Definition

“A polymer is defined as a macromolecule formed by the repeated

combination of several simple molecules (Monomers) through
covalent bonds”
Example- Polyethylene, nylon, PVC, Teflon, polyester, Bakelite, etc.

Polymerization:
Polymerization defined as “the chemical reaction in which
monomer is converted into polymer”

nCH2=CH2 Peroxide initiator [-CH2-CH2] n

Ethylene Polyethylene
Homopolymers: Addition polymers formed from single
monomeric species.
For Example: Polyethylene.

Copolymers: Addition polymers formed from two or more

different monomeric species.
For Example: BUNA-S(Styrene + 1,3 Butadiene)
Tacticity: It is simply the way pendant groups are arranged along the
backbone chain of a polymer.

• Random.

• R groups on alternating sides of backbone.

• R groups on same side of backbone.

Functionality

• The functionality of a monomer is the number of sites it has for

bonding to other monomers under the given conditions of the
polymerization reaction.
• Thus, a bifunctional monomer, i.e., monomer with functionality
two, can link to two other molecules under suitable conditions.
• A polyfunctional monomer is one that can react with more than
two molecules under the conditions of the polymerization
reactions.
Classification of Polymers

• Based on Origin or Source

1. Natural polymers: Those polymers which occur in nature. i.e., in plants or

animals. e.g. Starch, Cellulose, Rubber etc.
2. Synthetic polymers: The polymers which are prepared in the laboratory are
known as synthetic polymers or man-made polymers. e.g., Polythene,
Synthetic rubber, PVC, Nylon-66, Teflon, Orlon etc.
3. Semisynthetic polymers: Polymers obtained by making some modification in
natural polymers by artificial means, are known as semi synthetic polymers.
e.g., cellulose acetate (rayon), vulcanised rubber etc.
Classification of Polymers

• Based on Thermal Behaviour

Thermoplastics: The polymer which becomes soft on heating and hard on cooling
are called Thermoplastics.
Examples: Polyethylene, Teflon, Plexiglas, PVC, etc.

Thermosetting. The polymers which undergo chemical changes and cross likings
on heating and become permanently hard, rigid and infusible are called
Thermosettings.
Examples: Phenol-formaldehyde resins, Urea-formaldehyde resin, epoxy resin, etc.
Classification of Polymers
• Based on Structure
Linear polymers These are the polymers in which the monomer units are linked to one
another to form long linear chains. These linear chains are closely packed in space. The
close packing results in high densities, tensile strength and high melting and boiling points.
e.g., high density polyethene (HDPE), nylon and polyesters are linear polymers.
Branched chain polymers In such polymers, the monomer units are linked to form long
chains with some branched chains of different lengths with source. As a result of branching,
these polymers are not closely packed in space. Thus, they have low densities, low tensile
strength as well as low melting and boiling points. Some common examples of such
polymers are low density polyethene (LDPE), starch, glycogen etc.
Cross-linked polymers or network polymers In such polymers, the monomer units are
linked together to form three dimensional network. These are expected to be quite hard,
rigid and brittle. Examples of cross linked polymers are bakelite, melamine-formaldehyde
polymer etc.
Classification of Polymers
• Based on Synthesis or Chain Growth

Addition polymers The polymers formed by the addition polymerisation of

monomers containing double or triple bonds (olefins) to each other takes place
without elimination of by products are called addition polymers. Addition
polymers have the same empirical formula as their monomers.
Examples: PVC, polystyrene, Teflon, polyethylene, etc.

Condensation polymers: The polymers which are formed by intermolecular

condensation reaction through functional groups of monomers with continuous
elimination of by products (water, alcohol, hydrogen chloride etc.), are called
condensation polymers.
Examples: Nylons, polyesters, phenol-formaldehyde resin, etc.
Classification of Polymers
• Based on molecular forces

Elastomers These are rubber like solid polymers in which the polymer chains are
held together by weakest intermolecular forces, e.g., natural rubber, buna-S, buna-
N etc . The weak binding forces permit the polymers to be stretched.
A few ‘cross links’ are introduced in between the chains, which help the polymer
to retract to its original position after the force is released as in vulcanised rubber.

Fibres Fibres belong to a class of polymers which are thread-like and can be
woven into fabrics. These are widely used for making clothes, nets, ropes, gauzes,
etc. Fibres possess high tensile strength because the chains possess strong
intermolecular forces such as hydrogen bonding. The fibres are crystalline in
nature and have sharp melting points.
Few examples of this class are nylon-66, terylene and polyacrylonitrile.
 Addition Polymerization
• Addition polymerization: a reaction in which unsaturated
monomers combine with each other to form a polymer
• Example: Tetrafluoroethene can be polymerized to form
polytetrafluoroethene, commonly known as Teflon
CHAIN POLYMERIZATION: Free Radical
Polymerization

• Free radical are independently-existing species that have unpaired

electron. Normally they are highly reactive with short life time.

• Free radical polymerization’s are chain polymerization’s in which each

polymer molecules grows by addition of monomer to a terminal free-
radical reactive site known as active center.

• After each addition the free radical is transferred to the chain end.

• Chain polymerization is characterized by three distinct stages,

Initiation, propagation and termination.
 INITIATION
• This stage is a two steps stage

1. The formation of free radicals from an initiator.

2. The addition of one of these free radicals to a monomer molecules.

• Free radical can be formed by Homolytic scission (homolysis) or breakage of a

single bond.

• Homolytic can be achieved by heat (thermolysis) or by light such as U.V.

(photolysis).
Example
O O O
-C-O-O-C- 2 -C-O

Benzoyl peroxide Benzoyloxy radicals

• Sometimes the radicals undergo further breakdown (-

scissions) such as
O O
-C-O +C=O
PROPAGATION
• The addition of monomer molecules to the active center to grow the
polymer chain.

• Chain propagation

Head to Tail
R-CH2-CH + CH2=CH R-CH2-CH-CH2-CH
X X X X

Therefore polymer structure are like

-----CH2-CH-CH2-CH-CH2-CH-CH2-CH------
X X X X

Time of addition for each monomer is of the order of a millisecond.

Thus several thousands of additions can take place in a few seconds.
 TERMINATION
• The last stage of chain reaction in which the growth of the
polymer chain terminated (or stopped).
• There are two mechanisms of termination
1. Combination
• Coupling together of two growing chains to form a single
polymer molecules. E.g. polystyrene
--CH2-CH + CH - CH2--- ---- CH2-CH-CH-CH2---
X X X X
2. Disproportionation
when a hydrogen atom move from one growing chain to
another
H H
--CH2-CH+ C - C--- -CH2-CH2 + CH=CH2---
X X H X X
Saturated end Unsaturated end
group polymer group polymer
Cationic Polymerization Mechanism
 Anionc Addition Reaction Mechanism

• An anionic initiator will generate a carbanion

intermediate and thus the polymerization is of anionic
addition type.
• Here the active centre of the propagating species is
negatively charged.
• Hence it occurs easily with monomers containing
electron withdrawing groups such as phenyl, nitrile etc.,
which are able to stabilize the propagating species.
Initiation can be brought about by reagents such as n-butyl lithium or potassium
amide. In the initiation step, the base adds to a double bond to form a carbanion.

In the chain propagation, this carbanion adds to the double bond and the process
repeats to form a polymeric carbanion.

The chain reaction can be terminated by addition of an acid.

 Condensation Polymerization

• Condensation polymers form from

condensation reactions.
• In a condensation polymer a smaller molecule
such as water is eliminated
• In order to form a condensation polymer the
monomer must have two functional groups
Condensation Polymerization
 Teflon Polytetrafluroethylene)
The Teflon is manufactured by emulsion polymerization of tetrafluroethylene using peroxide as
initiator.
n.CF2=CF2 [-CF2-CF2-]n

Properties:
1. It is a thermoplastic and liner polymer.
2. It has high degree of crystallinity (93-98%).
3. It has high melting point (327oC).
4. Practically insoluble in any solvents.
5. It has high chemical resistance towards corrosive chemicals, oxidizing and reducing agents.
6). Not wetted by either oil or water.
7). Excellent electrical insulation properties.
Applications:
a). It is used for cables and wires insulation.
b). It is used as antis tic applications (Bakery trays & frying fans).
c). It is used as anticorrosive coating for army weapons.
d). It is used as lubricant.
 Polystyrene
PS is prepared by polymerization of styrene usually in the presence of a peroxide initiator.

Properties:
• It is usually a inert linear polymer.
• It is resistance to alkalis, halide acids, oxidizing or reducing agents.
• It transparent and have high refractive index (1.60).
• It has good tensile strength (8000 psi) and low dielectric loss.
• It is a good Electric insulator.
Applications/uses:
It is used for making toys, radio and TV cabinets, etc.
 Polyvinyl Chloride (PVC)

PVC is prepared by the polymerization of vinyl chloride by heating its water

emulsion in presence of benzoyl peroxide in autoclave under pressure.

Properties:
• It has high intermolecular attraction forces.
• It is hard and stiff amorphous plastic.
• It has glass transition temperature of 81C.
• It is soluble in cyclohexanone and tetrahydrofuran.
• It is hard and resistant to heat and chemicals.
Applications/uses:
It is used for making tanks, linings, display, wire coatings, pipes, etc.
 Cellulose acetate

Cellulose acetate is obtained by treating cellulose with concentrated acetic acid or acetic
anhydride in presence of a catalyst such as H2SO4 . The resulting cellulose triacetate is
partially hydrolysed to render it soluble in organic solvents such as acetone.

H2SO4
n[C6H7O2.(OH)3] + 3nCH3COOH n[C6H7O2(OCOCH3)3] + 3n.H2O

Properties:
• It has good clarity, stability, toughness, impact strength, and resistance to UV radiations.
• It has high dielectric strength, high tensile strength and resistance to mineral acids.
• It has good film and plastic strength.
Applications/Uses:
• It is used for preparing fibres and sheets.
• It is also used for combs, goggles, handles, radio-appliances, steering wheels etc.
• Films are also used for photography.
 Nylon is a generic term for synthetic polyamides capable of forming fibres.

Nylon 6,6:
It is obtained by the condensation of adipic acid and hexamethylenediamine with
the elimination of water molecule.

Properties:
• Nylon-6,6 is a linear polymer and has very high tensile strength, elasticity, toughness.
• It shows good resistance to abrasion.
• It is good solvent resistance except formic acid, phenols and cresols.
• Its mechanical properties are retained well upto 125C.
Applications/ Uses:
• It is used in bristles for brushes and in textile.
• It is used as substitute for metal in bearings, gears, etc.
• It is also used in making rollers, slides and door latches.
 Polyester

Properties:
• The glass transition point of this resin is about 80C.
• Resistance to chemical and solvent as that of Nylon.
• Good mechanical properties up to 150-175 C.
• Outstanding crease resistance and work recovery and its low moisture absorption.
Applications/Uses:
• Apparels, clothing etc.
• Magnetic recording tapes.
 Bakelite

Properties:
• Good resistant to heat and to cold flow
• Good dielectric properties
• Adhesive properties and bonding strength.
Applications/Uses:
• Impregnating paper, wood and other fillers for producing decorative laminates etc.
• Used in brake linings, abrasive wheels and sand paper etc.
• Used in varnishes, electrical insulation and protective coatings.
 Epoxy resin

Epoxy resins are basically polyether due to the starting material having epoxide group the are termed as epoxy resins.
The epoxy resins are cured by many types of materials including polyamides, phenol-urea formaldehyde etc., through
coupling or condensation to give cross linked 3D cross linked structures.
Properties:
• Show outstanding toughness, chemical inertness, flexibility and adhesion.
Applications/Uses:
• Moulding and laminating techniques.
• Industrial flooring
• Adhesives
• Glass fibre boats etc.
 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.”
Example: Natural and synthetic rubbers.

Natural Rubber

In the polymer chain of natural rubber, the residual double bonds are located
between C2 and C3 of the isoprene unit. All these double bonds have cis
configuration, and thus natural rubber is cis-l,4-polyisoprene.
In the natural rubber, there is no polar substituent. The only
intermolecular forces are van der Waals’ type. The cis-configuration
gives the polymeric chain of natural rubber a coiled structure. As a
result, it can be stretched by the application of a force. When the
force is removed, the chain returns back to its original coiled shape

Limitations:
• Natural rubber is soft and sticky.
• It can be used only in the temperature range 10°C-50°C.
• At higher temperature, it becomes soft and at low temperature, it
becomes brittle.
• It has high water absorption capacity.
• It is attacked by oxidising agents and organic solvents.
• As such, it cannot be used very extensively for commercial
purposes.
 Vulcanisation of Rubber
The properties of natural rubber can be modified by introducing -S-S- polysulphide
crosslinks in its structure. This process of introducing -S-S- crosslinks in the
structure of natural rubber by heating with sulphur at 110°C is called vulcanisation
of rubber.
Vulcanisation is carried out by adding sulphur (3-5%) and zinc oxide to the rubber,
and then heating the object at about 110°C for about 20-30 minutes. Zinc oxide
accelerates the rate of vulcanisation. Vulcanisation introduces polysulphide (-S-S-)
bonds between the adjacent chains. These crosslinks tend to limit the motion of
chains relative to each other.
Advantages
 Synthetic Rubbers
Neoprene
Polymer formed by free radical polymerisation of chloroprene is neoprene or
synthetic rubber.

Properties:
• A thermoplastic and need not to be vulcanised.
• It is a good general purpose rubber and superior to natural rubber as it is
resistant to the reaction of air, heat, light chemicals, alkalis and acids below
50% strength.
Uses:
• It is used for making transmission belts, printing rolls and flexible tubing
employed for conveyance of oil and petrol.
 Buna-N
It is a copolymer of buta-1,3-diene and acrylonitrile by emulsion polymerization. It
is formed as follows

Properties:
• It is insulator in nature, heat resistant.
• Resistant to swelling due to petrol, oil and other organic solvents.
Uses:
Used for making conveyor belts and printing rollers.
 Buna-S
It is a copolymer of three moles of butadiene and one mole of styrene and is an
elastomer. It is obtained as a result of free radical copolymerisation of its
monomers.

Properties:
• It is generally compounded with carbon black and vulcanised with sulphur.
• Tensile strength and flexibility is inferior to natural rubber.
• It is extremely resistant to wear and tear.
Uses:
Used in manufacture of lighter duty tyres and other mechanical rubber goods like
belts, electrical insulators etc..
 Thiokol or Polysulfide Rubber
Elastomers in which sulfur forms a part of the polymer chain.

ClCH2CH2Cl + Na2S4
Ethylene Dichloride Sodium Polysulfide

[CH2CH2S  S ]n
 
S S
Properties:
• Outstanding Resistance to swelling and disintegration by organic solvents.
• Fuel oil, lubricating oil have no effect.
• Benzene and its derivatives cause some swelling.
Uses:
• Life rafts and Jackets
• Lining of hoses for convey belts etc.
Molecular Mass of Polymers

The growth of the polymer chain depends upon the

availability of the monomers in the reaction. Thus, the
polymer sample contains chain of varying lengths and
hence, its molecular mass is always expressed as an
average molecular mass.

Number-Average Molecular Mass Mn

If N1 molecules have molecular mass M1 each, N2

molecules have molecular mass M2 each, N3 molecules
have molecular mass M3 each and so on
then, Mn = Σ Ni Mi / Σ Ni
It is determined by osmotic pressure method.
Mass Average Molecular Mass (Mw)

Supposing, as before that N1, N2 , N3 etc., molecules have

molecular mass M1, M2, M3 etc., respectively

Then, Mw = Ni Mi 2
Ni Mi
It is determined by light scattering and ultracentrifugation
method.
Poly dispersity Index

It is the ratio of the mass average molecular mass to the

number average molecular mass

PDI = Mw / Mn

For natural polymers, PDI is usually equal to one which

means that they are monodisperse. In other words, such
polymers are more homogeneous.

On the contrary, synthetic polymers generally have PDI >

1 which means that they are less homogeneous.
 Polyethene (LDPE)

• It is tough, flexible, transparent, chemically inert as well as poor conductor of

electricity. It has moderate tensile strength but good tearing strength.
• It is used in the insulation of electricity carrying wires and manufacture of
squeeze bottles, toys and flexible pipes.
 Polyethene (HDPE)

• It has high density due to close packing. It is also chemically inert and more
tougher and harder.
• It is used for making containers, house wares, bottles, toys, electric insulation
etc.