Polymers

Module - 6
 What are polymers?
Polymers are very large molecules made when hundreds of monomers
join together to form long chains.

Made up by linking together large

number of small molecular units by
chemical bonds.

The repeating small molecules which

combine with each other to form a
polymer are called monomers.
 What keeps the chain together?
The monomers in a polymer are joined together by covalent bonds
between atoms.

covalent
bond
 Addition Polymerization
The process by which polyethene and other polymers is made is called addition
polymerization.

monomers polymer
How are polymers made?
 Examples : Addition polymerisation

(C 6 H 5 ) 2 O 2
Teflon n C F2 – C F2 C F2 C F2
n PTFE
Tetraflouroethylene

n CH 2 =CHCl polymerisation
PVC CH 2 CH PVC
Vinyl chloride
n
Cl

CH2 = CH2 CH CH2

Catalyst PS
Polystyrene n

Styrene n
 Condensation Polymerization
Condensation polymerisation involves monomers reacting together
and releasing a small molecule in the process. The small molecule is
commonly water or hydrochloric acid (HCl).
Polyester is made from the two monomers, terephthalic acid and ethylene glycol.
This makes a popular plastic called PETE, which is short for Polyethylene
Terephthalate.

PETE

O
H O C

ESTER groups formed Hence the name POLYESTER

 Examples: Condensation polymers
Formed by repeated condensation reaction between two different bi-
functional or tri-functional monomeric units.
eg. terylene (dacron), nylon 6, 6, nylon 6.

TYPES OF POLYMERISATON:

nylon - 6, 6,
 Classification of Polymer
Natural Polymer
Based on Origin
Synthetic Polymer
Amorphous Polymer
Based on Physical State
Crystalline Polymer
Linear Polymer
Based on Structure Branched Polymer
Cross-Linked Polymer
Classification of Polymer Homopolymer
Based on Number of Monomers
Copolymer
Isotactic

Based on Tacticity Syndiotatic

Atactic

Addition Polymer
Based on Polymerization
Condensation Polymer
 Based on Origin
Polymer may be classified into:

• Natural Polymer: Polymers having origin in plants & animals. E.g.-

Carbohydrates, Proteins, DNA. Polymers are not just a human
invention. Nature has many examples of polymers. Cotton fibers are
made of sugar molecules that are repeated in a chain-like manner.
Hair, wool, and other natural fibers are polymers. They are made by
chaining one or two substances one after another.

• Synthetic Polymer: Plastic, Fibres, Rubber, Nylon etc.

 Based on Physical State
Polymer may be classified into:

• Amorphous: Polymer chains are flexible and easily folded. For e.g.- Rubber,
LDPE.

• Crystalline: Polymer chains are ordered structure. Degree of crystallinity

depends on the amount of ordering in polymer.

• Semi-crystalline: Polymers are amorphous as well as crystalline. For e.g.-

HDPE, Nylon, Polyester.
 Based on Structure
Polymer may be classified into:

1) Linear: Monomeric units are joined in the form of straight chain. Linear
structure allows close packing of polymer chains. Possess high melting point,
density & tensile strength.

2) Branched: Polymer which are linear and possess branches along the main
chain. Branched chain polymer do not allow efficient packing of polymer
chains. Posses low melting point, low density & low tensile strength.

3) Cross-linked: Polymer which are 3-D structure. They are hard, rigid, do not
melt on heating but decomposes & burn on excessive heating. Posses strong
covalent bond between the polymer chains.
 Based on Monomers
Polymer may be classified into:

1) Homopolymer: Polymer obtained by the repeated combination of only

one type of monomeric units. For e.g.- PVC

2) Copolymer: Polymer obtained by the repeated combination of two or

more type of monomeric units. For e.g.- Styrene, Nylon, Bakalite,
Dacron, Buna-S etc.
 Based on Tacticity

Tacticity is defined as the spatial arrangement of the substituent groups

on the asymmetric carbon atom. Based on the orientation of the group in
space polymer can be of three type:
a) Isotactic: orientation of side groups on all carbon atom is same.
b) Syndiotactic: orientation of side groups is alternating.
c) Atactic: orientation of side groups is random.
 Based on Polymerization
Polymer may be classified into:

1) Addition Polymerization: Here, the monomers are added to each

other without the formation of by-product. The elemental
composition of polymer is same as that of monomer and its molecular
weight is exact multiple of the original monomeric molecule.

2) Condensation Polymerization: In condensation polymerization

reaction proceeds step by step through reaction between functional
groups of the monomer with formation of by-product.
 Polystyrene
Prepared by the free radical polymerization of styrene in the presence of
benzoyl peroxide as catalyst.

Properties:
• Due to the presence of bulky phenyl group packing, it is amorphous.

• It has good optical properties & allow the transmission of all wavelength.

• Due to chain stiffening effect of benzene ring, PS is hard & brittle.

Used in the manufacturing of containers for talcum powder, housewares (Jars

& containers), Bottle caps, Combs and brush handles.
 Polyvinyl Chloride (PVC)

Preparation:
Vinyl Chloride is mixed with water in equal parts, small amount of
catalyst (benzyl peroxide/ hydrogen peroxide) and an emulsifier. The
polymerization takes place at 40-45ºC under high pressure.
Properties:
• It is colourless, odourless and non-inflammable, excellent oil
resistance and resistance to weathering.

• It has superior chemical resistance but soluble in ethyl chloride. The

presence of chlorine atom makes it hard and stiff.

Application:
• Used in acid recovery plants and in plants for handling hydrocarbons.

• Used in the manufacturing of pipes, toys, tumbler, buckets, bottles.

PVC is quite safe until it burns. The chlorines in the PVC

combine with the hydrogens in the PVC to form hydrogen
chloride gas (HCl). When this contacts water in lungs or
mouth, it turns to hydrochloric acid.
 Polymethyl Methaacrylate (PMMA) / Plexiglass
Preparation:

It is prepared by the polymerization of methyl methacrylate in the

presence of acetyle peroxide or hydrogen peroxide as catalyst.

Properties:
• It is colourless, light, hard, transparent thermoplastic with high optical
transparency.

• It has high softening point and having total internal reflection & allow the
transmittance of light of all the wavelength.
Application:
• Used in light fittings for street lamp housing, automobile rear lamp housing,
cock pit of helicopter, manufacturing of motorcycle windscreens, optical fibres.

• Used as a safer and stronger replacement for glass as it’s better at insulating
tool. It is half the weight of glass and does not shatter, it can also be cut and
shaped with a saw.
 Polytetra Fluroethylene / Teflon / PTFE
Preparation:

It is prepared by the polymerization of tetrafluoro ethylene under

pressure in the presence of benzoyl peroxide as catalyst.

Properties:
• Due to the presence of highly electronegative fluorine atom, there are very
strong attractive force between the chains.

• It is dense, chemically inert and high softening temperature.

Application:
• Used in the manufacturing of wire and cable insulation, coating of frying
pans, Non lubricating bearings.
 Phenolic Resins: Bakelite
Preparation:

The reaction mixture is heated and allowed to reflux under atmospheric

pressure at about 100ºC. The vacuum is applied for the removal of
volatiles.
Properties:
• It is hard, rigid, and strong. They have excellent heat and moisture
resistance, good abrasion resistance.

• They have good electrical insulation characteristics.

Application:
• Used in the manufacturing of electrical plugs and switches. Handles of
cooker.

• Used in the manufacturing of varnishes, electrical insulation and protective

coating.