Statistical theory for self-condensing vinyl polymerization system with any initial distribution

Hong, Xiao-Zhong; Wang, Haijun; Ba, Xinwu

doi:10.1360/032013-164

Cited by 1 publication

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“…Theoretically, a series of investigations on HBPs have been performed through different methods such as probabilistic analysis [8], solving kinetic differential equations [15][16][17][18], computer simulation [19][20][21], and generating function method [22][23][24]. Recently, the method of statistical mechanics has been applied to study a series of SCVP systems [25][26][27][28], and the equilibrium free energy and law of mass action were given in their explicit expressions.…”

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confidence: 99%

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

Zhao

Yao

et al. 2015

Sci. China Chem.

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A new self-condensing vinyl polymerization system consisting of * AB f -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. partition function, law of mass action, internal energy and specific heat, polydispersity index, structural parameter

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