Kinetics of reversible polymerization |
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Authors: | P. G. J. van Dongen M. H. Ernst |
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Affiliation: | (1) Institute for Theoretical Physics, State University, P.O. Box 80.006, 3508 TA Utrecht, The Netherlands |
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Abstract: | This paper extends the kinetic theory of irreversible polymerization (Smoluchowski's equation) by including fragmentation effects in such a way, that the most probable (equilibrium) size distribution from the classical polymerization theories is contained in our theory as the stationary distribution. The time-dependent cluster size distributionck(a(t)) in Flory's polymerization modelsRAf andAfRBg, expressed in terms of the extent of reaction, has the same canonical form as in equilibrium, and the time dependence of(t) is determined from a macroscopic rate equation. We show that a gelation transition may or may not occur, depending on the value of the fragmentation strength, and, in case a phase transition takes place, we give Flory- and Stockmayer-type postgel distributions.Inspec numbers: 0550, 6460, 8235, 6475. |
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Keywords: | Reversible polymerization coagulation fragmentation RAf andAfRBg models gelation clustering aggregation |
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