二元酸溶解度对二元醇与一些芳族二元酸的聚酯化反应动力学的影响

KINETICS OF POLYESTERIFICATION OF DIOLS WITH SOME ARYL DIACIDS

一些芳族二元酸与二元醇的聚酯化反应过程包含非均相和均相两个反应阶段，针对这一反应特性，提出了二元酸在反应混合物中溶解度及反应清晰点的两个计算方程，并据此将Ｃｈｅｎ和Ｗｕ提出的自催化聚酯化反应的动力学模型修改为两个分别适用于非均相和均相反应阶段的速率方程．将这两个速率方程应用于双（对羧苯基）苯基氧化膦与乙二醇的恒温自催化聚酯化反应，计算值与实验数据相一致。

In view of that polyesterification reactions of diols with some aryl diacids consists of the non homogeneous and homogeneous reaction stages,two equations were proposed for calculation of the solubilities of aryl diacids in reaction mixtures and of the “clear points” of reactions,respectively.On the basis of the two equations,the kinetic model proposed by Chen and Wu for self catalyzed polyesterification reactions was modified into two rate equations which were used for the non homogeneous and homogeneous reaction stages,respectively.The two rate equations fitted the experimental data well,as was confirmed by the reaction of bis(4 carboxyphenyl)phenyl phosphine oxide with ethylene glycol under constant reaction temperatures of 180～197℃ and at different ratios of diol to diacid,whose rate constant and activation energy were calculated.The reaction rate constant was affected by temperature according to Arrhenius'law.The results of application of the two calculation equations of solubility and clear point and of the two rate equations shows that these equations were reasonable.