烯类单体的聚合-解聚平衡以及聚合上限温度  

Polymerization-Depolymerization Equilibriumand Ceiling Temperature of Vinyl Monomer

作　　者：郭霖 GUO Lin(College of Materials Science and Engineering,Qingdao University,Qingdao 266071,China)

机构地区：[1]青岛大学材料科学与工程学院,山东青岛266071

出　　处：《化学教育（中英文）》2023年第22期107-117,共11页Chinese Journal of Chemical Education

基　　金：山东省普通高等学校教学改革试点课程“高分子化学”项目(鲁教高字[1999]27号);山东省省级精品课程“高分子化学”项目(150410030);山东省一流课程“高分子化学”暨青岛大学“以学为中心”课程“高分子化学”项目(RC1900004947);青岛大学第三批课程思政示范项目(KCSZ2021116);青岛大学研究生教育质量提升计划项目(RC1900016633);青岛大学2022年校级教学改革研究项目(RC2200003830)。

摘　　要：基于总反应讨论了烯类单体的聚合-解聚平衡以及聚合上限温度等2个重要的高分子化学热力学基本问题,指出了基于链增长反应的通行处理方法存在的问题,探讨了聚合物溶解及单体单元浓度变化带来的影响,推导出了相关公式,给出了新的聚合上限温度定义及典型应用例,并引入了随遇平衡与稳定平衡概念。预测结果与见诸报道的实验结果一致,并可解释文献中未被合理解释的实验现象。本文处理方法及所得结论亦可用于环状单体的开环聚合。Polymerization-depolymerization equilibrium and ceiling temperature of vinyl monomer are two important thermodynamic questions in polymer chemistry. A new approach treating the polymerization-depolymerization equilibrium of vinyl monomer is developed based on the overall reaction rather than the elementary propagation reaction, with new equations being derived, new definition of ceiling temperature(T_c) being established, and typical examples being given, which can explain the effects of dissolution and concentration of the produced polymer in its monomer on the equilibrium for monomers giving soluble polymers, that were all ignored in Dainton and Ivin's approach. Also, the concepts of neutral equilibrium and stable equilibrium are introduced. This approach and its conclusion are also applicable to ring-opening polymerization of cyclic monomers.

关 键 词：化学热力学 聚合-解聚平衡 聚合上限温度 混合熵 乙烯基单体 加聚 自由基聚合 相律 聚合反应自发性判据 基元反应 

分 类 号：O631.5[理学—高分子化学]