高等学校化学学报 ›› 2015, Vol. 36 ›› Issue (3): 575.doi: 10.7503/cjcu20140932

• 高分子化学 • 上一篇    下一篇

新型双苯并环己酮芳亚胺镍(Ⅱ)催化降冰片烯与甲基丙烯酸丁酯共聚合

贺晓慧(), 刘菁胤, 陈璐, 朱宏宇, 王娟   

  1. 南昌大学材料科学与工程学院, 南昌 330031
  • 收稿日期:2014-10-22 出版日期:2015-03-10 发布日期:2015-01-23
  • 作者简介:联系人简介: 贺晓慧, 女, 博士, 教授, 主要从事后过渡金属催化剂合成及烯烃催化配位聚合研究. E-mail: hexiaohui@ncu.edu.cn
  • 基金资助:
    国家自然科学基金(批准号: 21164006, 51463014) 和江西省主要学科学术和技术带头人培养计划项目(批准号: 赣财教指[2013]146 号)资助

Copolymerization of Norbornene and n-Butyl Methacrylate Catalyzed by Novel Ni(Ⅱ)(benzocyclohexan-ketoarylimino) 2

HE Xiaohui*(), LIU Jingyin, CHEN Lu, ZHU Hongyu, WANG Juan   

  1. School of Materials Science and Engineering, Nanchang University, Nanchang 330031, China
  • Received:2014-10-22 Online:2015-03-10 Published:2015-01-23
  • Contact: HE Xiaohui E-mail:hexiaohui@ncu.edu.cn
  • Supported by:
    † Supported by the National Natural Science Foundation of China(Nos.21164006, 51463014) and the Cultivation Projects of Main Subject of Academic and Technical Leader of Jiangxi Province, China(No.[2013]146)

摘要:

采用自制的新型双苯并环己酮芳亚胺镍催化剂双苯并环己酮-2,6-二甲基苯亚胺镍(Ⅱ)(Ni{C10H8(O)C[2,6-C6H3(CH3)2N]CH3}2, C1)和双苯并环己酮-2,6-二氯苯亚胺镍(Ⅱ)(Ni{C10H8(O)C[2,6-C6H3Cl2N]CH3}2, C2)与三五氟苯硼[B(C6F5)3]结合, 在一定的反应条件下可高效催化降冰片烯(NB)与甲基丙烯酸正丁酯(n-BMA)的乙烯基加成共聚合. 提出了催化聚合时存在的可能失活机理; 研究了不同单体投料比对催化活性、 产率及产物性能的影响. 根据Kelen-Tüdõs方法分别估算出2种单体在不同催化体系下的竞聚率, 即当催化体系为C1/B(C6F5)3时, 竞聚率rn-BMA=0.02, rNB=16.28, rNB·rn-BMA=0.32; 当催化体系为C2/B(C6F5)3时, rn-BMA=0.01, rNB=64.83, rNB·rn-BMA=0.65. 结果表明, 2种单体在2种体系催化下均为无规共聚合.

关键词: 镍催化剂, 降冰片烯, 甲基丙烯酸正丁酯, 竞聚率, 加成共聚合

Abstract:

Vinyl-addition copolymerization of norbornene(NB) and polar monomer n-butyl methacrylate(n-BMA) were carried out via two novel high activity catalysts, Ni(Ⅱ)(benzocyclohexan-ketoarylimino)2 (Ni{C10H8(O)C[2,6-C6H3(CH3)2N]CH3}2, C1) and Ni{C10H8(O)C[2,6-C6H3Cl2N]CH3}2, C2), in combination with tris(pentafluorophenyl)-borance[B(C6F5)3]. A possible catalytic deactivation mechanism of polymerization was presented. Influence of monomer feed ratio on catalytic activity, conversion rate and properties of outcomes were investigated. Reactivity ratios of co-monomers were estimated by Kelen-Tüdõs method, they are rn-BMA=0.02, rNB=16.28, rNB·rn-BMA=0.32 for C1/B(C6F5)3 catalytic system, and rn-BMA=0.01, rNB=64.83, rNB·rn-BMA=0.65 for C2/B(C6F5)3 catalytic system. These indicate the random copolymerization of NB/n-BMA occurs with both C1/B(C6F5)3 and C2/B(C6F5)3.

Key words: Nickel complex, Norbornene, n-Butyl methacrylate, Reactivity ratio, Addition copolymerization

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