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Chemistry Notes For Class 12 Chapter 15 Polymers: Polymerisation
Chemistry Notes For Class 12 Chapter 15 Polymers: Polymerisation
Polymerisation
The process by which the monomers get combined and transformed into polymers. is known as
polymerisation.
n [Monomer] → Polymer
Polymers are also called macromolecules due to their large size but converse is not always true.
A macromolecule mayor may not contain monomer units, e.g., chlorophyll (C 55H72O5N4Mg) is
a macromolecule but not a polymer since there are no monomer units present so we can
conclude that all polymers are macromolecules while all macromolecules may not be polymers
in nature.
(i) Natural polymers Those polymers which occur in nature. i.e., in plants or animals. are
called natural polymers.
(ii) 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.
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(i) 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, nylon and polyesters are linear polymers.
(ii) 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, starch, glycogen etc.
(iii) 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, glyptal, melamine-formaldehyde
polymer etc.
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
(ii) Condensation polymers The polymers which are formed by the combination of
monomers with the elimination of small molecules such as water, alcohol, hydrogen chloride
etc., are known as condensation polymers, e.g., nylon 6,6 is formed by the condensation of
hexamethylene diamine with adipic acid.
1. 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.
2. 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.
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3. Thermoplastics These are linear polymers and have weak van der Waals’ forces acting
in the various chains. These forces are intermediate of the forces present in the
elastomers and in the fibres. When heated, they melt and form a fluid which sets into a
hard mass on cooling. Thus, they can be cast into different shapes by using suitable
moulds, e.g., polyethene and polystyrene.
(Plasticizers are high boiling esters or haloalkanes. These are added to I plastics to make
them soft rubber like. …J
4. Thermosetting plastics These are normally semifluid substances with low molecular
masses. When heated, they become hard and infusible due to the cross-linking between
the polymer chains. As a result, they also become three dimensional in nature. A few
common thermosetting polymers are bakelite, melamine-formaldehyde resin and urea
formaldehyde resin.
(i) Free radical addition polymerisation The monomers used are generally
monosubstituted alkenes. The most commonly used catalysts are benzoyl peroxide, hydrogen
peroxide or t-butyl peroxide etc.
Step I Chain initiation step In this step, peroxide undergoes homolytic fission, e.g., benzoyl
peroxide on heating produces phenyl initiator free radical.
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Step II Chain propagation step The new free radical adds to another molecules of monomer
to form a larger free radical.
Step III Chain termination step There are three ways of chain termination: Coupling
reaction, disproportionation reaction, chain transfer reaction. One mode of termination of chain
is shown as under:
Higher the stability of carbocation intermediate, more is the reactivity of monomers towards
cationic addition polymerisation. It involves the following steps: Step I. Initiation Step
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.
If N1 molecules have molecular mass M1 each, N2 molecules have molecular mass M2 each,
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Mn = Σ Ni Mi / Σ Ni
PoLydispersity 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.
Polyolefins
These are obtained by the addition polymerisation of ethylene and its derivatives 1.
Polythene
It is tough, flexible, transparent, chemically inert as well as poor conductor pf electricity. It has
moderate tensile strength but good tearing strength.
It is used in the insulation of electricity carrying wires and manufacture of queeze bottles, toyes
and flexible pipes.
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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, toyes, electric insulation etc.
2. Polystyrene (Styrone)
The monomers are styrene molecules. It is thermoplastic. It is used for making toys, radio and
TV cabinets
3. Polyvinylchloride (PVC)
It is used for making rain coats, toys, electrical insulation. It is hard and resistant to heat and
chemicals.
4. Polypropylene (PP)
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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.
6. Polyacrylonitrile
Polyamides
The polymers which contain an amide linkage in chain are known as pOlyamide, e.g., nylon-6,
6.
1. Nylon-66
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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.
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
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
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bridge at ortho, para or both ortho and para positions. A linear or cross linked material is
obtained depending upon the condition of reaction.
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Uses
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.
2. Melamine-formaldehyde Resin
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.
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3. Urea-formaldehyde Resin
4. Natural Rubber
In the polymer chain of natural rubber, the residual double bonds are located between C 2 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.
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 higb water
absorption capacity. It is attacked by oxidising agents and organic solvents. As such, it cannot
be used very extensively for commercial puposes.
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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- crosslnks in the structure of natural rubber by
heating with sulphur at 11O°C is called vulcanlsation of rubber.
Vulcanisatlon 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
vulcanisation. Vulcanisation introduces polysulphide (-S-S-) bonds between the adjacent
chains. These crosslinks tend to limit the motion of chains relative to each other.
5. Neoprene
6. Buna-N
It is insulator in nature and is used for making conveyor belts and printing rollers.
Polyesters
The polymers which contain an ester linkage are known as polyester, e.g., dacron.
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1. Polymethylmethacrylate (PMMA)
The polymer is known by several commercial names such as lucite, acrylite, plexiglass and
perspex.
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. Glyptal
When its solution in a suitable solvent is evaporated, it leaves a tough but non-flexible film. It
is, therefore, used in the manufacture of paints and lacquers.
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3. Terylene (Dacron)
Polymerisation is carried out at 420 to 460 K in the presence of catalyst mixture of zinc acetate
and antimony trioxide.
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.
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.
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2. Nylon-2-Nylon-6
1. Saran is a copolymer of vinyl chloride and Isused for wrapping food materials.
2. ASS rubber is a copolymer of acrylonitrile, buta-1, 3-diene and styrene.
3. Bubble gum contains styrene butadiene rubber.
4. Epoxy resins are used In making adhesives such as araldite, etc. These are the
copolymer of epichlorohydrin and bisphenol-A.
5. Thikol is another variety of synthetic rubber which is a copolymer of ethylene chloride
and sodium tetrasulphide (Na2S4).
6. Dynells a copolymer of vinyl chloride and acrylonitrile and is used for making human
hair wigs.
7. Silk Is a thread like natural polymer which is obtained from cocoons of sllk worms. It is
a natural polyamide fibre.
8. Thermocol Is a foamed plastic obtained by blowing air through molter polystyrene or
polyurethane.
9. Superglue is a polymer of methyl α-cyanoacrylate and is obtained by anionic
polymerisation of monomer.
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