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化学学报
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化学学报 ›› 2008, Vol. 66 ›› Issue (8): 885-889. 上一篇    下一篇

研究论文

双官能团硫脲催化丙交酯开环聚合反应的理论研究

朱荣秀1，张冬菊1，王若曦2，刘成卜*,1   

  1. (1山东大学化学与化工学院 济南 250100)
    (2山东警察学院刑事科技系 济南 250014)
  • 投稿日期:2007-06-26 修回日期:2007-10-23 发布日期:2008-04-28
  • 通讯作者: 刘成卜

Theoretical Study on the Ring-opening Polymerization of D-Lactide Catalyzed by Bifunctional Thiourea Catalyst

ZHU Rong-Xiu 1 ZHANG Dong-Ju 1 WANG Ruo-Xi 2 LIU Cheng-Bu*,1   

  1. (1 School of Chemistry and Chemical Engineering, Shandong University, Jinan 250100)
    (2 Criminal Technological Department, Shandong Police College, Jinan 250014)
  • Received:2007-06-26 Revised:2007-10-23 Published:2008-04-28
  • Contact: LIU Cheng-Bu

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被引次数

3

用密度泛函理论在B3LYP/6-31G(d)水平上研究了双官能团硫脲催化丙交酯开环聚合反应的微观机理. 讨论了催化聚合反应的两条可能路径: 路径A和路径B. 计算结果表明沿路径A进行的开环聚合反应在能量上是有利的. 从理论上证实了催化剂在聚合反应中所起的双官能团催化作用, 即氨基活化引发剂, 硫脲活化单体, 通过两个基团共同作用, 完成催化开环.

关键词: 双官能团硫脲, 开环聚合, 丙交酯, 反应机理, 密度泛函理论

The Ring-opening polymerization (ROP) of D-lactide (D-LA) catalyzed by bifunctional thiourea catalyst has been studied by performing density functional theory calculations at the B3LYP/6-31G(d) level. Two pathways (A and B) for the catalyzed ROP of D-LA have been characterized in detail. It has been found that path A is much more favorable in energy than path B. The calculated results indicate that the catalyst promotes the ROP of D-lactide by bifunctional activation of the carbonyl of LA monomer and of the initiating/propagating alcohol via hydrogen bonding to the thiourea group and to the Bronsted basic (tertiary amino) group, respectively. The calculated results provide a general model that explains the mechanism of the title reaction.

Key words: bifunctional thiourea, ring-opening polymerization, lactide, reaction mechanism, density functional theory