高热稳定Lewis酸碱对催化L-丙交酯均聚及与乙交酯共聚的本体开环聚合研究

马钰琨; 沈勇; 李志波

doi:10.11777/j.issn1000-3304.2022.22042

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高热稳定Lewis酸碱对催化L-丙交酯均聚及与乙交酯共聚的本体开环聚合研究

研究论文 | 更新时间：2024-10-08

- 高热稳定Lewis酸碱对催化L-丙交酯均聚及与乙交酯共聚的本体开环聚合研究
- Bulk Ring-opening Polymerization of L-Lactide and Its Copolymerization with Glycolide Catalyzed by Highly Thermal Stable Lewis Pairs
- 高分子学报 2022年53卷第8期页码：923-932
- 作者机构：
  
  1.山东省高等学校生物基高分子材料重点实验室青岛科技大学高分子科学与工程学院
  2.青岛科技大学化工学院青岛 266042
- 作者简介：
  
  E-mail: shenyong@qust.edu.cn
  zbli@qust.edu.cn
- 基金信息：
  
  国家自然科学基金(基金号 ┣22031005);22075160┫;国家重点研究计划(2021YFA1500095)
- DOI：10.11777/j.issn1000-3304.2022.22042
  中图分类号：
- 纸质出版日期：2022-08-20，
  
  网络出版日期：2022-06-20，
  
  收稿日期：2022-02-17，
  
  录用日期：2022-03-24
- 稿件说明：
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马钰琨,沈勇,李志波.高热稳定Lewis酸碱对催化L-丙交酯均聚及与乙交酯共聚的本体开环聚合研究[J].高分子学报,2022,53(08):923-932.

Ma Yu-kun,Shen Yong,Li Zhi-bo.Bulk Ring-opening Polymerization of L-Lactide and Its Copolymerization with Glycolide Catalyzed by Highly Thermal Stable Lewis Pairs[J].ACTA POLYMERICA SINICA,2022,53(08):923-932.
马钰琨,沈勇,李志波.高热稳定Lewis酸碱对催化L-丙交酯均聚及与乙交酯共聚的本体开环聚合研究[J].高分子学报,2022,53(08):923-932. DOI： 10.11777/j.issn1000-3304.2022.22042.

Ma Yu-kun,Shen Yong,Li Zhi-bo.Bulk Ring-opening Polymerization of L-Lactide and Its Copolymerization with Glycolide Catalyzed by Highly Thermal Stable Lewis Pairs[J].ACTA POLYMERICA SINICA,2022,53(08):923-932. DOI： 10.11777/j.issn1000-3304.2022.22042.

摘要

聚丙交酯(PLA)和乙交酯-丙交酯共聚酯(PLGA)是性能优异的可降解聚酯材料，发展绿色、环境友好的催化剂实现丙交酯和乙交酯的本体熔融聚合具有重要的科学意义和实际应用价值. 本文研究了ZnCl

、MgCl

和FeCl

与3种有机碱构成的Lewis酸碱对在丙交酯(LA)本体熔融聚合的催化作用. 研究了包括Lewis酸碱对类型、比例和反应时间对LA开环聚合反应的影响. 这3类Lewis酸碱对在180 ℃高温下表现出较好的热稳定性和催化活性. 其中FeCl

/DBU催化体系能够同时实现高单体转化率和分子量. 同时，FeCl

/DBU能够有效催化LA和GA的随机共聚，通过调控LA和GA的单体投料比可以制备不同摩尔组成的PLGA共聚酯.

Abstract

Polylactide (PLA) and poly(lactic-

-glycolic acid) (PLGA) are degradable polyesters with excellent properties. It is p

ractically important to develop green and environment friendly catalysts that can realize the bulk melt ring opening polymerization (ROP) of lactide and its copolymerization with glycolide. In this work

we report the bulk polymerization of lactide catalyzed by Lewis pairs composed of ZnCl

MgCl

or FeCl

and three different oganobases. We then systematically studied the effects of Lewis pair structures

mixing ratios and polymerization time on the ROP of lactide. The three types of Lewis pairs all showed great thermal stability and high catalytic activities at 180 ℃. In particular

the combination of FeCl

/DBU can effectively catalyze the ROP of lactide and its copolymerization with glycolide at 180 ℃ to obtain high monomer conversion and high molecular weight at the same time. The resulting PLA homopolymer can reach molecular weight as high as 64.2 kg/mol

via

bulk polymerization

which are comparable to other metal catalytic systems. The molecular structures of PLLA and PLGA copolymer were verified by

H-NMR spectroscopy and MALDI-TOF MS. The microstructures of the PLGA copolymers were carefully analyzed by

C-NMR

and the results showed that the monomer sequence lengths can be easily modulated by varying the feeding ratio of two monomers. The resulting PLGA copolymer were all amorphous solids

and the glass transition temperature decreased with the increase of GA contents.

关键词

聚乳酸丙交酯开环聚合路易斯酸碱对可降解高分子

Keywords

PolylactideLactideRing opening polymerizationLewis acid-base pairDegradable polymer

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