Kinetics of Polymerization Involving Unimolecular Unopposed Irreversible First-Order Termination

1 Kinetics of Polymerization Involving Unimolecular Unopposed (Irreversible) First-Order Termination 

In principle, the knowledge of the momentary concentrations of the active species is not necessary to determine the rate constants (cf. Fig. 14) because both kp and kj can be simultaneously determined by solving equations describing the non-stationary kinetics, as was shown for the cationic polymerization of sts rene by Peppra (partial solution) and for the polymerization of a-epichlorohydrin (complete kinetic solution). 

For fast initiatnn and unimolecular termination (first-order idative to active specfes) we 

the value of kj can be calculated directly from Eq. (128). The knowledge of CP lo fast and quantitative initiation (P Jo = (Ilo) enables the termination of kp from Eq. 

This approach has been successfully applied to the polymerization of o-ejnchtorohydrin.  

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