高等学校化学学报 ›› 2015, Vol. 36 ›› Issue (11): 2329-2334.doi: 10.7503/cjcu20150633

• 高分子化学 • 上一篇    下一篇

PDLA-PBS-PDLA三嵌段共聚物的合成及性能

马丽莉1,3, 邵俊2, 杨晨光1, 汤朝晖1(), 陈学思1()   

  1. 1. 中国科学院长春应用化学研究所, 生态高分子重点实验室, 长春 130022
    2. 江西师范大学化学化工学院, 南昌 330022
    3. 中国科学院大学, 北京 100049
  • 收稿日期:2015-08-11 出版日期:2015-11-10 发布日期:2015-10-26
  • 作者简介:联系人简介: 汤朝晖, 男, 研究员, 主要从事聚酯和聚氨基酸材料研究. E-mail:ztang@ciac.ac.cn;陈学思, 男, 博士, 研究员, 博士生导师, 主要从事生物医用高分子研究. E-mail:xschen@ciac.ac.cn
  • 基金资助:
    国家自然科学基金(批准号: 51273198, 51373169, 51233004, 51303176, 51390484, 51321062, 51403089)和国家“八六三”计划项目(批准号: 2011AA02A202)资助

Synthesis and Property of PDLA-PBS-PDLA Tri-block Copolymer

MA Lili1,3, SHAO Jun2, YANG Chenguang1, TANG Zhaohui1,*(), CHEN Xuesi1,*()   

  1. 1. Key Laboratory of Polymer Ecomaterials, Changchun Institute of Applied Chemistry,Chinese Academy of Sciences, Changchun 130022, China
    2. College of Chemistry and Chemical Engineering, Jiangxi Normal University, Nanchang 330022, China
    3. University of Chinese Academy of Sciences, Beijing 100049, China
  • Received:2015-08-11 Online:2015-11-10 Published:2015-10-26
  • Contact: TANG Zhaohui,CHEN Xuesi E-mail:ztang@ciac.ac.cn;xschen@ciac.ac.cn
  • Supported by:
    † Supported by the National Natural Science Foundation of China(Nos.51273198, 51373169, 51233004, 51303176, 51390484, 51321062, 51403089) and the National High Technology Research and Development Program of Advanced Materials of China(No.2011AA02A202)

摘要:

合成了末端均为羟基的聚丁二酸丁二醇酯(PBS)预聚物, 再以PBS的端羟基引发D-丙交酯(D-LA)开环聚合, 得到聚右旋乳酸(PDLA)与PBS的三嵌段共聚物(PDLA-PBS-PDLA). 通过凝胶渗透色谱和核磁共振氢谱进行了结构表征. 随着m(D-LA):m(PBS)由0.51:1逐渐增加至2.60:1, PDLA-PDS-PDLA中PDLA链段的长度逐渐增加. 随着PDLA嵌段长度的增加, PDLA嵌段对PBS嵌段的限制作用增强, 并导致PBS嵌段结晶温度下降, 结晶焓降低. 当m(D-LA):m(PBS)=2.60:1时, PBS嵌段不再能形成结晶. 而m(D-LA):m(PBS)在0.51:1~3.04:1范围内, PDLA嵌段均可形成结晶, PDLA嵌段的熔点随其在嵌段共聚物中含量的增加而逐渐升高, 但PDLA嵌段的熔融焓呈现先增加后降低的趋势. 在部分嵌段共聚物中, PBS和PDLA嵌段可各自形成结晶, 且PBS和PDLA的结晶结构不随组分的变化而发生改变, 表明该嵌段共聚物中PDLA嵌段和PBS嵌段呈微相分离结构.

关键词: 聚丁二酸丁二醇酯, 右旋聚乳酸, PDLA-PBS-PDLA三嵌段共聚物

Abstract:

Poly(D-lactide)-poly(butylene succinate)-poly(D-Lactide)(PDLA-PBS-PDLA) was synthesized by the ring-opening polymerization of D-lactide(D-LA) in the presence of Sn(Oct)2 and the pre-polymerized PBS as the macro-initiator. The PDLA-PBS-PDLA tir-block polymers were confirmed by gel permeation chromatography(GPC) and nuclear magnetic resonance(1H NMR). Results of differential scanning calorimeter(DSC) and X-ray diffraction(XRD) revealed that with the increase of Mn of PDLA blocks, the melting temperature and enthalpy of PBS blocks decreased, and the crystallites of PBS blocks could not be detected by DSC when m(D-LA):m(PBS) was set as 2.60:1. For all the samples, PDLA segment could crystallize. With the increase of the amount of PDLA in the copolymers, the melting temperature of PDLA blocks increased gradually, but the melting enthalpy of PDLA blocks increased first and then decreased. Furthermore, both PDLA and PBS blocks could crystallize separately, and the crystal structures PDLA and PBS blocks did not change with m(D-LA):m(PBS), which revealed that the microphase separation formed in the copolymers.

Key words: Poly(butylene succinate), Poly(D-lactide), PDLA-PBS-PDLA tri-block copolymer

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