Elementary kinetics of free-radical addition polymerisation

1 Elementary Kinetics of Free-radical Addition Polymerisation 

Polymerisation kinetics will be dealt with here only to an extent to be able to illustrate some points of technological significance. This will involve certain simplifications and the reader wishing to know more about this aspect of polymer chemistry should refer to more comprehensive studies.  

In a simple free-radical-initiated addition polymerisation the principal reactions involved are (assuming termination by combination for simplicity) 

The rate of Initiation, Vj, i.e. the rate of formation of growing polymer radicals, can be shown to be given by 

The propagation rate is governed by the concentrations of growing chains [M—] and of monomers [M], Since this is in effect the rate of monomer consumption it also becomes the overall rate of polymerisation 

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Elementary kinetics of free-radical addition polymerisation 29... 

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