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 statistical thermodynamic characteristics of binary self-condensation of vinyl polymerization system (composed of monomers and initiating monomers) are studied by the principle of statistical mechanics.First, the partition function of the polymerization reaction is given from two different perspectives The equilibrium free energy, the law of mass action and the number distribution function of hyperbranched polymer were obtained, and then the thermodynamic quantities such as specific heat and isothermal compressibility of the system were calculated. The spatial scale of hyperbranched polymer was further studied, The mean square radius of gyration of the k-th system was calculated. The mean square radius of gyration under different solvent conditions was calculated. The influence of initiator concentration, reaction degree and solvent effect on the spatial scale of hyperbranched polymer was pointed out.