UNIT IV

POLYMERS INTRODUCTION
Polymers
Polymers are macro molecules (giant molecules of higher
molecular weight) formed by the repeated linking of large number
of small molecules called monomers.

Polyethylene is a polymer formed by the repeated linking of

large number of ethylene molecule.
Monomer
 Monomer is a micro molecule (small molecule) which
combines with each other to form a polymer.

 Some monomers and repeating unit of the polymers are

given below.
POLYMERISATION
Polymerisation is a process in which large number of small

molecules (called monomers) combine to give a big molecule

(called a polymer) with or without elimination of small molecules

like water.
 Degree of Polymerization (DP)
The number of repeating units (n) in a polymer chain is
known as degree of polymerisation. It is represented by the
following relationship.

molecular weight of the polymeric network

Degree of polymerization (n)
molecular weight of the repeating unit
 In this example, five repeating units are present in the

polymer chain. So, the degree of polymerization is 5.

Oligomers
Polymers with low degree of polymerisation
are known as Oligomers, their molecular weight
ranges from 500 - 5000.
High Polymers

Polymers with high degree of

polymerisation are known as High polymers, their
molecular weight ranges from 10,000 - 2,00,000.
FUNCTIONALITY AND
ITS SIGNIFICANCE
The number of bonding sites or reactive sites or
functional groups, present in a monomer, is known as

its functionality.
3. Polyfunctional Monomers
 Poly functional monomers form cross-linked
polymer(three-dimensional network polymer).
 All the monomers in the polymer are connected
to each other by strong covalent bonds.
 Therefore the movement of polymer chain is
totally restricted.
 This type of polymers are hard and brittle and
possess very high strength and heat
resistance.
 They are insoluble in almost all organic
solvents.
CLASSIFICATION OF POLYMERS

Based on the source, polymers are broadly

classified into two types.
1. Natural polymers.
2. Synthetic polymers.
I. Natural Polymers

The polymers obtained from nature (plants

and animals) are called natural polymers.
EXAMPLES OF NATURAL POLYMERS

1. Starch
It is a polymer of glucose. It is a chief food reserve of plants.

2. Cellulose
It is also a polymer of glucose. It is a chief structural material of
the plants. Both starch and cellulose are produced by plants during
photosynthesis.
3. Proteins

 These are polymers of  amino acids.

 They have generally 20 to 100  amino acids
joined together in a highly organized arrangement.
 These are building block of animals.
4. Nucleic Acids
These are polymers of various nucleotides. RNA and
DNA are common nucleotides.
5. Natural Rubber
It is a polymer of unsaturated hydrocarbon,
2-methyl-1, 3 butadiene, called isoprene. It is obtained from
latex of rubber trees.
II. Synthetic Polymers

The polymers which are prepared in the laboratories,

are called synthetic polymers. These are also called
man-made polymers.

PVC, polyethylene, nylon, teflon,

bakelite, terylene, etc.,
Types of Synthetic Polymers
1. Organic Polymers
These are polymers containing hydrogen,
oxygen, nitrogen, sulfur and halogen atoms apart from
carbon atoms.
Polyethylene, Polyvinyl alcohol, PVC,
Epoxy polymers, Polyurethane.
2. Elemento-organic (or) Hetero-organic Polymers
 These are polymers composed of carbon atoms
and hetero-atoms (like N, S & O).
 The main chain consists of carbon atoms and
whose side groups contain hetero atoms linked
directly to the C atoms in the chain.

Polysiloxanes, Polytitoxanes
3. Inorganic Polymers

 These are polymers containing no carbon atoms.

 The chains of these polymers are composed

of different atoms joined by chemical bonds.
PLASTICS
Plastics are high molecular weight organic
materials, that can be moulded into any desired shape
by the application of heat and pressure in the
presence of a catalyst.
 Originally, plastics were discovered and then
developed based on trial and error method.
 The present time is sometime referred as plastic age,
because the use of polymeric material is perculated
in large variety of applications.
 This rapid growth has taken place only in the last 50
years.
 It was man’s desire to develop plastics for
engineering applications to replace, glass, metal, ceramic,
wood and other materials of constructions.
 Since plastics possess the following advantages,
they have wider applications.
 Advantages of Plastics Over other Materials
1. They are light in weight.
2. They possess low melting point.
3. They can be easily moulded and have excellent finishing.
4. They possess very good strength and toughness.
5. They possess good shock absorption capacity.
6. They are corrosion resistant and chemically inert.
7. They have low co-efficient of thermal expansion and possess
good thermal and electrical insulating property.
8. They are very good water-resistant and possess good
adhesiveness.
 Disadvantage of Plastics
1. Softness.
2. Embrittlement at low temperature.
3. Deformation under load.
4. Low heat-resistant and poor ductility.
5. Combustibility.
6. Degradation upon exposure to heat and UV- radiation.
7. Non bio-degradable.
Classification of Plastics
Based on the structure and type of resin used for the
manufacture of plastics, plastics are classified into
two main types.
1. Thermoplastics.
2. Thermosetting plastics.
A resin is a basic binding material, present in
plastics, which undergoes polymerization reaction
during moulding.
1.Thermoplastic Resins
 Thermoplastics are prepared by addition
polymerisation.
 They are straight chain (or) slightly branched
polymers and various chains are held together
by weak vanderwaal’s forces of attraction.
 Thermoplastics can be softened on heating and
hardened on cooling. They are generally soluble in
organic solvents.
Polyethylene, Polyvinyl chloride.
2.Thermosetting Resins (or) Thermosets
 Thermosetting plastics are prepared by
condensation polymerisation.
 Various polymer chains are held together by
strong covalent bonds (called crosslinks).
 Thermosetting plastics get harden on
heating and once harden, they cannot be
softened again.
 They are almost insoluble in organic
solvents.
Bakelite, Polyester.
Difference between thermoplastic and
thermosetting resins
TYPES OF POLYMERISATION
Polymerisation reactions may be carried out by
any one of the following methods.

1. Addition (or) chain growth polymerisation

2. Condensation (or) step wise polymerisation
3. Copolymerisation
 1. Addition (or) Chain Growth Polymerisation
 It is a reaction that yields a polymer, which
is an exact multiple of the original
monomeric molecule.

 The original monomeric molecule, usually,

contains one or more double bonds.

 In this addition polymerisation there is no

elimination of any molecule.
 2. Condensation (or) step wise polymerisation

It is a reaction between simple polar groups

containing monomers with the formation of polymer and

elimination of small molecules like H2O, HCl, etc.,

 3. Co-polymerisation

 It is the joint polymerisation in which two (or) more

different monomers combine to give a polymer.
 High molecular weight polymers, obtained by
co-polymerisation, are called copolymers.

Copolymerisation is mainly carried out to

vary the properties of polymers such as hardness,
strength, rigidity, heat resistance etc.
Differences between addition (chain) polymerisation
and condensation (step) polymerisation
 Stereospecific Polymer (or) Tacticity
 The orientation of monomeric units or
functional groups in a polymer molecule can
take place in an orderly (or) disorderly manner
with respect to the main chain is known as
Tacticity.
 Tacticity do affect the physical properties of
the polymer.
 This orientation results in three types of
stereo- regular polymers.
a. Isotactic Polymer
If the functional groups are arranged on the same
side of the main chain, the polymer is called Isotactic
polymer.
b. Syndiotactic Polymer
If the functional groups are arranged in an
alternating fashion, the polymer is called Syndiotactic
polymer.
c. Atactic Polymer
If the functional groups are arranged randomly, the
polymer is called Atactic polymer.
IMPORTANT POLYMERS
I. Polyamide (Nylon)
Properties of Nylon-6:6

(i) Nylon-6:6 is a less soft and stiff material when

compared to nylon 6.
(ii) Its melting point is 2640C.
Properties of Nylon-6

(i) Nylon-6 is a light weight, soft and less stiff material.

(ii) Its melting point is 2250C.
General Properties of Nylons
(i) They behave as plastic as well as fiber.
(ii) They are translucent, white, horny and high melting
polymers.
(iii) They are insoluble in common organic solvents but
soluble in phenol and formic acid.
(iv) They possess good mechanical properties and fairly
resistant to moisture.
(v) They are characterised by combination of high
strength, elasticity, toughness and abrasion resistance.
`
Uses of Nylons

(i) Nylon-6:6 is used for fibers, which are used in

making socks, ladies shoes, dresses, carpets, etc,.
(ii) Nylon-6 is mainly used for moulding purposes for
gears, bearings, electrical mountings, etc,. Nylon
bearings work without any lubrication.
(iii) Nylons are used for making filaments for ropes,
bristles for tooth-brushes, films and tyre-cords
 II. Epoxy Resins (or) Epoxide Polymers

 These are cross-linked thermosetting resins.

 They are polyethers because the monomeric units

in the polymer have an ether type of structure i.e.,
R - O - R.
Preparation

 Epoxy polymer (or) Epoxy resins are prepared by

condensing epichlorohydrin with bisphenol.

 The reactive epoxide and hydroxyl groups give a

three dimensional cross-linked structure.

 The value of n ranges from 1 to 20.

Properties

. Due to the presence of stable ether linkage,

epoxy resin possess high chemical- resistance to
water, acids, alkalis, various solvents and other
chemicals.
. They are flexible, tough and possess very
good
heat resisting property.
. Because of the polar nature of the molecules,
they possess excellent adhesion quality.
Uses
 Epoxy resins are used as surface coatings,
adhesives like araldite, glass-fibre- reinforced
plastics.
 These are applied over cotton, rayon and
bleached fabrics to impart crease-resistance and
shrinkage control.
 These are also used as laminating materials
in electrical equipments.
 Moulds made from epoxy resins are employed
for the production of components for aircrafts
and automobiles.