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 CH 3 H CH 3 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 Polymerization
C C
H H n
H H
Ethylene polyethylene

polystyrene is formed by linking styrene molecules

H H H
H
n C C Polymerization
C C
H n
H
styrene polystyrene
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.
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
Branched 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

thermosetting polymers
under go chemical change on heating and convert
themselves into an infusible mass
 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 glassy appearance

These constitutes the major essential part of the plastics

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!
 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

- a 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 POLYMERIZATION
ADDITION
Monomers undergo self addition to
each other without loss of by products
It follows chain mechanism
Unsaturated vinyl compounds undergo
addition polymerization
Monomers are linked together
through C – C covalent linkages
High polymers are formed fast
Linear polymers are produced
with or without branching
e.g., polystryrene, plexiglass,
PVC, etc.,
CONDENSATION
Monomers undergo intermolecular
condensation with continuous elimination
of by products such as H2O, NH3, HCl, etc.,
It follows step mechanism
Monomers containing the functional
groups (-OH, -COOH, -NH2, ….) undergo
this polymerization
Covalent linkages are through
their functional groups
The reaction is slow and the polymer
molecular weight increases steadily
throughout the reaction
Linear or cross linked polymers
are produced
e.g., nylons, terylene, PF resins, 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 (Growing 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
(growing free Vinyl monomer (another growing free
radical) 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)
TECHNIQUES OF POLYMERISATION
Addition polymerization is brought about using four different
techniques

 Bulk or Mass polymerization

 Solution polymerization

 Suspension polymerization

 Emulsion polymerization
Bulk or Mass Polymerization
only the monomer and the initiator are involved

monomer is taken in the liquid state

the initiator should dissolve in the monomer

Initiation can be done either by heating or by exposing

to radiation

the reaction is exothermic

As the reaction proceeds, the reaction mixture becomes

viscous

the polymer molecules with wide range of molecular masses

will be obtained
Advantages:
The method is simple
It needs simple equipments
The percentage of conversion is high
Product obtained is pure with high optical clarity
Disadvantages:

as the reaction proceeds stirring become difficult as the

product becomes more and more viscous
Uncontrolled temperature rise may lead to
discoloration
thermal degradation
branching
cross linking
and some times explosion also
Solution Polymerization
the medium chosen is an inert solvent
the monomer, the initiator and a chain transfer agent
should dissolve in an inert solvent
The solution is heated with constant agitation
After the reaction is over,
the polymer formed may dissolve in the solvent
along with the monomer or may be precipitated
Advantages:
Solvent will reduce the viscosity of the reactant mixture
heat transfer will be better
Disadvantages:
the polymer will not be pure and has to be isolated
by chemical techniques
high molecular mass polymers will not be obtained
Suspension Polymerization
Water is used as a solvent
the monomer is suspended in water as droplets of
colloidal size
Initiators used are soluble in monomer droplets
protective colloids are added to suppress the coagulation
of the monomer molecules
The reaction mixture is heated or exposed to radiation
with constant stirring.

Polymerization takes place inside the droplet

the polymer formed being insoluble in water, produce
spherical pearls or beads
Advantages:
Process is cheap since it uses water as a solvent
instead of costly solvents

Viscosity increase is negligible

Agitation and thermal control are easy
Product isolation is easy since the product is
insoluble in water
Product formed is pure

Disadvantages:
the method can be used only for water insoluble monomers

it is difficult to control polymer size

Emulsion Polymerisation

This method is used for solvent insoluble monomers

Emulsion of water and the monomer is allowed to form

Emulsion is the colloidal dispersion of a liquid in

another immiscible liquid
To maintain the system stable, a small amount of an
emulsifier will be added
Soaps and detergents are examples for emulsifiers
Emulsifier contains
a hydrophilic (water loving) polar end group (head) and
a hydrophobic (water hating) non polar end group (tail)
At very low concentration, the soap or detergent (emulsifier)
dissolves completely in water
at slightly higher concentrations, the emulsifier molecules
form aggregates, called miscelles
The monomer molecules dissolve in the hydrocarbon centre
of the miscelles
water soluble initiator will be added and the system is kept
agitated at the required temperature.
The initiator molecules diffuse into the centre of miscelles
through its polar head

Reaction takes place at the centre of the miscelles

The polymer is formed and the miscelles begins to swell
The monomer consumed inside the miscelles is replenished
by diffusion from aqueous phase

This continues till the size of the polymer is big enough

to come out of the miscelles
Advantages:

Rate of polymerization is high

polymers with higher molar masses are formed

thermal control is easy

control over the polymer molar mass is possible

No significant viscosity build up and hence agitation is easy

Disadvantages:

the polymer formed may contain impurities such as

the emulsifiers and coagulants

It needs further purification by other chemical techniques

GLASS TRANSITION TEMPERATURE (Tg):

Amorphous polymers do not have sharp melting points

They possess softening point

At low temperature, polymers exist as glassy substances

Since the molecular chains can not move at all easily in

this state, the solid tends to shatter, if it is hit

If the solid polymer is heated, eventually it softens and

becomes flexible

This softness and flexibility is obtained at the

glass transition temperature
 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

When all chain motions are not possible, the rigid solid results

On heating beyond Tg segmental motion becomes possible

but molecular mobility is disallowed. Hence flexible
 The glassy state and the glass transition

In general for ordinary compounds of low molar mass:

crystalline solid
melting

liquid A
V
B

C
increase in volume at Tm; F

Tm T
slopes of FC and BA: expansion coefficients of crystalline
phase and liquid, respectively.
 Non-crystallisable materials
Some materials CANNOT
crystallize, e.g. ordinary glass

Why?
Molecular structure is too
irregular V A
B
D
liquid amorphous or E
rubber C
glassy phase F

Tg Tm T
• Cooling of liquid via AB continues until D
• The area BD has elastomeric properties and is the rubbery state
• D is called the glass-rubber transition, Tg = glass transition temperature
• DE has the same slope as CF
 Crystalline vs. Amorphous
Phase transitions for long-chain polymers.
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 
4 H
+ +
+ + + bonds
+ Waals
Van der
+
Hydrogen bonds
+  + +
 + +
H H
H  O H  O
  ||  |  || C C
|
   
 N  C   N  C  C   N  C  H H
   
|  |  |  |  |
H H 
6 H 
H 
4 H


 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 CH 2 CH2 CH2 CH3
O CH 2 CH2 CH2 CH3
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

- 90 0C
PE (high Mw)
 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
 T
Callister,
rubber
viscous
Fig. 16.9
mobile liquid Tm
liquid tough
plastic
Tg

partially
crystalline
crystalline
solid
solid

Molecular weight
Tm: melting over wide range of T depends upon history of sample,
a consequence of lamellar structure
thicker the lamellae, higher the Tm.

Tg: from rubbery to rigid as T lowers

The fundamental parameters which influence the
structure-property relationship are

molecular mass
polarity

crystallinity

molecular cohesion

the nature of polymeric chains and

stereochemistry of the molecules

The properties like tensile strength, crystallinity,

elasticity, resistance to chemicals, wear and tear
depend mostly on the polymer structure
STRUCTURE – PROPERTY RELATIONSHIP OF POLYMERS

Macromolecules show a wide range of properties which are

quite different from those of respective monomers

They may be
elastic or rigid
hard or soft
transparent or opaque
have strength of steel but can have very light weight
soften on heating or
can set to a hard mass on cooling the melt

These properties may vary from one type of polymer to

another and even among the same type
Tensile Strength
This can be discussed based on
the forces of attraction and
slipping power

Based on forces of attraction:

Strength of the polymer is mainly determined by

the magnitude and distribution of attraction forces

between the polymer chains

These attractive forces are of two different types

primary or covalent bond
secondary or intermolecular forces
In straight chain and branched chain polymers,
the individual chains are held together by
weak intermolecular force of attraction

strength increases with increase in chain length

(in turn increase in molecular weight)
as the longer chains are entangled (anchored) better
In cross-linked polymers, monomeric units are held together
only by means of covalent forces

Increase in Strength
Examples:
Linear Polymers: Polyethylene, polyvinyl chloride (PVC), polystyrene,
polymethyl methacrylate (plexiglass), nylon, fluorocarbons (teflon)

Branched Polymers: Many elastomers or polymeric rubbers

Cross-linked Polymers: Many elastomers or polymeric rubbers are cross-

linked (vulcanization process); most thermosetting polymers

Network Polymers: Epoxies, phenol-formaldehydes.

Based on slipping power:

It is defined as the movement of molecules one over the other

It depends on the shape of the molecule

E.g., polyethylene molecule is simple and uniform

the movement of molecules one over other is easy

i.e., slipping power is high

Hence it has less strength.

in case of poly vinyl chloride (PVC), the bulky chlorine atoms are
present along the chain length hence movement is restricted

i.e., slipping power is less

Hence PVC has higher strength than PE

Cl Cl Cl Cl

Cl Cl Cl Cl

Cl Cl Cl Cl

Cl Cl Cl Cl
Polystyrene (PS) possess greater strength when compared to
PE because of the presence of bulky phenyl group.

R
 Plastic deformation
When a polymer is subjected to some stress in the form
of heat or pressure or both, permanent deformation in
shape takes place, which is known as plastic deformation

Slippage is more in case of linear molecules than branched

and cross-linked, because of the presence of only the weak intermolecular
forces
at high pressure and temperature, the weak
Vander waal’s forces between molecules become
more and more weak

Hence linear molecules show greatest degree of

plastic deformation, under pressure

Such type of materials are called thermoplastic materials

 No slippage occurs in case of cross-linked molecules,
because of only primary covalent bonds are present
throughout the entire structure

i.e., plasticity does not increase with rise in temperature

or pressure or both

Such type of polymers are known as thermosetting polymers

However, when considerable external force

or temperature exceeding the stability of material is applied,
it will result in total destruction
Chemical Resistance
Chemical resistance of the polymer depends upon the

• chemical nature of monomers and

• their molecular arrangement

As a general rule of dissolution,

‘like materials attract’ and
‘unlike materials repel’

Thus a polymer is more soluble in structurally similar solvent

e.g.,
polymers containing polar groups like – OH, - COOH etc.,
usually dissolve in polar solvents like water, ketone, alcohol etc.,

but these are chemically resistant to non-polar solvents

Similarly non-polar groups such as methyl, phenol dissolve
only in non-polar solvents like benzene, toluene, etc.,
polymers of more aliphatic character are more soluble in
aliphatic solvents, hence chemical resistance is less in
aliphatic solvents and more in aromatic solvents

polymers with more aromatic groups dissolve more in

aromatic solvents, hence chemical resistance is less in
aromatic solvents and more in aliphatic solvents
Polymers containing ester groups (e.g., polyesters) undergo
Hydrolysis with strong alkalis at high temperature
Implies less chemical resistance in alkalies

Polyamides like nylon containing –NHCO– group can undergo

easily the hydrolysis by strong acid or alkali
 Polymers containing residual unsaturation e.g., rubbers
(natural and some synthetic) easily undergo degradative
oxidation in air in presence of light or ozone
Because of the dissolution of polymers in suitable solvents,
there occurs softening, swelling and loss of strength of
polymer material

The tendency of swelling and solubility of polymers

in a particular solvent decreases with increase in
molecular weight
Linear polymers have lower resistivity than branched chain
and cross linked polymers
Permeability of the solvents in the polymers also depends
on crystallinity
crystalline polymers exhibits higher chemical resistance than
less crystalline polymers because of denser packing
Elasticity

Elasticity of the polymer is mainly because of the uncoiling and

recoiling of the molecular chains on the application of force

a polymer to show elasticity the individual chains should not

break easily on prolonged stretching
a polymer to show elasticity, the structure should be
amorphous
By introducing a plasticizer the elasticity of polymer
can enhance

to get an elastic property, any factor that introduces

crystallinity should be avoided
 Which polymer more likely to crystallize? Can it be decided?

Linear syndiotactic polyvinyl chloride Linear isotactic polystyrene

• For linear polymers, crystallization is more easily accomplished as chain

alignment is not prevented.
• Crystallization is not favored for polymers that are composed of chemically
complex mer structures, e.g. polyisoprene.

• Linear and syndiotactic polyvinyl chloride is more likely to crystallize.

• The phenyl side-group for PS is bulkier than the Cl side-group for PVC.
• Generally, syndiotactic and isotactic isomers are equally likely to crystallize.
• A linear polymer will have a high degree of crystallinity, and be
stronger, denser and more rigid.

• The more “lumpy” and branched the polymer, the less dense
and less crystalline.
• The more crosslinking the stiffer the polymer.
And, networked polymers are like heavily crosslinked ones.
• Polymers with a long repeating unit or
with low degree of symmetry do not crystallize easily
• Isotactic and syndiotactic polymers are stronger and
stiffer due to their regular packing arrangement.

• Optical properties: crystalline -> scatter light (Bragg)

amorphous -> transparent.

Most covalent molecules absorb light outside visible spectrum, e.g. PMMA
(lucite) is a high clarity tranparent materials.
 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.
upon polymerization, it forms polyethylene and we encounter
an indefinite chemical structure of --(-CH2 – CH2 -)n—

where ‘n’ can change its value from one polyethylene

molecule to another present in the same polymer sample

When ethylene is polymerized to form polyethylene,

a number of polymer chains start growing at any instant,
but all of them do not get terminated after growing to the
same size
The chain termination is a random process
hence, each polymer molecule formed can have a
different number of monomer units and thus
different molecular weights
So, a sample polymer can be thought of as a mixture of
molecules of the same chemical type, but of different
molecular weights
Molecular Weight of Polymers

A simple compound has a fixed molecular weight

e.g., acetone has mol. Wt. of 58 (regardless of how it is made)
in any given sample of acetone, each molecule
has the same molecular weight
This is true for all low molecular weight compounds
In contrast, a polymer comprises molecules of different
molecular weights
hence, its molecular weight is expressed in terms of an
‘average’ value
e.g., ethylene gas, which is a low mol. wt. compound
each of its molecules have the same chemical structure and
hence, a fixed molecular weight of 28
In this situation, the molecular weight of the 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
 Which polymer more likely to crystallize? Can it be decided?
Networked Linear and highly crosslink
Phenol-Formaldehyde cis-isoprene
(Bakelite)

+ H
+ H20

• Networked and highly crosslinked structures are near impossible to reorient to

favorable alignment.

• Not possible to decide which might crystallize. Both not likely to do so.
 Assume that there are n number of molecules in a
polymer sample
n1 of them have M1 molecular weight (each)
n2 of them have M2 molecular weight

ni of them have Mi molecular weight

Total no. of molecules (n) is given by
n = n1 + n2 + n3 + n4 + n5 + n6 + …………+ ni

No. of molecules in fraction 1 = n1

Number fraction of fraction 1  n1

 ni
 n1M1
Molecular weight contributi on by fraction 1 
 ni
Similarly,

Molecular weight contribution by other fractions are

n1M1 n2M2 n3M3 n iMi
; ; ;
 ni  ni  ni  ni
Number average molecular mass of the whole polymer
is given by
n1M1 n2M2 n3M3 n4M4 niMi
Mn      ............................ 
 ni  ni  ni  ni  ni

Mn 
 nM i i

n i
 In computing the weight average molecular mass
of a polymer, we consider the weight fractions

Total weight of the polymer (W) is given by

W = S ni Mi

Weight of fraction 1 = W1= n1M1

n1M1 n1M1
weight fraction of fraction 1  
W  niMi
 n1M1 
Molecular weight contributi on by fraction 1    M1
  niMi 
 

n1M12

 niMi
 Molecular weight contribution by other fractions are
n1M12 n2M2 2 n3M3 2 niMi 2
; ; ;
 niMi  niMi  niMi  n iMi

Mw 
n1M12
Weight average molecular mass of the whole polymer
n2M2 2

n3M3 2

n4M4 2
 ................. 
niMi 2
 niMi  niMi  niMi  niMi  niMi
is given by

Mw 
 n i M i
2

nM i i
 Polymers: Molecular Weight
N : no. of molecules with degree of polymerization of i
i

Mi: molecular weight of i

number average, M n

 weight average, Mw
Ratio of Mw to Mn is known as the polydispersity index (PI)
a measure of the breadth of the molecular weight
PI = 1 indicates Mw = Mn, i.e. all molecules have equal length
(monodisperse)

PI = 1 is possible for natural proteins whereas synthetic

polymers have 1.5 < PI < 5

At best PI = 1.1 can be attained with special techniques

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
 i Ni Mi NiMi NiMi2
1 50 500 25000 12500000
2 100 1000 100000 1E+08
3 300 1500 450000 6.75E+08
4 400 2000 800000 1.6E+09
5 600 4000 2400000 9.6E+09
6 400 5000 2000000 1E+10
7 300 10000 3000000 3E+10
8 100 15000 1500000 2.25E+10
9 50 30000 1500000 4.5E+10
SUM 2300 69000 11775000 1.19E+11
         
Mn= 5119.565      
Mw = 10147.56      
PDI= 1.982113      
 Polymers: Molecular Weight

• Biomedical applications: 25,000<M <100,000 and

n
50,000<Mw<300,000

• Increasing molecular weight increases physical properties;

however, decreases processibility
 Problems

1. A polymer sample contains 2,3 and 5 molecules

having molecular weights of 2000, 4000 and 3000
respectively. Calculate Mn and Mw.

2. A polymer sample contains1,2,3 and 4 molecules

having molecular weights 105, 2 x 105, 3 x 105 and 4
x 105 respectively. Calculate number average and
weight average molecular weights of the polymer.
3. A protein sample consists of an equimolar mixture of
Haemoglobin (M =15.5 Kg mol-1), Ribonuclease (M=
13.7 Kg mol-1 ) and myoglobin (M = 17.2 Kg mol-1).
Calculate Number average and wt. average mol.wt.
4.Polymer molecules with different degree of
polymerization such as 2600,2500,2750 and 3050 are
mixed in molecular ratio 5:4:3:2 in a sample of high
polymer of vinyl chloride (Mol.wt.=62.5). Calculate
number average and weight average molecular mass.
TEFLON or FLUON or Polytetrafluoroethylene (PTFE):

Preparation

F F F
F Water emulsion
n C C polymerization C C
F F peroxide
n
F F
Properties
• a highly regular and linear polymer without branching
• a highly crystalline polymer with a melt temperature of
around 330oC
• Its mechanical strength remains unchanged over a wide
temperature range from -100 oC to 350 oC
 • It does not dissolve in any of the strong acids including
hot fuming nitric acid
• It is resistant to corrosive alkalies and known organic solvents
• It reacts with only molten alkali metals (to any significant
extent) probably, this is because fluorine atoms from the
polymer chain get removed by the alkali metals
• It has very low dielectric constant
• The conventional techniques used for the processing of
other polymers can not be applied to Teflon because
of its low melt flow rates
• The strong attractive forces between the polymer chains
gives the extreme toughness, high softening point,
exceptionally high chemical resistance
• It has high density 2.1 to 2.3 gm/cm3
 • It has low coefficient of friction (low interfacial forces
between its surface and another material)
• It has very low surface energy

Uses
• It is used in making articles such as pump valves and
pipes where chemical resistance is required
• It is used in non-lubricated bearings
• It is used in non-sticking stop-cocks like burettes etc.,
• It is used for coating and impregnating, glass fibers,
asbestos fibers (to form belts), filter cloth etc.,
• It is used for products where resistance to acid and
alkalies are needed
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)
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 roaps
• 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 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

o-methylol phenol
CH2OH
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
 • 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
 Epoxy resins
Preparation
CH3

n Cl CH2 CH CH2 + HO C OH
O CH3
epichlorhydrin
Alkaline catalyst bis phenol
60 OC
-n HCl

CH3
O C O CH2 CH CH2
CH3 OH n
In epoxy resins, n ranges from 0 to 20

The molecular weight of the epoxy resin depends upon

the relative proportions of the reactants
The epichlorohydrin acting as a chain stopper

Molecular weight ranges from 350 to 8000

It is a mobile and easy flowing liquid at a mol. Wt. of 350

It is a solid at higher mol. wt. with a melting range

of 145 oC - 155 oC

Linear epoxy resins are converted into 3D polymers

by curing with some chemicals like diethylene triamine,
triethylene tetramine and meta-phenylene diamine
Properties

• Epoxy resins have ability of getting cured, without

application of heat
• They have good resistance to chemicals

• They have less shrinkage during curing process

• They may be used in solid or liquid form

• They possess excellent electrical resistance

• Epoxy resins stick well to a number of substances
including metal and glass
• Their properties can be modified by adding compounds
like unsaturated fatty acids or amines and
some of the solvents
 • No size-change upon cross-linking/hardening
This means they make ideal adhesives
Shrinkage causes adhesive failures
Adhesives require no dimensional change
• Resins can be changed to modify epoxy properties

Uses
• epoxy resins are mainly used as adhesives
• They are used for surface coatings
• Moulds are made with epoxy resins, which are used for
the production of metallic components of aircrafts
and automobiles
• They are used as laminating and casting materials
• Epoxy resins are used as potting compounds for
electrical equipment
• They are used as stabilizers for PVC resins
• Epoxy resins are used for skit-resistant surfaces, for
highways rendering a number of advantages
• Delayed wearing of road surfaces in hot and cold climates
• Excellent resistance to freezing conditions,
de-icing salts, solvents and water
• Non-porosity which protects the original pavements
from scaling and spalling
• Permanent high traction even under wet or oily conditions
• Fast curing, causing minimum interruption to the flow of
traffic
• Light weight, especially useful for surfacing bridges
• Epoxy resins are applied over cotton, rayon and
bleached fabrics to impart crease resistance and
shrinkage control
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
 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
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
 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 heat Cold condition it is hard Withstand effect of
and brittle, at higher heat over a range of
temps soft and temperature.
sticky

With organic Swells and dissolves Do not swell and

solvents dissolve
Ageing Undergoes quickly Resists ageing

Elasticity On increased stress undergoes Has high elasticity.

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

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 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
Advantages of vulcanization
Vulcanized rubber
• has good tensile strength, when a tensile force is applied,
can bear a load of 2000 kg/cm2 before it breaks

• 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 electrical insulator, although it tends to

absorb small amounts of water
Compounding of rubber
Compounding is mixing of the raw rubber (synthetic or
natural) with other substances so as to impart the
specific properties to the product, which are suitable
for a particular job

Besides rubber, the following materials may be incorporated

• Softners and plasticizers
These are added to give the rubber greater tenacity and
adhesion. Important materials are vegetable oils, waxes, stearic
acid, rosin, etc.
• Vulcanizing agents
The main substance added is sulphur
Depending on the nature of the product required, the
% of sulphur added varies between 0.15 and 32.0%
 Many other vulcanizing agents are now-a-days added to
rubber, among them are sulphur monochloride,
hydrogen sulphide, benzoyl chloride, trinitrobenzene and
alkylphenol sulphides
• Accelerators
These materials drastically shorten the time required
for vulcanization
The most used accelerators are 2-mercaptol,
benzothiozole and zinc alkyl zanthate

• Antioxidants

Natural rubber has a tendency to perish, due to oxidation

For this reason, anti oxidation materials, such as complex
amines like phenyl naphthylamine and phosphates are
added
• Reinforcing fillers
These are added to give strength and rigidity to the
rubber products
Common reinforcing fillers are carbon black, zinc oxide,
calcium carbonate and magnesium carbonate

• Colouring matter
These are added to give the desired colour to the
rubber product
for white colour titanium dioxide
Green chromium oxide
red ferric oxide
Crimson antimony sulphide
yellow lead chromate
---- pigments are added
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
Properties

 It possess high abrasion-resistance

 It possess high load-bearing capacity and resilience

 It gets readily oxidized, especially in presence of
traces of ozone present in the atmosphere
 It swells in oils and solvents
 It can be vulcanized in the same way as natural
rubber either by sulphur or sulphur monochloride
However, it requires less sulphur, but more
accelerators for vulcanization
 Styrene rubber resembles natural rubber in
processing characteristics as well as the quality
of the finished products
Uses

It is used for the manufacture of

• motor tyres
• floor tiles
• shoe soles
• gaskets
• wire and cable insulations
• carpet backing
• adhesives
• tank-lining etc.,
 Dimethyl silicone dichloride is bifunctional and
can yield very long chain polymer

CH3 CH3
Hydrolysis
n Cl Si Cl n HO Si OH
- HCl
CH3 CH3

unstable

H 2O
CH3 CH3
polymerization
Si O ( Si O)

CH3 n
CH3
unstable
Vulcanized silicone rubbers are obtained by mixing
high molecular weight linear dimethyl silicone polymers
with filler

The fillers are either a finely divided silicon dioxide

or a peroxide

It may also contain the curing agents

Peroxide causes the formation of dimethyl bridge

(cross link) between methyl groups of adjacent chains
 CH3 CH3 CH3 CH3 CH3

Si O Si O Si O Si O Si O

H CH2 CH3 CH3 CH3 CH3

O +

H CH2 CH3 CH3 CH3 CH3

Si O Si O Si O Si O Si O

CH3 CH3 CH3 CH3 CH3

H 2O
CH3 CH3 CH3 CH3 CH3

Si O Si O Si O Si O Si O

CH2 CH3 CH3 CH3 CH3

CH2 CH3 CH3 CH3 CH3

Si O Si O Si O Si O Si O

CH3 CH3 CH3 CH3 CH3

Properties
They possess exceptional resistance to
• prolonged exposure to sun light
• weathering
• most of the common oils
• boiling water
• dilute acids and alkalies

They remain flexible in the temp. range of -90 – 250 OC

hence, find use in making tyres of fighter aircrafts,
since they prevent damage on landing. Ordinary rubber
tyre becomes brittle and hence disintegrates
Uses
• as a sealing material in search-lights and an aircraft engines
• for manufacture of tyres for fighter aircrafts
• for insulating the electrical wiring in ships
• In making lubricants, paints and protective coatings for
fabric finishing and water proofing
• as adhesive in electronics industry
• For making insulation for washing machines and electric
blankets for iron board covers
• For making artificial heart valves, transfusion tubing and
padding for plastic surgery
• For making boots for use at very low temp., since they are
less affected by temperature variation
e.g., Neil Armstrong used silicone rubber boots when he
walked on the moon
Reclaimed rubber
Reclaimed rubber is rubber obtained from waste rubber
articles
like worn out tyres, tubes, gaskets, hoses, foot-wears etc.,

The waste is cut to small pieces and powdered by using a

cracker, which exerts powerful grinding and tearing action

The ferrous impurities, if any, are removed by the

electro-magnetic separator
The purified waste powdered rubber is then digested with
caustic soda solution at about 200 oC under pressure for
8 – 15 hours in steam-jacketed autoclave

By this process, the fibers are hydrolyzed

After the removal of fibers, reclaiming agents like petroleum
and coal-tar based oils and softeners are added

Sulphur gets removed as sodium sulphide and rubber

becomes devulcanized

The rubber is then thoroughly washed with water sprays

and dried in hot air driers

Finally, the reclaimed rubber is mixed with small

proportion of reinforcing agents like clay, carbon black etc.,
Properties

The reclaimed rubber has

• less tensile strength
• possesses lesser wear-resistance than
natural rubber

• it is much cheaper, uniform in composition

• it is quite easy for fabrication

Uses

 for manufacturing tyres

 tubes
 automobile floor mats
 belts
 hoses
 battery containers

 shoes, heals etc.,

 Assignment-2
1).What are polymers? How they classified?
2).Write the preparation of nylon 6,6 and give any two
properties and applications of it.
3). Account for the following.
a). Silicon rubber can be vulcanised only in presence of
organic peroxides or in presence of radiation
b) Natural rubber perishes when exposed to atmospheric
conditions.
4).Explain the term compounding of rubber?
5).Compare bulk and solution polymerization techniques
6).Write any four differences between number average and
weight average molecular weight.
7). What is vulcanization process? Mention any four merits of
vulcanized rubber.
8). Discuss the preparation of phenol-formaldehyde resin and epoxy
resin.
9). If the polymer sample consists of 1,2,3 and 4 molecules having the
molecular masses of 100, 250,300 and 500 respectively. Calculate
number average and weight average molecular mass of the polymer.
10).Give reason for the following.
a) Molecular size control is difficult in suspension polymerization.
b) Heat control is difficult in bulk polymerization
 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
Silicone rubber
Silicone resins contain alternate silicone – oxygen
structure, which has organic radicals attached to
silicone atoms

H H

H C H H C H

O Si O Si O

H C H H C H

H H
 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 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
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
 • 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
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
 • 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