Kinetics of Nonstoichiometric Polymerization

The kinetics of polymerizations involving nonstoichiometric amounts of A and B functional groups can be handled in a straightforward manner. Consider the external acid-catalyzed A—A plus B—B polymerization with r 1. The polymerization rate, defined as the rate of disappearance of the functional groups present in deficient amount, is given by 

When r is close to unity the polymerization rate is adequately described by the expressions in Secs. 2-2a and 2-2b for the case of r — 1. Only when r is considerably different from unity does it become necessary to use Eq. 2-85 or its equivalent. Most step polymerizations 

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