Chain Length Dependence of Propagation Rate Constants

4 Chain Length Dependence of Propagation Rate Constants 

There have been attempts at direct measurements of these important kinetic parameters in AN, MAN, MMA and polymerizations. 

When the rcaetion is compared to a reference reaction care must be taken to establish the influence of chain length on the reference reaction. 

Frequency factors for addition of small radicals to monomers are higher by more than an order of magnitude than those for propagation (Table 4.12). Activation energies are typically lower. However, trends in the data are very similar suggesting that the same factors are important in determining the relative reactivities for both small radicals and propagating species. The same appears to be true with respect to reactivities in copolymerizalion (Section 7.3.1.2). 

Chain Structure ami Conformation of Macromolecules Wiley New York, 1982. 

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Chain length dependence of propagation rate constants... 

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