高等学校化学学报

高等学校化学学报

• 研究论文 • 上一篇    下一篇

支化高分子溶胶-凝胶相变的热力学

王海军1,3, 刘进军1,2, 巴信武1   

  1. 1. 河北大学化学与环境科学学院, 保定 071002; 2. 承德医学院中药研究所, 承德 067000;
    3. 中国科学院国际材料物理中心, 沈阳 110016
  • 收稿日期:2008-09-19 修回日期:1900-01-01 出版日期:2008-12-10 发布日期:2008-12-10
  • 通讯作者: 王海军

Thermodynamics Theory for Sol-gel Transition of Branched Polymers

WANG Hai-Jun1,3*, LIU Jin-Jun1,2, BA Xin-Wu1   

  1. 1. College of Chemistry and Environmental Science, Hebei University, Baoding 071002, China;2. Institute of Chinese Traditional Medicine, Chengde Medical University, Chengde 067000, China;3. International Center for Materials Physics, Chinese Academy of Sciences, Shenyang 110016, China
  • Received:2008-09-19 Revised:1900-01-01 Online:2008-12-10 Published:2008-12-10
  • Contact: WANG Hai-Jun

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摘要： 以典型的Aa-Bb型缩聚反应为例, 应用统计力学和热力学的基本原理对反应体系的一些平衡特征进行研究. 基于从两种不同角度所构造的正则配分函数, 导出反应体系的平衡自由能以及质量作用定律的解析形式, 同时指出获得数量分布函数的新方法, 并通过计算反应体系的等温压缩系数从而得到反应体系的凝胶化条件. 进一步利用数量分布函数的不变性, 给出临界点后溶胶相和凝胶相的平衡自由能, 探讨了溶胶-凝胶相变的相关问题.

关键词: 平衡自由能, 质量作用定律, 数量分布函数, 溶胶-凝胶相变

Abstract: Several equilibrium properties of typical polycondensation system of Aa-Bb type were studied by the principle of statistical thermodynamics. Starting with the canonical partition functions constructed from two viewpoints, the explicit expressions of the equilibrium free energy and the law of mass action are obtained. Meanwhile, two new methods were proposed to derive the equilibrium size distribution, and the gelation condition was carried out by the isothermal compressibility. Furthermore, based on the invariant property of the equilibrium size distribution, the equilibrium free energies of sol and gel phases in postgel regime were given, and the relevant issues on the sol-gel phase transition were discussed.

Key words: Equilibrium free energy, Law of mass action, Size distribution, Sol-gel phase transition

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