高等学校化学学报 ›› 2018, Vol. 39 ›› Issue (8): 1853-1858.doi: 10.7503/cjcu20180089

• 高分子化学 • 上一篇    

苯氧基亚胺钛催化降冰片烯与1-辛烯共聚合

孟嘉锋1, 倪旭峰1(), 郑豪2(), 沈之荃1   

  1. 1. 高分子合成与功能构造教育部重点实验室, 浙江大学高分子科学与工程学系, 杭州 310027
    2. 浙江大学海洋学院海洋化学与环境研究所, 舟山 316021
  • 收稿日期:2018-01-29 出版日期:2018-08-10 发布日期:2018-06-26
  • 作者简介:联系人简介: 郑 豪, 女, 博士, 副教授, 主要从事功能高分子材料和海洋化学研究. E-mail: zhenghao@zju.edu.cn; 倪旭峰, 男, 博士, 副教授, 主要从事高分子合成和应用研究. E-mail: xufengni@zju.edu.cn
  • 基金资助:
    国家自然科学基金(批准号: U1709201, 21174121)资助.

Copolymerization of Norbornene and 1-Octene Catalyzed by Bis(phenoxy-imine) Titanium Complex

MENG Jiafeng1, NI Xufeng1,*(), ZHENG Hao2,*(), SHEN Zhiquan1   

  1. 1. Key Laboratory of Macromolecular Synthesis and Functionalization, Ministry of Education,Department of Polymer Science and Engineering, Zhejiang University, Hangzhou 310027, China
    2. Institute of Marine Chemistry and Environment, Ocean College, Zhejiang University, Zhoushan 316021, China
  • Received:2018-01-29 Online:2018-08-10 Published:2018-06-26
  • Contact: NI Xufeng,ZHENG Hao E-mail:xufengni@zju.edu.cn;zhenghao@zju.edu.cn
  • Supported by:
    † Supported by the National Natural Science Foundation of China(Nos.U1709201, 21174121).

摘要:

以3,5-二叔丁基水杨醛缩苯胺氯化钛(Ti)、 三异丁基铝(Al)和四(五氟苯基)硼酸三苯基甲酯(B)组成的三元催化体系实现了降冰片烯(NBE)与1-辛烯(OC)的共聚合, 得到NOC无规共聚物. 探索了催化剂组成、 聚合时间及聚合温度等对共聚合反应的影响. 结果表明, 当n(Al)/n(Ti)=5:1, n(B)/n(Ti)=1:1, n(Monomer)/n(Ti)=400:1, n(NBE)/n(OC)=5:5 时, 于40 ℃在甲苯中聚合6 h, 共聚合产率达到43.7%, 2种单体的竞聚率分别为rNBE=3.01; rOC=0.08. 改变助催化剂三异丁基铝的用量可在一定范围内调节所得NOC无规共聚物的分子量及分子量分布(MWD), 得到Mw=3.0×104~6.5×104, MWD=1.91~2.45的NOC共聚物. NOC无规共聚物具有饱和的主链结构且带有较长的侧链, 其玻璃化转变温度较高(约87~174 ℃), 并对NOC无规共聚物组成具有很强依赖性. NOC共聚物的热分解温度超过300 ℃, 热稳定性能优异.

关键词: 苯氧基亚胺钛, 降冰片烯, 1-辛烯, 无规共聚物, 热稳定性

Abstract:

The copolymer of norbornene with 1-octene was prepared by the catalysis of the ternary catalytic system consisted of bis(phenoxy-imine) titanium complex(Ti), triisobutyl aluminum(Al) and organoboron compound(B). The obtained copolymer showed a modest molecular weight(Mw: ca. 3.0×104—6.5×104) and broad molecular weight distribution(MWD: ca. 2.0). The influence of copolymerization conditions was explored. The optimal copolymerization conditions are as follows: n(Al)/n(Ti)=5:1, n(B)/n(Ti)=1:1, n(Monomer)/n(Ti)=400:1, n(NBE)/n(OC)=5:5, polymerized at 40 ℃ for 6 h and the copolymer yield reached up to 43.7%. The reactivity ratios of norbornene and 1-octene were 3.01 and 0.08, respectively, tending to form a random copolymer. The copolymer exhibited good thermal stability(Td>300 ℃) and moderate glass transition temperature(Tg=87—174 ℃) controlled by the content of norbornene in the backbone.

Key words: Bis(phenoxy-imine) titanium complex, Norbornene, 1-Octene, Random copolymer, Thermal stability

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