15 POLYMERS
Polymerisation - Process of formation of polymers from respective monomers.
Classification of Polymers
1.Classification Based on Source
Natural polymers
Semi-synthetic polymers
Synthetic polymers
Polymers found in
Obtained from natural polymers by
Polymers that are man
plants and animals.
subjecting them to some chemical
made
Eg: proteins, cellulose,
processes. eg: vulcanised rubber.
Eg : Buna S, Nylon - 6
starch
rayon
2.Classification Based Structure
Linear polymers
Branched chain polymers
Cross linked or
Network polymers
Consist of long and
Contain linear chains having
Contain strong covalent
straight chains. Eg :
some branches. Eg: LDP
bonds between various
PVC
linear polymer chains,
e.g. bakelite,
3 Classification Based on Mode of Polymerisation
Addition polymers
Condensation polymers
Formed by the repeated addition of
Formed by repeated condensation reaction
monomer molecules possessing double or
between two different bi-functional or tri-
triple bonds. Eg : polythene , PVC
functional monomeric units. Eg : terylene
(dacron), nylon 6, 6
4 Classification Based on Molecular Forces
Elastomers
Fibres
Thermoplastic
Thermosetting
polymers
polymers
Polymer chains are
Possess high tensile Can be softened
On heating undergo
held together by the
strength and high
repeatedly on
extensive cross
weakest
modulus due to the
heating and
linking in moulds
intermolecular
strong
hardened on
and again become
forces. These weak
intermolecular
cooling.
infusible. These
binding forces
forces like hydrogen
Possess
cannot be
permit the polymer
bonding.
intermolecular
remoulded &
to be stretched.
Eg : polyamides
forces of attraction
reused. Eg :
Eg : Neoprene,
(nylon 6, 6),
intermediate
bakelite, urea-
Buna-S, Buna-N
polyesters
between elastomers
formaldelyde resins
(terylene), etc.
and fibres. Eg:
polythene,
polystyrene,
polyvinyls
Order of strength of intermolecular forces : Elastomer < Thermoplastics
< Fibres < Thermosetting
Classification Based on Growth Polymerisation
The addition and condensation polymers are referred as chain growth polymers and step
growth polymers depending on the type of polymerisation mechanism they undergo
during their formation.
Types of Polymerization Reactions
There are two broad types of polymerisation reactions, i.e., the addition or chain growth
polymerisation and condensation or step growth polymerisation.
Addition Polymerisation or Chain Growth Polymerisation
The molecules of the same monomer or diferent monomers add together on a
large scale to form a polymer.
The monomers used are unsaturated compounds, e.g., alkenes, alkadienes and
their derivatives.
This mode of polymerisation leading to an increase in chain length or chain
growth can take place through the formation of either free radicals or ionic
species.
Free radical mechanism
A variety of alkenes or dienes and their derivatives are polymerised in the presence of a
free radical generating initiator (catalyst) like benzoyl peroxide, acetyl peroxide, tert-butyl
peroxide, etc. Chain initiation steps
Chain terminating step
For termination of the long chain, these free radicals can combine in different ways to
form polythene. One mode of termination of chain is shown as under:
PREPARATION OF POLYMRES
Low density polythene: It is obtained by the polymerisation of ethene under high
pressure of 1000 to 2000 atmospheres at a temperature of 350 K to 570 K in the
presence of traces of dioxygen or a peroxide initiator (catalyst).
Has highly branched structure. It is chemically inert and tough but flexible and a poor
conductor of electricity. Hence, it is used in the insulation of electricity carrying wires and
manufacture of squeeze bottles, toys and flexible pipes.
High density polythene: It is formed when addition polymerisation of ethene takes place
in a hydrocarbon solvent 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.
It consists of linear molecules and has a high density due to close packing. It is also
chemically inert and more tougher and harder. It is used for manufacturing buckets,
dustbins, bottles, pipes, etc.
Natural rubber
Rubber is a natural polymer and possesses elastic properties. Natural rubber may be
considered as a linear polymer of isoprene (2-methyl-1, 3-butadiene) and is also called
as cis 1, 4 polyisoprene.
The cis-polyisoprene molecule consists of various chains held together by weak van der
Waals interactions and has a coiled structure. Thus, it can be stretched like a spring and
exhibits elastic properties.
Vulcanisation of rubber: Natural rubber becomes soft at high temperature (>335 K) and
brittle at low temperatures (On vulcanisation, sulphur forms cross links at the reactive
sites of double bonds and thus the rubber gets stiffened.
In the manufacture of tyre rubber, 5% of sulphur is used as a crosslinking agent. The
probable structures of vulcanised rubber molecules are depicted below:
Phenol formaldehyde polymer (Bakelite and related polymers)
Phenol formaldehyde polymers are the oldest synthetic polymers. These are obtained
by the condensation reaction of phenol with formaldehyde in the presence of either an
acid or a base catalyst. The reaction starts with the initial formation of o-and/or phydroxymethylphenol derivatives, which further react with phenol
to form compounds having rings joined to each other through CH groups. The initial
2
product could be a linear product Novolac used in paints.
Novolac on heating with formaldehyde undergoes cross linking to form an infusible solid
mass called bakelite. It is used for making combs, phonograph records, electrical
switches and handles of various utensils.
4. Melamine formaldehyde polymer
Melamine formaldehyde polymer is formed by the condensation polymerisation of
melamine and formaldehyde.
It is used in the manufacture of unbreakable crockery.
