Ring-opening Polymerization of Lactide by Bifunctional Organocatalyst at Ambient Conditions

Hai-qiang Li; Jing-yi Wang; Li Wu; Wei Liu; Rui-hua Cheng; Bo-ping Liu

doi:10.11777/j.issn1000-3304.2019.19080

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Ring-opening Polymerization of Lactide by Bifunctional Organocatalyst at Ambient Conditions

Research Article | 更新时间：2021-01-26

- Ring-opening Polymerization of Lactide by Bifunctional Organocatalyst at Ambient Conditions
- Acta Polymerica Sinica Vol. 50, Issue 12, Pages: 1290-1297(2019)
- 作者机构：
  
  1.华东理工大学化学工程联合国家重点实验室　上海 200237
  2.华南农业大学材料与能源学院　广州 510642
- 作者简介：
- 基金信息：
- DOI：10.11777/j.issn1000-3304.2019.19080
  CLC：
- Published：2019-12，
  
  Published Online：6 June 2019，
  
  Received：17 April 2019，
  
  Revised：15 May 2019，
扫描看全文
Hai-qiang Li, Jing-yi Wang, Li Wu, Wei Liu, Rui-hua Cheng, Bo-ping Liu. Ring-opening Polymerization of Lactide by Bifunctional Organocatalyst at Ambient Conditions. [J]. Acta Polymerica Sinica 50(12):1290-1297(2019)
DOI：

Hai-qiang Li, Jing-yi Wang, Li Wu, Wei Liu, Rui-hua Cheng, Bo-ping Liu. Ring-opening Polymerization of Lactide by Bifunctional Organocatalyst at Ambient Conditions. [J]. Acta Polymerica Sinica 50(12):1290-1297(2019) DOI： 10.11777/j.issn1000-3304.2019.19080.

摘要

采用3种氨基甲酰基季铵盐双功能有机小分子催化剂考察了丙交酯的溶液聚合与本体聚合. 催化剂由二甲酰亚胺和季铵盐在回流条件下以定量收率制备，原料廉价易得，在空气中性质稳定且毒性低，可在温和无惰性气体保护条件下催化丙交酯的开环聚合. 在以甲苯为溶剂的聚合条件下，

催化剂(2-氨基甲酰基苯甲酸四乙基铵)常温常压下反应1 h，丙交酯转化率为42.7%. 由正交法得出的最佳聚合条件下，丙交酯/

催化剂/叔丁醇钠的摩尔比为200/10/1，75 °C，反应4 h后，丙交酯转化率为88.5%，产物聚乳酸的分子量为8.03 kg·mol

−1

. 采用本体聚合的方法，3种催化剂均可在无引发剂的条件下合成聚乳酸. 通过调控引发剂、金属醇盐及温度条件合成的聚乳酸，在150 °C下丙交酯转化率达95.7%. 几种方式所得产物熔融温度在130 ~ 134 °C之间. 产物经MALDI-TOF-MS表征，证实氨基甲酰基季铵盐催化剂具有协同双重活化单体和引发剂/链端的性能，双功能团位于同一结构中.

Abstract

Ring-opening polymerization of lactide (LA) is one of the most important techniques to synthesize poly(lactic acid) (PLA). In this work

a series of organocatalysts have been prepared for both solution polymerization and bulk polymerization of LA at ambient conditions. Derived from the facile reactions between phthalimide and quaternaryammonium salt

these catalysts are inexpensive and stable in air. Tetraethylammonium 2-aminobenzoate (TEACB) (catalyst

) was first applied to polymerize LLA in toluene solvent

and a conversion of 42.7% was achieved after the reaction proceeded at 25 °C for 1 h. Orthogonal experiments suggested that the optimum condition was reaction temperature of 75 °C

reaction time of 4 h

and the molar ratio of lactide:catalyst

:alkoxide equal to 200:10:1

which afforded PLA product with molecular weight of 8.03 kg·mol

–1

polydispersity index (PDI) of 1.53

and a high conversion of 88.5%. Next

bulk polymerization of LLA was carried out at different temperatures to explore the effects of initiator

alcohol salt

reaction time

and the molar ratio of lactide:catalyst:alkoxide. The catalytic activity of the catalysts depended largely on their chemical structures. Under the same reaction temperature

catalyst

with larger cation part led to a higher conversion; meanwhile

catalysts

and

with phenyl group in the anionic part were more active than catalyst

bearing an aliphatic group although the latter produced PLA with higher molecular weight and narrower molecular weight distribution. The catalysts developed in this study worked well in the absence of alkoxide

whilst alkoxide and alcohol could improve the performance of the catalyst system. LLA polymerizations could be conveniently performed under atmospheric conditions and increasing temperature resulted in PLA products with higher molecular weight and narrower molecular weight distribution. The conversion reached up to 95.7% after polymerization at 150 °C

in which the

and PDI of the PLA product equaled 2.57 kg·mol

–1

and 1.24

respectively. DSC measurements indicated that PLAs obtained

via

varied methods displayed similar melting temperatures in the range of 130 – 134 °C. Further

cooperative dual activation of both the monomer and the initiator/chain-end could be confirmed based on MALDI-TOF-MS analyses. This novel catalyst system possesses specific monocomponent hetero-bifunction with H-bonding capability.

关键词

丙交酯双功能有机小分子催化剂开环聚合聚乳酸

Keywords

LactideBifunctional organocatalystRing-opening polymerizationPoly(lactic acid)

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