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

Science China Chemistry 2015年第9期58卷 1478-1488页

作者： Zuofei Zhao Yuanfeng Li Ning Yao Haijun Wang Faculty of Physics and Electronic Information Langfang Teachers University College of Chemistry and Environmental Science Hebei University International Centre for Materials Physics Chinese Academy of Sciences

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

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