低转化率条件下nonMarkovian链的多状态可逆共聚合
Multistate reversible copolymerization of nonMarkovian chains under low conversion conditions
摘要：
本文用解析法求解了B. D. Coleman和T. G. Fox [J.Chem.Phys.38，1065（1963）]在低转化率条件下进行，其中单体物质的浓度是化学稳定的并随时间保持恒定。虽然这一机制的速率只取决于当前连接或分离的单体，但增长的大分子链形成了一个非马尔可夫序列，其特征在于与组成序列的每个单体单元相关的矩阵。这些矩阵是通过求解动力学方程得到的，它们决定了共聚物的生长速度、其可能序列的统计特性以及共聚过程的热力学。
英文摘要：
The reversible kinetics of copolymerization is solved analytically for the multistate mechanism proposed by B. D. Coleman and T. G. 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 depends on the currently attached or detached monomer, the growing macromolecular chain forms a nonMarkovian 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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