POLYMERS

Polymer

A polymer is a compound of high molecular mass formed by the combination of

large number of small molecules and process is called polymerisation. The small
molecules which constitute the repeating units in a polymer are called monomer
units.

Polymerisation

The process of formation of polymers from respective monomers.

Natural polymers

Found in plants and animals. Examples: proteins, cellulose, starch.

Synthetic polymers:

Synthesised in laboratory from natural material. Example, nylon 6, 6 , Buna-S

Addition Polymers

Formed by repeated addition of monomers having multiple bonds. e.g. Polyethylene

Homopolymers.

The polymer formed from one kind of monomer is called homopolymer

Copolymers

polymers formed from two different monomeric species eg Buna . S

monomer units are linked together to form long straight chains. Such polymers have
high densities
the monomeric units are linked to consitute long
Branched chain
chains (called main chain). There are side chains of different lengths which
polymers :
constitute branches
Cross linked polymers The monomeric units are linked together to constitute a three dimensional
network, Cross linked polymers are hard, rigid and brittle because of their network
structure.eg. Bakelite, Formladehyde, resin etc.
Linear polymers

Condensation polymer Formed by repeated condensation of different bi or tri-functional monomer units.

Fibres
Elastomers
Thermoplastic
polymers

These are the polymers which have quite strong interparticle forces such as
H.bonds. eg. Nylon, dacron etc.
These are the polymers having elastic character. The polymer chains in such type of
polymers are held together by weakest intermolcular forces. eg. Natural rubber
Soften on heating and stiffen on Cooling. These are the polymers which can be easily
moulded into desired shapes by heating and subsequent cooling to room
temperature. The intermolcular forces in thermoplastic polymers are
intermediate to those of elastomers and fibers. eg. Polyethene and polystyrenee.g
polythene, polystyrene, PVC

Thermosetting
polymers
HDP

Gutta Percha

These are the polymers which become hard and infusible on heating. Heating
reuslts in excessive cross linking between the chains forming three dimensional
network of bonds. eg. Bakelite, melamine
High density polythene: in the presence of a catalyst such as triethylaluminium and
titanium tetrachloride (Ziegler-Natta catalyst) at a temperature of 333 K to 343 K and
under a pressure of 6-7 atmospheres.
The rubber in which the arrangement of carbon chain is trans Gutta Percha

Addition Polymerisation or Chain Growth Polymerisation ( In chain-reaction polymerization)

Some important polymer and their uses

Rubber (elastomers)
Rubber
(i)Neoprene rubber

Monomers

Formula

CH 2 C CH CH 2

CH = CH2

CH

CH

CH

2
2
|

Cl

Cl
Chloropren e

Styrene (25%)

(ii) Styrene Butadiene

Rubber (SBR) or BunaS

CH 2 CH CH CH 2 and

CH 3
|

CH 2 C
|

CH 2 C CH CH 2

CH 3
Isobutylen e (98 %)

(iv) Nitrile rubber or

Buna N or GRA

CH 2 CH CH CH 2 CH CH 2

Butadiene (75%)

(iii) Butyl rubber

Applications
Making automobile,
refrigerator parts and
electric wire.

CH 3
Isoprene (2- 3 %)

and
CH 2 CH CH CH 2 and
Butadiene (75 %)

CH 2 CH CN
Acrylonitrile ( 25 %)

Making of tyre and other

mechanical rubber goods.

CH 3
CH 3

|
|
CH 2 C CH CH 2 C CH 2
|

CH 3

Making of toys, tyre, tube

etc.

CH

C
H

CH

CH

CH

CH

2
2
2

CN

Used for make of fuel tank.

Plastics and resin

Name of polymer
(i) group -Polyolefines
(a) Polyethylene or
polyethene

(b) Polypropylene or
polypropene

Starting materials (monomers)

Nature of polymer

LDPE (Low
density
polyethene)

CH 2 CH 2

Low density
homopolymer
(branched) chain

Transparent,
moderate tensile
strength, high
toughness.

Packing material carry

bags, insulation for
electrical wires and
cables.

HDPE (high
density
polyethene)

CH 2 CH 2

High density
homopolymer
(linear) chain
growth.

Transluscent,
chemically inert,
greater tensile
strength,
toughness.

Manufacture of buckets,
tubs, house ware, pipes,
bottles and toys.

PP

CH 3 CH CH 2

Homopolymer,
linear, chain
growth.

Harder and
stronger than
polyethene.

Packing of textiles and

foods, liners for bags,

C 6 H 5 CH CH 2

Homopolymer,
linear, chain
growth

Transparent

Plastic toys, house hold

wares, radio and
television bodies,
refrigerator linings.

CH 2 CH Cl

Homopolymer
chains growth

Thermoplastic

(i) Plasticised with high

boiling esters PVC used
in rain coats, hand bags,
shower curtains, fabrics,
shoe soles, vinyl flooring
(ii) Good electrical
insulator (iii) Hose
pipes.

Homopolymer,
high melting point

Flexible and inert to

solvents boiling
acids even aqua
regia. Stable upto
598 K.

(i) For nonstick utensiles

coating (ii) Making
gaskets, pump packings
valves, seals, non
lubricated bearings.

Abbreviation

(c) Polystyrene or Styron or

styrofoam

(a) Polyvinyl chloride

PVC

Vinyl chloride

(b) Polytetrafluoroet-hylene
or Teflon

(iii) Formaldehyde resins

PTFE

F2 C CF2

Properties

Applications

Cross linked

(a) Phenol formaldehyde

resin or Bakelite

Phenol and formaldehyde

Copolymer, step growth

Thermosetting polymer, hard and brittle

Linear
polymers
(b) Novloac
Copolymer, step
growth

(b) Melamine formaldehyde

resin

Thermosetting
polymer, hard but
not so breakable.

(i) With low degree

polymerisation
as
bindings glue for wood
varnishes, lacquers.
(ii) With high degree
polymerisation for
combs, for mica table
tops, fountain pen
barrels electrical goods
(switches and plugs).
Non-breakable crockery.

and HCHO
Melamine and formaldehyde
Table : 30.6 Fibre

Name of
polymer

Abbreviation

Starting materials

Nature of polymer

HO CH 2 CH 2 OH and

(i) Polysters
(a) Terylene or
Dacron or mylar

Ethylene glycol or Ethane -1, 2- diol

HOOC

Properties

Applications

Copolymer, step growth linear condensation

polymerFibre crease resistant, low moisture
absorption, not damaged by pests like

For wash and wear

fabrics, tyre cords
seat belts and sails.

Thermoplastic,
dissolves in suitable
solvents
and
solutions
on
evaporation leaves a
tough but not flexible
film.

Paints and lacquers.

COOH

Terephthalic acid

HO CH 2 CH 2 OH

(b) Glyptal or alkyd

resin

Ethylene glycol

and

COOH
Phthalic acid

COOH

(ii) Polyamides
(a) Nylon-66

||

||

Copolymer, linear
step growth
condensation
polymer

HO C[CH 2 ] 4 C OH

Copolymer, linear, step growth

condensation polymer Thermoplastic high
tensile strength abrasion resistant.

Textile fabrics,
bristles for brushes
etc.

Adipic acid

and H 2 N [CH 2 ]6 NH 2
Hexamethyl lenediamin e

H 2 N [CH 2 ]6 NH 2

(b) Nylon-2,6

Hexamethyllene diamine

and

Copolymer, linear,
step growth

biodegradable.

H 2 N CH 2 COOH

(ii) Substitute of
metals in bearings.

glycin

H
N

(c) Nylon-6 or Perlon

(i) Textile fabrics,

carpets, bristles for
brushes etc.

Homopolymer, linear
Thermoplastic high tensile strength
abrasion resistant.

Mountaineering
ropes, tyre cords,
fabrics.

Copolymer

Orlon, arcrilon
used for making
clothes, carpets
blankets and
preparation of
other polymers.

Caprolactum or H2N [CH2]5 COOH

(iii) Polyacryloni-trile
or orlon or acrilon

PAN

CH 2 CH CN

Hard, horney and

high melting
materials.

Difference between addition and condensation polymers

Addition polymers
Or Chain growth
Formed by addition reaction.

Condensation polymers
Or Step growth
Formed by condensation process
with
elimination
of
small
molecules like H O.
Molecular mass is not whole
number multiple of the monomer
units.
Generally involve more than one
monomer unit.
Monomer units must have two
active functional groups.
They are generally step growth
polymers.

original chain. This leads to lowering of average molecular mass of the polymer
such reagents are called chain transfer agents. The common example
CCl4 , CBr4 etc.
For example in the presence of CCl4 styrene polymerizes to form a
polymer of lower average molecular mass which also contains some chlorine.

CH 2 CH

Molecular mass is a whole number

multiple of the monomer.
Generally involve one monomer
unit.
Monomers
are
unsaturated
molecules.
They are generally chain growth
polymers.

Difference between thermoplastic and thermosetting polymers

Thermoplastic polymers
(1) These soften and melt on
heating.

(2) These can be remoulded recast

and reshaped.
(3) These are less brittle and
soluble in some organic solvents.
(4) These are formed by addition
polymerisation.
(5) These have usually linear
structures.
Ex. Polyethylene, PVC, teflon.

Thermosetting polymers
These do not soften on heating
but rather become hard in case
prolonged heating is done these
start burning.
These can not be remoulded or
reshaped.
These are more brittle and
insoluble in organic solvents.
These are formed by condensation
polymerisation.
These have three dimensional
cross linked structures.
Ex. Bakelite, urea, formaldehyde,
resin.

(1) Natural rubber

Thus isoprene is a monomer of natural rubber the no. of isoprene unit are 11,000 to
20,000 which linked together in a chain.
CH 3

|
|

Polymerisa tion
nCH 2 C CH CH 2
CH 2 C CH CH 2
Isopreme

CH 3

Natural rubber

CH

|
~CH C CH CH ~
| |
2

S
2

CH

C6 H 5

C6 H 5

CH 2 C H
|

CH 2 CH Cl CCl3

Cl3 C CH 2 C H

CCl

C6 H 5

C6 H 5

Styrene

Cl3 C CH 2 C H CH 2 C
|
|

C6 H 5
C6 H 5 n

Chain transfer agents determinate chain reaction and inhibit further

polymerisation and are also called inhibitors.
(ii) Cationic mechanism : Cationic polymerisation is initiated by use of acids such
as H 2 SO 4 , HF or BF3 in H 2 O . The following steps are involved :

(a) Chain initiation : The acid furnishes proton.

H 2 SO 4 H HSO 4

HF H F
BF3 H 2 O H BF 3 (OH )
The proton adds to the carbon of the double bond of the alkene to form a
carbonium ion.

H CH 2 CH 2 CH 3 C H 2
(b) Chain propagation : The carbonium ion combines with another
molecule of alkene to form a new carbonium ion and the process continues to
form a long chain.

CH 3 CH 2 CH 2 CH 2 CH 3 CH 2 CH 2 CH 2

CH 3 CH 2 CH 2 CH 2 nCH 2 = CH

Biodegradable polymers
These are the polymers which are degraded by micro-organisms within a
suitable period so that biodegradable polymers and their degraded products do
not cause any serious affects on the environment
Among these aliphatic polyesters are one important class of biodegradable
polymers which are commercially potential biomaterials. The common examples of
biodegradable polymers are polyhydroxy butyrate (PHB), polyhydroxy butyrate
co--hydroxy valerate (PHBV), polyglycolic acid (PGA), polylactic acid (PLA), poly
(-caprolactone) (PCL), etc.
(ii) Poly-Hydroxybutyrate-co--Hydroxy valerate (PHBV) : It is copolymer of 3hydroxy butanoic acid and 3-hydroxy pentanoic acid, in which the monomer units
are joined by ester linkages.
nCH 3 CH CH 2 COOH n CH 3 CH 2 CH CH 2 COOH
|

OH

3 -Hydroxy butanoic acid

OH

3 -Hydroxy pentanoic acid

~CH C = CH CH ~
|
2

| |
~CH C CH CH ~
|
2

C6 H 5

(2) Synthetic rubber : The synthetic rubber is obtained by polymerising certain

organic compounds which may have properties similar to rubber and some
desirable properties. Most of these are derived from butadiene derivatives and
contain carbon-carbon double bonds. The synthetic rubbers are either
homopolymers of 1, 3 butadiene or copolymer in which one of the monomers is 1,
3 butadiene or its derivative so that the polymer has the availability of double
bonds for its vulcanization. Some important examples are Neoprene, styrene,
butadiene rubber (SBR) thiokol, silicones, polyurethane, rubber etc.
Vulcanization of rubber : The process of heating natural rubber with sulphur to
improve its properties is called vulcanization. Vulcanization was introduced by
Charles Goodyear.
Although natural rubber is thermoplastic substance in which there are no
cross link between the polymer chain and it on vulcanization set into a given
shape which is retained.

CH

Initiator

CH 2 CH

|
~CH CH = C CH ~
|
2

CH

Chain transfer agents : In free radical Vinylic polymerisation various other

molecules react with main growing chain to interrupt the further growth of the

Super glue is a polymer of methyl -cyanoacrylate.

Ebonite is high sulphur (20-30%S) rubber and is obtained by
vulcanization of natural rubber
Low density polythene is a branched polymer and is prepared by free
radical polymerization while high density polythene is a linear polymer
and is prepared by coordination polymerization