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Multistate reversible copolymerization of non-Markovian chains under low conversion conditions
1Center for Nonlinear Phenomena and Complex Systems, Université Libre de Bruxelles (U. L. B.), Code Postal 231, Campus Plaine, B-1050 Brussels, Belgium.
Abstract:
The reversible kinetics of copolymerization is solved analytically for the multistate mechanism proposed by Coleman and Fox [J. Chem. Phys. 38, 1065 (1963)] under low conversion conditions where the concentrations of monomeric species are chemostatted and stay constant in time. Although the rates of this mechanism only depend on the currently attached or detached monomer, the growing macromolecular chain forms a non-Markovian sequence that is characterized by matrices associated with every monomeric unit composing the sequence. These matrices are obtained by solving the kinetic equations, and they determine the growth velocity of the copolymers, the statistical properties of its possible sequences, as well as the thermodynamics of the copolymerization process.
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