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3. Copolymerization
1. Additional polymerization or Chain polymerization: This polymerization yields an exact multiple
of basic monomeric molecules. This monomeric molecule contains one or more double bonds. By
intermolecular rearrangement of these double bonds makes the molecule bifunctional. In this
polymerization process light, heat and pressure or catalyst is used to breakdown the double covalent
bonds of monomers.
R + M M1 ……….(2)
Free radical monomer molecule
M1 + M M2
M2 + M M3
M3+ M M4 or in general terms Mn + M Mn + 1
c. Termination step: At some time, the propagation polymer chain steps growing and terminates.
H H H H
- CH2 – C + C – CH2 - CH2 – C – C – CH2
Y Y Y Y
Disproportion in which a hydrogen atom of one radical center is transferred to another radical center. This
results in the formations of two polymer molecules, are saturated and one unsaturated e.g.
H H H H H
CH2 – C + C – CH2 CH2 – CH + C = C –
Y Y Y Y
The two different modes of terminations can be represented in general terms by:
M*n + M*m M*n+m (Coupling)
M*n + Mm* Mn + Mm (Disproportionation)
Compounding of plastics:
Compounding of the plastics may be defined as the mixing of different materials like
plasticizers, fillers of extenders, lubricants, dies and pigments to the thermoplastic and thermosetting plastics
to increase their useful properties like strength, toughness, etc. Resins have plasticity or binding property, but
need other ingredients to be mixed with them for fabrication into useful shapes.
b. Fabrication of plastics:
Many methods of fabricating plastics into desired shaped articles are employed. This production of plastics is
known as fabrication of plastics. The methods, usually depends upon the types of resins used i.e., whether
thermosetting or thermoplastic. Different fabrication techniques are described below.
Moulding of Plastics
Moulding of plastics comprises of forming an article to the desired shape by application of heat and
pressure to the moulding compounds in a suitable mould and hardening the material in the mould. The method
of moulding depends upon the type of resins used.
i) Compression moulding:
This method is applied to both thermoplastic and thermosetting resins. The predetermined quantity of plastic
Ingredients in proper properties are filled between the two half –pieces of mould which are capable of being
moved relative to each other heat and pressure are than applied according to specifications. The containers
filled with fluidized plastic. Two halves are closed very slowly. Finally curing is done either by heating or
cooling. After curing the moulded article is taken out by opening the mould parts.
d) Extrusion moulding:
This process is useful in the preparation of continuous wires with uniform cross section. The heated plastic is
pushed into the die with the help of screw conveyor. In the die, the plastic gets cooled due to the exposure to
atmosphere and by artificial air jets.
Extrusion moulding is used mainly for continuous moulding of thermoplastic materials into articles of
uniform cross section like tubes, rods, strips, insulated electric cables. The thermoplastic ingredients are
heated to plastic condition and then pushed by means of a screw conveyor into a die, having the required outer
shape of the article to the manufactured. Here the plastic mass gets cooled, due to the atmospheric exposure
(or artificially by air jets). A long conveyor carries away continuously the cooled product.
Applications: It is used for making electric insulator parts like switches, plugs, switch boards etc. For making
moulded articles like telephone parts cabinet of radio and television.
Properties:
a. The structure of nylons are linear that permits side-by-side alignment. Moreover, the molecular chains are
held together by hydrogen bonds. Thus, nylons have high crystalline which imparts high strength, high
melting point, elasticity, toughness, abrasion resistance and retention of good mechanical properties upto
1250C.
b. They are also sterilisable.
c. Since nylons are polar polymers, they have good hydrocarbon resistance. Larger the number of carbon
atoms, greater will be ease of processing and hydrocarbon and moisture resistance.
Applications:
Nylon-6,6 is primarily used for fibers, which find use in making socks, under-garments, carpets.
Nylon-6.6 is also used in mechanical engineering for well known applications like gears, bearings, bushes,
cams.
Nylon-6 is mainly used in manufacture of tyre cord.
Nylon6-10 is suitable for monofilaments which are used for bristles, brushes.
Polyethylene also known as polyethene. It is prepared by the process of addition polymerization of ethylene.
Polyethylene is two types on the basis of density.
a. Low density polyethylene(LDPE):
Preparation: it is prepared by polymerizing ethylene at high pressures of 1000 to 5000 atmospheres and at 250 0C
in the presence of free radical initiator (Oxygen).
Properties: LDPE molecules are branched and don’t allow the molecules to pack efficiently.
LDPE has a density 0.91 to 0.925 g/cm 3
LDPE Crystalline nature is also low (55%)
LDPE is chemically inert and has good chemical resistance.
LDPE is non-polar; hence it has excellent electrical insulation properties.
LDPE is tough and flexible even at low temperatures.
Uses: LDPE is used in following applications:
a. Films for general packing and carrier bags.
b. Squeeze bottles particularly for detergents.
c. Moulded toys & gift articles
d. Ink tubes for pens & Mugs.
b. High density polyethylene (HDPE):
Preparation: it is prepared by polymerizing under 6 -7 atmospheric pressure at 60 – 70 0C in the presence of
Zeigler – Natta (TiCl4 + Al(C2H5)3) as a catalyst.
Properties: The HDPE molecules are linear and their packing is very easy.
HDPE has a density 0.941 to 0.965 g/cm 3
HDPE has excellent chemical resistance.
HDPE has excellent electrical insulation properties.
HDPE has sufficiently low water and gas permeability.
HDPE is free from odour and toxicity.
HDPE is stiffer, hard and possesses greater tensile strength.
PVC :
Poly Vinyl Chloride is obtained by heating a water emulsion of vinyl chloride in presence of a small amount
of benzoyl peroxide or hydrogen peroxide in an auto clave under pressure.
Vinyl chloride, so needed is generally prepared by treating acetylene at 1 to 1.5 atmospheres with hydrogen
chloride at 600C to 800C in the presence of metal chloride as catalyst.
CH = CH + HCl CH2 = CH Cl
Acetylene Vinyl chloride
Properties: It occurs as a colourless rigid material.
It is having high density and low softening point.
It is resistant to light, atmospheric oxygen, inorganic acids and alkalis.
It is most widely used synthetic plastic.
Uses: It is mainly used as cable insulation, leather cloth, packing and toys.
It is used for manufacturing of film, sheet and floor covering.
PVC pipes are used for carrying corrosive chemicals in petrochemical factories.
Properties: Due to the presence of highly electronegative fluorine atoms and the reqular configuration of the
polytetrafluoro ethylene molecule results in very strong attractive forces between the different chains.
These strong attractive forces give the material extreame toughness, high softening point, exceptionally high
chemical-resistance towards all chemicals, high density, waxy touch, and very low coefficient of friction,
extremely good electrical and mechanical properties: It can be machined, punched and drilled. The material,
however, has the disadvantage that it cannot be dissolved and cannot exist in a true molten state. Around
3500c, it sinters to form very viscous, opaque mass, which can be moulded into certain forms by applying high
pressures.
Uses: as insulating material for motors, transformers, cables, wires, fittings, etc, and for making gaskets,
packing, pump parts, tank linings, chemical-carrying pipes, tubing’s and tanks, etc,; for coating and
impregnating glass fibres, asbestos fibres and cloths; in non-lubricating bearings and non-sticking stop-cocks
etc.
Properties:
i. Because of the presence of bulky phenyl groups, packing of PS chains is not efficient and hence it is
amorphous polymer. Its specific gravity (1.054) is also low.
ii. It has good optical properties like it is transparent polymer allowing high transmission of all wave
lengths. Moreover, its high refractive index (1.592) gives it a particularly high ‘brilliance’.
iii. Due to chain stiffening effect of benzene ring, PS is hard but brittle. It emits a characteristic metallic
sound when dropped.
iv. Being non-polar amorphous polymer, its softening temperature (82-1000C) is low. It cannot withstand
the temperature of boiling water.
v. As it is non-polar so it has low tendency for moisture absorption. Moreover, it has good electrical
insulation characteristics.
vi. It has reasonable chemical resistance but mediocre oil resistance.
Applications: Polystyrene is used for making: audio cassettes, containers for talcum powder, house-wares
(small jars & storage containers), bottle caps, combs and brush handles.
Natural Rubber: Rubbers also known as Elastomers, they are high polymers, which have elastic
properties in excess of 300%.
Natural rubbers consist of basic material latex, which is a dispersion of isoprene. During the treatment, these
isoprene molecules polymerize to form, long-coiled chains of cis-polyisoprene. Natural rubber is made from
the saps of a wide range of plants like Hevea brasillians and guayule.
Latex: is a milky white fluid that oozes out from the plant Hevea brasillians when a cut is made on the steam
of the plant.
The latex is diluted with water. Then acetic or formic acid is added [1kg of acid per 200kgs of latex] to
prepare coagulum. This is processed to give wither crepe rubber or smoked rubber.
Vulcanization:
Vulcanization discovered by Charles Goodyear in 1839.
It consists of heating the raw rubber at 100 – 1400C with sulphur. The combine chemically at the
double bonds of different rubber spring and provides cross-linking between the chains. This cross-linking
during vulcanization brings about a stiffening of the rubber by anchoring and consequently preventing
intermolecular movement of rubber springs. The amount of sulphur added determines the extent of stiffness of
vulcanized rubber. For example, ordinary rubber (say for battery case) may contain as much as 30% sulphur.
Advantages of vulcanization:
i. The tensile strength increase.
ii. Vulcanized rubber has excellent resilience.
iii. It has boarder useful temperature range (-40 to 1000C)
iv. It has better resistance to moisture, oxidation and abrasion.
v. It is resistance to organic solvents like CCl4, Benzene petrol etc.
vi. It has only slight thickness.
vii. It has low elasticity.
Q.No. 6: a. Write a short note on conducting polymers & mention its applications?
b. Describe preparation, conduction properties & applications of Polyactylene & polyanilline
a. Conducting polymers: Those polymers which conduct electricity are Conducting polymers. The
conduction of polymers may be due to unsaturation or due to the presence of externally added ingredients in
them. The conducting polymers can classify in the following way.
Conducting polymers divided in to two types.
1. Intrinsic conducting polymers
2. Extrinsic conducting polymers
Intrinsic conducting polymers: These polymers are characterized by intensive conjugation of double bonds in
their structure i.e. the backbone of the polymer. Again intrinsic conducting polymers are two types.
a. Conducting polymers having conjugation
b. Doped conducting polymers
Conducting polymers having conjugation: Such polymers having conjugated double bonds in the backbone
possess their conductivity due to pi electrons. In pi bonding the overlapping of the orbital is lateral over the
entire backbone resulting in the formation of valence bands and conducting bands which were separated by a
significant Fermi energy gap. The electrical conductivity takes place only after thermal or photolytic
activation of the electrons, which give them sufficient energy to jump the gap and reach into conduction band.
Doped conducting polymers: The conducting polymers having pi electrons in their backbone can easily be
oxidized or reduced because they possess low ionization potential and high electron affinities. Hence their
conductance can be increased by introducing a positive charge or negative charge on polymer backbone by
Doping of poly acetylene: poly acetylene possesses alternate single and double bonds that give rise to mobile
–electrons when doped, i.e. become anisotropic metallic conductors. There are two types of doping, oxidation
or reduction.
1. oxidation with halogen- (P-doping)
2. Reduction with alkali metal – (n-doping)
Preparation of poly-aniline: poly-aniline is prepared by the redox polymerization of aniline in protonic and
aqueous solution in the presence of ammonium per di sulphate as oxidant. It can be regarded as conducting
polymer under certain stimulating conditions like UV light, heat or addition of a suitable dopant to the
polymer.
Doping of poly-aniline: it can be made conductive by p-type (oxidation) doping or n-type (reduction) doping
of polymer. In undoped state, it is a poor semi conductor. On doping with dopant para-hydroxy benzene
sulphonic acid, its conductivity is increased by a factor of 10 dm -1/cm or more and forms polaron/ bipolaron
structure. The conductivity σ of a conducting poly-aniline is related to number of charge carriers ‘n’ and their
mobility µ .
Therefore, σ = neµ
Properties of poly-aniline: Due to the presence of extended π –bond system of conjugated polymers, it is
highly susceptible to chemical and electrochemical oxidation or reduction. As a result, the electrical and
optical properties of the polymer are altered.
Electronically conducting polymers are extensively conjugated molecules and possess specially delocalised
band line structure.
Disadvantages:
1. Poly-aniline decomposes prior to melting. Hence, it is difficult to process.
2. It is insoluble in common solvents except strong acids and N-methyl prolidone.
3. It has poor mechanical properties.
Applications:
1. Poly-aniline is used for corrosion protection, sensors, smart windows, printed circuit boards,
conductive fabrics and conductive pipes for explosives.
The macromolecule with the above structure produces very strong fibers. When this polymer dissolved in
tetra-methyl urea (II) and calcium chloride, the polymer molecules behave strongly. The Kevlar molecular
which were long, straight, and stiff, lined up like logs floating down a river, because of the strange opalescent
look of the solution.