Kinetics of Radical Chain Polymerization: 1. Time-Dependent Distributions of Macroradicals and Oligomers
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Numerical and analytical solutions of kinetic equations and the relevant equations for the moments of distribution of macroradicals and oligomers during radical chain polymerization are presented. It has been shown that the initial chain growth occurs in the ballistic mode involving first-generation primary radicals. The chain transfer in which a macroradical, reacting with a solvent, forms an oligomer and the primary radical of the next generation, causes a transition from the ballistic to the diffusion mode in which distributions of chains of different generations are mixed. Time-dependent distributions have been found for chain propagation and transfer rate constants independent of chain length.
Keywords:radical polymerization kinetic equations distribution moments ballistic and diffusion chain growth
This work was supported by the Russian Academy of Sciences under the Presidium Program for Basic Research no. PFI I.55P and as the subject of the state assignment no. 0089-2014-0025.
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