二元自缩合乙烯基聚合反应体系的统计热力学

Statistical and thermodynamic properties of binary self-condensing vinyl polymerization

应用统计力学原理对二元自缩合乙烯基聚合反应体系(由单体和引发单体组成)的统计热力学特征予以研究.首先从两种不同的角度给出与聚合反应相应的配分函数,据此得到反应体系的平衡自由能、质量作用定律以及超支化高分子的数量分布函数,进而计算了体系的比热和等温压缩系数等热力学量.进一步研究了超支化高分子的空间尺度,给出反应体系k次均方回转半径的递推公式,计算了各种不同溶剂条件下的均方回转半径,指出引发单体分数、反应程度和溶剂效应对超支化高分子空间尺度的影响.

The thermodynamic properties of a binary self-condensing vinyl polymerization system consisting of monomers and inimers are investigated by the principle of statistical mechanics. In detail, in terms of two types of canonical partition functions constructed from different viewpoints, the equilibrium free energy, the law of mass action and the size distribution of hyperbranched polymers are obtained. As an application, the specific heat, equation of state and isothermal compressibility concerning the polymerization are given as well. To study the dimension of hyperbranched polymers in the system, a recursion formula satisfied by the （k＋1）-th and k-th mean square radius of gyration is derived, and then the first, second and third radius of gyration under different solvent conditions are presented. The influences of the fraction of inimers, the conversion of vinyl groups and the solvent effect on the average dimension of hyperbranched polymers are discussed.