新型α-二亚胺镍配合物的合成及其对乙烯聚合的催化  

Synthesis of a new α-diimine nickel complex for ethylene polymerization

作　　者：杨敏[1] 李向柳 崔咪咪 孟浩[2,3] 姜湃 宋小雪 侯彦辉 YANG Min;LI Xiang-liu;CUI Mi-mi;MENG Hao;JIANG Pai;SONG Xiao-xue;HOU Yan-hui(School of Chemical Engineering and Technology,Hebei University of Technology,Tianjin 300130,China;School of Material Science and Engineering,Tianjin Polytechnic University,Tianjin 300387,China;State Key Laboratory of Separation Membranes and Membrane Processes,Tianjin Polytechnic University,Tianjin 300387,China)

机构地区：[1]河北工业大学化工学院,天津300130 [2]天津工业大学材料科学与工程学院,天津300387 [3]天津工业大学省部共建分离膜与膜过程国家重点实验室,天津300387

出　　处：《天津工业大学学报》2018年第4期42-47,共6页Journal of Tiangong University

基　　金：河北省自然科学基金资助项目(B2015202049)

摘　　要：为了提高催化剂的热稳定性,设计合成了一种新型的大骨架结构的α-二亚胺配体L及其Ni(Ⅱ)配合物Cat,并采用红外(FTIR)、核磁(NMR)、元素分析(EA)等手段对其进行了表征,进而探究了在助催化剂一氯二乙基铝的作用下,聚合温度、压力及铝镍比等因素对催化性能的影响,并采用DSC、GPC、13C NMR分别对聚乙烯产物进行了表征.结果表明:压力的增加将导致聚合活性的增加,在聚合压力为0.5 MPa时,催化剂的活性随着温度先升后降,并在温度为50℃时达到最高值为4.22×106 g/(mol·h).同时,当聚合温度从50℃升高至70℃后,聚乙烯数均分子质量从143 kg/mol降低到125 kg/mol,支化度则从125个支链/1 000 C升高到了135个支链/1 000 C.A newα-diimine compound L with larger size backbone substituents and its corresponding Ni(II)complex Cat were successfully synthesized and were characterized by IR,NMR and EA.In the presence of cocatalyst,the influence of polymerization temperature,ethylene pressure and Al/Ni on the catalytic properties were investigated in detail.The polyethylene(PE)samples were characterized by DSC,GPC and 13C-NMR.The increasing of ethylene pressure made the catalytic activity increase.Under pressure of 0.5 MPa,the activity firstly increased and then decreased quickly with the temperature and reached a maximum at 50℃(4.22×10^6 gPE/(molNi·h)).When the temperature increased from 50℃to 70℃,Mn value decreased from 143 kg/mol to 125 kg/mol,meanwhile the branching degree rised from 125 branches/1 000 C to 135 branches/1 000 C.

关 键 词：Α-二亚胺 镍配合物 后过渡金属催化剂 乙烯聚合 支化聚乙烯 

分 类 号：TQ316.3[化学工程—高聚物工业] TQ314.242