三元高分子系统液液相平衡的Monte+Carlo+模拟研究.pdfVIP

A041 三元高分子系统液－液相平衡的Monte Carlo 模拟 杨建勇，彭昌军，刘洪来1 ，胡英 (华东理工大学化学系，上海200237) 摘 要 采用先前开发的构型偏倚蒸发法(CBVM)对三元高分子系统相平衡进行了Monte Carlo 模拟，分别 考察了高分子链长、溶剂及高分子链节间相互作用参数对相区的影响。模拟结果显示，在保持交换能参数 一定的情况下，互溶区随高分子之一的链长的增加而减小; 在系统链长不变的情况下，互溶区随交换能的 减小而变小。修正的Freed 理论可较满意再现模拟结果，但Flory －Huggins 理论总是过低地估计互溶区。 关键词 三元系 液液相平衡 构型偏倚蒸发法 计算机模拟 中图分类号 O642.4 文献标识码 A MONTE CARLO SIMULATIONS OF LIQUID-LIQUID EQUILIBRIA FOR TERNARY CHAIN MOLECULE SYSTEMS YANG Jianyong, PENG Changjun, LIU Honglai1 and HU Ying (Department of Chemistry, East China University of Science and Technology, Shanghai 200237) Abstract This paper presents the results of Monte Carlo simulation for phase equilibria of ternary chain molecule systems by previous configuration-bias-vaporization method (CBVM) based on lattice model, and reviews the influences of length of chains, interreaction parameters between segments and/or solvents. It shows that when exchange interaction-energy parameters are kept as fixed, the miscible region becomes smaller with the chain length of one component increasing and when chain lengths are kept as invariants, the miscible region diminishes with exchange interaction-energy parameters decreasing. The agreement between the simulation results and the revised Freed theory is satisfactory, but Flory-Huggins theory gives too narrow miscible region. Key words ternary system, liquid-liquid equilibria, configuraion-bias-vaporization method, computer simulation 1联系人：刘洪来（E-mail: hlliu@ecust.edu.cn ，Tel ：021） * 国家自然科学基金20025618)和上海市教委资助项目 1 引 言 近些年来，相平衡的计算机模拟已取得了长足的进步 [1,2] 。突出的有，Panagiotopoulos[3,4] 的直方图几率再权重MC 方法可模拟出长达1000 个链节的高分子溶液的相图，当其与混合 场有限尺寸标度理论结合时，能够精确模拟出高分子溶液在临界点附近的相行为。但