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and
(d) Copolymerization
Addition Polymerisation
In this type of polymerisation, the molecules of the same monomer
Termination.
polymer chain
this process starts with the addition of phenyl free radical formed by
the peroxide to the ethene double bond thus generating a new and
larger free radical
the product radical formed reacts with another radical to form the
polymerized product
Ionic Polymerisation
The
addition
polymerization
that
takes
place
due
to
(C6H5CH=CH2)
carbocation
include
acrylonitrile
[CH2=C(CN)],
vinyl
chloride
Coordination polymerization
It is also a subclass of addition polymerization
It usually involve transition-metal catalysts
Here, the "active species" is a coordination complex, which initiates
Ziegler-Natta
catalysts
combine
transition-metal
compounds
are involved; the active site of the growing chain is the carbon atom
directly bonded to the metal
Zeigler-Nata catalysts
These are a special type of coordination catalysts, comprising two
The Ti ion attracts the electrons pair or the monomer and forms
bond (Fig. 4)
This transition state now gives rise to the chain growth at the metal
Copolymerization
It is a polymerisation reaction in which a mixture of more than one
polymeric chain
Condensation Polymerisation
This type of polymerisation generally involves a repetitive
groups and monomers with more than two end groups give three
dimensional polymers which are cross linked.
Polyester is created through ester linkages between monomers, which
involve the functional groups carboxyl and hydroxyl (an organic acid
and an alcohol monomer)
The formation of polyester like terylene or dacron by the interaction
which involve the functional groups carboxyl and amine (an organic
acid and an amine monomer)
Nylon-6 is an example which can be manufactured by the
This type of polymerization normally employs two difunctional monomers that are
catalyst to afford polyester, in this case, chain growth is initiated by the reaction of
one of the diacid's carboxyl groups with one of the diol's hydroxyl groups
The free carboxyl or hydroxyl group of the resulting dimer can then react with an
days
(2) All of the monomers are quickly converted to oligomers, thus,
Bulk polymerization
Bulk polymerization is the simplest technique and produces the
highest-purity polymers
Only monomer, a monomer-soluble initiator are used
This
contamination of product
The viscosity of the mixture is low initially to allow ready mixing,
heat transfer, and bubble elimination, this method is used for the
preparation of polyethene, polystyrene, etc.
Disadvantages:
Reaction medium becomes increasingly viscous as reaction goes to higher
leads
to
uneven
polymerization
and
loss
of
monomer,
very higher than that of termination rate, this method is seldom used in
commercial manufacture
Solution polymerization:
This method is used to solve the problems associated with the bulk
monomer be soluble in each other and that the solvent are suitable
for boiling points, regarding the solvent-removal steps
It is often used to produce copolymers, this method is used for the
Advantages:
(i) Solvent has low viscosity, reaction mixture can be stirred
(ii) Solvent acts as a diluent and aids in removal of heat of
polymerization
(iii) Solvent reduces viscosity, making processing easier
(iv)Thermal control is easier than in the bulk and
(v) Cheap materials for the reactors (stainless steel or
glass lined)
Disadvantages:
(i) Reduce monomer concentration which results in decreasing the rate of
reaction is increased
(iii) Solvent may terminate the growing polymer chain, leading to low
properties
(v) Clean up the product with a non solvent or evaporation of solvent
(vi) Small production per reactor volume
(vii) Not suitable for dry polymers
polymerisation
of
monomer
(containing
the
initiator)
are
formed,
Advantages:
(i) Polymerisation to high conversion
(ii) Low viscosity due to the suspension
(iii) Easy heat removal due to the high heat capacity of water
(iv) Excellent heat transfer because of the presence of the solvent
(v) Solvent cost and recovery operation are cheap
(vi) Polymerization yields finely divided, stable latexes and
Disadvantages
(i) Contamination by the presence of suspension and other
product
(iii) Reactor cost may higher than the solution cost
Emulsion polymerisation:
An emulsion polymerization consists of
(a)Water (solvent or as the heat-transfer agent),
(b) Monomer,
(c) Initiator (is soluble in water and insoluble in the monomer),
(d) A surfactant or emulsifier (such as sodium salt of long-chain
fatty acid)
This method is used for the preparation of polyvinyl acetate,
ions move around freely, the soap anion consists of a long oil-soluble
portion (R) terminated at one end by the water-soluble portion,
so emulsifier molecules arrange themselves into colloidal particles called
micelles
In
water
containing
insoluble
monomer
molecule,
their stability; these growing polymer particles absorb the soap of the
parent micelles
Advantages:
(i) Overcomes many environmental problems: solvent is water
(ii) If final desired product is polymer is washed with water to