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二茂钛/锡/环氧化合物引发苯乙烯活性自由基聚合的研究
  • ISSN号:1000-3304
  • 期刊名称:《高分子学报》
  • 时间:0
  • 分类:O631.5[理学—高分子化学;理学—化学] TQ325.3[化学工程—合成树脂塑料工业]
  • 作者机构:[1]北京化工大学化工资源有效利用国家重点实验室材料科学与工程学院,北京100029, [2]中国石油化工股份有限公司北京化工研究院,北京100013
  • 相关基金:国家自然科学基金(基金号20574003)资助项目、北京市教委重点学科共建项目(项目号XK100100540,XK100100640)
中文摘要:

采用单茂钛CpTiCl3和二茂钛金属化合物(n—BuCp)2 TiCl2,引发剂4-甲氧苯基缩水甘油基醚(I1),1,4-丁二醇二缩水甘油基醚(I2),4,4'-亚甲基二(N,N-二缩水甘油基苯胺)(I4)和苯基缩水甘油基醚甲醛共聚物(I5)及还原剖Sn组成引发体系,引发苯乙烯活性自由基聚合,合成线型和多臂聚合物。探讨了不同茂钛金属化合物、引发剂和还原剂对苯乙烯聚合的影响;并采用^13 C-NMR和GPC对聚苯乙烯的结构和性能进行了表征。结果表明所得聚合物是无规聚苯乙烯,聚合物分子量高,分子量分布窄。聚合行为属于活性自由基聚合。

英文摘要:

Linear and multi-arm atactic polystyrene with functional groups --OH was synthesized via living freeradical polymerization promoted by titanocene complexes in the presence of glycidyl-4-methoxyphenyl ether (I1), 1, 4-butanediol diglycidyl ether ( I2 ), 4,4'-methylenebis ( N, N-diglycidylaniline ) ( I4 ) and poly [ ( phenylglycidyl ether)-co-formaldehyde] (I5) as initiators, and Sn as reducing agent in this catalyst system. The polymerization mechanism was expatiated. In this article, for the first time, titanocene complexes, for example CpTi( Ⅳ )Cl3 was treated with Sn to form primary free radical CpTi' (Ⅲ)Cl2 at room temperature, this radical reacted with epoxide(initiator) to give the chain radical which initiated styrene to propagate successfully. The effect of polymerization conditions, such as the structure of the initiator and titanocene complexes, as well as the ratio of initiator to monomers on' the performance was investigated. The properties of the obtained polymer were also characterized by GPC. These results showed that the structure of initiator had little influence on the conversion of monomer, the molecular weight and molecular weight distribution of the obtained polymer. Compared with ( n-BuCp)2TiCl2 andSiMe2 (Ind)2TiCl2, half-titanocene, CpTICl3 was favorable for the polymerization of styrene via radical mechanism. The monomer conversion was more than 80%, the molecular weight of the polymer was higher than 1.0 × 10^5 , and the molecular weight distribution was at the range of 1.18 to 1.42. However, when ( n-BuCp)2TiCl2 and SiMe2 (Ind)2TiCl2 were used as catalysts, the monomer conversion and the molecular weight of the obtained polymer were lower. But the structure of titanocene complex had less impact on the molecular weight distribution (1.26-1.30).The effect of the ratio of monomer to initiator on the polymerization performance was also studied. A linear dependence of M, of the obtained polymer on the monomer concentration was

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期刊信息
  • 《高分子学报》
  • 中国科技核心期刊
  • 主管单位:中国科学院
  • 主办单位:中国化学会 中国科学院化学研究所
  • 主编:张希
  • 地址:北京市海淀区中关村北一街2号
  • 邮编:100190
  • 邮箱:gfzxb@iccas.ac.cn
  • 电话:010-62588927
  • 国际标准刊号:ISSN:1000-3304
  • 国内统一刊号:ISSN:11-1857/O6
  • 邮发代号:2-498
  • 获奖情况:
  • 国家优秀期刊二等奖,中科院优秀期刊二等奖,中国科协优秀期刊
  • 国内外数据库收录:
  • 俄罗斯文摘杂志,美国化学文摘(网络版),荷兰文摘与引文数据库,美国科学引文索引(扩展库),英国高分子图书馆,日本日本科学技术振兴机构数据库,中国中国科技核心期刊,中国北大核心期刊(2004版),中国北大核心期刊(2008版),中国北大核心期刊(2011版),中国北大核心期刊(2014版),中国北大核心期刊(2000版)
  • 被引量:19174