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含吡啶配体的钌催化剂合成及在离子液体中开环易位聚合反应
  • ISSN号:0251-0790
  • 期刊名称:《高等学校化学学报》
  • 时间:0
  • 分类:O631.5[理学—高分子化学;理学—化学]
  • 作者机构:[1]华东师范大学化学系,上海200062
  • 相关基金:国家自然科学基金(批准号:20474017)资助.
中文摘要:

合成了离子液体负载的钌催化剂,考察了该催化剂在离子液体中对极性环烯烃单体的开环易位聚合(ROMP)反应规律.首先设计合成含离子液体的吡啶配体1,2-二甲基-3-己氧基吡啶六氟磷酸盐咪唑离子液体配体,利用其与Grubbs第二代催化剂配位反应,制备离子液体负载的钌催化剂,通过^1H,^13C NMR等方法对合成的化合物和催化剂进行表征.催化剂中与钌连接的苯亚甲基上氢(Ru=CH—Ph)的振动峰由原来Grubbs第二代催化剂的619.2移至618.6,表明得到了新的催化剂,ICP测定催化剂混合物中纯催化剂的质量分数为36.2%.该催化剂易溶于丙酮、甲醇及咪唑类离子液体等极性溶剂,解决了Grubbs催化剂不溶于离子液体的问题,实现了在纯离子液体中均相ROMP反应.考察了催化剂对极性单体5-羟基环辛烯在离子液体[BMIm]BF4中的ROMP反应规律,研究了离子液体中ROMP反应动力学.

英文摘要:

Ring-opening metathesis polymerization (ROMP) is a widespread tool to synthesize well-defined and highly functionalized polymers. The catalyst is a key factor which affects the polymerization behavior. The Grubbs' catalysts have good solubility in non-polar solvents such as CH2Cl2, benzene, THF, and toluene, but their solubility in polar solvents such as alcohol, acetone, and ionic liquid is usually very poor, which limited their application for ROMP in polar solvents. In this paper, the pyridyl-based imidazolium salt-supported ruthenium catalyst was synthesized and its use in polymerization of polar cyclooctene derivative in ionic liquid [ BMIm ] BF4 was investigated. The novel pyridyl-based ligand 2,3-dimethyt-1- [ 6- (4-pyridyloxy) hexyl ] imidazol-1-ium hexafluorophosphate was first synthesized, and then the pyridyl ligand coordinated with the second generation Grubbs catalyst to generate the imidazolium salt-supported ruthenium catalyst. The characterizations of the synthesized compounds, the ligand, and the catalyst were undertaken by NMR analyses. In ^1H NMR spectroscopy, the signal of the benzylidene proton shifted from δH19.2 in the second generation Grubbs catalyst upfield to δH 18.6 in the novel catalyst, which meant the ligand exchange had occurred successfully and the novel catalyst formed indeed. The novel imidazolium salt-supported ruthenium catalyst is soluable in CH2Cl2, alcohol, acetone, and ionic liquid, thus, ROMP in pure ionic liquid could be carried out. ROMP of the polar monomer 5-hydroxyl-1-cyclooctene was explored in ionic liquid [ BMIm] BF4. The polymerizations of the monomer performed conveniently under varied reaction conditions, and the conversion of monomer reached to more than 95%. The results also proved that the ionic liquid of [ BMIm] BF4 without group of methyl (-CH3 ) in 2-position couldn't result in the poisoning of Grubbs' catalyst, and had no influence on the activity of the catalyst. GPC measurement showed the polymer had controlled molecular wei

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期刊信息
  • 《高等学校化学学报》
  • 北大核心期刊(2011版)
  • 主管单位:中华人民共和国教育部
  • 主办单位:吉林大学 南开大学
  • 主编:周其凤
  • 地址:吉林大学南胡校区
  • 邮编:130012
  • 邮箱:cjcu@jlu.edu.cn
  • 电话:0431-88499216
  • 国际标准刊号:ISSN:0251-0790
  • 国内统一刊号:ISSN:22-1131/O6
  • 邮发代号:12-40
  • 获奖情况:
  • 首届及第二届国家期刊奖,连续两届“百种中国杰出学术期刊”,中国期刊方阵“双高”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,美国工程索引,美国科学引文索引(扩展库),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),英国英国皇家化学学会文摘,中国北大核心期刊(2000版)
  • 被引量:50676