Unit 2: Advanced Polymeric Materials

Introduction, Classification of Polymers,- based on origin, based on

polymer type, polymerization mechanism, Characteristics of
polymers, thermo-softening and thermosetting plastics, conducting
polymers: Intrinsic conducting polymers, extrinsic conducting
polymers, doped conducting polymers, factors responsible for
conduction, examples and applications.
 Polymer

Polymer word is derived from two Greek words

Polys Meros

Many Parts / Units

Defination of polymer: It is a large molecule formed by repeated linking of small

molecules called monomers via chemical reaction.
e.g. Polyethelene

n H2C
Polymerisation H2
CH2 H2C C
Ethylene n

Polyethylene
Degree of polymerization: The number of repeating units i.e. monomers in the
polymeric chain is called degree of polymerization.
High Polymers: Polymers with high degree of polymerization i.e Macromolecules
Low Polymers: Polymers with low degree of polymerization i.e Oligomers
Homopolymers: Polymers containing monomers of identical chemical structure.
e.g. A = Monomer A A A A
n

Polymerisation H H H
n H2C C OH H2C C CH2 C CH2 C
H
OH OH OH
Vinyl alcohol n
A A A
Polyvinyl alcohol

Polymerisation H H H
n H 2C C Cl H2C C CH2 C CH2 C
H
Cl Cl Cl
Vinyl chloride n
Polyvinyl chloride
Copolymer or Mixed polymer: Polymers containing monomers of different chemical
structure.
e.g. A and B = Different monomers A B A B
n

O O
n HO C H2C C OH n H2N H2C NH2
4 6
Adipic acid Hexamethylene diamine

Polymerisation
2n H2O

O O O O
H
n C H2C C NH H2C N C H 2C C NH H2C NH
4 6 4 6
A B A B
Nylon-6,6
Block copolymer: A block copolymer is a polymer formed when the two monomers
cluster together and forms blocks of repeating units.
e.g. A and B = Different monomers
A A A A B B B B A A A A B B B B

Polystyrene is a rigid polymer and

polybutadiene is a rubbery polymer which
are incompatible with each other and
therefore they tend to segregate in to
different regions.
Graft copolymer: A graft copolymer is a branched copolymer with one kind
of monomer in their main chain and another kind of monomer in their side
chain.
e.g. High impact polystyrene:
Polystyrene mixed with polybutadiene
rubber
Addition Polymer
H H H H H
H H H H H
C C C C C
C C C C C
H H H H H
H2 H H H H H
H2C C
H H H H H
n C
H
C
H
C
H
C
H
C
H
C C C C C
H H H H H
Polyethylene H H H H H

Condensation Polymer

O O O O
H
C H2C C NH H2C N C H2C C NH H2C NH
4 6 4 6

O O O O
H
C H2C C NH H2C N C H2C C NH H2C NH
4 6 4 6

O O O O
H
C H2C C NH H2C N C H2C C NH H2C NH
Nylon-6,6 4 6 4 6
Differentiation between Thermoplastic and Thermosetting Polymers/plastics

Sr. No. Thermoplastic Polymer Thermosetting Polymer

1 They are mostly formed by addition They are formed by condensation
polymerization polymerization
2 They exhibit linear long-chain structures with They have three-dimensional network
negligible cross links structure joined by strong covalent bonds
3 They undergo reversible change on heating. They undergo irreversible change on
heating and degrade.
4 They are soft, weak and less brittle They are hard, strong and more brittle
5 They are soluble in organic solvents as their They are insoluble in almost all organic
intermolecular bonds are weaker solvents as their intermolecular bonds are
stronger and cross-linked.
6 They consists of polymers of low molecular They consists of polymers of high
weight. molecular weight.
7 They can be softened, reshaped and reused by They retain their shape and structure even on
heating to suitable temperature. heating. Hence they cannot be reshaped
and reused.
8 There is no change in chemical composition and They undergo chemical changes, such as
structure during molding process. further polymerization and cross linking
during molding process.
9 For example: Polyethylene, PVC, Teflon, For example: Urea formaldehyde, Epoxy
etc. resin etc.
 Conducting Polymer
Defination: Organic polymers having electrical conductance of the order of conductors are
called conducting polymers.

Classification: Conducting polymers

Intrinsically Conducting Polymers OR Extrinsically Conducting Polymers

Conjugated - electron conducting polymers

Doped Conducting Polymers

Conductive element Blended
filled polymer conducting
polymer
p-Doped n-Doped
Conducting Polymers Conducting Polymers
Intrinsically Conducting polymer:
1. It is a polymer whose backbone consists of delocalized electron pair or residual
charge.
2. Overlapping of orbitals over entire polymer backbone results in the formation of
valence band and conduction band which extends over the entire polymer
molecule.
3. In an electric field conjugated electrons get excited and thereby can be
transported through solid polymeric material.
e.g. trans-Polyacetylene

Poly-para-phenylene
 H H H H H H H
C C C C C C C
n HC CH C C C C C C C
Acetylene H H H H H H H
trans-Polyacetylene

External Electric field

Doped conducting polymers:
1. Conjugated organic polymers in pure state are semiconductors.
2. The conductivity of these polymers can be increased by creating either positive
or negative charge on the polymeric backbone by oxidation or reduction i.e.
doping.
p-Doped conducting polymers:
It involves oxidation of Intrinsically conducting polymer with lewis acid.
p-Dopant: I2, Br2, AsF5, PF5, Napthylamine
e.g. Conductivity of trans–polyacetylene in pure state = 4.4 × 10-4 S/cm
Conductivity of trans–polyacetylene = 400 S/cm

n-Doped conducting polymers:

It involves reduction of Intrinsically conducting polymer with lewis base. Due to reduction
process negative charges on polymeric backbones are created.
n-Dopant: Sodium napthalide
p-Doped conducting polymers: Conduction Band
Polyacetylene
Valance Band
I2 in CCl4
Diradical

- -
1st Oxdn I2 in CCl4 e I2 1/2 I2 I3

Radical cation

2nd Oxdn I2 in CCl4

Diradical
dication
Semiconductor
n-Doped conducting polymers: Conduction Band
Polyacetylene
H Valance Band
NaH Na

Diradical

C10H7 Na 1st Redn

Radical anion

C10H7 Na 2nd Redn

Diradical anion
Semiconductor
Extrinsically conducting polymers: The conductivity of these polymers is due to the
externally added ingredients.

1. Conductive element filled polymers:

a) It is a polymer filled with conducting elements such as carbon black, metal
fibers, metal oxides, carbon fibers, aluminum flake, stainless steel fibers,
metal-coated fillers, metal particles, etc.

b) Polymer acts as a binder to hold the conducting element in solid entity.

c) Amorphous polymers (polystyrene, PVC, polycarbonate, acrylonitrile

butadiene styrene (ABS), polyethersulphone, polyetherimides, etc.) and
crystalline polymers (polyethylene, polypropylene, polyphenylene sulphide,
nylons, etc.) can be made electrically conducting.
These polymers are low in cost, light in weight, mechanically
durable, strong and easily convertible in different forms,
shapes and size.
2. Blended Conducting polymers (Polymers filled with conjugated
conducting polymers):

a) These polymers are obtained by bending conventional polymer with

conducting polymer.
b) These polymers have better physical, chemical and mechanical
properties.

c) E.g. Ploy (3-octyl thiophene): Conducting and Poly (methyl

methacrylate): Non- conducting
Ploy (3-octyl thiophene) : Conducting and Poly (p-phenylene
terephthalamide) : Non- conducting
Applications of Conducting polymer:
1. For making rechargeable batteries.
2. Used as analytical sensors for phenol, O₂, NH3, Glucose, Humidity etc.
at low concentrations.
3. For manufacture of transistors, LEDs, lasers and solar cells.
4. In telecommunication systems.
5. In the construction of photovoltaic cells.
6. As a artificial nerves: Due to biocompatibility of some conducting
polymers they may be used to transport small electric signals through the
body.
Applications of Conducting polymer:

Light-emitting diodes Smart" windows

Solar cell