高等学校化学学报 ›› 2014, Vol. 35 ›› Issue (7): 1553-1558.doi: 10.7503/cjcu20140301

• 高分子化学 • 上一篇    下一篇

高分子量立构复合结晶的三枝化PPO-PDLA-PLLA嵌段共聚物

李伟, 马艳, 李远翔, 范仲勇()   

  1. 复旦大学材料科学系, 上海 200433
  • 收稿日期:2014-04-02 出版日期:2014-07-10 发布日期:2014-06-10
  • 作者简介:联系人简介: 范仲勇, 男, 博士, 教授, 主要从事高分子材料结构与性能研究. E-mail: zyfan@fudan.edu.cn
  • 基金资助:
    国家自然科学基金(批准号: 51373041)资助

Three-arm Stereocomplexed PPO-PDLA-PLLA Copolymer with High Molecular Weight

LI Wei, MA Yan, LI Yuanxiang, FAN Zhongyong*()   

  1. Department of Materials Science, Fudan University, Shanghai 200433, China
  • Received:2014-04-02 Online:2014-07-10 Published:2014-06-10
  • Contact: FAN Zhongyong E-mail:zyfan@fudan.edu.cn
  • Supported by:
    Supported by the National Natural Science Foundation of China(No.51373041)

摘要:

以三枝化低不饱和度聚环氧丙烷(PPO)引发D-丙交酯(D-LA)逐步开环聚合, 合成了三枝化聚环氧丙烷-聚右旋乳酸(PPO-PDLA)共聚物. 用辛酸亚锡Sn(Oct)2与PPO-PDLA端羟基反应进行Sn(Oct)封端, 制备了三枝化PPO-PDLA-Sn(Oct)预聚物. 再于130 ℃下, 以其作为大分子引发剂与L-丙交酯(L-LA)开环聚合, 合成了分子量>105的三枝化PPO-PDLA-PLLA嵌段共聚物. 活性端基的引入, 降低了聚合反应温度, 从而降低了聚合中的酯交换或热降解反应发生的概率. 实现了高分子量PPO-PDLA-PLLA嵌段共聚物的合成. 结构测试结果表明, 合成的嵌段共聚物具有分子结构易控及立构规整度高等特点. 在结晶-熔融-再结晶重复热处理下, 三枝化PPO-PDLA-PLLA嵌段共聚物仅发生立构复合聚乳酸结晶, 且结晶能力稳定.

关键词: 封端, 开环聚合, 立构嵌段聚乳酸, 三枝化PPO-PDLA-PLLA嵌段共聚物, 立构复合结晶

Abstract:

Three-arm poly(propylene oxide)(PPO) was used as a macroinitiator for the ring-opening polymerization(ROP) of D-lactide to obtain three-arm poly(propylene oxide)-block-poly(D-lactic acid)(PPO-PDLA). PPO-PDLA copolymer was then reacted with stannous octoate [Sn(Oct)2] to obtain Sn(Oct) end-capped PPO-PDLA[PPO-PDLA-Sn(Oct)]. The PPO-PDLA-Sn(Oct) can be used as an efficient macroinitiator for the ROP of L-lactide to synthesize three-arm PPO-PDLA-PLLA at 130 ℃, which reduces the occurrence of hydrolysis and transesterification reaction. PPO-PDLA-PLLA copolymers with high molecular weight were synthesized by this novel and simple method. The results show that the composite of PPO-PDLA-PLLA can be easily tuned by controlling the feed ratio of L-lactide and D-lactide, and the stereoregularity of PPO-PDLA-PLLA is high. Moreover, the stereocomplexes of PPO-PDLA-PLLA can survive melting to reform the stereo-complex crystallites.

Key words: End capping, Ring-open polymerization, Stereoblock poly(lactic acid), Three-arm PPO-PDLA-PLLA copolymer, Stereocomplex crystallite

中图分类号: