Statistical thermodynamic properties of a new self-condensing vinyl polymerization system  

作　　者：Zuofei Zhao Yuanfeng Li Ning Yao Haijun Wang 

机构地区：[1]Faculty of Physics and Electronic Information, Langfang Teachers University [2]College of Chemistry and Environmental Science, Hebei University [3]International Centre for Materials Physics, Chinese Academy of Sciences

出　　处：《Science China Chemistry》2015年第9期1478-1488,共11页中国科学（化学英文版）

基　　金：supported by the National Natural Science Foundation of China(21274056,21374028);Natural Science Foundation of Hebei province(B2015408007);the doctoral funds of Langfang Teachers University(LSBS201308)

摘　　要：A new self-condensing vinyl polymerization system consisting of *ABf-type inimers is studied by the principle of statistical mechanics. To obtain the relevant average properties of the system, a differential equation satisfied by the polymeric moment of interest is given, and as a result the zeroth, first, second, and third polymeric moments together with the size distribution function of hyperbranched polymers(HBPs) are explicitly presented. As an application of the method of statistical mechanics, several thermodynamic quantities such as the equilibrium free energy, law of mass action, isothermal compressibility, internal energy, and the specific heat associated with the polymerization are all derived. Furthermore, the scaling behavior of asymptotic size distribution function is discussed, by which a reasonable interpretation of the polydispersity index near the end of polymerization can be made. Also, the expressions of some structural parameters such as the numbers of inimers, terminal units, chain units, branched units, and the degree of branching(DB) are calculated. It is found that a high functionality is helpful to improve the DB of the resultant HBPs. These results show that the functionality f has a significant effect on the thermodynamic quantities and structural properties of HBPs.A new self-condensing vinyl polymerization system consisting of ＊ABf-type inimers is studied by the principle of statistical mechanics. To obtain the relevant average properties of the system, a differential equation satisfied by the polymeric moment of interest is given, and as a result the zeroth, first, second, and third polymeric moments together with the size distribution function of hyperbranched polymers（HBPs） are explicitly presented. As an application of the method of statistical mechanics, several thermodynamic quantities such as the equilibrium free energy, law of mass action, isothermal compressibility, internal energy, and the specific heat associated with the polymerization are all derived. Furthermore, the scaling behavior of asymptotic size distribution function is discussed, by which a reasonable interpretation of the polydispersity index near the end of polymerization can be made. Also, the expressions of some structural parameters such as the numbers of inimers, terminal units, chain units, branched units, and the degree of branching（DB） are calculated. It is found that a high functionality is helpful to improve the DB of the resultant HBPs. These results show that the functionality f has a significant effect on the thermodynamic quantities and structural properties of HBPs.

关 键 词：partition function law of mass action internal energy and specific heat polydispersity index structural parameter 

分 类 号：O631[理学—高分子化学]