高等学校化学学报 ›› 2014, Vol. 35 ›› Issue (9): 2007-2013.doi: 10.7503/cjcu20140468

• 高分子化学 • 上一篇    下一篇

极性单体锂系阴离子嵌段共聚物的合成与表征

陈波, 王继铭, 束民泽, 邹斌, 管涌, 郑安呐   

  1. 华东理工大学材料科学与工程学院, 上海市先进聚合物材料重点实验室,超细材料制备与应用教育部重点实验室, 上海 200237
  • 收稿日期:2014-05-19 出版日期:2014-09-10 发布日期:2019-08-01
  • 作者简介:联系人简介: 郑安呐, 男, 博士, 教授, 博士生导师, 主要从事阴离子聚合及反应挤出研究. E-mail: zan@ecust.edu.cn
  • 基金资助:
    基金项目: 国家自然科学基金(批准号: 50933002)资助

Synthesis and Characterization of Block Copolymers with PMMA Segment Initiated by Organic Lithium

CHEN Bo, WANG Jiming, SHU Minze, ZOU bin, GUAN Yong, ZHENG Anna*   

  1. School of Materials Science and Engineering, Shanghai Key Laboratory of Advanced Polymeric Materials, Key Laboratory for Ultrafine Materials of Ministry of Education, East China University of Science and Technology, Shanghai 200237, China
  • Received:2014-05-19 Online:2014-09-10 Published:2019-08-01
  • Contact: ZHENG Anna
  • Supported by:
    Supported by the National Natural Science Foundation of China(No.50933002)

摘要:

以酚锂作为副反应抑制剂, 以正丁基锂或1,1-二苯基乙烯盖帽的正丁基锂为引发剂, 通过顺次添加单体的方法, 合成了结构明确的聚异戊二烯-b-聚甲基丙烯酸甲酯(PI-b-PMMA)和聚甲基丙烯酸正丁酯-b-聚甲基丙烯酸甲酯(PBMA-b-PMMA)2种嵌段聚合物. 嵌段聚合反应中甲基丙烯酸甲酯(MMA)的转化率均高于90%, 通过核磁图谱计算的链节摩尔比与理论设计值吻合. PI-b-PMMA和PBMA-b-PMMA的分子量分别达到4×104和1.6×104. 在环己烷中, 通过顺次添加单体的方法, 合成了结构明确的聚苯乙烯-b-聚异戊二烯-b-聚甲基丙烯酸甲酯(PS-b-PI-b-PMMA)三嵌段共聚物, 各单体的转化率均达到100%, 并且产物中的链节摩尔比和理论设计值一致, 最终产物的分子量达到7.4×104, 分子量分布仅为1.28, 为极性三嵌段热塑性弹性体以及有机玻璃透明增韧剂的工业化奠定了基础.

关键词: 阴离子活性聚合, 酚锂, 甲基丙烯酸甲酯, 嵌段共聚物

Abstract:

Well-defined block copolymers polyisoprene-b-poly(methyl methacrylate)(PI-b-PMMA) and poly(butyl methacrylate)-b-poly(methyl methacrylate)(PBMA-b-PMMA were synthesized in THF initiated by n-BuLi and DPHLi with the addition of P-Complex. The polymerizations were carried out under the conditions which could be achieved in industry through adding monomers by sequence. The conversion of MMA was higher than 90% both in PI-b-PMMA and PBMA-b-PMMA, and the molar ratios of each segment in block copolymers detected by 1H NMR fit to those calculated. The Mn of PI-b-PMMA and PBMA-b-PMMA were 4.0×104 and 1.6×104, respectively. Well-defined triblock polymer PS-b-PI-b-PMMA was synthesized in cyclohexane under the condition which could be achieved in industry. The conversions of monomers were all completed, and the molar ratio in the final triblock polymer was consistent to the one calculated. The final Mn was 7.4×104, and the molecular weight distribution(MWD) was only 1.28.

Key words: Living anionic polymerization, Lithium phenoxide, Methyl methacrylate, Block copolymer

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