高等学校化学学报 ›› 2018, Vol. 39 ›› Issue (8): 1806.doi: 10.7503/cjcu20170841

• 高分子化学 • 上一篇    下一篇

单取代芳氧钛合成与催化乙烯及乙烯与α-烯烃共聚

王建伟, 任迎春, 米普科(), 许胜()   

  1. 华东理工大学材料科学与工程学院, 化学与分子工程学院, 上海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:2017-12-22 出版日期:2018-08-10 发布日期:2018-05-14
  • 作者简介:联系人简介: 米普科, 男, 教授, 主要从事聚α-烯烃和聚烯烃材料研究. E-mail: pkmi@ecust.edu.cn;许 胜, 男, 博士, 副教授, 主要从事烯烃聚合研究. E-mail: xusheng@ecust.edu.cn
  • 基金资助:
    国家重点研发计划项目(批准号: 2017YFB0306701)和上海重点学科和重点实验室项目(批准号: B502, 08DZ2230500)资助.

Synthesis of TiCl3 Complexes Containing Aryloxy Groups and Application for Ethylene Polymerization and Copolymerization

WANG Jianwei, REN Yingchun, MI Puke*(), XU Sheng*()   

  1. School of Materials Science and Engineering, School of Chemistry and Molecular Engineering,Shanghai Key Laboratory of Advance Materials,Key Laboratory for Ultrafine Materials, Ministry of Education,East China University of Science and Technology, Shanghai 200237, China
  • Received:2017-12-22 Online:2018-08-10 Published:2018-05-14
  • Contact: MI Puke,XU Sheng E-mail:pkmi@ecust.edu.cn;xusheng@ecust.edu.cn

摘要:

使用廉价原料和简单工艺方法合成了芳氧钛类烯烃聚合和共聚催化剂, 得到了(2-OMeC6H4O)TiCl3(C1), (2,4-Me2C6H3O)TiCl3(C2), TiCl3(1,4-OC6H4O)TiCl3(C3), TiCl3(1,4-OC6H2O-Me2-2,5)TiCl3(C4)以及相应的(ArO)2TiCl2类络合物TiCl2(OC6H4-OMe-2)2(C5) 和 TiCl2(OC6H3-Me2-2,6)2(C6). 通过 1H NMR, 13C NMR, MS以及元素分析进行了结构表征, 确认了化学组成, 以甲基铝氧烷(MAO)为助催化剂, ArOTiCl3/MAO体系显示了对乙烯聚合和共聚的高活性, 13C NMR结果表明, 聚合物中1-己烯插入率最高达6.88%(摩尔分数), 而且得到的聚合物呈现高度支化, 除了α-烯烃支链, 还有甲基、 乙基和长支链, 并对其形成机理进行了研究, 此外, 对聚合温度、 时间及共聚单体浓度对聚合反应的影响也进行了探讨.

关键词: ArOTiCl3类络合物, 烯烃聚合催化剂, 乙烯/1-己烯共聚

Abstract:

Novel olefin polymerization catalysts with lower cost and simple synthetic process were developed. ArOTiCl3 complexes[(2-OMeC6H4O)TiCl3(C1), (2,4-Me2C6H3O)TiCl3(C2), TiCl3(1,4-OC6H4O)TiCl3(C3), TiCl3(1,4-OC6H2O-Me2-2,5)TiCl3(C4)] and corresponding (ArO)2TiCl2 complexes [TiCl2·(OC6H4-OMe-2)2(C5) and TiCl2(OC6H3-Me2-2,6)2(C6)] were synthesized and well characterized. When combined with methylaluminoxane(MAO), the ArOTiCl3 /MAO system shows moderate activity for ethylene copolymerization with 1-hexene. The 13C NMR result of polymer indicates that the 1-hexene incorporation in polymer reached up to 6.88%(molar fraction). The polymer was characterized by 13C NMR and the mechanisms of methyl, ethyl and long side chain formation were given. The effects of polymerization temperature, concentration of polymerization monomer and polymerization time on the catalytic activity were investigated.

Key words: ArOTiCl3 complex, Olefin polymerization catalyst, Ethylene/1-hexene copolymerization

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