Polymers

Synthetic resins and plastics, classification of polymers, general properties of polymers, structure

of PE,PP,PVC,PS, Nylon 6, Nylon 66, PTFE,PET and their uses; from monomer to plastic,
polymer requirements for polymer formation; biodegradable polymers.
• The word ‘polymer’ is coined from two Greek words: poly means many
and mer means unit or part.
• The term polymer is defined as very large molecules having high
molecular mass. These are also referred to as macromolecules, which are
formed by joining of repeating structural units on a large scale.
• The repeating structural units are derived from some simple and reactive
molecules known as monomers and are linked to each other by covalent
bonds. This process of formation of polymers from respective monomers
is called polymerisation.
 • The degree of polymerization (DP) is defined as the number of monomer units in the polymer. It is
calculated as the ratio of molecular weight of a polymer and molecular weight of the repeat unit.
molecular weight of a polymer
DP =
molecular weight of the repeat unit
Classification of polymers
There are several ways of classification of polymers based on some special considerations. The
following are some of the common classifications of polymers:

Classification Based on Source

Under this type of classification, there are three sub categories.

1. Natural polymers
These polymers are found in plants and animals. Examples are proteins, cellulose, starch, resins and
rubber.
2. Semi-synthetic polymers
Cellulose derivatives as cellulose acetate (rayon) and cellulose nitrate, etc. are the usual examples of this
sub category.
3. Synthetic polymers
A variety of synthetic polymers as plastic (polythene), synthetic fibres (nylon 6,6) and synthetic rubbers
(Buna - S) are examples of manmade polymers extensively used in daily life as well as in industry.
Classification Based on Structure of Polymers
There are three different types based on the structure of the polymers.
1. Linear polymers
These polymers consist of long and straight chains. The examples are high density polythene,
polyvinyl chloride, etc. These are represented as:

2. Branched chain polymers

These polymers contain linear chains having some branches, e.g., low density polythene.
These are depicted as follows:

3. Cross linked or Network polymers

These are usually formed from bi-functional and tri-functional monomers and contain strong
covalent bonds between various linear polymer chains, e.g. bakelite, melamine, etc. These
polymers are depicted as follows:
Classification Based on mode of polymerisation

Polymers can also be classified on the basis of mode of polymerization into two sub groups.
1. Addition polymers
The addition polymers are formed by the repeated addition of monomer molecules possessing double or triple
bonds, e.g., the formation of polythene from ethene and polypropene from propene. However, the addition
polymers formed by the polymerisation of a single monomeric species are known as homopolymers, e.g.,
polythene.

The polymers made by addition polymerisation from two different monomers are termed as copolymers, e.g.,
Buna-S, Buna-N, etc.
2. Condensation polymers
The condensation polymers are formed by repeated condensation reaction between two different
bi-functional or tri-functional monomeric units. In these polymerisation reactions, the
elimination of small molecules such as water, alcohol, hydrogen chloride, etc. take place. The
examples are terylene (dacron), nylon 6, 6, nylon 6, etc. For example, nylon 6, 6 is formed by
the condensation of hexamethylene diamine with adipic acid.
Classification Based on Molecular Forces

A large number of polymer applications in different fields depend on their unique mechanical
properties like tensile strength, elasticity, toughness, etc. These mechanical properties are
governed by intermolecular forces, e.g., van der Waals forces and hydrogen bonds, present in the
polymer. These forces also bind the polymer chains.

1. Elastomers
These are rubber – like solids with elastic properties. In these elastomeric polymers, the polymer
chains are held together by the weakest intermolecular forces. These weak binding forces permit
the polymer to be stretched. A few ‘crosslinks’ 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. The
examples are buna-S, buna-N, neoprene, etc.
2. Fibres
Fibres are the thread forming solids which possess high tensile strength and high
modulus. These characteristics can be attributed to the strong intermolecular forces like
hydrogen bonding. These strong forces also lead to close packing of chains and thus
impart crystalline nature. The examples are polyamides (nylon 6, 6), polyesters
(terylene), etc.
 Classification Based on effect of heat on them

1. Thermoplastic polymers
These are the linear or slightly branched long chain molecules capable of
repeatedly softening on heating and hardening on cooling. These polymers possess
intermolecular forces of attraction intermediate between elastomers and fibres.
Some common thermoplastics are polythene, polystyrene, polyvinyls, etc.

2. Thermosetting polymers
These polymers are cross linked or heavily branched molecules, which on heating
undergo extensive cross linking in moulds and again become infusible. These
cannot be reused. Some common examples are bakelite, urea-formaldelyde resins,
etc.
Classification Based on Growth Polymerisation

The addition and condensation polymers are nowadays also referred as chain growth polymers
and step growth polymers depending on the type of polymerisation mechanism they undergo
during their formation.

Addition Polymerisation
In this type of polymerisation, the molecules of the same monomer or different monomers add
together on a large scale to form a polymer. The monomers used are unsaturated compounds, e.g.,
alkenes, alkadienes and their derivatives. This mode of polymerisation leading to an increase in
chain length or chain growth can take place through the formation of either free radicals or ionic
species. However, the free radical governed addition or chain growth polymerisation is the most
common mode.
Condensation Polymerisation
This type of polymerisation generally involves a repetitive condensation reaction between two
bi-functional monomers. These polycondensation reactions may result in the loss of some
simple molecules as water, alcohol, etc., and lead to the formation of high molecular mass
condensation polymers.
In these reactions, the product of each step is again a bi-functional species and the sequence of
condensation goes on. Since, each step produces a distinct functionalised species and is
independent of each other, this process is also called as step growth polymerisation.
Some important addition polymers
(a) Polythene
There are two types of polythene as given below:
(i) Low density polythene: It is obtained by the polymerization of ethene under high pressure of 1000 to
2000 atmospheres at a temperature of 350 K to 570 K in the presence of traces of dioxygen or a peroxide
initiator (catalyst). The low densitypolythene (LDP) obtained through the free radical addition and H-atom
abstraction has highly branched structure.
Low density polythene is chemically inert and tough but flexible and a poor conductor of electricity.
Hence, it is used in the insulation of electricity carrying wires and manufacture of squeeze bottles, toys
and flexible pipes.
(ii) High density polythene: It is formed when addition polymerisation of ethene takes place in a
hydrocarbon solvent in the presence of a catalyst such as triethylaluminium and titanium tetrachloride
(Ziegler-Natta catalyst) at a temperature of 333 K to 343 K and under a pressure of 6-7 atmospheres.
High density polythene (HDP) thus produced, consists of linear molecules and has a high density due to
close packing. It is also chemically inert and more tougher and harder. It is used for manufacturing
buckets, dustbins, bottles, pipes, etc.
(b) Polytetrafluoroethene (Teflon) (PTFE)
Teflon is manufactured by heating tetrafluoroethene with a free radical or persulphate
catalyst at high pressures. It is chemically inert and resistant to attack by corrosive
reagents. It is used in making oil seals and gaskets and also used for non – stick surface
coated utensils.
(PP)

(PS)
Condensation Polymerisation
Polyamides
These polymers possessing amide linkages are important examples of synthetic fibres and are termed
as nylons. The general method of preparation consists of the condensation polymerisation of
diamines with dicarboxylic acids and also of amino acids and their lactams.

(i) Nylon 6,6: It is prepared by the condensation polymerization of hexamethylenediamine with

adipic acid under high pressure and at high temperature.
Nylon 6, 6 is used in making sheets, bristles for brushes and in textile industry.

(ii) Nylon 6: It is obtained by heating caprolactum with water at a high temperature.

Nylon 6 is used for the manufacture of tyre cords, fabrics and ropes.
Polyesters
• These are the polycondensation products of dicarboxylic acids and diols.
Dacron (PET)
• Dacron or terylene is the best known example of polyesters.
• It is manufactured by heating a mixture of ethylene glycol and terephthalic acid at
420 to 460 K in the presence of zinc acetate-antimony trioxide catalyst.
• Dacron fibre (terylene) is crease resistant and is used in blending with cotton and
wool fibres and also as glass reinforcing materials in safety helmets, etc.
• The formation of terylene or dacron by the interaction of ethylene glycol and
terephthalic acid is an example of this type of polymerisation.

Polyethylene terephthalate (PET)

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