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研究了茂金属催化体系[2-C5Me4-6-tBuC6H3O]TiCl2/Al(iBu)3/Ph3CB(C6F5)4催化5-亚乙烯基-2-降冰片烯(ENB)与乙烯(E)的共聚反应。考察了聚合条件对催化活性、共聚物中ENB的含量和共聚物分子量的影响。利用氢核磁共振谱(1H-NMR)、差示扫描量热仪(DSC)和凝胶渗透色谱仪(GPC)对合成的共聚物进行表征。结果表明,在ENB/E共聚反应中,ENB环内双键参与聚合,ENB环外双键(亚乙烯基)保留。合成了ENB物质的量分数高达50.1%和玻璃化转变温度高达170.5℃的共聚物。合成的共聚物分子量分布较窄(PDI=1.93~2.11),最高分子量达到193 kg/mol。

Copolymerization of 5-Ethylidene-2-norbornene(ENB) with ethylene(E) was performed using metallocene 2-tetramethylcyclopentadienyl-6-butylphenoxytitanium dichloride in the presence of Al(iBu)3 and Ph3CB(C6F5)4.The effect of the reaction conditions on the catalytic activity,content of ENB in the poly(E-co-ENB),and molecular weight of the produced copolymers was examined.The resultant copolymers were characterized using 1H-NMR,GPC and DSC techniques.The results show that ENB is regiosectively incorporated into the copolymer backbone through the endocyclic double bond,leaving the ethylidene group unreacted.High ENB content(mass fraction 50.1%) copolymer with high glass transition temperature(170.5 ℃) was obtained.The resulting copolymers possessed narrow molecular weight distributions(PDI=1.93~2.11).High molecular weight of 193 kg/mol was achieved.

参考文献

[1] Kaminsky W.;Arndt-Rosenau M.;Beulich I. .Copolymerization of ethene with cyclic and other sterically hindered olefins[J].Macromolecular symposia,2001(0):211-225.
[2] 洪浩群,何慧,贾德民,丁超,徐焕翔.聚烯烃功能化的研究进展[J].高分子材料科学与工程,2006(06):23-27.
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