Thermodynamics of the Free-Radical Polymerization Reaction

The polymer-nitroxyl adduct P-X reversibly dissociates thermally, in process 1 into the polymer radical P and the nitroxyl radical X. The rate constants of dissociation and combination are and kc, respectively. The, so-called, degenerative transfer takes place in process 11. The second-order rate constant for active species in either direction is k y. Here all the rate constants are assumed to be independent of chain length. Since the frequency of cleavage of the P-X bond is proportional to [P-X] in process 1 and to [P l [P -X]] in process 11, the overall frequency,/ per unit time and per unit volume, of the bond-cleaving or activation reactions, may be expressed by [277]  

Matyjaszewski et al. wrote the kinetic equation for atom transfer polymreization [290, 291]. It is based on the ATP reaction mechanism that was described above. By assuming fast initiations, insignificant termination reactions and steady concentrations of the propagating radicals, the following relationship was derived [290,291]  

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