High polymers

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 CH3
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
 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.
 Functionality
The total number of functional groups, bonding sites
or reactive sites present in the monomer is called the
functionality of the monomer.
The reactive functional groups can be
• –OH, -COOH, -NH2, -SH , –NCO etc.
• Eg: In CH3CH2OH one reactive - OH group is
present, hence functionality is one (monofunctional)
• HO- CH2 -CH2 – OH has two – OH groups hence
bifunctional
• HOOC CH2 CH (COOH) CH2 COOH has three -
COOH groups, hence trifunctional
• The presence of double or triple bonds in the
molecule imparts polyfunctionality to the molecules.
• Eg: Ethylene - due to the presence of a double bond
Classification of polymers based on their
molecular structure:
Linear
Branched
Cross-linked

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

secondary bonding

• Linear polymers tend to have high strength and stiffness due to the ability
of the chains to align and crystallize.
• They also exhibit good resistance to solvents and chemicals, as well as
relatively high melting and glass transition temperatures.
Branch polymers

• Branched polymers have a main linear backbone with

additional side chains or branches attached to it.

• Branched polymers generally have lower densities and

lower crystallinity compared to their linear
counterparts.
Cross linked polymers

• Network or cross-linked polymers are formed when linear or branched

polymer chains are chemically connected at various points along their
lengths, creating a three-dimensional network structure.
• They are highly resistant to solvents, heat, and chemicals due to their rigid
network structure.
• They exhibit high strength, toughness, and dimensional stability, but they
are also relatively inflexible and insoluble.
• Eg: vulcanized rubber, thermoset resins like epoxy and polyurethane
STRUCTURE – PROPERTY RELATIONSHIP OF POLYMERS
1. Tensile Strength

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 - weak
intermolecular force of attraction

strength increases with increase in chain length -

as the longer chains are entangled (anchored) better

In cross-linked polymers, - 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

the movement of molecules one over other is easy

i.e., slipping power is high
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 and PVC because of the presence of bulky phenyl group.

In cross linked polymers, connected by strong covalent

forces and so the movement of the intermolecular chains is
totally restricted.
 2. 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

linear molecules - because of the presence of only the

weak intermolecular forces show greatest degree of
plastic deformation, under pressure .

Such type of materials are called thermoplastic materials

cross-linked molecules - covalent bonds - plasticity does
not increase with rise in temperature or pressure or both in
cross-linked molecules.

Such type of polymers are known as thermosetting

polymers.
 3. Chemical Resistance

Chemical resistance of the polymer depends upon

the

• chemical nature of monomers and

• their molecular arrangement

Thus a polymer is more soluble in structurally similar solvent

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, phenyl dissolve
only in non-polar solvents like benzene, toluene, etc.,
polymers of more aliphatic character - soluble in
aliphatic solvents, chemical resistance more in aromatic
solvents

polymers with more aromatic groups dissolve more in

aromatic solvents, chemical resistance more in aliphatic
solvents

Polymers containing ester groups - Hydrolysis with strong

alkalis at high temperature.

Polyamides like nylon containing –NHCO– group can undergo

easily the hydrolysis by strong acid or alkali.
 Polymers containing residual unsaturation - 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

Permeability of the solvents in the polymers also depends

on crystallinity. Hence crystalline polymers exhibits higher
chemical resistance than less crystalline polymers
because of denser packing.
4. Crystallinity

Polymers are part crystalline and part amorphous

An amorphous state is characterized by complete

random arrangement of molecules
crystalline form by regular arrangement of molecules

Crystalline
region

Amorphous
region
 5. Elasticity
Elasticity of the polymer is mainly because of the uncoiling and
recoiling of the molecular chains on the application of force
When a polymer is stretched the snarls begin to disentangle
and straighten out
i.e., the orientation of the chains occurs which in turn
enhances the forces of attraction between the chains
and thereby causing the stiffness of the materials
However when the strain is released snarls return to their
original arrangement.
The slippage can be avoided by

• introducing cross-linking at suitable molecular positions

• introducing bulky side groups such as aromatic and
cyclic groups on repeating units
• introducing non-polar groups on the chains

The polymer must be amorphous to enhance elasticity

By introducing a plasticizer the elasticity of polymer

can be enhanced. Any factor that introduces crystallinity
should be avoided
 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.
 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 and brittle plastic) (soft and 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.
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 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
Molecular weight of polymers

A polymer comprises of molecules of different molecular weights and hence,

its molecular weight is expressed in terms of an ‘average’ value.

The molecular weight of a polymer can be expressed by the two most and

experimentally verifiable methods of averaging –

(i) Number – average molecular weight

(ii) weight – average molecular weight

Number – average molecular weight: 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.

∑ 𝑛𝑖 M𝑖
𝑀𝑛 =
∑ 𝑛𝑖
Weight – average molecular weight: The sum of the fractional masses that

each molecule contributes to the average according to the ratio of its mass to

that of the whole sample.

The formula to determine 'weight average molecular weight' of polymers is,

∑ 𝑛𝑖 M𝑖
𝑀𝑤 =
∑ 𝑛𝑖𝑀𝑖
1) A polymer sample contains 1, 2, 3 & 4 molecules having molecular

weight 105, 2X 105, 3X105 and 4X 105 respectively. Calculate the number

average & weight average molecular weight of the polymer.

2. Calculate the number average & weight average molecular weight of

a polymer sample in which 30 % molecules have molecular mass of

20000, 40 % have molecular mass of 30000 & rest 30 % have molecular

mass of 60000.
3) Polymer molecules with different degrees of polymerization such as 500,

750, 950 and 1500 are mixed in molecule ratio1:2:3:4 in a sample of high

polymer of ethylene. ( Mole. Mass= 28). Calculate the number average and

weight average mol.mass

3) A polymer sample contains:
Polymer 400 500 600 800 1000
of DP
Percenta 10 15 35 15 25
ge

Calculate the average degree of polymerization.

Determination of Molecular weight of polymers by viscometry
Viscosity Average Molecular Weight (𝑀𝑣M v ): This is a type of average
molecular weight obtained from viscosity measurements.

Viscosity of Polymer Solution: The viscosity of a polymer solution is

significantly higher than that of the pure solvent because the presence of
macromolecules increases the solution's resistance to flow.
 Mark-Houwink Equation: This equation describes the relationship
between the intrinsic viscosity [η] of a polymer solution and the
molecular weight M of the polymer.

[η] = KMa

Where [η] is the intrinsic viscosity,

M- molecular weight

and a and K are constant for a particular polymer/solvent/temperature

system. Values of K and a are available for may known polymers.

A plot of log [η] against log M gives a
straight line. From the graph, the
value of K and a can be determined
from their ordinate intercept and
slope of the line.

[η] = KMa log [η] = log K + a logM