Stereoselective Ring-opening Polymerization of <italic style="font-style: italic">rac</italic>-Lactide Using Chiral Urea/Strong Organobase Binary Catalyst System

Xin-hui Kou; Yong Shen; Zhi-bo Li

doi:10.11777/j.issn1000-3304.2020.20117

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Stereoselective Ring-opening Polymerization of rac-Lactide Using Chiral Urea/Strong Organobase Binary Catalyst System

更新时间：2021-01-26

- Stereoselective Ring-opening Polymerization of rac-Lactide Using Chiral Urea/Strong Organobase Binary Catalyst System
  增强出版
- Acta Polymerica Sinica Vol. 51, Issue 10, Pages: 1121-1129(2020)
- 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　青岛 266042
  2.青岛科技大学化工学院　青岛 266042
- 作者简介：
- 基金信息：
- DOI：10.11777/j.issn1000-3304.2020.20117
  CLC：
- Published：1 September 2020，
  
  Published Online：11 August 2020，
  
  Received：9 May 2020，
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Xin-hui Kou, Yong Shen, Zhi-bo Li. Stereoselective Ring-opening Polymerization of rac-Lactide Using Chiral Urea/Strong Organobase Binary Catalyst System. [J]. Acta Polymerica Sinica 51(10):1121-1129(2020)
DOI：

Xin-hui Kou, Yong Shen, Zhi-bo Li. Stereoselective Ring-opening Polymerization of rac-Lactide Using Chiral Urea/Strong Organobase Binary Catalyst System. [J]. Acta Polymerica Sinica 51(10):1121-1129(2020) DOI： 10.11777/j.issn1000-3304.2020.20117.

摘要

聚乳酸是应用广泛的可降解高分子材料，由于主链重复单元含有手性中心，它的物理与力学性能与其立构规整度密切相关. 丙交酯的开环聚合是制备聚乳酸的重要手段. 除了具有手性中心的金属有机催化剂，手性有机催化剂在丙交酯立构选择性开环聚合中受到越来越多的关注. 本文中，我们用L-苯丙氨酸甲酯(L-Phe-OMe)、L-丙氨酸甲酯(L-Ala-OMe)以及L-缬氨酸甲酯(L-Val-OMe)分别与4-三氟甲基苯异氰酸酯反应得到3种含手性中心的脲(L-Phe-U，L-Ala-U以及L-Val-U). 这些手性脲与有机碱1

8-二氮杂二环十一碳-7-烯(DBU)形成的二元催化体系可以在常温下催化外消旋丙交酯(

rac

-LA)立构选择性开环聚合，制备具有高立构规整度的聚乳酸(

= 0.87). 进一步降低聚合温度可以提高聚乳酸的立构规整度，在−20 °C时

高达0.90. 通过

H同核去耦谱分析发现，

rac

-LA在开环聚合过程中同时存在增长链末端控制机理以及催化剂活性中心控制机理，研究表明增长链末端控制机理对立构规整度的影响随聚合温度降低而增加.

Abstract

Poly(lactic acid)

as a kind of biocompatible and degradable polymer

has considerable potential in a wide range of applications. Because the main chain repeating unit has a chiral center

its physical and mechanical properties are closely related to its stereoregularity. In recent years

chiral organocatalysts have attracted increasing attention in stereoselective ring-opening polymerization (ROP) of lactide in addition to organometallic catalysts with chiral centers. In this contribution

we synthesized three types of chiral ureas (L-Phe-U

L-Ala-U and L-Val-U)

which were prepared by reactions of L-Phenylalanine methyl ester (L-Phe-OMe)

L-alanine methyl ester (L-Ala-OMe) and L-valine methyl ester (L-Val-OMe) with 4-(trifluoromethyl)phenyl isocyanate. They can form binary catalytic system with DBU

which can catalyze the stereoselective ROP of

rac

-lactide (

rac

-LA) to produce stereoblock PLA (

up to 0.87) at room temperature. In addition

the stereoregularity (

) can be improved by reducing the polymerization temperature with regularity as high as 0.90 at −20 °C. Using

H homonuclear decoupling spectroscopy

it was found that the contribution of chain-end control mechanism to stereo-regularity increased with decreasing temperature.

关键词

聚乳酸有机催化剂开环聚合立构选择性

Keywords

Poly(lactic acid)OrganocatalystRing opening polymerizationStereoselectivity

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State Key Laboratory of Organic-Inorganic Composite Materials, Beijing Laboratory of Biomedical Materials, College of Life Science and Technology, Beijing University of Chemical Technology

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Stereoselective Ring-opening Polymerization of rac-Lactide Using Chiral Urea/Strong Organobase Binary Catalyst System

DOI：10.11777/j.issn1000-3304.2020.20117

摘要

Abstract

关键词

Keywords

references