POLYMERS

Polymers are high molecular weight compounds in the range of 104-106,

whose structures are composed of a large number of simple repeating
units. The repeating units are usually referred to as monomers. The
conversion process of monomer into polymer is known as
polymerization.
Example for polymerization:
The formation of polyethylene is an example for polymerization.

CH2 =CH2 -CH2-CH2-CH2-CH2-CH2-

ETHYLENE POLYETHYLENE
(Monomer) (Polymer)
The equations for polymerization are represented as below, where n
stands for a large number.

n CH2=CH2 [-CH2-CH2-]n
Ethylene Polyethylene
Polymers are said to be linear, if the repeating units are joined together
like links in a chain. The chains may be branched, or joined together by
cross-links, or both. More extensive cross-linking may lead to the
formation of a three dimensional cross-linked or net-work polymer.

TYPES OF POLYMERISATION:
There are two main types of polymerization processes namely addition
polymerization and condensation polymerization.
Addition polymerization:
In addition polymerization process, all the atoms in the monomer are
present in the polymer with out the elimination of any molecule.
Eg.

n CH2=CH2 [-CH2-CH2-]n
Ethylene Polyethylene

n CH3-CH=CH2 [-CH- (CH3)-CH2-]n

Propylene Polypropylene

Condensation Polymerization:
Condensation polymerization proceeds with the elimination of simple
molecules like water, ammonia, carbon-dioxide, methanol etc.
Eg.,
A well known example for the condensation polymerization reaction is
the formation of Nylon-6,6. It is obtained by heating adipic acid with
hexamethylene diamine under Nitrogen at 180-2200C.Nylon-6,6 derives
its name from its starting materials, adipic acid and hexamethylene
diamine both of which have six carbons.
∆
HOOC(CH2)4COOH + HNH(CH2)6NH2
- H2O

HOOC(CH2)CONH(CH2)6NH2

[-CO(CH2)4CONH(CH2)6NH-]n
Nylon-6,6
FREE RADICAL MECHANISM OF ADDITION
POLYMERISATION:
Addition polymerization takes place either by a free-radical or ionic
mechanism depending upon the reagents employed. Free radical
polymerization is catalyzed organic peroxides or other reagents which
decompose to give free radicals.
(1) Chain Initiation: Organic peroxides undergo hemolytic fission to
give free radicals.
R-CO-O-O-CO-R 2R-CO-O*
Unstable
2R* + CO2
(2) Chain Propagation: Free radical produced in the above step adds
to an alkene molecule to form a new free radical.
R* + CH2=CH2 R-CH2-CH2*
Ethylene
This free radical can attack another alkene molecule and so on.

(3) Chain Termination: The chain can be interrupted when two free
radical chains combine, or by disproportionation.
Combination:
2R(CH2CH2)nCH2CH2*
R(CH2CH2)nCH2CH2:CH2CH2(CH2CH2)nR
Disproportionation:
R(CH2CH2)nCH2CH2* + R(CH2CH2)n-CH2-CH2*
R(CH2CH2)nCH2CH3 + R(CH2CH2)nCH=CH2
 PLASTICS
Plastics can be defined as “non-metallic moldable compounds which are
produced from polymerization of simple molecules”. Plastics can be
classified on the basis of their physical properties and chemical sources
from which they are produced.
Classification on the basis of the chemical sources:
(1) Cellulose Plastics: Eg, Cellulose nitrate and Cellulose acetate.
(2) Synthetic Resin Plastics: Eg. Phenol-formaldehyde, phenol-
furfural, urea-formaldehyde, vinyl, styrene and acrylic plastics.
These plastics made from phenol, HCHO, urea, acetylene,
glycerol and phthalic anhydride.
Classification on the basis of physical property:
(1) Thermoplastic: A thermoplastic polymer is one which softens on
heating and becomes rigid again on cooling.
(2) Thermosetting polymer: A thermosetting polymer is one which
becomes hard on heating. It cannot be softened by heating.
DIFFERENCES BETWEEN THERMOPLASTICS &
THERMOSETTING PLASTICS:
S.No Thermoplastics Thermosetting plastics
1 They are readily softened by They do no soften on heating, on
heat. further heating they burn.
2 They are linear in nature. They have three dimensional
network structure, joined by
strong covalent bond.
3 They are addition polymers. They are condensation
polymers.
4 They can be remolded and
reused. They cannot be remolded and
5 They are soft, weak and less reused.
brittle in nature. They are hard, strong and more
brittle.
6 They reclaimed from wastes
and soluble in organic They cannot be reclaimed from
solvents. wastes and insoluble in all the
organic solvents.

Preparation of Nylon 6,6:

Nylon-6,6 is obtained by heating adipic acid with hexamethylene under

Nitrogen at 180-2200C.Nylon-6,6 derives its name from its starting
materials, adipic acid and hexamethylene, both of which have six
carbons.
∆
HOOC(CH2)4COOH + HNH(CH2)6NH2
- H2O

HOOC(CH2)CONH(CH2)6NH2
[-CO(CH2)4CONH(CH2)6NH-]n
Nylon-6,6
Properties:
(i) They have high stability because of its melting
point(1600-2640C) towards heat and good abrasion-
resistance.
(ii) They are insoluble in common organic solvents except in
phenol and formic acid.
(iii) They are very flexible and retain original shape after
use.
Applications:

(i) Nylon 6,6 is used for the manufacture of socks, dresses,

undergarments, carpets etc due its flexible nature.
(ii) It is mainly used for gears, bearings, electrical mountings etc.
(iii) They are also used for making filaments of ropes, bristles for
tooth-brushes and films, tyre-cords, etc.

Preparation of Polyvinyl chloride (PVC):

PVC is prepared by heating a water-emulsion of vinyl chloride in

presence of a small amount of benzyl peroxide or H2O2 in an
autoclave under pressure.

Polymerization
n (CH2=CHCl) (-CH2-CHCl-)n
vinyl chloride Polyvinyl chloride

Properties:
(i) It is a colorless, odorless, and chemically inert powder.
(ii) It is resistant to light, atmospheric oxygen, inorganic acids and
alkalis but soluble in hot chlorinated ethyl chloride.
Applications:
(i) PVC is used for the tank-linings, light-fittings, safety helmets,
refrigerator components, tyres.
(ii) Plasticized PVC is used for making of rain-coats, table cloths,
toys, tool-handles, plastic coated cloth, chemical containers,
etc.

Preparation of Teflon: Ploytetrafluoroethylene (PTFE):

Teflon is obtained by the polymerization of tetrafluoroethylene, under

pressure in presence of benzoyl peroxide as a catalyst.
Polymerization
n (CF2=CF2) (-CF2-CF2-)n

Properties:
(i) Teflon has extreme toughness, high softening point and it
shows high resistance towards all chemicals.
Applications:
(i) It is used as insulating material for motors, transformers,
cables, wires, fittings.
(ii) It is used for the manufacture of gaskets, chemical carrying
pipes, tanks, etc.

Preparation of Polycarbonate:

Polycarbonates are prepared by interaction of diphenyl carbonate

with bisphenol-A [2,2-bis(4-hydroxyphenyl)propane].

n [ -O- ]2 C=O + n HO- -C (CH3)2 - -OH

Diphenyl carbonate Bisphenol-A

[-O-CO-O- -C(CH3)2- --] +2n -OH

Polycarbonate

Polystyrene:
Polystyrene is prepared from the polymerization of styrene.

Polymerization

n CH2=CH(C6H5) [-CH2- CH(C6H5)-]n

styrene Polystyrene

Applications: Polystyrene is used in the making of audio cassettes, house

wares, bottle caps, brush handles etc.
Polyethyleneterephthalate (PET) or Terylene (Dacron):

Preparation:

PET is one of the commercially important thermoplastic polymer which

is obtained by the condensation of ethylene glycol with terphthalic acid
in the presence of Antimony Oxide(Sb2O3) at elevated temperature.

n OH-(CH2)2-OH + HOOC - -COOH

Ethylene glycol (Sb2O3)

Terephthalic acid

[ - OH – (CH2)2-O-CO- CO- ] n
PET

Properties:
(i) PET is a colorless transparent mass.
(ii) It has a good fibre forming property with high tensile strength
for wrinkle free crease resistant garments.

Applications:
(i) PET is used for the manufacture of garments with wool and
cottons.
(ii) It is also used for the manufacture of bottles and containers.

Polyurethanes:
Preparation:

Polyurethanes are prepared by reaction of diisocynates and diols in the

presence of Stannic chloride or Stannous octoate at 50-1000C.

n HO-(CH2)4-OH + n OCN - - CH2 ─ NCO

 [ - CONH CH2 - NHCOO(CH2)4O-] n

Polyurethanes

Applications:
(i) Polyurethanes are used in construction and interior decoration
of buildings.

RUBBER

Rubbers are high polymers which have elastic properties in excess of

300 %. Natural rubber consists of basic material index which is a
dispersion of isoprene. These isoprene molecules polymerize to form
long-coiled chains of cis-polyisoprene.

n [ CH2 =C(CH3) −CH=CH2 ] ------→ [ -CH2-C(CH3) = CH-CH2- ] n

isoprene Cis-polyisoprene
(Natural rubber)

-CH2-C(CH3)=CH-CH2- CH2-C(CH3)=CH- CH2- CH2-C(CH3)=CH- CH2

!---------------------------!-------------------------------!-----------------------------
Isoprene unit isoprene unit isoprene unit

The m.wt of raw rubber is about 1,00,000- 1,50,000. Natural rubber is

obtained from saps of the plants like havea brasillians and guayule
found in tropical and semi-tropical countries like Indonesia, Malaysia,
Ceylon, India .
Vulcanization of Rubber:

Raw rubber cannot be used directly due to its low tensile strength. To
and which makes the rubber as the hard one and this process is known
as vulcanization of rubber. Normally vulcanization is done by heating
the rubber with sulphur at 100-1400C. The sulphur chemically
combines with the rubber at the double bonds and makes a cross linking
between the chains.
-CH2-C(CH3)=CH-CH2- CH2-C(CH3)=CH- CH2- CH2-C(CH3)=CH- CH2

-CH2-C(CH3)=CH-CH2- CH2-C(CH3)=CH- CH2- CH2-C(CH3)=CH- CH2

Sulphur
100-1400C

-CH2-C(CH3)-CH-CH2- CH2-C(CH3)-CH- CH2- CH2-C(CH3)-CH- CH2

| | |
S S S
| | |
-CH2-C(CH3)-CH-CH2- CH2-C(CH3)-CH- CH2- CH2-C(CH3)-CH- CH2

Vulcanized rubber

Synthetic Rubber
Synthetic Rubbers which has more tensile strength and hard in nature
and some of the synthetic rubbers are namely,

BUTYL-1-RUBBER:(GR-I or Polyisobutylene)
Preparation:
Butyl rubber is prepared by the cop[polymerization of isobutene
with the trace amount of isoprene in the presence of Aluminum
Chloride. The reason for the addition of isoprene, which makes the
resulting product vulcanizable.

n CH2=C(CH3)2 + n CH2=C(CH3)-CH=CH2
Isobutene isoprene

[- CH2-C(CH3)2-CH2-C(CH3)=CH-CH2-] n
Polyisobutylene
Properties:
(i) It is amorphous but crystallizable solid.
 (ii) Due to its low unsaturation it can be vulcanized and cannot be
hardened.
(iii) It is very much soluble in solvents like benzene not in alcohol,
HCl, HF, etc.

Applications:
(i) It is used for the manufacture of insulators employed in high
voltage.
(ii) Inner tubes of automobile tyres,
(iii) For the making of conveyor belts, lining of tanks, hoses etc.

STYRENE RUBBER: (GR-S or Buna-S or SBR)

Preparation:
It is prepared by the co-polymerization of butadiene(75%) and
styrene(25%) in an emulsion system at 500C in the presence of cumene
hydroperoxide as a catalyst.

nCH2=CH-CH=CH2 + CH2=CH
│

-CH2-CH=CH-CH2-CH2-CH=CH-CH2-CH2-CH-CH2-CH=CH-CH2-
│

Stryene Butadiene Rubber

Properties:
(i) SBR contains double bonds so vulcanization can be done with
sulphur or sulphur monochloride(S2Cl2).
(ii) It swells in oils and solvents and it gets oxidized in the
atmosphere.
Applications:

SBR is used in the manufacture of the followings, motor tyres, foot

wears, gaskets, adhesives, tank-lining etc.

COMPOSITES
Definition:
A composite may be defined as “any multiphase material which
consists of two or more physically and/or chemically distinct phases
with an interface separating them.” Composites are obtained from
conventional materials like metals, ceramics and polymers by adding
fibers, particles etc.

Composites have properties like toughness and strength with low

weights and high temperature resistance.

Types of Composite Materials:

Composite materials can be classified on the basis of type of
reinforcement used in the matrix, on the basis of type of matrix, and on
the basis of number of layers.

On the basis of type of reinforcement used in the matrix :

(a) Particle-reinforced composite (b) Fibre-reinforced

On the basis of type of matrix:

(a) Polymer matrix composites(PMC)
(b) Metal matrix composites(MMC)
(c) Ceramic matrix composites (CMC)

On the basis of number of layers:

(a) Uni-layer composites
(b) Multilayer composites.

Polymer Matrix Composites (PMC):

Polymer matrix Composites which contain both thermoplastic and

thermosetting resins.
(i) PMC are tougher and have high strains to failure.
 (ii) (ii) They posses improved resistance to both hot and wet
conditions.
(iii) No gases liberated due to chemical inert nature.

Eg. Epoxy resins, polyimide, polysulfone and phenolics.

Fibre-Reinforced Composites(FRP):

When fibers are used as dispersed phase for the reinforcement of

matrices, the resultant composites are known as FRP.

FRP have high specific strength and high specific modulus and its
strength depends on the following
(a) Nature and properties of fibre and matrix materials
(b) Strength of the interfacial bond between the fiber and the matrix
phases.
(c) Length of the fiber.

Model Questions:

1. Define polymer and degree of polymerization.

2. What is nylon – 6,6.
3. Write the preparation properties and uses of PVC, Teflon,
polycarbonate, polyurethane and PET.
4. Differentiate thermoplastics and thermosetting plastics.
5. Define composites.
6. What is co-polymerization?
7. What are composites? Explain the advantages of composites.
8. Explain Fibre reinforced polymer composite.
9. Write notes on matrix composite.
10.Write the preparation, properties and uses of Butyl – rubber to
SBR.
11.What is monomer? Give one example.
12.What is condensation polymerization? Give one example.
13.What is nylon 6:6? How is it prepared?
14.What is Co – polymerization ? Give example
15.Name the mechanism by which addition polymerization by which
addition polymerization later black.
16.What is PVC prepared and its uses?
 17.Give any two applications of poly carbonate?
18.Define degree of polymerization?
19.Define vulcanization?
20.What are plastics?
21.Name the two types of plastics?
22.What is thermoplastic?
23.What is a thermosetting plastic?
24.What is rubber?
25.What is a preparation, properties and uses of Teflon?
26.Give two example of synthetic rubber?
27.Distinguish between national and synthetic rubber?
28.What are the steps involved in free radial mechanism?
29.What is isoprene?
30.Write the use of PET?
31.Give an example for polycarbonate.
32.Write the uses of butyl rubber.
33.Mention the uses of nylon 6:6.
34.Give the properties of nylon 6:6.
35.Define composites?
36.What is FRP give example?
37.Differentiate thermoplastics and thermosetting plastics.
38.Example free radical mechanism.
39.Give the preparation and uses of (i) Teflon, (ii) PVC, (iii) PET,
(iv) Polycarbonate, (v) poly urethane, (vi) nylon 6:6

Reference Books:

1.Bahl and Arun Bahl, Advanced organic chemistry

2.Jain and Jain, Engineering chemistry
3.Shashi Chawla, A Text book of Engineering Chemistry.