化学学报 ›› 1959, Vol. 25 ›› Issue (1): 10-17,30,31. 上一篇    下一篇

论文

Ⅱ.二元酸与二元醇的聚酯反应动力学

唐敖庆, 岳国粹   

  1. 中国科学院应用化学研究所
  • 投稿日期:1958-07-18 发布日期:2013-06-03

Ⅱ.STUDIES ON THE KINETICS OF POLYESTERIFICATION REACTIONS BETWEEN DIBASIC ACIDS AND GLYCOLS

TANG AU-CHIN, YAO KUO-SUI   

  1. Institute of Applied Chemistry, Academia Sinica
  • Received:1958-07-18 Published:2013-06-03

聚酯反应象单元酸与单元醇的酯化反应一样,都是氢离子催化机构。这种机构与现在公认的聚酯反应的氢离子催化机构的区别在于氢离子的来源和氢离子参与反应的详细历程,肯定了氢离子不仅由外酸供给,而且也可由二元酸本身供给。另外,二元酸与二元醇均可作为氢离子的载体。聚酯反应的动力学方程与二元酸与二元醇的起始克分子比有密切关系,应由前篇(3)式表示。当酸与醇以等克分子比起反应,又无外酸存在时,聚酯反应是2(1/2)级反应;若有外酸作催化剂时,当外酸的量加得适当多,由二元酸本身供给的氢离子的贡献可以忽略时,是二级反应,与以往结论相一致:当外酸的量加得少,必须考虑氢离子的同离子效应,它就不再是简单的二级反应,当酸与醇以不等克分子比起反应我们的实验结果亦与理论一致。

Much experimental studies on the polyesterification reactions between dibasic acids and glycols have been reported by various authors, among them Menshyt-kind[1], Dostal and Raff[2], Flory[3,4], Rafikov and Korshak[5], Davies[6,7], Colonge and Stuchlik[8], and others, but quite diversed results were obtained. According to polyeaterification in the absence of a foreign acid, owing to catalytic effect of the dibasic acid molecule, is a third-order reaction[3,4].