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Free radical are independently-existing species that have unpaired electron. Normally they are highly reactive with short life time. Free radical polymerizations are chain polymerizations in which each polymer molecules grows by addition of monomer to a terminal free-radical reactive site known as active center. After each addition the free radical is transferred to the chain end. Chain polymerization is characterized by three distinct stages, Initiation, propagation and termination.
Example
The
INITIATION
This
stage is a two steps stage 1. The formation of free radicals from an initiator. 2. The addition of one of these free radicals to a monomer molecules. Free radical can be formed by two principal 1. Homolytic scission (homolysis) or breakage of a single bond. 2. Single electron transferred to or from an ion or molecule (redox reactions) Homolytic can be achieved by heat (thermolysis) or by light such as U.V. (photolysis).
Example
O
O 2
O -C-O
-C-0-0-CBenzoly peroxide
CN CN Azobisisobutyronitril
O -C-0
PHOTOLYSIS is the second principle of free radical formation. The advantage of this method is that the formation of free radicals begins at the instant of exposure and cases as soon as the light source is removed.
Photolysis
REDOX REACTION
Redox reaction defined as the generation of free radicals by electron transfer and it is use when polymerization performed at low temperature. Example
O O O O-S-O-O-S-O + HO-S-O
O O Presulphate ion
Bisulphate ion
An active center is crated when a free radical (Ro) which is generated from an initiator attacks the T-bond of the monomer molecules.
R + CH2 = CH X R-CH2-CH X or R-CH - CH2 X
Sometime free radical react with each other such as: O O O 2 OR 2 -C-0 -C-O+C=O
PROPAGATION
The addition of monomer molecules to the active center to grow the polymer chain. There are two modes of chain propagation R-CH2-CH-CH2-CH X X R-CH2-CH-CH-CH2 X X
like -----CH2-CH-CH2-CH-CH2-CH-CH2-CH-----X X X X
Time of
addition for each monomer is of the order of a millisecond. Thus several thousands of additions can take place in a few seconds.
TERMINATION
The last stage of chain reaction in which the growth of the polymer chain terminated (or stopped). There are two mechanisms of termination 1. Combination Coupling together of two growing chains to form a single polymer molecules. polystyrene
--CH2-CH + CH - CH2-----CH2-CH- CH-CH2--X X X X 2. Disproportionation when a hydrogen atom move from one growing chain to another H H --CH2-CH + C - C------CH2-CH2 + CH=CH2-- X X H X X Saturated end Unsaturated end group polymer group polymer
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