化学学报 ›› 1962, Vol. 28 ›› Issue (3): 181-186. 上一篇    下一篇

研究简报

用红外光譜研究聚顺丁烯二酸乙二酯的顺-反異构化

張德龢, 秦文懋, 錢人元   

  1. 中国科学院化学研究所
  • 修回日期:1961-11-09 发布日期:2013-06-03

INFRA-RED SPECTROSCOPIC STUDIES ON THE CIS-TRANS ISOMERIZATION OF THE POLYESTER FROM MALEIC ANHYDRIDE-ETHYLENE GLYCOL

CHANG TE-HO, CHING WEN-MER, CHIEN JEN-YUAN   

  1. Institute of Chemistry, Academia Sinica
  • Revised:1961-11-09 Published:2013-06-03

1.以顺式和反式丁烯二酸二乙酯为模型化合物,确定表征聚酯中顺、反构型的红外光谱特征吸收带。顺式为825,1410和3052厘米-1,反式为780,1371和3072厘米-1。2.测定一系列顺式聚酯和反式聚酯混合弑样在825和780厘米-1的光密度比值,得到可以定量顺、反构型的工作曲线。3.缩聚反应温度和反应时间对顺-反异构化有显著的影响。提高温度和延长反应时间都会增加聚酯中反式构型的含量。顺-反异构化反应系属一极反应,反应活化能为19千卡/克分子。4.在顺丁烯二酸酐和乙二醇的缩聚过程中反式构型的增多是聚合物粘度增大的主要因素。

The characteristic infra-red absorption bands for the cis-and traps-forms of the polyester from malefic anhydride-ethylene glycol have been identified by comparison with the absorption bands of the corresponding model compounds, i.e., diethyl maleate and diethyl fumarate: Cis-form-825, 1410, 3052 cm-1;traps-form-780, 1371, 3072 cm-1.The ratio of the optical densities of the 825 and 780 cm-1 bands has been chosen for the deterurination of the ratio of cis-and trans-forms present in the polyester.Increased temperature and duration of polycsterification increased the traps-content of the polyester obtained.The cis-trans isomerization reaction has been shown to be a first order reaction with an activation energy of 19 kcalimole.The large increase of viscosities of reaction mixture during polyesterification or malefic anhydride and ethylene glycol is mainly due to the increase of trans-content of the polyester formed.