POLYMER MATERIALS

POLYMER
Poly =Many ; Mer =Units (parts)
Polymer :-
Polymer is a large molecule, or macromolecule, composed
of many repeated subunits.
Monomer:-
Simple repeating chemical units in polymer
Polymerization:-
The process of formation of polymers from monomers
Example:- Formation of polyethylene from ethylene
nCH2=CH2 -CH2-CH2-CH2-CH2- ( CH2-CH2 )n
ethylene polyethylene
Repeating units
 polymerization
n momomer units polymer
• Thus, polymer is a large molecule (Macromolecule), formed by
repeated linking of small molecules called ‘monomers’ by covalent
bonds.

• Polymer Vs macromolecule: All polymers are macromolecules in

nature where as all macromolecules are not polymers.

polymerization
 The chemical process by which the monomer molecules are linked
to form a big molecule (polymer) is called as “polymerization”.
 usually polymerization will be carried out in presence of catalyst
under reduced pressure at elevated temperature.
 The number of repeating units in the chain so formed is
called the ‘degree of polymerization’ (DP).
 Polymers with a high degree of polymerization are
called ‘high polymers’
 and those with low degree of polymerization are called
‘oligopolymers’.
 High polymers have very high molecular weights and
hence are called as ‘macromolecules’.
 CLASSIFICATION

BASED ON SOURCE

Natural(occur in Synthetic(man
nature) Semi synthetic made)
Eg : Protein, cellulose, Eg :Cellulose nitrate, Eg : Plastics,
starch etc cellulose acetate Nylon, Buna-s etc
 CLASSIFICATION
BASED ON STRUCTURE

Cross linked or
Linear
Branched Network polymer
polymers(long
chains) chain(chain with (string covalent
branches) bond between
Eg : High density
Eg : Low density chains)
polythene,
polythene Eg : Bakelite ,
Poly vinyl chloride.
Melamine
 Elastomers Fibres
weakest intermolecular forces Strongest inter molecular forces.
Eg : Rubber, buna-S etc Eg : Nylon, Polyesters, terylene …

CLASSIFICATION BASED ON MOLECULAR FORCES

Thermoplastic can be remoulded by Thermosetting Plastic cannot

heating and cooling be reused
Eg : Polythene , PVC etc Eg : Bakelite, urea…
 CLASSIFICATION
MODE OF POLYMERIZATION

Addition polymers Condensation polymers

Polymers are formed by the This involves repetitive
repeated addition of condensation between two
monomers with double and bifunctional monomers, with loss
triple bonds of some simple molecules such as
water, alcohol etc.
Ex:- Polythene, PVC etc.
Ex:- Polyamides, polyesters
(iii) According to the composition of main chain
Two types.
(1) Organic polymers (2) Inorganic Polymers
(1) Organic polymers : main chain is formed by
carbon atoms
Ex : Polyethylene, Polystyrene, PVC etc.
(2) Inorganic Polymers : main chain is formed by
other than carbon atoms

Ex. Polydimethylsiloxane (silicone rubber)

IV. According to the total composition of the polymer
On this basis polymers are divided into 2 types.
(i) Homo polymers (ii) Co polymers
(i) Homo Polymers : Polymers formed from only one type of
monomers

nCH2=CH2 → (—CH2—CH2—)n
ethylene Polyethylene

(2) Co polymers : Polymers formed from 2 or more than 2

different types of monomers
Depending upon the structure, co polymers are divided into 4
types
A. Random co – polymers B. Alternate co – polymers
C. Block co – polymers D. Grafted co – polymers
—B—A—B—A—B—A—B—A—B—A— (Alternating copolymer)

—A—A—B—A—B—B—A—B— (Random polymer)

 A—A—A—A—B—B—B—B—B (Block Copolymer)

graft copolymer
A—A—A—A—A—A—A—A—A
B—B—B

B—B—B
TYPES OF POLYMERIZATION
 TYPES OF POLYMERIZATION
Addition polymerization:
 Reaction in which unsaturated (double or triple bond)
monomers combine with each other to form a polymer (addition
polymer)
 Rearrangement of bonds-during addition polymerization the
double bond breaks and becomes a single bond.
 This reaction takes place in presence of catalyst or light, heat.
POLYMERISATION OF PROPENE - ANIMATION
AN EXAMPLE OF ADDITION POLYMERISATION

Animation may not work in

earlier versions of Powerpoint
 POLYMERISATION OF ALKENES
EXAMPLES OF ADDITION POLYMERISATION

ETHENE POLY(ETHENE)

PROPENE POLY(PROPENE)

CHLOROETHENE POLY(CHLOROETHENE)
POLYVINYLCHLORIDE PVC

TETRAFLUOROETHENE POLY(TETRAFLUOROETHENE)
PTFE “Teflon”
MECHANISM OF ADDITION POLYMERIZATION

Depend on the nature of reactive species, there are

three types of mechanism

• Free Radical
• Cationic
• Anionic

Steps involved in the mechanism are:-

1. Chain initiation step
2. Chain propagation step
3. Chain termination step
 FREE RADICAL MECHANISM

1.Chain Initiation step :

 Radical initiators which are substances that can

produce radical species under mild conditions.

 Initiators undergo homolytic cleavage when excited in

presence of light or heat.

 This radical reacts with one of the monomer unit in which σ

bond of monomer remains as such and weak π bond
breaks.

 E.g. for initiators: acetyl peroxide, azocompounds (-N=N-),

benzoyl peroxide.
2.Chain propagation step :

 Free radicals combines with another monomer to give a new

radical and this radical will again added with another monomer
to give a longer chain radicals.

 This process goes on continuing and producing a high polymer.

3.Chain termination step:-

a) coupling reaction-combination of two chains

b) Reaction with inhibitors: Polymeric chain can be terminated by
the reaction of inhibitors, such as hydroquinone, phenol, amines, etc.
2) Condensation polymerization (Step growth polymerization):

• A condensation polymer generally involves 2 monomers that have

different functional groups.

• They also involve the elimination of water or another small

molecule. Hence the term condensation polymer.

• This rate is lower than chain growth polymerization.

Examples polyamides (nylon)

polyesters (terylene)
peptides
starch
The functionality of the monomer must be two or more than two.
 The Reactions are not exothermic.
 The molecular weight of the polymer is not the sum of the
molecular weights of the monomers.
Ex; polyester (dacron, mylar,), polyamide (nylon 6.6, kevlar, nomax,
perlon)
Mechanism
 POLYAMIDES
 amide groups of: R-CO-NH-R’

 Formed the condensation of a polyamine with a carboxylic acid

 Nylon 6, 6
• Monomers:- hexamethylene diamine and adipic acid

• Preparation:-

Nylon 6:6 is prepared by the condensation polymerization of adipic

acid and hexamethylene diamine in the absence of air.
The 6,6 designation represents the number of carbons in the amine
and the number of carbons in the acid.
Properties:

 It has remarkably low efficient of friction against many metals

 Self extinguishing when it comes in contact with a flame.

 Low water absorption and good strength which does not

deteriorate even when used for a long period.

Engineering applications:-

• used in parachutes (light material).

• sed to make swimwear, machine parts (waterproof in nature).

• used in in airports , offices and other places which are more

liable to wear and tear (high melting point).

• used in airbags, Carpets, ropes, hoses etc.

 POLYESTER
• Polyester is a category of polymers which contain the ester
functional group in their main chain.
Ex:- Dacron (Terylene, Polyethylene Terephthalate, PET)
USES

Apparel: Every form of clothing

Home Furnishings: Carpets, curtains, draperies, sheets and
pillow cases, wall coverings, and upholstery
Other Uses: hoses, power belting, ropes and nets, thread, tire
cord, auto upholstery, sails, floppy disk liners, and fiberfill for
various products including pillows and furniture

Cardiothoracic and Vascular grafts and implants

 Comparison
Addition polymerisation Condensation polymerisation

1. It is also known as chain growth 1) It is also known as step growth

polymerisation Polymerization
2. It takes place only in monomers 2) It takes place in monomers having
having multiple bonds reactive functional groups.
3. It takes place without elimination 3) It takes place with elimination of simple
of simpler molecule molecule like H2O, NH3, HCl etc.
4. Reaction rate is fast. 4) Reaction rate is slow.
5. Mechanism: 5. Mechanism
 PLASTICS

 Intermolecular forces are between that of elastomers and

fibres

Classification of plastics- by physical properties

a) Thermo plastic Resins

b) Thermo setting Resins

Thermo Plastics

 These are linear or slightly branched molecules.

 polymers which are softened on heating and hardened on cooling.,

 Repeated heating or cooling not having any chemical change.

 These are prepared by addition/condensation polymerization.

 These are made of long chains attached by weak vander waal’s force of
attraction.

 These are soft, weak and less brittle.

 These are reclaimed from waste.

 These are soluble in some organic solvents.

Ex : PVC, PE, PS, poly propylene etc.,

Thermo setting Resins
 The polymers which are hardened during their moulding process.

 Once they are hardened they cannot be softened. Hence these are
called permanent setting resins.

 These acquire cross – linked, 3D, Network structure.

 The bonds retain their structure.

 Prolongated heating causes charring of the polymer.

 These are produced by condensation polymerization.

 These are hard, strong and more brittle.

 These cannot be reclaimed from waste.

 These are not soluble in organic solvents. Ex : Bakelite.

 Polyvinyl Chloride
Monomer:- Vinyl chloride

By reacting acetylene with hydrogen chloride in presence of

catalyst.
150
HCl + CHΞCH Catalyst
H2C=CHCl
Polyvinyl chloride:-

Obtained by heating a water emulsion of vinyl chloride in

presence of small amount of benzoyl peroxide or hydrogen
peroxide in an autoclave under pressure.

Properties
 Chemically inert
 High softening point of 148oC
 There are two kinds of PVC plastics; Plasticised PVC and
Rigid PVC
 Plasticised PVC:- is produced by mixing plasticisers

like dibutyl pthalate, tricresyl phosphate etc., with

PVC resin uniformly.

Uses:- for making rain coats, table cloths, curtains, coatings for electric wire
and cables ,toilet articles, tool handles, radio, T.V
components,conveyer belts,pipes,bends,coupling,valves etc.

 Rigid PVC or unplasticized PVC:-

has high rigidity and high chemical inertness.

Uses: -used for making sheets used to line big containers, tanks etc.Other
materials like refrigerator components, tray,cycle and motor cycle mud
guards,tubes,pipes etc are also manufactured out of unplasticised
PVC.
 Teflon or Polytetra fluoroethylene (PTFE)
Monomer:- Tetra flouroethylene

Preparation: -

Tetra flouroethylene Polymerizes at higher temperature and pressure

in the presence of free radical initiators or catalysts like persulfate or
hydrogen peroxide in aqueous media. Redox initiators such as ferrous
sulphate and hydrogen peroxide can also be used.

 PTFE is commercially known as Teflon.

 It is highly crystalline(93-98%) material.

 It is a linear with very little branching.

 The density of Teflon is 2.3 g/cm 2.

 It is highly chemical resistant.
 It has a very good insulating property.
Engineering applications
 It is used to make insulation of motors, transformers, coils,
capacitors etc.
 Used to make self lubricating ball bearings.
 Teflon is used to make articles like pump valves, pipes, etc.
 Used for storage chemicals.
 Teflon is the coating material used in non sticking frying pans.
 Bakelite
Monomer:- phenol & formaldehyde

Preparation:-

It is formed by condensation reaction of phenol & formaldehyde

in presence of acid or alkali catalyst at proper temperature
produces bakelite or phenol formaldehyde resin.

 Methanal is substituted in the 2- or 4- position in the phenol

HCHO
H+
 It then undergoes a condensation reaction with another
phenol molecule results in the formation of novalac (linear).

-H2O

Long chain of phenol-methanal plastics (covalent cross linking)

is built up when further polymerization takes place

Novalac

 Further heating of linear polymer (Novolac) forms cross linking

with other chains in presence of hexamethylene tetramine resulting
in the formation of bakelite
Properties:
Set to rigid, hard, scratch resistant, in soluble, water resistant.
They posses excellent electrical insulating character.
Engineering applications:

 For making electric insulator parts like switcher plugs, switch

boards, heater handles etc..,

 For impregnating fabrics, wood and paper, adenines for grinding

wheels.

 For making bearings, used in propeller shafts for paper industry

and rolling mills.
 Fiber reinforced plastics/polymers (FRP)
Fiber-reinforced plastics (FRP), are a category of composite plastics
specifically using fiber materials to mechanically augment the
elasticity and strength of the plastic. They consist of a polymer matrix
– the original plastic which is usually tough but weak – which is blended
with a reinforcing material to yield a final product with the desired
properties. Polymer allows the material to be formed by moulding,
wrapping etc. A variety of fibres are available for this like glass, carbon
etc. FRP are not vulnerable to corrosion.
Applications: glass – which acts as a good insulator – forms fiberglass
or glass reinforced plastics. Plastics reinforced with glass are ideal for
the power industry as they have no magnetic field and are resistant to
electrical sparks.
Aerospace industry.
Automotive industry.
Construction field.
Consumer goods.
Power industry.
Protective equipment.
Marine infrastructure.
RUBBER
 Rubber

Rubber is of two types n

isoprene polyisoprene
1) Natural Rubber (polyisoprene)
2) Synthetic Rubber

• Natural rubber is the cis-form

Disadvantages
When hot, it melts (becomes sticky)
When cold, it gets hard and brittle
Currently, rubber is harvested mainly in the form of
the latex from certain trees.
 Coagulation with formic acid
 Creep rubber-by passing through creeping machine
 Smoking
Vulcanization (curing):

 To improve the properties of rubber it is compounded with some

chemicals like sulphur, H2S etc. is called VULCANIZATION.

 The process consist in heating the raw rubber with sulphur at 100-
140oc.

 The sulphur is added on monomer double bonds.

 Thus these bonds stiffen the material and prevents inter molecular
movement of rubber springs.

 Vulcanite rubber contains about 32% sulphur.

Does not melt when hot

Advantage
Does not get hard and brittle when cold
 CH3 CH3

CH2 C CH CH2 CH CH2

C

+
CH3 CH3

CH2 C CH CH2 CH CH2

C

CH3 CH3
H
CH2 C C CH2 CH2
C CH

S S S S

CH2 C C CH2 CH2

C CH
H

CH3 CH3

VULCANIZATION OF RUBBER WITH SULPHUR

• ADVANTAGES
When vulcanized rubber is heated, the polymer chains are still held
together by sulphur cross-linkages. Thus,
1. they cannot slip across one another
 does not melt when heated
2. the cis to trans conversion is prohibited.
 does not become brittle when cooled
Properties of rubber improved by
vulcanization:

 tensile strength
 elasticity
 hardness
 tear strength
 abrasion resistance
 resistance to Solvents.
USES
1. Car tyres are made of rubber with carefully controlled
vulcanization
 do not melt when they get hot at high speed but still
possess high grip
2. Bowling ball / mouthpiece of saxaphone
hard but still possess certain degree of elasticity
 Elastomers
Elastomers are polymers that have viscosity and elasticity. The
molecules of elastomers are held together by weak intermolecular
forces. They inherit the unique property of regaining their
original shape and size after being significantly stretched.
Eg: Natural rubber, Buna-S
 BUNA–S (GR-S)

 BUNA–S is a copolymer of a mixture of 1,3- Butadiene

and styrene in the ratio of 3:1 in the presence of sodium
(which is polymerizing agent) gives styrene – butadiene
copolymer (styrene – butadiene rubber) or BUNA –S.

 The name BUNA–S is made up of Bu which indicates 1, 3

– Butadiene, NA is for Sodium (Na) and S indicates
Styrene.
 H H
H H H H
nx + n C C
C C C C
H
H H

butadiene 75 parts styrene 25 parts

Na, heat co polymerization

H H H H H H

C C C C C CH

H H H
x

styrene-butadiene rubber
Properties of Buna–S
 It is very tough and a good substitute for natural rubber.
 It possesses high abrasion resistance.
 It has high load bearing capacity.

Uses of Buna–S
It is used for manufacturing automobile tyres.
It is used for making floor tiles, footwear components,
cable insulation etc.
 Butyl rubber, or polyisobutylene (IIR)

Butyl rubber is a copolymer of isobutylene (97.5%) and isoprene (2.5%).

The polymerization is carried out at low temperature using aluminum
chloride (AlCl3) cocatalyzed with a small amount of water.

It is made by a process called cationic

vinyl polymerization from the
monomer isobutylene. Usually, 1-2%
isoprene is added to the isobutylene.
The reaction is very fast so it is usually
synthesized at very low temperatures.
Applications of Butyl rubber
• As fuel and lubricant additive
• As explosives
•In Damp proofing and roof Repair
•In Gas masks and chemical agent protection
•In Tyres
Properties of Butyl rubber
• Impermeable to air and gases
• long polyisobutylene segments of its polymer chains give it
good flex properties.
 Thiokol Rubber

Monomers: Ethylene chloride and sodium polysulphide.

Thiokol is chemically resistant polymer. It is used in the manufacture of

hoses and tank linings, engine gaskets and rocket fuel.
Properties of Thiokol rubber
 low moisture and gas permeability,
 good flex crack resistance.
 outstanding low temperature flexibility
good resistance to oil, ozone, oxygen and many chemicals
including ethers.

Uses of Thiokol rubber

• making gaskets, seals and hard rubber products to be
exposed to oil and pressure.
• making hoses and linings of vessels used in the manufacture
of chemicals.
• Thiokol rubber mixed with oxygen releasing chemicals is used
 Conducting polymers
 Most of polymeric materials are poor
conductor of electricity, because of non
availability of large number of free electrons
in the conduction process.

 Polymeric materials which shows electrical

conductivities called CONDUCTING POLYMERS.

 Example:- poly acetylene, poly anilene.

 Conducting polymers
Conducting
Polymers

Intrinsic C.P Extrinsic C.P

1. INTRINSIC C.P :

C.P.having Conjugation : Conductance is due to the pi electrons

present in the backbone of the polymer chain.

Eg :- Polyacetylene and polyaniline

Doped C.P : Conducting is due to a +ve or –ve charge created on

polymer backbone by doping. By this we can increase the conductivity
of polymers.

2. EXTRINSIC C.P : The ingredients are added externally for conductance

Conductivity elements filled polymers : Polymers holds a conducting

element

Eg :- carbon black in polymers

Blended C.P. : Blending the conducting and non conducting polymers.

Eg:- 40% polypyrrole

Polymers with Unsaturated (Conjugated)
backbone structure

• A conjugated main chain with alternating

single and double bond

• First example of conjugate polymer:

– Polyacetylene
Doping:

The conductivity of a polymer can be increased by creating either

+ve or -ve charges on polymer back bone by oxi’n or red’n by
which conductivity of polymer increases is called doping. it is two
types

1. n-type doping

2.p-type doping
1)p-DOPING:
 Treating a conducting polymer with a lewis acid
there by oxi’n process takes place and +ve charges
on polymer are created.
 Polymer + lewis acid = (polymer)n+ + (L.a)n-

 Common p-dopants are I2,Br2,AsF5,PF6 etc…

(C2H2)n + 2 I2  2(C2H2)n+ I3-

2) n-DOPING:

 Treating an intrinsically conducting polymer with

a lewis base there by red’n process takes place
and -ve charges on polymer are created.

 Polymer + lewis base = (polymer)n- +(L.b)n+

 Common n-dopants are Li, Na, NH3 etc..,

 Ex:(C2H2)n + NH3  (C2H2)n-NH3+

 Conductivity elements filled polymers
• In this, the polymers act as the binder to hold the conducting element
(such as carbon black, metallic fibers, metallic oxides etc.) together
in the solid entity.

• Both electrical and thermal conductivity are enhanced

• Example: silver-loaded epoxy adhesives

• Applications:

– Self-regulating heaters:

– Resistors
Blended Conducting Polymers
These polymers are obtained by blending a conventional polymer with
a conducting polymer.
Eg:- 40% polypyrrole
 POLYACETYLENE

Synthesis

By Ziegler-Natta Catalyst

Effect of Temperature:

At -78 °C or below: all-cis PA

At 180 °C or higher: all-trans PA
 MECHANISM OF CONDUCTION IN POLYACETYLENE
Due to the presence of conjugation, polyacetylene is conductive in
nature. The conductance can improve by doping. Mechanism of
conduction in polyacetylene can be explain by p-doping and n-doping
separately doping in polyacetylene.
P-doping
In this, polyacetylene is combined with lewis acid like I2, Br2 etc which
are electron acceptors. In the first step the reaction between
polyacetylene and Iodine (in CCl4) occurs. In this process a positive
charge is formed due to removal of an electron (acceptance of an
electron by the dopant) from the polymer i.e., the formation of
polaron takes place.
Subsequent attack by another molecule of Iodine (in CCl4) results in the
formation of bipolaron. Due to separation of charges In bipolaron
conduction process takes place
n – doping
N-doping

•In the case of n - doping, n - doping agent (Na, NH3 etc.) adds electron
to the polymer leading to the formation of negative charge.

•In this mechanism the first step is the formation of polaron followed by
bipolaron and finally soliton. Here charged solitons are responsible for
conduction in polyacetylene
Pure polyacetylene: s ~ 10-9 (cis) and 10-5 (trans) S cm-1
High electrical conductivity was observed when the polymer was “doped” with
oxidizing or reducing agents
Applications:
 Wiring in air crafts and aerospace components
 In telecommunication systems
 In antistatic coatings for clothing
 In electro magnetic screening materials
 In electronic devices such as transistors and diodes
 In solar cells, drug delivery system for human body
 In photo voltaic devices eg: Al / polymer / Au, photo
voltaic cells.
 In rechargeable light weight batteries
 In optically display devices