POLYMER

GENERAL INTRODUCTION AND ITS SCOPE:-

Polymers form a very important class of materials without

which the life seems very difficult. They are all around us in everyday
use; in rubber, in plastic, in resins, and in adhesives and adhesives tapes.
The word polymer is derived from greek words, poly= many and
mers= parts or units of high molecular mass each molecule of which
consist of a very large number of single structural units joined together
in a regular manner. In other words polymers are giant molecules of high
molecular weight, called macromolecules, which are build up by linking
together of a large number of small molecules, called monomers. The
reaction by which the monomers combine to form polymer is known as
polymerization. The polymerization is a chemical reaction in which two
or more substances combine together with or without evolution of
anything like water, heat or any other solvents to form a molecule of
high molecular weight. The product is called polymer and the starting
material is called monomer.

HISTORICAL DEVELOPMENT OF POLYMERS:-

Polymers have existed in natural form since life began and

those such as DNA, RNA, proteins and polysaccharides play crucial
roles in plant and animal life. From the earliest times, man has exploited
naturally-occurring polymers as materials for providing clothing,
decoration, shelter, tools, weapons, writing materials and other
requirements. However, the origin of today’s polymer industry is
commonly accepted as being the nineteenth century when important
discoveries were made concerning the modification of certain natural
polymers. In eighteenth century, Thomas Hancock gave an idea of
modification of natural rubber through blending with certain additives.
Later on, Charles Goodyear improved the properties of natural rubber

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through vulcanization process with sulfur. The Bakelite was the first
synthetic polymer produced in 1909 and was soon followed by the
synthetic fiber, rayon, which was developed in 1911. The systematic
study of polymer science started only about a century back with the
pioneering work of Herman Staudinger. Staudinger has given a new
definition of polymer. He in1919 first published this concept that high
molecular mass compounds were composed of long covalently bonded
molecules.

CLASSIFICATION OF POLYMERS:-

Polymer is a generic name given to a vast number of materials of

high molecular weight. These materials exist in countless form and
numbers because of very large number and type of atoms present in their
molecule. Polymer can have different chemical structure, physical
properties, mechanical behavior, thermal characteristics, etc., and on the
basis of these properties polymer can be classified in different ways,
which are summarized in Table 1.1, whereas, important and broad
classification of polymers are described in the next section.

Table1.1:
Classification of Polymers
Basis of Classification Polymer Type

Origin - Natural, Semi synthetic, Synthetic

Thermal Response - Thermoplastic, Thermosetting
Mode of formation - Addition, Condensation
Line structure - Linear, Branched, Cross-linked
Application and Physical
Properties - Rubber, Plastic, Fibers
Tacticity - Isotactic, Syndiotactic, Atactic
Crystallinity -Non crystalline(amorphous)
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Crystalline Polarity - Polar, Non polar
Chain - Hetro, Homo-chain

Origin:-

On the basis of their occurrence in nature, polymers have been

classified in three types:-

A. Natural polymer:-
The polymers, which occur in nature are called natural polymer
also known as biopolymers. Examples of such polymers are natural
rubber, natural silk, cellulose, starch, proteins, etc..

B. Semi synthetic polymer:-

They are the chemically modified natural polymers such as
hydrogenated, natural rubber, cellulosic, cellulose nitrate, methyl
cellulose, etc.

C. Synthetic polymer:-
The polymer which has been synthesized in the laboratory is
known as synthetic polymer. These are also known as manmade
polymers. Examples of such polymers are polyvinyl alcohol,
polyethylene, polystyrene, polysulfone, etc.:-

Classification of Polymers Based on Molecular Forces:-

A. 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

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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.

B. 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. A few
examples of this class are nylon-66, terylene and polyacrylonitrile.

C. Thermoplastic polymers:-
They can be softened or plasticized repeatedly on application of
thermal energy, without much change in properties if treated with certain
precautions. Example of such polymers are Polyolefins, nylons, linear
polyesters and polyethers, PVC, sealing wax etc..

D. Thermosetting polymers:-
Some polymers undergo certain chemical changes on heating
and convert themselves into an infusible mass. The curing or setting
process involves chemical reaction leading to further growth and cross
linking of the polymer chain molecules and producing giant molecules.
For example, Phenolic, resins, urea, epoxy resins, diene rubbers, etc.

Mode of Formation:-

On the basis of mode of formation, polymers can be classified as :-

A. Addition polymers:-
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 They are formed from olefinic, diolefnic, vinyl and related
monomers. They are formed from simple addition of monomer
molecules to each other in a quick succession by a chain mechanism.
This process is called addition polymerization. Examples of such
polymers are polyethylene, polypropylene, polystyrene.

Homopolymers:-
The polymers which are obtained by the polymerisation of a single
type of monomer are called homopolymers.

Copolymers:-
The polymers which are obtained by the polymerisation of two or
more monomers are called copolymers.

B. Semi synthetic:-
such as hydrogenated, natural rubber, cellulosic, cellulose nitrate,
methyl cellulose, etc.

C. Synthetic polymer:-
The polymer which has been synthesized in the laboratory is
known as synthetic polymer. These are also known as manmade
polymers. Examples of such polymers are polyvinyl alcohol,
polyethylene, polystyrene, polysulfone, etc..

D. Condensation polymer:-
They are formed intermolecular relation between bifunctional or
polyfunctional monomer molecules having reactive function group
Such as:- terylene, nylon6, 6, nylon 6

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Classification Based on structure:-

They are three types:-

A. Linear polymer:-
These polymer consists of long and straight chains ex. High density
polythene ,polyvinylchloride(PVC) etc.

B. Branch chain polymer:-

These polymer contain linear chains having some branches ex. Low
density polythene

C. Cross linked or network polymer:-

These are usually formed from bifunctional or trifunctional
monomer and contain strong covalent bond between various linear chain
polymer ex. Bakelite , melamine etc.

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Types of polymerization reactions:-

A. Condensation Polymerization or Step-growth Polymerization:-

Condensation Polymerization is a chemical reaction in which

polymer is formed and a small molecule of by-product with a lower
molecular weight is released. The by-product eliminated is called as
condensate. The reaction can take place between two similar or different
monomers. It is also called as step-growth polymerization.

B. Addition Polymerization or Chain Polymerization:-

In addition polymerization, two or more molecules of

monomers attach together to form a polymer. In this polymerization,
there is no elimination of any molecule. It is a chain reaction and no by
product is released. It is obtained by linking together the monomer
molecules by a chain reaction to give a polymer whose molecular weight
is exactly an integral multiple of that of the monomer as in the case of
polyethylene obtained by polymerization of ethylene. Only a single
monomer is involved in addition polymerization and hence the polymer
is homopolymer and contains the same monomer units. Addition
polymerization reaction is usually induced by light, heat or a catalyst for
opening the double bond of the monomer and creating the reactive sites.

MECHANICAL PROPERTIES OF POLYMERS:-

To study the necessary set of valuable properties, polymers

differing from one another by their chemical structure and properties are
usually mixed together, either homogeneously or heterogeneously. The
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mechanical properties of inhomogeneous mixture are worse than those
of individual polymers, while the mechanical properties of homogeneous
mixture are good.
Polymers can exhibit the features of glassy, brittle solid or an elastic
rubber, or that of a viscous liquid, depending on the temperature and
time scale of measurement. The studies on mechanical properties of
polymer can, therefore, be carried out by subjecting them to some form
of mechanical stress either continuous or in a periodic manner at
different rate. Some of the important properties of polymers with regard
to their use as engineering material are tensile strength, compressive and
flexural strength, hardness, creep, fatigue resistance and impact
resistance.

Polyolefins:-

These are obtained by the addition polymerisation of ethylene and its

derivatives

1. Polythene:-
Polymer of ethylene or ethene. They are two type-

(i) Low density polythene (LDP):-

It is tough, flexible, transparent, chemically inert as well as
poor conductor of electricity. It has moderate tensile strength but good
tearing strength.
Ldpe are prepared at 100-1500c under pressure 1000-2000atm.

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It is used in the insulation of electricity carrying wires and manufacture
of queeze bottles, toyes and flexible pipes.

(ii) High density polythene (HDP):-

It has high density due to close packing. It is also chemically
inert and tougher and harder.
Hdpe are prepared at the present of ziezlernata catalyst

It is used for making containers, house wares, bottles, toyes, electric

insulation etc.

2. Polytetrafluoroethene (Teflon):-
It is chemically inert and resistant to attack by corrosive
reagent.

It is used in making oil seals, gaskets and also for non-stick surface
coated utensils.

3. Polyacrylonitrile (PAN) or ORLON:-

It is used as a substitute for wool in making commercial fibres
as orIon or acrilan.

Condensation polymerization reaction characterized:-

Polyamides
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The polymers which contain an amide linkage in chain are known as
polyamide, e.g., nylon-6, 6.

1. Nylon-66
It is obtained by the condensation of adipic acid and
hexamethylenediamine with the elimination of water molecule.

The polyamides are identified by numbers. These numbers refer to the

number of carbon atoms in diamine and in the dibasic acid. As in the
above case, the carbon atoms are 6 in each case, therefore the product is
described as _nylon-66.

Properties and uses

Nylon-66 is a linear polymer and has very high tensile strength. It
shows good resistance to abrasion. Nylon-66 is usually fabricated into
sheets. It is used in bristles for brushes and in textile.

2. Nylon-6 or perlon:-
Nylon-6 is obtained by heating caprolactam with water at a high
temperature

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Polyesters

The polymers which contain an ester linkage are known as

polyester, e.g., Dacron or terylene

1. Polymethylmethacrylate (PMMA):-
It is prepared by the polymerisation of
methylmethacrylate in the presence of suitable organic peroxide.
The polymer is known by several commercial names such as lucite,
acrylite, plexiglass and perspex.

Properties and uses

It is a hard and transparent polymer and is quite resistant to the effect of

light, heat and ageing. It is used, in the manufacture of unbreakable
lights, protective coatings, dentures, and in making windows for
aircrafts.

2. Terylene (Dacron):-
It is a condensation product of ethylene glycol and terephthalic
acid. Polymerisation is carried out at 420 to 460 K in the presence of
catalyst mixture of zinc acetate and antimony trioxide.

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Properties and uses

Terylene is highly resistant to the action of chemical and biological

agents. Its fibres are quite strong and durable. It can also be blended with
wool or cotton to obtain fabrics of desired composition.
Terylene is used in the manufacture of a variety of clothes such as
terycot, terywool and terysilk as a result of blending with other yerns. It
is also used for preparing magnetic recording tapes, conveyer belts,
aprons for industrial workers etc.

3. Phenol-Formaldehyde Polymer (Bakelite and Related Polymers):-

These polymers are obtained by the condensation reaction of
phenol with formaldehyde in the presence of either acid or a base
catalyst. The reaction involves the formation of methylene bridge at
ortho, para or both ortho and para positions. A linear or cross linked
material is obtained depending upon the condition of reaction.

Uses
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Bakelite is used for making combs, photograph records, electrical
switches etc. Soft bakelites with low degree of polymerisation are used
as binding glue for laminated wooden plants, in varnishes and lacquers.

4. Melamine-formaldehyde polymer:-
It is a copolymer formed by the polymerisation of melamine
(which is a heterocyclic triamine) and formaldehyde as follows :

Properties and Uses

It is very hard and tough. It has assumed great importance these days
particularly in making crockery. They do not break even when droped
from a height.

Copolymerization:-
When two or more different monomer are allowed to
polymerize together the product formed is called copolymer and the
process is called Copolymerization.
A copolymer can be made not be chain growth polymerization but also
by step growth polymerization. it contains multiple unit of monomers
used in same polymeric chain for example:- A mixture of 1,3- butadiene
rubber and styrene in the ratio of 3:1 in present of sodium and heat then
they formed styrene butadiene rubber (SBR) or Buna-s

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Properties and uses

The properties of copolymer are usually quite difference from the

homopolymers:-
Copolymers have better physical and mechanical properties. It is good
substitute for natural rubber. It is very tough and it is used for
manufacture of automobile tyres. It is also used for making floor tiles,
footwear component, cable insulation etc.

RUBBER

1. Natural Rubber:-
Natural.rubber is a coiled linear 1, 4-polymer of isoprene. In the polymer
chain of natural rubber, the residual double bonds are located between
C and C 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.

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

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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
11O°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°Cfor about 20-30
minutes. Zinc oxide accelerates the rate of vulcanization. Vulcanisation
introduces polysulphide (-S-S-) bonds between the adjacent chains.
These crosslinks tend to limit the motion of chains relative to each other.

2. Synthetic rubbers:-
Synthetic rubber may be defined as any vulcanisable rubber like
polymer which are capable of getting stretched to twice its length
however it returns to its original size and shape when the stretching
force is withdrawn.

Some important synthetic rubbers are:-

Neoprene
Polymer formed by polymerisation of chloroprene is neoprene or
synthetic rubber.

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It is used for the manufacturing conveyers belts, gasket and hoses.

Buna-N
It is a copolymer of buta-I, 3-diene and acrylonitrile. It is formed as
follows

Properties and Uses

It is insulator in nature and is used for making conveyor belts and
printing rollers.

Molecular Weight and its Distribution:-

The molecular weight of a polymer is of prime importance in the

polymer’s synthesis and application. It is important because it
determines many physical properties. The term molecular weight is a
ratio of the average mass per formula unit of substance to 1/12 th of an
atom of 12C. Molecular weight (MW) and its distribution (MWD) has a
considerable effect on macroscopic properties of polymer such as
toughness, tensile strength, adherence and environmental resistance, etc..
A simple chemical has fixed molecular weight but when we discuss
about the molecular weight of polymer, we mean something different
from that which applies to small sized compounds. Since polymers are
mixture of molecules of different molecular weight, the molecular
weight is expressed in the term of “average” value. This average
molecular weight is basically based on either average number of
repeating units, known as number average molecular weight, or average
weight, known as weight average molecular weight. The number
average molecular weight is obtained from the number ni of
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macromolecules for each degree of polymerization Pi by taking for each
degree of polymerization the product of the number of polymer
molecules and their degree of polymerization ni pi and dividing the sum
of these product by the total number of monomers No:

Biopolymers and Biodegradable Polymers:-

Synthetic polymers are mostly non-biodegradable i.e., it is very

difficult to dispose off the polymeric waste, e.g., polythene bags. Nature
has provided us a variety of polymers which can be produced by the
biological systems in plants and animals. These are called biopolymers,
e.g., polysaccharides, proteins, nucleic acids, etc. In the biological
system, these polymers decompose or hydrolyse in the Presence of
different enzymes. This means that they are biodegradable.
Aliphatic polyesters are the common examples of biodegradable
Polymers.

1. Poly β hydroxybutyrate-co-β-hydroxyvalerate (PHBV) :-

It is a copolymer of 3-hydroxybutanoic acid and 3-
hydroxypentanoic acid.

2.Nylon-2-Nylon-6:-

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 It is an alternating polyamide copolymer of glycine (HN-CH-
COOH) and amino caproic acid [H-N(CH)-COOH] and is
biodegradable.

Some commercially important polymers:-

1. Poly vinyl chloride (PVC) :-

It is made by polymerization of a monomer unit vinyl chloride to
form a poly vinyl chloride

polymerization
nCH2=CH-Cl -CH2-CH- n

Cl

2. Poly mono chloro triflouro ethylene (PCTFE);-

It is made by polymerization of a monomer unit chloro triflouro
ethylene to form a PCTFE

polymerization
nCl-CF=CF2 -CF-CF2- n

Cl
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3. Saran is a copolymer of vinyl chloride and Issued for wrapping food
materials.
4. ASS rubber is a copolymer of acrylonitrile, buta-1, 3-diene and
styrene.
5. Bubble gum contains styrene butadiene rubber.
6. Epoxy resins are used In making adhesives such as araldite, etc. These
are the copolymer of epichlorohydrin and bisphenol-A.
7. Thikol is another variety of synthetic rubber which is a copolymer of
ethylene chloride and sodium tetrasulphide (Na S 4).
8. Dynells a copolymer of vinyl chloride and acrylonitrile and is used for
making human hair wigs.
9. Silk Is a thread like natural polymer which is obtained from cocoons
of silk worms. It is a natural polyamide fibre.
10. Thermocol is a foamed plastic obtained by blowing air through
molter polystyrene or polyurethane.
11. Superglue is a polymer of methyl α-cyanoacrylate and is obtained by
anionic polymerization of monomer.

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