the doping can delocalize the pi-electrons responsible for
conduction.

Mechanism of conduction in polyacetylene:

Polyacetylene is a semiconductor on its own, but when doped, its

conductivity increases. It can be doped by oxidation with halogen (I2) called P-
doping or by reduction with alkali metal (Na) called N-doping.

Mechanism of conduction in polyacetylene can be explained by taking any one of

the doping.

P-doping mechanism:

In this process Pi-electrons of polymer are partially oxidized using a suitable

oxidizing agent like I2 vapor. This creates positively charged sites on polymer
backbone, which are current carriers for conduction.

The removal of an electron (oxidation) from polymer pi-back bone using I2

as oxidizing agent leads to the formation of delocalized radical ion called
“polaron”.

A second oxidation of a chain containing polaron followed by radical

recombination yields 2 charge carriers on each chain. The positive charge sites on
the polymer chain are compensated by anions I3¯ formed by oxidizing agent during
doping.

The delocalized positive charges on the polymer chain are mobile. Thus
these delocalized positive charges are current carriers for the conduction. These
charges must move from chain to chain.

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Polyacetylene

I oxidation (I2 – e¯ + I3)

.
Polaron

II oxidation
.
.

Recombination of radicals

Conducting polyacetylene polymer (P-doped)

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