Statistical and thermodynamic properties of binary self-condensing vinyl polymerization

• Published in: Science China. Chemistry Vol. 54; no. 3; pp. 438 - 445
• Main Authors: Gu, Fang, Wang, HaiJun, Zhao, ZuoFei
• Format: Journal Article
• Language: English
• Published: Heidelberg Science China Press 01.03.2011; Springer Nature B.V
• Subjects: Chemistry; Chemistry and Materials Science; Chemistry/Food Science; Compressibility; Equations of state; Free energy; Gyration; Partitions (mathematics); Polymerization; Polymers; Recursive functions; Size distribution; Solvent effect; Statistical mechanics; Thermodynamic properties; Thermodynamics; law of mass action; mean square radius of gyration; solvent effect; self-condensing vinyl polymerization
• ISSN: 1674-7291; 1869-1870
• DOI: 10.1007/s11426-011-4222-1

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.