1

UMAR BAGWAN
MSc ,(Ph.D)
SIET ,Bijapur
POLYMERS
Syllabus
i)Introduction

ii)Types of polymerization: addition and condensation,

iii)Mechanismof polymerization- free radical mechanism taking vinyl chloride as an example.
iv) Molecular weight of polymers: number average and weight average
numerical problems.

v) Glass transition temperature (Tg): Factors influencing
Tg-Flexibility, inter molecular forces, molecular mass, branching & cross
linking, and stereo regularity. Significance of Tg.

vi) Structure property relationship: crystallinity, tensile strength, elasticity, plastic
deformation &chemical resistivity.

vii) Synthesis, properties and applications of
PMMA (plexiglass), Teflon, Polyurethane and polycarbonate.

viii)Elastomers: Introduction, synthesis, properties and applications of Silicone rubber.

ix) Adhesives: Introduction, synthesis, properties and applications of epoxy resin.

x) Polymer Composites: Introduction, synthesis, properties and applications of kevlar
and carbon fiber.

xi) Conducting polymers: Introduction, mechanism of
conduction in Poly aniline and applications of conducting poly aniline








2
UMAR BAGWAN
MSc ,(Ph.D)
SIET ,Bijapur

POLYMERS

Polymer is a macromolecule formed by repeating unit of several simple molecules called
monomer. The process of linking of monomers (repeating unit) is called as polymerization.
Monomer is a simple molecule which undergo self addition to form long chain called polymer
.Monomers are building blocks of polymers. A molecule is said to be monomer ,if it has at least two
bonding sites in the form of double bond or triple bond or should contain groups like OH , COOH
,NCO, NH
2
etc.
Polymerisation: the process of conversion of substance of low molecular mass (monomers) into
substance of high molecular mass with or without elimination of by products like HCl ,H
2
O, NH
3
etc.
Polymerization reaction usually takes place in presence of initiator.
Degree of polymerization: The number of repeating unit present in a polymer is called degree of
polymerization. Here n is the degree of polymerization .When the value of n is very large (in range of
100 or 1000)the polymers are said to be high polymers. When the value of n is less than 10 , the
polymers are called as oligopolymers.
Functionality :The total number of bonding sites or functional groups present in the monomer is
called as functionality of monomer.
For Ex: Ethylene , methylmethaacrylate , adipic acid are bi functional. Phenol and glycerol are
trifunctional.
TYPES OF POLYMERISATION
There are two types of polymerization.
1)Addition Polymerisation
2)Condensation Polymerisation
1)Addition Polymerisation:The process of addition of monomer to each other by covalent bonds
without elimination of by products is called addition polymerization and the polymer is called
addition polymer.
For ex: Polyethylene, Polyvinylchloride(PVC), Polymethylmethaacrylate (PMMA) ,Teflon,
Polypropylene




3
UMAR BAGWAN
MSc ,(Ph.D)
SIET ,Bijapur
a)it is also called chain polymerization.
b)Only alkene or vinyl compounds undergo addition polymerization.
c)Polymer initiates by an initiator like free radical
d) The composition of the polymer is same as monomer.
e)Addition polymerization occurs rapidly
f)No elimination of byproducts.
2)Condensation polymerization: The process of condensation of two or more monomers (similar or
different) with elimination of by products like water , HCl ,NH
3
. Alcohol,etc is called condensation
polymerisaton and the polymer is called condensation polymer.
For ex: Nylon 6,6 , Expoxy resin , Polyesters.


1)It is called as step-growth polymer
2)Elimination of byproducts occurs
c) Reaction catalyzed by acid or base
d)The polymer chain built up is slow and stepwise.
e)The composition of polymer is different from monomer.
f) Polymerization proceeds through inter molecular condensation.

Mechanism of polymerization of Vinyl Chloride by Free radical method (6MARKS)
Polymerisation of vinyl chloride is an example of addition polymerization and takes place by free
radical mechanism. It involves four steps.
1)Generation of free radical
2)Chain Initiation Step
3)Chain Propagation step
4)Chain Termination step.
4
UMAR BAGWAN
MSc ,(Ph.D)
SIET ,Bijapur
1)Generation of free radical In this step homolytic dissociation of dibenzoyl chloride (initiator) takes
place. This results in generation of pair of free radical. Free radicals are highly active species with
unpaired (odd) electron.



2)Chain initiation Step: It involves addition of free radical to monomer, which leads to formation of
chain initiating species(radical).






3)Chain propogation step: The radical formed in above step ,attacks another monomer to give new
radical. This process continuous and growth of polymer chain occurs
.






4)Chain termination: The propagating chain stops growing and terminates. Termination occurs by
two methods a) Coupling b) Disproportion
a)Coupling: Combination of two long chain radical occurs .



5
UMAR BAGWAN
MSc ,(Ph.D)
SIET ,Bijapur

b)Disproportion. Here transfer of hydrogen atom of one polymer chain to another chain occurs. It
leads to formation of two dead polymer chains, out of which one is saturated and other is
unsaturated








Molecular weight of polymers
Polymer chains contain chains of different length, so it is not possible assign specific molecular mass.
Hence average molecular mass is taken. The average molecular mass is expressed in two ways
a) Number average molecular mass: it is given by Mn
b) Weight average molecular mass
a)Number average molecular mass: It is represented by Mn, If a sample is having
n
1
molecules with molecular mass M
1

n
2
molecules wit molecular mass M
2

n
i
molecules with molecular mass M
i

The number average molecular mass , Mn = n
1
M
1
+n
2
M
2
++n
i
M
i

. . n
1
+n
2
++n
i

n represents number of each species
M represents molecular mass of each species

b) Number average molecular mass: It is represented by Mw, If a sample is having
w
1
weight of molecules with molecular mass M
1

w
2
weight molecules with molecular mass M
2

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UMAR BAGWAN
MSc ,(Ph.D)
SIET ,Bijapur
w
i
weight molecules with molecular mass M
i


The weight average molecular mass , Mw = w
1
M
1
+w
2
M
2
++w
i
M
i

. . w
1
+w
2
++w
i


We know that , W=n M
Mw = n
1
M
1
2
+n
2
M
2
2
++n
i
M
i
2

. . n
1
M
1
+n
2
M
2
++n
i
M
i


n represents number of each species
M represents molecular mass of each species
The ratio of Mw/Mn is either equal to or greater than 1. {Mw/Mn 1} .The ratio is called
poldispersity index , if the ratio is equal to one the polymer is said to be mono dispersed . If the ratio
is greater than one the polymer is said to be polydispersed. Polydispersity is the measure of
distribution of molecules of different sizes.
Glass transition temperature(6 marks)
Definition: Glass transition temperature is the temperature at which a polymer transforms
from glassy (hard) to the rubbery state (soft).
OR
Definition: The temperature below which a polymer is hard, brittle and above which is soft
and flexible is called glass transition temperature.
It is denoted by T
g
. The hard and brittle state is known as glassy sate and soft flexible state is
called rubbery state or viscoelastic state. At below T
g
, molecular rotations are not possible
so the polymer is hard (glassy).At above T
g ,
molecules can undergo rotation about single
bond .So the polymer becomes soft(rubber). When heated beyond T
g
,the polymer melts
and reaches a molten state or viscofluid state.
Following factors affect the glass transition temperature.
a)Flexibility: Linear polymers containing single bond ( CC ,CO and CN ) have high
degree of freedom of rotation and hence low T
g
. If rigid and bulky groups such as aromatic ,
cyclic are present ,T
g
increases due to less freedom of rotation.
Eg Polythene 110
0
C Flexible backbone
PVC +80
0
C restricted rotation due to strong polar attraction.
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UMAR BAGWAN
MSc ,(Ph.D)
SIET ,Bijapur
b) Intermolecular forces : Presence of a large number of polar group in the molecular chain
lead to strong intermolecular cohesive forces, which restricts the molecular rotation and
mobility . This leads to an increase in T
g
.
For example: Polyproplyene which contains no polar group , has low Tg of 18
0
C
compared to nylon-6,6 which contains polar group has high T
g
of 57
0
C.
c) Stereo regularity: T
g
of an syndiotactic polymer has higher than atactic polymer ,which
in turn has higher T
g
than isotactic.
syndiotactic polymer >atactic polymer >isotactic polymer
NOTE:
Syndiotactic polymer :functional groups are present on alternate side of chain.
Atactic polymer:functional groups are randomly present in chain.
Isotactic :functional groups are present on same side of chain.


d) Branching and cross linking: A small amount of branching will reduce the value of T
g
,
because the free volume increases with branching and thus decreases the T
g
. On the other
hand , a high density of branching and cross linking brings the polymer chain closer , lowers
free volume and thus reduces the chain mobility, thereby increasing T
g
value.
e) Molecular Mass : Higher the molecular mass more is the restriction in molecular rotation.
Generally Tg of a polymer increases with molecular mass up to 250 and beyond that there is
no change.
SIGNIFICANCE OF Tg
1) It is used to evaluate the flexibility of a polymer and to predict its response to mechanical
stress.
2) It is useful in choosing proper temperature range during processing operations such as
moulding , extrusion , calendring.
3) Coefficient of thermal expansion , heat capacity ,refractive index ,electrical properties etc.
at Tg determine the usefulness of a polymer over a temperature range.
STRUCTURE - PROPERTY RELATIONSHIP (6 marks)
1)Crystallinity
2) Tensile strength
3) Elasticity
4) Plastic deformation
5)Chemical resistivity
8
UMAR BAGWAN
MSc ,(Ph.D)
SIET ,Bijapur
1) Crystallinity :The crystallinity of polymer depends upon structure of monomer , nature of
groups present and stereo regularity of polymeric chain
1) A polymer may be crystalline or amorphous. A polymer will be crystalline, if the chain
has regular and symmetrical molecular structure. Because ploymer chains can pack up
closely and orderly.
2)Linear polymer like HDPE is more crystalline than polysterene.This is because polysterene
is branched and contains bulky groups like benzene.
3)Presence of polar groups in polymer chain leads to high crystallinity , because of
hydrogen bonding with neighboring chain. Eg: nylon 6,6
4) isotactic and syndiotactic polymers have high degree of crystallinity than actactic
,because in actactic groups are present randomly.

2)Tensile strength: Impact strength ,tensile strength and melt viscosity are mechanical
properties of a polymer
1)Polymers with low molecular mass are soft.
2) Polymers with high molecular mass are hard, tough and heat resistant.
3) Cross-linked polymers are stronger than linear and less branched polymers.
4)Tensile and impact strength increases with molecular mass up to certain point and then
becomes constant.
5)The melt viscosity of polymer show gradual increase with molecular mass and a steep
increase at high molecular mass.
6) For commercial use , polymer should have low melt viscosity ,high tensile and impact
resistant.







9
UMAR BAGWAN
MSc ,(Ph.D)
SIET ,Bijapur
3) Elasticity :The property of polymer to uncoil on stretching and recoil on leaving is called
elasticity of polymer. A polymer to show elasticity, individual chains should not break on
stretching. Usually of breaking occurs when chain slip past each other. This is avoided by
1)introducing cross linking at suitable molecular position.
2) Avoiding bulky side groups such aromatic and cyclic structures in repeating units.
3) introducing more non polar groups in chain so that chain don not separate on stretching.
4)Plastic deformation:
Deformation of a polymer is studied applying stress and by finding the deformation caused.
A polymer contains both crystalline and amorphous part .Both the region show elasticity in
glassy state. The deformation depends upon
i)crystallinity
ii)degree of cross linking
iii)glass transition temperature
Thermoplastic polymers turns soft, flexible on heating. On Further heating , polymer melts
such a property is called plastic deformation. On cooling they return to their original shape.
But thermosetting polymer do not show plastic deformation, because all the monomers are
held together by covalent bonds. When they are heated charring of polymer occurs instead
of plastic deformation.
5)Chemical resistivity
Chemical resistivity of a polymer depends upon structure of polymer , molecular mass,
degree of crystalllinity extent of cross linking, presence of polar and non polar groups and
nature of attacking agent. Polymers containing polar groups like OH ,COOH are soluble in
polar solvents like water, alcohol etc .Similarly polymers containing non polar groups such as
CH3 ,C6H5 are soluble in non polar solvents like benzene, toluene. Chemical resistivity can
be increased by i) By increasing molecular mass ii) By increasing crystallinity iii)By increasing
degree of cross linking.
Synthesis, properties and applications of
a) PMMA (plexiglass) b)Teflon
c) Polyurethane d) polycarbonate.
Polymethyl methacrylate :PMMA (plexiglass)
Synthesis(5marks) Plexi glass is obtained by the polymerization of methyl metha acrylate at 60-
70
0
C using hydrogen peroxide as initiator.

10
UMAR BAGWAN
MSc ,(Ph.D)
SIET ,Bijapur







Properties:
1) Amorphous, High resistance to sunlight ,High optical transparency.
2) It allows U.V light to pass.
3) It is resistant to water, alkalis and inorganic salts but dissolves in organic salts.
4) Low scratch resistance compare to glass.
5) Softening point 130 to 140
0
C

Applications: Lenses, artificial eye, dentures (artificial teeth),paints, transparent bath tubs
and wash basins ,TV screens, laser disks and DVD ,attractive sign boards, used in buildings
for decorative purposes.
b)Teflon
Synthesis(5marks)
Teflon is manufactured by emulsion polymerization of tetrafluoroethylene(TFE) using ammonium
persulphate as initiator.
Tetrafluroethylene is used as monomer.It is produced in two steps , in first step chloroform is
treated with hydrogen fluoride to form chlorodifluromethane.
CHCl
3
+2HF CHF
2
Cl
chlorodifluromethane
+ 2HCl
In second step , dechlorination is done to get tetrafluromethane
2CHF
2
Cl
dechlorination
CF
2
=CF
2

Polytetrafluroethylene is made by heating under pressure with ammonium persulphate as initiator
n [CF2 =CF2] [ --CF
2
-CF
2
--]n
11
UMAR BAGWAN
MSc ,(Ph.D)
SIET ,Bijapur
Properties
1) Highly crystalline polymer, high melting point (327
0
C) , high temperature stability
and low temperature flexibility.
2) Low coefficient of friction hence remains slippery and not wetted by oil , water.
3) Practically insoluble in any solvent.
4) It has excellent electrical insulating property

Applications: Used as insulating material, gaskets, tank linings, chemical carrying
pipes, insulator for motor generators, transformers and capacitors. It is used as dry
lubricant, coating material for weapons to prevent corrosion. It is used in making
frying pans, bakery trays , because not wetted by oil and water.
c) Polyurethane :
Synthesis (5marks)
These are the polymers in which the monomers are linked through NHCOO group.
Polyurethane is produced by addition polymerization reaction between alkyl di-isocyanate
and alkyl dihydroxy compound (diols).
















During reaction, H atom of OH group migrates and adds to nitrogen atom; hence it is called
rearrangement addition polymerization.
Properties
1)They are spongy transparent and linear thermoplastics.
2) They have low melting point and high degree of flexibility.
3)They are resistant to water, oil, and corrosive chemical.
4)It has high tensile strength and crystallizes on stretching.
5) It has excellent abrasion resistance.
12
UMAR BAGWAN
MSc ,(Ph.D)
SIET ,Bijapur

Applications
1) They are used to make cushions for furnitures and automobiles.
2) Polyurethane fabrics are used make light weight garments like swimsuits.
3) They are used as good thermal insulators in refrigerators.
4) They are used ac coating on dance floors, because of high abrasion resistance.
5) They are used in making soles for shoes, gaskets, tyres, and industrial wheels.
d) Polycarbonate.
These are the polymers in which monomers are linked through carbonate group .
Synthesis: (5 marks) Polycarbonate is formed by condensation reaction of bisphenol-A (dihydroxy
compound) with diphenyl carbonate at 200
o
C under reduced pressure.
Dipehnyl carbonate is obtained by the reaction between phenol and phosgene in an alkaline
medium in presence of tertiary amine catalyst.











Properties:
1)it has high impact-resistance,
2)it has low scratch-resistance
3)Polycarbonate is highly transparent to visible light
4)polycarbonate can undergo large plastic deformations without cracking or breaking
5)Low flammability and Good UV Resistance
Applications
1)It is used in making bullet proof windows
2)It is used in making roof of cockpit in fighter jets.
3)It is used in making break free lenses.
13
UMAR BAGWAN
MSc ,(Ph.D)
SIET ,Bijapur
4)They are used in making headlamps and optical reflectors in automobiles.
5)Used in production of Compact Discs, DVDs, and Blu-ray Discs
6)They are used in making body case of smart phones , mp3 players and computers.
ELASTOMERS
Are the polymers which elongates on stretching and regain their original shape on leaving.
Ex :Rubber is an example of elastomer
A linear polymer can be converted into rubber if it meets following characteristics
1)It should posses glass transition temperature less than working temperature of rubber.
2)Possibility of cross linking should be there to get required rigidity.
3)Long chains should be geometrically irregular , so that coiling can takes place on thermal agitation.
Synthesis , properties and applications of silicon rubber
Silicon rubber is an example of inorganic polymerIt is chain of alternating silicon and oxygen
atoms. Each silicon atom carries two methyl groups.
Synthesis(5marks)
Silicon rubber is synthesized by condensation polymerization of dimethyl silanol.The
dimethyl silanol is prepared by hydrolysis of dimethyl dichlorosilane. Dimethyl silanol is
unstable and immediately undergoes intermolecular condensation to give silicone











Properties:
1) They have high thermal stability and can be heated up to 200
0
C.
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UMAR BAGWAN
MSc ,(Ph.D)
SIET ,Bijapur
2)They are water repellent.
3) They are not affected by common acids and bases
Applications:
1) They used to make tyres of fighter air crafts
2) To make water proof surfaces and clothes.
3) They are used in making lubricants ,gaskets.
4) They are used for insulation of electrical wires in ships.
5) They are used in making artificial heart valves, transfusion tubing.
6) Used as adhesives in electronic industry.

ADHESIVES:
Adhesive is polymeric substance used to bind together two or more materials so that the
resulting material can be used as single piece.Eg: expoxy resins
Adhesives are applied to surfaces by brushing , rolling , dusting or by trowel. The surface of
objects to be bonded are cleaned , impurities like dust and organic material are removed.
The required amount of adhesive is applied on surface. Uniform thickness is maintained
otherwise , adhesive looses its ability to bind.
Adhesives are classified into two types
i) Natural Adhesives: These are natural occurring. Eg: phenyl-formaldehyde , Urea-
formaldehyde , Resorcinol- formaldehyde, Epoxides.

ii) Synthetic adhesives: These are artificially synthesized. Eg: Gums , glues

The effectiveness and strength of an adhesive depends on
a) Material bonded
b) Solvent used
c) Effect of external conditions such as heat, light and environment.
Each type of adhesive is useful for bonding only a selective group of materials
i) Epoxy resin: metals, wood ,glass , concrete , ceramic and leather

ii) Phenol-HCHO Wood
iii) Urea-HCHO
iv) Resorcinol:Leather


15
UMAR BAGWAN
MSc ,(Ph.D)
SIET ,Bijapur



Synthesis, properties and applications of expoxy resin
Synthesis (5marks)
Epoxy resins are polymeric materials containing the epoxy group at the end of chain.
Epoxy resin is synthesized by condensation polymerization of bis phenol-A and
epicholrohydrin in presence of alkali catalyst








Properties (3marks)

1)The epoxy resins have excellent adhesion quality for various surfaces
2) They are highly viscous liquids and are soluble in organic solvents
3) After adhesion, they are highly resistant to water, solvents, acids, alkalis and weather .
4)They have very good electrical insulating property.
5)The epoxy resins can be used with substances such as polyamines, polysulfides and
polyamides.

Applications(3marks)

1) Epoxy resins are used to bind many surfaces like glass, metals, wood etc
2)They are used as surface coatings for skid-resistant surfaces for highways
3) Epoxy resins are used for production of components of aircrafts and automobiles
4) Epoxy resins are applied over cotton, rayon and bleached fabrics to impart crease-
resistance (anti folding) and shrinkage control
5)They are one of the principal constituents of fiber -reinforced plastics
6) They are used as laminating materials for electrical equipments.



16
UMAR BAGWAN
MSc ,(Ph.D)
SIET ,Bijapur
Polymer Composites
Two or more distinct polymeric components are combined to form new material used for structural
applications is called as polymer composite.
The components of a polymer do not dissolve or merge with each other. But act together ,while
retaining their individual property. Polymer composites are made up of two components.
a) Fibre b) Matrilx
a)Fibre: Fibres are main source of strength .Fibre is embedded in matrix to make the matrix
stronger..Eg: Glass fibre, carbon fibre, Kevlar, polyethylene.
b)Matrix: It holds the fibres together. Matrix is usually a thermosetting material such as epoxy resin
or polyamide. Eg: Vinyl resins , polyurethanes.
Eg for polymer composite: Glass fibre [ fibres =glass , matrix =polymeric resin]
The composite may be made stronger by lining up all the fibres in the same direction .If the fibres
are used (lined up) in more than one direction, the resulting composite will be strong in all the
directions.
synthesis , properties and applications of
KEVLAR b) CARBON FIBRE

A) KEVLAR
Synthesis (5marks)

Kevlar is synthesized by condensation polymerization between 1,4- phenylene diamine and
1,4- benzenedicarbonyl chloride (terphtaloylchloride).In this reaction HCl is by product. The
linkage is through para position of phenyl rings . This creates stretching property in Kevlar.














17
UMAR BAGWAN
MSc ,(Ph.D)
SIET ,Bijapur

Properties(3marks)

1)Kevlar a strong ability to stretch
2)It is light weight and has high strength
3)Kevlar has resistance to impact and abrasion damage.
4)I has very low coefficient of thermal expansion.
5) It has high chemical and flame resistance.

Applications Used in making light weight boat hulls, aircraft panels, pressure
vessels, high performance race cars, bulletproof jackets and puncture resistant
bicycle tyres. Kevlar is used in making combat helmets and face masks.

a) CARBON FIBRE( graphite fibre)
Carbon fibre is a polymer formed by linking of carbon atoms in hexagonal ring form. It is
also called graphite fibre. The fibre is obtained in thin sheets which forms long
ribbons.Bunch of ribbons are packed together to form fibres. These ribbons dont have wide
applications , but when combined with material like expoxy resins, thermosetting resins
improved mechanical properties are observed.

Synthesis(5 marks)
1)Carbon fibre is made by heating polyacrylonitrile.
2) Polyacrylonitrile is heated carefully and sowly to, get polycyclic chain. The CN group
present in polyacrylonitirile involves in cyclisation.
3) It is further heated slowly and ring becomes aromatic by loosing hydrogen atoms.
4)Now it is roasted at 400 to 600
0
C , adjacent chains join together by loosing more hydrogen
atoms.
5)The temperature is gradually raised to 2000
0
C and maintained until all the nitrogen atoms
are expelled to get wider ribbon like pure carbon fibre














18
UMAR BAGWAN
MSc ,(Ph.D)
SIET ,Bijapur
Properties (3marks)
1)They are light weight and stronger than steel.
2)High chemical resistance ,high temperature tolerance and low thermal expansion.
3)High tensile strength and stiffness.



Applications of Carbon fibres (3 marks)
1. In aerospace: wings, fuselage, antennae, helicopter blades, landing gears, seats, floors
rocket motor cases.
2. In automobiles: body panels, bumpers, shafts, gears, bearings, automobile brakes,
clutches.
3. In boats: hulls, decks, masts, engine shrouds.
4. Interior and exterior panels, chairs, tables etc.
5. Protective helmets, archery bows, surfboards, fishing rods, diving boards.6. Pipes, tanks,
pressure vessels, hoppers, valves, pump etc.

CONDUCTING POLYMERS
The polymers which conduct the electric current in the order of conductor are called
conducting polymer.
Introduction
Polymers are used as insulating material due to low conductivity (10
10
Sm
1
to 10
8
Sm
1
)
But in 1977 , a conducting polymer was synthesized accidently by a chemist shirakwa.Poly
phenylene and polythiophene shows conductivity upto 10 Sm
1
. Polyacetylene conducts
almost like a metal. Conducting polymers have number of applications in electrical,
electronics and medical fields.

Conditions for a polymer to show conductivity.
1) A polymer should contain conjugation system (alternate single and double bonds)
2) Polymer should undergo structural changes , when an electron is removed (p-
typing doping ) or when an electron is added(n-type doping)
Eg: polyphenylene , polythiophene, polypyrrole,polyaniline.

Conduction in Polymers
Note* There will be no question in external exam on mechanism of conduction in
polyacetylene.It is for understanding only.
Conduction in polymer is explained by band theory. There is wide forbidden gap between
conduction band and valence band. The valence band is formed the collection of pi bonding
molecular orbitals. The conduction band is formed by the collection pi* anti bonding
molecular orbitals.A polymer can be transformed into conducting polymer by doping.
19
UMAR BAGWAN
MSc ,(Ph.D)
SIET ,Bijapur
In conjugated polymers, pi electrons are localized and do not take part in conductivity. But
these electrons delocalize on doping and conduct electric current. Doping are two types.
P-type (oxidative doping): P type of doping leads to removal of electron from pi system. It is
done by oxidizing agent For Eg: Iodine in CCl
4
.
P type doping creates free radical and positive charge.The combination of
charge and radical is referred as polaron(radical cation). On further oxidation of this polaron
, followed by radical recombination gives two positive charge carries called as
bipolaron(dication).The two positive charges become mobile and can move along the chain
to conduct electric current.When a polymer is heavily doped , a continuous bipolaroon band
is formed. Hence conduction and valence band merge , which results in metallic like
conductivity.













a) n- type doping (reductive doping): It is done by reducing agent. N-type of doping
leads to addition of electron to pi-system and formation polaron(radical anion).
On further reduction, followed by recombination gives biplaron( dianion). The two
negative charges become mobile and can move along the chain to conduct
electric current.









20
UMAR BAGWAN
MSc ,(Ph.D)
SIET ,Bijapur
POLYANILINE (imp)
Introduction :Polyaniline exists in three forms .Its oxidation state is represented by
(1y). Poly aniline exists in three forms.
a)Leuco-emeraldine: It is fully reduced form. It undergoes oxidation readily when exposed to
air, not suitable to make conducting polymer.
b) Emeraldine : It is partially oxidized form.
c) Pernigraniline: It is fully oxidized form .It undergoes degradation, hence cannot be used to
make conducting polymer.
Conduction mechanism in Polyaniline. (6 marks)
Polyaniline is doped with proton to get bipolaron. The para hydroxybenzene sulphonoc acid (PHBSA)
for doping.
1) The hydrogen ions from PHBSA attract to nitrogen atoms which are bonded to quinoid ring,
2) This results in instability in structure due to high energy .So the quinoid ring transforms into
benzene ring.
3) The new benzene ring formed is very unstable, due to repulsive force from adjacent positive
charges.
4) To stabilize the structure, the positive charge attracts electrons from neighboring benzene.
5) This creates a new positive charge on next nitrogen atom. Now the distance between positive ly
charged nitrogen atoms increase.
6) The bipolaron transforms into polaron (two positive charges separate.
7).Now two positive charges formed delocalize and can move along the chain to conduct electric
current.








21
UMAR BAGWAN
MSc ,(Ph.D)
SIET ,Bijapur

Applications of polyaniline.
1) It is used as electrode material in making rechargeable batteries.
2) Emeraldine form of polyaniline is used as resist material in lithography.
3) It is used in making conducting track on printed circuit boards.
4) They are used to make smart windows.
5) They are used in display devices.
6) They are used in making gas sensors ,bio sensors , radiation sensors.
7) They are used as membrane for gas separation.
ASSIGNMENT
ii)Explain the types of polymerization with an example? 6M

iii)Explain the mechanism of polymerization of vinyl chloride ? 6M
iv) What do you mean by number average and weight average molecular mass?


v) What is Glass transition temperature (Tg): Explain the following factors influencing
Tg Flexibility, inter molecular forces, molecular mass, branching & cross
linking, and stereo regularity. (6M)

vi)Write the Significance of Tg. 3M

vii)Explain the following structure property relationship
crystallinity, tensile strength, elasticity, plastic deformation &chemical resistivity.

viii)Write the Synthesis, properties and applications of following polymers
a)PMMA (plexiglass) b Teflon c)Polyurethane d) polycarbonate.

ix)What are Elastomers? Write the synthesis, properties and applications of Silicone
rubber.

x)What are Adhesives? Write the synthesis, properties and applications of epoxy resin.

xi) What are Polymer Composites? Write the synthesis, properties and applications of
a)kevlar
b) carbon fiber.

xi)What are Conducting polymers? Explain the mechanism of
conduction in Poly aniline (6M)
xii)Write the applications of conducting poly aniline? (4M)