Welcome to
Polymers
Introduction
Rubber
Classification
Biodegradable
polymers
Types of
polymerisation
Commercial
importance
Polymers
Polymer
Greek words
Macromolecules
Poly + mer Very large molecules having
high molecular mass.
Many Unit/part
103 107u
Polymerisation
Polymers are The process of formation of the
formed by the polymers from the respective
joining of repeating monomers that are linked by a
structural units on covalent bond.
a large scale.
Polymerisation
Formation of polythene from ethene
Example
Polymerisation
n n
Ethene monomer
Repeating unit
n
Polythene polymer
Classification of Polymers
Source
Structure
Classification of
polymers on the Mode of polymerisation
basis of
Molecular forces
Growth polymerisation
Classification Based on Source
Natural
Polymers
Semi-Synthetic
Synthetic
Natural Polymers
Polymers that are derived from
plants and animals
Example
Proteins, cellulose, starch,
natural rubber, and more
Semi-Synthetic Polymers
Polymers that are derived Cellulose nitrate was
from both petroleum and used as film negatives.
natural products
Rayon, cellulose
nitrate, and more
Cellulose
acetate
Synthetic Polymers
Polymers that are man–made
or derived from petroleum oil
Computer
Machinery
Examples
Plastic Polythene
Synthetic
Nylon 6,6
fibre
Synthetic
Buna–S
rubber
Nylon 6,6 Buna-S
Classification Based on Structure
Linear
Polymers
Branched
Cross-linked
Linear Polymers
Ex: High-density polythene,
Polyvinyl chloride (PVC), and more.
Polymer consisting of long
and straight chains
Branched-Chain Polymer
Ex: Low density polythene,
polypropylene, and more
Polymer consisting of
linear chains having some
branches
Cross-linked or Network Polymers
Ex: Bakelite, They are formed from
Melamine, bifunctional and
and more trifunctional monomers.
3o amide
They contain strong covalent bonds
between various linear chains.
Classification Based on Mode of Polymerisation
Polymers
Addition Condensation
Addition Polymers
They are formed
by repeated
addition of Ethene
monomers
possessing double
or triple bonds.
Propyne
Formation of polythene No part from the monomer units are lost
from ethene during polymerisation; they are simply added.
Types of Addition Polymers - Homopolymers
An addition polymer formed
by the polymerisation of only
single monomeric species
Homopolymer
Homopolymers
Formation of polythene
from ethene
n
n
Ethene Polythene
Homopolymer
Types of Addition Polymers - Copolymers
Addition polymers formed by
polymerisation of two
different monomers
Examples: Buna-S,
Buna-N, and more
Copolymers
Buna - S
Catalyst: Na
Buna-S
1,3-Butadiene Styrene
The two different type of
monomers (1,3-Butadiene and
Styrene) react and form this
copolymer.
Buna - S
Reaction
n +n
n
Butadiene-styrene copolymer (Buna-S)
Buna - N
Catalyst: Na
Buna-N
1,3-Butadiene Acrylonitrile
The two different type of
monomers (1,3-Butadiene and
Acrylonitrile) react and form this
copolymer.
Buna - N
Reaction
n
n + Acrylonitrile
1,3-Butadiene
Buna-N n
Uses of Buna – S and Buna - N
Copolymer Uses
Auto tyres, floor tiles, footwear
Buna-S
components, and more
Buna-N Oil seals, tank lining, and more
Condensation Polymers
They are formed by repeated
condensation reactions between
two different bifunctional or
trifunctional monomeric units.
Water, HCl, Generally, in
and more condensation
reactions, the
elimination of
small molecules
takes place.
Condensation Polymers
The two different type of
monomers
Nylon 6,6 (Hexamethylene diamine
and Adipic acid) react and
form this copolymer.
Hexamethylene
diamine Adipic acid
n H2N(CH2)6NH2 + n HOOC(CH2)4COOH
NH(CH2)6NHCO(CH2)4CO
+ n
n H2O
Condensation Polymers
n + n
Adipic Acid
Hexamethylene diamine
_nH O
2
n
Nylon 6,6
Classification Based on Molecular Forces
The mechanical properties of Elastomer
polymer- like tensile strength,
elasticity, toughness, etc.,
are governed by
Fibres
Polymers
Intermolecular forces like Van der
Waals forces and hydrogen bonds Thermoplastic
Binds the
polymer chain Thermosetting
Elastomers
The polymer chains are held
together by the weakest
intermolecular forces.
Buna-S, Buna-N,
Neoprene, and more
Permit stretching
This forms a few crosslinks
between the chains that help
the polymer to retract to its A synthetic rubber
original position after the force
is released.
Fibres
They are thread-forming solids that Nylon 6,6, terylene
possess high tensile strength and and more
modulus.
Hydrogen bonding
Strong intermolecular
forces present.
Terylene
Monomers Terephthalic
Ethylene
acid
glycol
n + n
+ n H2O
n
Terylene or Dacron
Thermoplastic Polymers
Linear or slightly branched In thermoplastics, the
long-chain molecules intermolecular forces of attraction
are intermediate between
elastomers and fibres.
Capable of repeatedly being
soft on heating and hard on Fibres > Thermoplastics > Elastomers
cooling.
Polythene, polystyrene,
polyvinyl chloride(PVC) and Decreasing order of force of attraction
more
Thermosetting Polymers
They are cross-linked
or heavily branched polymers.
Bakelite, Urea-formaldehyde
resins, and more
On heating, they undergoes
extensive cross-linking in moulds
and again become infusible.
Cannot be used
Thermoplastic Thermosetting
It contains long-chain linear
It contains a 3D network
polymers and are held
structure constructed with
together by weak van der
strong covalent bonds.
Waals forces.
It usually becomes soft on
It does not become soft on
heating and hard on
heating.
cooling.
It is expensive. It is less expensive.
It is soluble in organic It is insoluble in organic
solvents. solvents.
It is usually soft, weak, and It is usually hard, strong, and
less brittle in nature. more brittle in nature.
It can be remoulded. It cannot be remoulded.
Growth Polymerisation
Depending on the type of
polymerisation mechanism,
polymers undergo
Addition Condensation
Chain growth Step growth
Chain Growth
In this type of polymerisation, the molecules of the same monomer or different
monomers add together on a large scale to form a polymer. The monomers used
are unsaturated compounds. For example, alkenes, alkadienes and their
derivatives. This mode of polymerisation leads to an increase in chain length, and
chain growth can take place through the formation of either free radicals or ionic
species. However, the free radical governed addition or chain-growth
polymerisation is the most common mode.
Step Growth
The product of each step is again a bifunctional species, and the sequence of
condensation goes on. Since each step produces a distinct functionalised species and
is independent of each other, this process is also known as step-growth polymerisation.
Types of Polymerisation Reactions
Polymerisation
reactions
Addition Condensation Copolymerisation
Chain–growth
polymerisation
Addition Polymerisation
The molecules of same monomer or
different monomers add together
This mode leads to an increase
in the chain length.
Example
Polymerisation of ethene Benzoyl
to polythene n
peroxide
n
Mechanism of Addition Polymerisation
The mechanism of addition
polymerisation involves
three steps.
Generally, in addition
polymerisation, Step 1 Chain initiation
an increase in chain
length is governed
by free radical
mechanism. Step 2 Chain propagation
Step 3 Chain termination
Chain Initiation
.
2
Benzoyl peroxide
Chain initiator . + CO2
Phenyl free radical
The process starts with generation of
phenyl radical from benzoyl peroxide
Chain Initiation
.
. +
Ethene
Here, phenyl radical formed adds to the ethene double
bond and thus generating a new and larger radical.
Chain Propagation
. .
+
The radical formed adds another molecule of
ethene forming new and bigger radical. This
repetition of sequence to form bigger radical when .
reaction goes forward, is chain propagation step.
( )
n
Chain Termination
. .
( )n + ( )n
( )n ( )n
At certain stage, the two radicals combine with each other to
form the polymeric product. It is the chain terminating step.
Addition Polymers
Low density
Polythene
High density
Addition
polymers Polytetra-
fluoroethene
Polyacrylonitrile
Low Density Polythene (LDP)
It is obtained by the polymerisation of ethane
under certain conditions (High pressure
1000–2000 atm, Temperature 350–570 K) in
the presence of O2 or a peroxide initiator.
Reaction
n O2, 350–570 K
1000–2000 atm n
LDP
Reaction occurs by free
radical mechanism.
Characteristics of LDP
Chemically inert
01
Tough
02
Flexible
03
Poor conductor of electricity
04
In bottles
In electric wires
Uses
In toys
In pipes
In wrappers
High Density Polythene (HDP)
It is obtained by the addition polymerisation of
ethene in a hydrocarbon solvent in the presence
of a catalyst (Ziegler–Natta catalyst).
Reaction
TiCl4 + (C2H5)3Al
n
333–343 K, n
6–7 atm HDP
Low temperature and
pressure is required.
Characteristics of HDP
Highly dense
01
Chemically inert
02
Tougher and harder
03
In bottles In buckets
and pipes and dustbins
Uses
In making of
plastic plates
Teflon
It is manufactured by heating
tetrafluoroethene with any free
radical or persulphate catalyst.
At high pressure
Reaction
Persulphate
n
High pressure n
Teflon
Characteristics and Uses of Teflon
Chemically inert
01
Resistant to attack by
02 corrosive agents
Uses
In oil seats As surface coating
and gaskets on non-stick utensils
Polyacrylonitrile
It is obtained by the addition
polymerisation of acrylonitrile
in the presence of a catalyst.
Peroxide
Reaction
Peroxide
n
n
Polyacrylonitrile (PAN)
Condensation Polymerisation
Generally, it involves repetitive
condensation between two
bifunctional groups with loss
of simple molecules.
H2O, ROH,
and HCl
The product of each step is
again, a bifunctional species.
Thus, the sequence goes on.
Step growth
Polyamides
Generally, it is prepared by the
condensation polymerisation of
diamines with dicarboxylic acids.
They possess amide linkages
and are an important class of
synthetic fibres.
Nylons
Nylon 6,6
6 carbons 6 carbons
Reaction
n + n
Hexamethylene diamine Adipic acid
High 553 K
pressure
n
Nylon 6,6
Nylon 2,6
Reaction 6 carbons
2 carbons
n +n
Glycine Aminocaproic acid
–nH2O
n
Nylon 2,6
Nylon 6
It is obtained by heating
caprolactum with water
at a high temperature
Reaction
6 carbons
n 533–543 K
H2 O n
Caprolactam Nylon 6
Polyester
Polycondensation products of
dicarboxylic acids and diols.
Examples: Dacron or Terylene
It is manufactured by heating a mixture of ethylene
glycol and terephthalic acid at 420 to 460 K in the presence of
zinc acetate-antimony trioxide catalyst.
Dacron/Terylene
n + n
Ethylene glycol
(Ac)2Zn
420–460 K Terephthalic acid
SbO3
n
Terylene
Crease
resistant
Water
In footwear repellent
Uses
In woollen In safety
fibres helmets
Phenol-Formaldehyde Polymer
It is obtained by the condensation
reaction of phenol with
formaldehyde.
In the presence of
an acid or a base
catalyst
Phenol-Formaldehyde Polymer
Preparation Step 1 Formation of novolac
H+ or OH
−
+ CH2O
+ +
o-Hydroxymethyl phenol derivatives
Phenol-Formaldehyde Polymer
−OH
n
Novolac
Used in paints
Phenol-Formaldehyde Polymer
Novolac, on heating with HCHO,
Step 2
undergoes crosslinking to form Bakelite.
HCHO
Phenol-Formaldehyde Polymer
Infusible
solid mass
Bakelite
Melamine-Formaldehyde Polymer
It is formed by the condensation polymerisation of
melamine and formaldehyde.
+ HCHO
Formaldehyde
Melamine Resin intermediate
Polymerisation
Melamine-Formaldehyde Polymer
n
Melamine–formaldehyde
polymer
Used in Making of
Unbreakable Crockery
Types of Polymerisation Reactions
Addition
Polymerisation
reactions Condensation
Copolymerisation
Made by chain
growth as well
as step growth
Copolymerisation
Polymerization reaction in
which more than one monomeric
species are allowed to polymerize.
Example Buna-S
Rubber
Rubber
Natural Synthetic
rubber rubber
It is manufactured from
rubber latex.
Colloidal
dispersion of
rubber in water
Natural Rubber
Cis-polyisoprene consists of
It is a linear polymer chains held together by
of isoprene. weak van der Waals
interaction.
2-Methyl-1,3-butadiene
And due to its coiled
structure, it can be stretched
like spring.
Also known as
cis-1,4-polyisoprene
Elastic
properties
Natural Rubber
Isoprene
Cis-polyisoprene
Polymerisation
Natural rubber
Gutta–Percha
Cis-isoprene
Trans-
polyisoprene
Polymerisation
n
Gutta–percha
Gutta–Percha
Gutta–percha is trans–isomer
of polyisoprene.
It is used to fill a teeth to
prevent reinfection.
Natural rubber becomes soft at
high temperature and brittle at
low temperature.
> 335 K < 283 K
Properties of Rubber
1 Soluble in non-polar solvents
Non-resistant to attack
2
by oxidising agents
Shows high water
3 absorption capacity
Vulcanisation
It involves heating a mixture
of raw rubber with sulphur
in a temperature range.
373–415 K
And sulphur forms cross-links at
the reactive sites of double
bonds.
Rubber
stiffens
Structure of Vulcanised Rubber
Points to Remember
In the manufacture of rubber tyres
5% of sulphur is used as
crosslinking agent.
Rubber
It is any vulcanisable rubber-like
polymer that is capable of getting
stretched to twice its length.
However, it returns to its
original shape and size once
the external force is released.
Examples: Buna-N, Neoprene
Neoprene
It is formed from polymerisation of chloroprene.
Polymerisation
n
Chloroprene n
Neoprene
Resistant to
vegetable and
mineral oils
In gaskets In hoses
Uses
In diving suits
clothing
Biodegradable Polymer
Polymers that
undergo These polymers
environmental contain functional
degradation and groups that are
do not similar to functional
accumulates as groups present in
solid waste biopolymers.
Proteins,
Nylon 2,6 PHBV carbohydrates,
and more
PHBV
3-Hydroxybutanoic
acid
Poly-β-hydroxybutyrate-Co-β-hydroxyvalerate
(PHBV)
3-Hydroxypentanoic acid
PHBV
It is obtained by
copolymerisation
of 3-hydroxybutanoic acid
and 3-hydroxypentanoic acid.
PHBV
Reaction
ꞵ 𝛂 ꞵ 𝛂
n + n
3-Hydroxybutanoic 3-Hydroxypentanoic
acid acid
+ n H2O
n
PHBV
Undergoes
bacterial
degradation
PHBV
n + n
−nH2O
n
Uses of PHBV
1 Packaging
2 Orthopaedic devices
3 Controlled release of drug
Polymers Used in Daily Life
Polypropene
Polystyrene
Polymers Polyvinyl chloride
Urea-formaldehyde resin
Glyptal
Polypropene
Polypropene
Monomer Structure Uses
Ropes, toys,
Propene pipes, and
n more
Polystyrene
Polystyrene
Monomer Structure Uses
Wrapping
Styrene materials,
n toys, radios,
and more
Polyvinyl Chloride (PVC)
Polyvinyl chloride
Monomer Structure Uses
Raincoats,
Vinyl handbags,
chloride water
n
pipes,
and more
Urea-Formaldehyde Resin
Urea-formaldehyde resin
Monomer Structure Uses
Unbreakable
(i) Urea cups and
(ii) Formaldehyde laminated
n
sheets
Glyptal
Glyptal
Monomer Structure Uses
Paints
(i) Ethylene glycol and
(ii) Phthalic acid lacquers
( )
n
