DEFINITION:

The word polymer is derived from the two greek words

poly and mers

many parts or units

e.g.
mer mer mer
H H H H H H H H H H H H H H H H H H
C C C C C C C C C C C C C C C C C C
H H H H H H H Cl H Cl H Cl H CH3 H CH3 H CH 3
Polyethylene (PE) Polyvinyl chloride (PVC) Polypropylene (PP)

Polymers are macro molecules formed by linking smaller

molecules repeatedly, called monomers.
Examples:
Polyethylene is formed by linking a large number of
ethylene molecules
H H
H H
n C C Polymerisation
C C
H H n
H H
Ethylene polyethylene

polystyrene is formed by linking styrene molecules

H H H
H
n C C Polymerisation
C C
H n
H
styrene polystyrene
Classification of Polymers

Polymers can be classified in several ways, based on

origin

structure

methods of formation

response to heat

properties (or applications)

Based on the origin
polymers can be classified as
Natural polymers
synthetic polymers
Natural polymers are those which are obtained naturally
e.g., Cellulose, Silk, Starch, RNA, DNA, Proteins etc.,

Synthetic polymers are those which are made by man

e.g., polyethylene, polystyrene, PVC, polyester, etc.,

semi-synthetic polymers which are chemically modified

natural polymers
e.g., cellulose acetate, cellulose nitrate, halogenated
rubbers etc.,
Based on the molecular structure
polymers can be classified as

Linear
Branched
Cross-linked

In linear polymers,
the monomeric units combine linearly with each other

secondary bonding
Branch polymers

Cross linked polymers

 Based on the method of formation

Addition polymers
Condensation polymers

Addition polymers are formed by self-addition of monomers

The molecular mass of a polymer is an integral multiple of
the molecular mass of a monomer

Condensation polymers are formed by condensation reaction

i.e., reaction between two or more monomer molecules
with the elimination of simple molecules like water,
ammonia, HCl etc.,
 Based on the response to heat

Thermo softening
Thermosetting

thermosoftening or thermoplastics
soften on heating and can be converted into any shape and can retain its shape
on cooling, are soluble & fusible even after many cycles of heating/cooling.

thermosetting polymers
under go chemical change on heating and convert themselves into an infusible mass,
Chemical reaction lead to further growth & cross linking of the polymer chain molecules.
Based on the properties or applications

Plastics
Elastomers
Fibers
Resins

Plastics
The polymers, which are soft enough at some temperature
to be moulded into a desired shape and hardened on cooling
so that they can retain that shape.
e.g., polystyrene, polyvinylchloride, polymethylmethacrylate etc.,
Elastomers
The polymers in which the structural units are either zig zag or
in helical chains.
They undergo elastic changes when subjected to an external force
but readily regain their original shape when the force is withdrawn.

e.g., natural rubber, synthetic rubbers, silicone rubbers etc.,

Fibers
In these polymers, the molecular chains are arranged parallel to
each other in a spiral or helical pattern and the molecular length is
at least 100 times its diameter
e.g., nylons, terylene, etc.,
Resins

These polymers have a glossy appearance

These suffers the polymerization reactions and impart

different properties to plastics

e.g., polysulphide sealants, epoxy adhesives, etc.,

Functionality

the number of reactive sites or bonding sites

Some mono functional hydrocarbons

Alcohols Methyl alcohol

Ethers Dimethyl Ether

Acids Acetic acid

Aldehydes Formaldehyde

Aromatic
hydrocarbons Phenol

Some bi functional hydrocarbons

adipic acid (hexanedioic acid)

Terephthalic acid

ethylene glycol

1,6-hexanediamine
 Stereo regular polymers (or) Tacticity of Polymers

Isotactic
On one side

Syndiotactic
Alternating sides

Atactic
Randomly placed

- Conversion from one stereoisomerism to another is not possible by simple

rotation about single chain bond; bonds must be severed first, then reformed!
 The number of repeating units (n) in the chain is
known as the degree of polymerization.

e.g.,

D.P.

Polymers with high degree of polymerization are called

high polymers and these have very high molecular weights
(104 to 106).

Polymers with low degree of polymerization are called

oligomers.
 Types of polymerisation

Polymerisation occurs basically in two different modes.

• addition (chain growth) polymerization
• condensation (step growth) polymerization
• Addition
– monomers react through stages of initiation, propagation,
and termination
– initiators such as free radicals, cations, anions opens the
double bond of the monomer
– monomer becomes active and bonds with other such
monomers
– rapid chain reaction propagates
– reaction is terminated by another free radical or another
polymer
• Condensation
- two monomers react to establish a covalent bond

- small molecule, such as water, HCl, methanol or CO2 is

released.

- the reaction continues until one type of reactant is used

up
 DISTINGUISHING FEATURES OF
ADDITION AND CONDENSATION POLYMERISATION
ADDITION CONDENSATION
Monomers undergo self addition to Monomers undergo intermolecular
each other without loss of by products condensation with continuous elimination
of by products such as H2O, NH3, HCl, etc.,
It follows chain mechanism It follows step mechanism
Unsaturated vinyl compounds undergo Monomers containing the functional
addition polymeristion groups (-OH, -COOH, -NH2, ….) undergo
this polymerization
Monomers are linked together Covalent linkages are through
through C – C covalent linkages their functional groups

High polymers are formed fast
Linear polymers are produced
with or without branching
The reaction is slow and the polymer
molecular weight increases steadily
throughout the reaction
Linear or cross linked polymers
are produced

e.g., polystryrene, plexiglass, e.g., nylons, terylene, PF resins, etc.,

PVC, etc.,
 CoPolymers

• Random, Alternating, Blocked, and Grafted

• Synthetic rubbers are often copolymers.

e.g., automobile tires (SBR)

Styrene-Butadiene Rubber random polymer

Addition polymerization can be explained on the basis of
free radical mechanism

It involves three stages

viz., (i) Initiation
(ii) Propagation
(iii) termination
Initiation

I D or R*
u.v.light (Free radical)
(Initiator)
 H H H H
R* + C C R C C*
(Free radical) X H H X
Vinyl monomer (new free radical)
Propagation
The new free radicals attack monomer molecules further in quick
succession leading to chain propagation

H H H H H H H H

R C C* + C C R C C C C*

H X X H H X H X
(Free radical) Vinyl monomer (new free radical)
 H H H H H H H H H H H H
R C C C C* + C C R C C C C C C*
H X H X X H H X H X H X
(new free radical) Vinyl monomer (another new free radical)

at m th stage,

H H H H H H H H
R C C C C C C* + C C
H X H X m-2 H X X H

H H H H H H
R C C C C C C*
H X H X m-1 H X
At some stage this chain propagation is terminated when the
free radicals combine either by coupling (combining) of the two radicals
or by disproportionation
coupling

H H H H H H H H
R C C C C* + C* C C C R
H X m-1 H X X H X H m-1

H H H H H H H H
R C C C C C C C C R
H X m-1 H X X H X H m-1

saturated highpolymer (dead polymer)

disproportionation

H H H H H H H H
R C C C C* + C* C C C R
H X m-1 H X X H X H m-1

H H H H H H H
R C C C C + H C C C C R
H X m-1 H X X H X H m-1

unsaturated oligomer saturated oligomer

(dead polymer) (dead polymer)
Polymer Structure

stretch

leave

ENTROPY WORK!
 GLASS TRANSITION TEMPERATURE (Tg):

•Different polymers have different segments on their backbones. The ease of movement of these
segments (portions of the chain) depends on the structure, physical environment of the chain etc.
of the segment.

• Any movement of these segments require energy. Thus, each different polymer would have
different energy requirement for the movement of these segments (different polymer = different
structure, different physical environment of the chain etc).

• Below glass transition temperature, these segments do not have sufficient energy to move. So, if
you apply some stress, if you try to bend a polymer which is below its Tg then the segments won’t
be able to move into new positions to relieve the stress which you have placed on them; which
will make the polymer brittle. Above Tg they would, so they would be flexible.

• Always keep this in mind: Tg IS A PROPERTY RELATED WITH THE AMORPHOUS

REGIONS OF THE POLYMER, NOT CRYSTALLINE!

• So it should now be obvious that elastomers are elastomers above their Tg. Below, they are not
elastomers, they are glassy, because they are not flexible anymore.
 Mechanical Properties
• Mechanical behavior of amorphous and semi-crystalline polymers is
strongly affected by the glass transition temperature.
• In general (although there are exceptions):
– Polymers whose glass transition temperature is above the service
temperature are strong, stiff and sometimes brittle
• e.g. Polystyrene (cheap, clear plastic drink cups)
– Polymers whose glass transition temperature is below the service
temperature are weaker, less rigid, and more ductile
• Polyethylene (milk jugs)
• If the service temperature changes, and Tg is crossed, the behavior can
change drastically.
So, the glass transition temperature can be defined as the
temperature below which an amorphous polymer is brittle, hard
and glassy and above the temperature it becomes flexible, soft
and rubbery.

Glassy state rubber state

(Hard brittle plastic) (soft flexible)

In the glassy state of the polymer, there is neither molecular

motion nor segmental motion.
• These images are representative of the behavior of a material above and below its
glass transition temperature. The image on the (left) is Silly Putty that has been
slowly stretched. The image on the (right) is Silly Putty which has been hit with a
hammer. The speed of the hammer raised the rate of the application of the force and
in turn raised the Tg. This caused the Silly Putty to react as if it were below its Tg and
to shatter. Even though both reactions took place at the same ambient temperature,
one reaction appeared to be above the effective Tg and the other appeared to be
below.
Factors influencing the glass transition temperature
Glass transition temperature of a polymer depends on
parameters such as

• chain geometry
• chain flexibility
• molecular aggregates
• hydrogen bond between polymer chains
• presence of plasticizers and
• presence of substrates in the polymer chains

A polymer having regular chain geometry show high

glass transition temperature
crystalline polymers have higher Tg s than amorphous polymers
HIGH-DENSITY POLYMERS
Linear polymers with chains that can pack closely
together. These polymers are often quite rigid.

LOW-DENSITY POLYMERS
Branched-chain polymers that cannot pack together as
closely. There is often a degree of cross-linking.
These polymers are often more flexible than high-
density polymers.
the bulky groups on chain, increases the Tg of the polymer

Polyethylene
Tg = -110 0C

Polypropylene
Tg =

Polystyrene
Tg = 100 0C
 The presence of H-bonds between the polymer molecules
increases the Tg
• e.g., the Tg of nylon 6,6 (Tg = 50 0C) is higher than PE (Tg = -110 0C)

H  O H  O
H H
nylon 6,6  |  ||  | 
 
|| polyethylene
 N  C   N C  C   N C 
C C
   
| | | | | H H
H H  6 H H  H
4
+ +
Hydrogen + + + +
Van der Waals bonds
+ + + +
bonds
 +

+
H H
H  O H  O
  ||   || C C
|
  |
 N  C   N C  C   N C  H H
   
|  | | | |
H H  6 H H  H
4


 With H-bonds vs vdW bonds, nylon is expected to have (and does) higher Tg.
The presence of a plasticizer reduces the Tg of a polymer

The plasticizers are usually dialkyl phthalate esters,

such as dibutyl phthalate, a high boiling liquid.
O
C
O CH2CH2CH2CH3
O CH2CH2CH2CH3
C
O dibutyl phthalate

The plasticizer separates the individual polymer chains

from one another. It acts as a lubricant which reduces
the attractions between the polymer chains.
The Tg of a polymer is influenced by its molecular weight
With increase in molecular mass, the Tg increases
However, it is not significantly affected if molecular weight is
around 20000
e.g., PE (low Mw) -110 0C

PE (high Mw) - 90 0C
The glass transition temperature helps in choosing the right
processing temperature

It also gives the idea of

thermal expansion
heat capacity
electrical and mechanical properties
Which polymer more likely to crystallize? Can it be decided?

alternating random
Poly(styrene-Ethylene) poly(styrene - ethylene) copolymer
Copolymer

• Alternating co-polymer more likely to crystallize than random ones, as they

are always more easily crystallized as the chains can align more easily.
 Molecular Weight of Polymers

The molecular weight of a polymer can only be viewed

statistically and expressed as some average of the Mol. Wt.s
contributed by the individual molecules that make the sample
the molecular weight of a polymer can be expressed by
two most and experimentally verifiable methods of averaging
(i) Number – average
(ii) weight – average
Number average molecular mass of a polymer can be defined
as the total mass of all the molecules in a polymer sample
divided by the total number of molecules present
The molecular mass of a polymer can use either
number fractions or the weight fractions of the
molecules present in the polymer

In computing the number average molecular mass of a

polymer, we consider the number fractions
 Polymers: Molecular Weight
Ni: no. of molecules with degree of polymerization of i
Mi: molecular weight of i
• number average, Mn

• weight average, Mw
The number-average molecular mass (Mn)is determined
by the measurement of colligative properties such as

lowering of vapour pressure

osmotic pressure
depression in freezing point
elevation in boiling point

The weight-average molecular mass (Mw) is determined by

light scattering and

ultra-centrifugal techniques
 Preparation of LDPE

Production of LDPE by addition polymerization requires:

• temperature range of 100-300oC
• very high pressure 1500-3000 atmospheres
• oxygen or an organic peroxide such as dibutyl peroxide, benzoyl peroxide or diethyl
peroxide as initiator.
• An initiator is a substance which is added in small quantities and is decomposed by light
or heat to produce a free radical (R.). A free radical is formed when a covalent bond is
broken and a bonding electron is left on each part of the broken molecule. Since the O-
O covalent bond is weak, free radicals are easily formed from oxygen or peroxides.
• benzene or chlorobenzene used as the solvent since both polymer (polythene) and
monomer (ethene) dissolve in these compounds at the temperature and pressure used.
• Water or other liquids may be added to dissipate the heat of reaction as the
polymerization reaction is highly exothermic.
• CH2=CH2 + R. -----> .CH2-CH2-R
ethene initiator
• CH2=CH2 + .CH2-CH2-R -----> .CH2-CH2-CH2-CH2-R
• Process continues to form polythene (polyethylene) [-CH2-CH2-]n
 Preparation of HDPE

• Production of HDPE by addition polymerization with a supported metal oxide catalyst

requires:
– temperature ~300oC
– 1 atmosphere pressure (101.3kPa)
– aluminium-based metal oxide catalyst (metallocene catalyst)
The catalyst can be used in a variety of operating modes including fixed-bed,
moving-bed, fluid-bed or slurry processes
– The ethene (ethylene) monomer is fed with a paraffin or cycloparaffin diluent
(diluting agent).
After polymerization the polymer (polythene) is recovered by cooling or by
solvent evaporation.
• Production of HDPE by coordination polymerization requires:
– temperature 50-75oC
– slight pressure
– a coordination catalyst is prepared as a colloidal suspension by reacting an
aluminium alkyl and titanium chloride (TiCl4) in a solvent such as heptane
(C7H16).
– The polymer (polythene) forms as a powder or granules which are insoluble in
the reaction mixture. When the polymerization is completed, the catalyst is
destroyed by adding water or alcohol to the reaction mixture. The polymer
(polythene) is then filtered or centrifuged off, washed and dried.
 Properties and uses of LDPE and HDPE

Property Low Density Polyethylene High Density Polyethylene

(LDPE)
Crystallinity low crystallinity (50-60% crystalline) Main chain
contains many side chains of 2-4 carbon atoms
leading to irregular packing and low crystallinity
(amorphous)
Flexibility more flexible than HDPE due to lower crystallinity
Strength not as strong as HDPE due to irregular packing of
polymer chains
Heat retains toughness & pliability over a wide
Resistance temperature range, but density drops off
dramatically above room temperature.
Transparen good transparency since it is more amorphous
cy (has non-crystalline regions) than HDPE
Chemical chemically inert
Properties Insolvent at room temperature in most solvents.
Good resistance to acids and alkalis.
Exposure to light and oxygen results in loss of
strength and loss of tear resistance.
Uses sandwich bags, cling wrap, car covers, squeeze
bottles, liners for tanks and ponds, moisture
barriers in construction
(HDPE)
highly crystalline (>90% crystalline)
contains less than 1 side chain per
200 carbon atoms in the main chain
leading to long linear chains that
result in regular packing and high
crystallinity
more rigid than LDPE due to higher
crystallinity
strong as a result of regular packing of
polymer chains
useful above 100oC
less transparent than LDPE because
it is more crystalline
chemically inert
freezer bags, water pipes, wire and
cable insulation, extrusion coating
NYLON 6, 6
The aliphatic polyamides are generally known as nylons

The nylons are usually indicated by a numbering system

The nylons obtained from dibasic acids and diamines

are usually represented by two numbers
the first one indicating the number of ‘C’ atoms in the
diamine and the second that in the dicarboxylic acid
Nylons made by the self condensation of an amino acid
or by the ring opening polymerization of lactams are
represented only by a single number as in the case of
nylon 6

Polyamides are prepared by the melt poly condensation

 Preparation

n +n

Heat
- 2n H2O
Properties
• It has a good tensile strength, abrasion resistance and
toughness upto 150 oC
• It offers resistance to many solvents. However, it
dissolves in formic acid, cresols and phenols
• They are translucent, wheatish, horny, high melting
polymers (160 – 264 oC)
• They possess high thermal stability

• Self lubricating properties

• They possess high degree of crystallinity
• The interchain hydrogen bonds provide superior
mechanical strength
(Kevlar fibers stronger than metals)

• Its Hardness is similar to tin

Uses

• It is used as a plastic as well as fiber

• This is used to produce tyre cord

• It is used to make mono filaments and ropes
• Nylon 6,6 is used to manufacture articles like brushes
and bristles
• Nylon 6,6 used as sutures
P – F Resins

These are formed by condensation polymerization and

are thermosetting polymers

The phenol ring has three potential reactive sites

while the formaldehyde has two reactive sites
The polycondensation reaction between these two
are catalyzed by either acids or alkalies
The nature of the product formed depends largely
on the molar ratio of phenol to formaldehyde and also
on the nature of the catalyst
There are two important commercial PF resins
• Novolacs
• Resoles
Both novolacs and resoles are linear, low molecular
weight, soluble and fusible prepolymers

During moulding operations, these two undergo

extensive branching leading to the formation of highly
cross linked, insoluble, hard, rigid and infusible products

Novolacs
When P/F molar ratio is > 1 and the catalyst used is an acid,
low mol. wt. polymers formed are called Novolacs

The first step in the reaction is the addition of

formaldehyde to phenol to form ortho or para methylol
phenols
 OH
H
+ C=O
H
Phenol (excess) formaldehyde
H+

OH
OH

CH2OH

and
CH2OH
o-methylol phenol
p-methylol phenol
These methylol phenols condense rapidly to form Novolacs

OH
OH

CH2OH
or
CH2OH
o-methylol phenol OH
p-methylol phenol

OH H2 H2 OH H2 H2 OH
C C C C

HO OH

Novolacs
 These novolacs are linear and low mol. wt. polymers

About 5 – 6 phenol rings per molecule are linked through

methylene bridges

They are soluble and fusible

Since they contain no active methylol groups, they

themselves do not undergo cross linking

However, when heated with formaldehyde or hexamine, they

undergo extensive cross linking, resulting in the formation
of infusible, insoluble, hard and rigid thermosetting product
 OH H2 H2 OH H2 H2 OH
C C C C

HO OH
Novolacs (prepolymer) Curing with
Formaldehyde or
hexamine
Resoles
When the molar ratio of P/F is < 1 and the catalyst used is a
base, the polymer formed are called Resoles
The first step in the reaction is the formation of mono,
di and trimethylol phenols.
They undergo condensation to form resoles

OH

H
+ C=O
H
Phenol Formaldehyde
OH--
(excess)
 OH OH OH OH

CH2OH CH2OH HOH2C CH2OH

+
+ +
CH2OH CH2OH CH2OH

o-methylol phenol p-methylol di methylol tri methylol phenol

phenol phenol
Curing
The resoles in which phenols are linked through
methylene bridges are soluble and fusible

Since they contain alcoholic groups, further reaction

during curing leads to cross linking, resulting in a
network, infusible and insoluble product
Properties

• These are (bakelite) set to rigid and hard

• They are scratch-resistant

• They are infusible
• They are water-resistant
• They are insoluble solids
• They are resistant to non-oxidizing acids, salts and
many organic solvents
• but are attacked by alkalis, because of the presence
of free hydroxyl group in their structures

• They possess excellent electrical insulating character

• Their Hardness is similar to copper

• These are usable up to 400 °F (204°C)

• These tends to be brittle

• The properties can be modified by fillers

& reinforcements

• These have the highest compressive strength

• These are machinable

• Phenolics are the resin in plywood

Uses
• For making electric insulator parts like switches, plugs,
switch-boards, heater-handles etc.,
• For making moulded articles like telephone parts,
cabinets for radio and television

• For impregnating fabrics, wood and paper

• As adhesives (e.g., binder) for grinding wheels
• In paints and varnishes

• As hydrogen-exchanger resins in water softening

• For making bearings, used in propeller shafts for

paper industry and rolling mills
ELASTOMERS
Elastomer is defined as a long chain polymer which
under stress undergoes elongation by several times and
regains its original shape when the stress is fully released

Stretched

Returned to
randomization
Elastomers are high polymers, which have elastic
properties in excess of 300 %
The elastic deformation in an elastomer arises due to
the fact that the molecule is not a straight chained
in the unstressed condition and is in the form of a coil

Hence, it can be stretched like a spring

So, the unstretched rubber is in an amorphous state
As stretching is done, the macromolecules get partially
aligned with respect to another, thereby causing
crystallization
Consequently, stiffening of material (due to increased
attractive forces between these molecules) taking place
On releasing the deforming stress, the chains get reverted
back to their original coiled state and the material again
becomes amorphous
Natural rubber is an addition polymer formed from the
monomer called isoprene i.e., 2-methyl-1,3-butadiene
The average D.P. (n) of rubber is around 5000

Addition between molecules of isoprene takes place by

1,4 addition and one double bond shifts between 2nd and
3rd positions
 As each isoprene unit contains C = C bond,
polyisoprene exists in two isomeric forms
viz., cis and trans

Cis-polyisoprene trans-polyisoprene
where R= CH3

Natural rubber contains the cis isomer while the

gutta percha contains the trans isomer
Natural rubber consists of basic material latex, which is
a dispersion of isoprene
During the treatment, these isoprene molecules polymerize
to form long-coiled chains of cis-polyisoprene
The mol. wt. of raw rubber is about 100,000 – 150,000
Natural rubber is made from the saps of a wide range of
plants like havea brasillians and guayule, found in
tropical countries (such as Indonesia, Malaysia, Thailand,
Ceylon, India, South America, etc.,)
The rubber latex (or milky liquid rubber ) is obtained by
making incisions in the bark of the rubber trees and
allowing the saps to flow out into small vessels
Tapping is, usually done at intervals of about six months
The latex is emptied into buckets and transferred to a
factory for treatment
Gutta Percha is trans-polyisoprene and is obtained from
the mature leaves of dichopsis gutta and palagum gutta
trees (belonging to sapetaceae family)

These trees are grown mostly in Broneo, Malaya and Sumatra

Gutta percha may be recovered by solvent extraction

Alternatively, the mature leaves are ground carefully;

treat with water at about 70 oC for half an hour and
poured into cold water, then the gutta percha floats on
water surface and can be easily removed
Deficiencies of natural rubber
Natural rubber is addition product of isoprene units
and still contains a large number of double bonded
carbon atoms
Hence it exhibits a large number of deficiencies

• At low temp. it is hard and brittle but as the temp.

rises it becomes soft and sticky
• It gets oxidized easily in air and produces bad smell even
if kept as such for a few days
• It is soluble in many organic solvents
• It absorbs large quantities of water
• Its chemical resistivity is low and is attacked by acids,
alkalies, oxidizing and reducing agents
• Its tensile strength, abrasion resistance wear and tear
resistances are low
• It possesses marked tackiness
i.e., when two fresh raw rubber surfaces are pressed
together, they coalesce to form a single piece

• It has little durability

• When stretched to a great extent, it suffers permanent

deformation, because of the sliding or slippage of
some molecular chains over each other

Synthetic rubbers have slightly modified structures from

natural rubber they exhibit properties that are more
conducive for their technical uses
 A comparative account of the properties of
natural and synthetic rubbers
Property Natural rubber Synthetic rubber
Tensile Low (only 200 kg/cm2) High
strength
Chemical Low – gets oxidized High – not oxidized in
resistivity even in air air
Action of Cold condition it is hard Withstand effect of
heat and brittle, at higher heat over a range of
temp.s soft and temperature.
sticky
With organic Swells and dissolves Do not swell and
solvents dissolve
Ageing Undergoes quickly Resists ageing

Elasticity On increased stress Has high elasticity.

undergoes permanent
deformation.
Vulcanization of rubber
This process was discovered accidentally by Goodyear
when he dropped rubber and sulfur on a hot stove
To improve the properties of rubber, it is compounded
with some chemicals like sulphur, hydrogen sulphide,
benzoyl chloride etc., It is known as vulcanisation of rubber

The process consists of heating the raw rubber with

sulphur at 100 – 140 oC
The added sulphur combines chemically at the double
bonds of different rubber springs
Thus this process serves to stiffen the material by a sort of
anchoring and consequently, preventing the intermolecular
movement of rubber springs
The extent of stiffness of vulcanized rubber depends on
the amount of sulphur added
e.g., a tyre rubber may contain 3 to 5% sulphur,
but a battery case rubber may contain as much as 30% sulphur
H H H

H
H C H H
H C H H
H C H
H H H
H H H

C C C C C C
C C
C C C C

H H H H H H

+S+
H H H H H H

C C C C C C

C C C C C C
H H H
H H H

H H H H H H
C H C H C H

H H H
 H H H

HH H HH H HH H
C H C H C H
H H H

C C C C C C
C C C C
C C

H H H H H H

S S
H H H H H H

C C C C C C
C C C C C C
H H H H H H

H C HH H C HH H C HH

H H H
Advantages of vulcanization
Vulcanized rubber
• has good tensile strength and extensibility, when a
tensile force is applied, can bear a load of 2000 kg/cm2
before it breaks
• has excellent resilience
i.e., article made from it returns to the original shape,
when the deforming load is removed
• possesses low water-absorption tendency
• has higher resistance to oxidation and to abrasion
• has much higher resistance to wear and tear as
compared to raw rubber
• is better a electrical insulator, although it tends to
absorb small amounts of water
• is resistant to organic solvents (such as petrol,
benzene, and carbon tetrachloride), fats and
oils. However, it swells in these liquids
• is very easy to manipulate the vulcanized rubber to
produce the desired shape articles
• has useful temperature range of - 40 to 100 oC

• has only slight tackiness

• has low elasticity and is depending on the extent of
vulcanization
e.g., vulcanite (32% Sulphur) has practically no elasticity
Styrene rubber (GR-S or Buna-S or SBR)
Preparation
This is produced by copolymerization of butadiene
(about 75% by wt.) and styrene (about 25% by wt.)

H2C CH
n x H2C CH CH CH2 + n

H2C CH CH CH2 H2C CH

x
n
 Styrene-butadiene copolymer

Styrene domains act as

anchors or junctions

Butadienes provide
flexible linkages

The desire to maximize the ways you can arrange the flexible
links is what causes rubbers to return to given shapes