路径积分方法计算聚合物溶液热力学性质  

CALCULATION OF THERMODYNAMIC PROPERTIES OF POLYMER SOLUTIONS BYPATH INTEGRAL METHOD

作　　者：乔宝福[1] 赵得禄[1] 

机构地区：[1]中国科学院化学研究所分子科学中心高分子化学与物理国家重点实验室,北京100080

出　　处：《高分子学报》2004年第2期153-159,共7页Acta Polymerica Sinica

基　　金：国家重点基金研究专项经费 (项目号G19990 64 80 8); 863项目高分子加工的科学基础及软件化资助项目 (课题号 2 0 0 2AA3 3 612 0 )

摘　　要：提出了把聚合物溶液的自由能分解为 3部分 ,平动部分、构象部分和热修正项部分 .其中后两部分具有相对于链段的可加性 ,在引入了“有效浓度”的概念后可以用路径积分方法计算 .当采用体积分数代替有效浓度时 ,就回到了李晓毅和赵得禄的溶液理论 .还利用本理论研究了不同分子量聚苯乙烯 环己烷体系的相分离曲线 ,同Flory Huggins(FH)理论相比 。It is proposed that the overall free energy of a polymer solution has three fundamentally different types of contributions, i.e. the translational, the configurational and the thermal correction parts. The second and the third parts have the additive properties for segments and can be calculated by path integral method with the introduction of a new concept of effective concentration. Taking the volume fraction as the effective concentration, one obtains the Li-Zhao theory of polymer solutions reported previously. The results calculated by the present theory match the spinodals data of PS/cyclohexane systems with different molecular weights much better than those based on the Flory-Huggins theory.

关 键 词：聚合物溶液 热力学性质 路径积分法 自由能 有效浓度 体积分数 相分离 

分 类 号：O631[理学—高分子化学]