文献类型：期刊文献

中文题名：双核苯氧亚胺类催化剂的制备及烯烃聚合

英文题名：Synthesis of Binuclear Complexes Containing Phenoxyimine Ligands and Application for Ethylene Polymerization and Copolymerization

作者：张翠[1];王立娟[2];吕中文[1];许胜[1];米普科[1]

机构：[1]华东理工大学化学与分子工程学院,材料科学与工程学院,上海200237;[2]中石油石油化工研究院,大庆化工研究中心,大庆163714

年份：2018

卷号：39

期号：12

起止页码：2811

中文期刊名：高等学校化学学报

外文期刊名：Chemical Journal of Chinese Universities

收录：CSTPCD;;EI(收录号：20190806532305);Scopus;WOS:【SCI-EXPANDED(收录号:WOS:000456959800028)】；北大核心:【北大核心2017】；CSCD:【CSCD2017_2018】；

基金：Supported by the National Key R&D Program of China (No. 2017YFBO306701) and the National Natural Science Foundation of China (No. U1362111).

语种：中文

中文关键词：双核苯氧亚胺;乙烯/1-辛烯;共聚;烯烃聚合催化剂

外文关键词：Binuclear phenoxyimine;Ethylene/1-octene;Copolymerization;Catalyst of ethyene polymerization

摘要：合成了5个不同结构的苯氧亚胺配体L1～L5,用Et_3N,Me_3SiCl或HNa处理后与TiCl_4·2THF或CpZrCl_3·DME进行配位反应得到不同取代基结构的化合物C1～C6,经过~1H NMR,^(13)C NMR,IR和元素分析等表征,确认了化学结构.以甲基铝氧烷(MAO)为助催化剂,化合物C1～C6为催化剂催化乙烯聚合,考察了聚合温度、乙烯压力、铝钛或铝锆比对催化剂活性及聚合物分子量的影响.聚合实验结果表明,刚性桥基结构提高了双核化合物(LMCl_3)_2的稳定性,催化剂的活性基本都能达到10~5～10~~6g/(mol M·h),其中C5的催化活性最高,达到1. 23×10~6g/(mol Zr·h); C4在Al/Ti摩尔比为50∶1时也具有较好的催化活性[5. 89×10~5g/(mol Ti·h)],聚合物分子量1. 11×10~6.该类催化剂还可以有效催化乙烯与1-辛烯共聚,1-辛烯插入率达到10. 65%(摩尔分数).
Binuclear complexes with phenoxyimine ligand were designed and synthesized,in which the ligands were synthesized by a condensation reaction of p?phenylenediamine and substituted salicylaldehyde.Binuclear complexes C1-C6 were synthesized by the TiCl4·2THF or CpZrCl3·DME reacted with the ligands treated with triethylamine,trimethylchlorosilane or sodium hydride.Both the ligands and the compounds were well characterized by 1H NMR,13C NMR,IR,element analysis and MS.When combined with methylaluminoxane(MAO),the binuclear complexes show higher activity for ethylene polymerization.The effects of polymerization factors such as temperature,pressure of ethylene,ratio of aluminum to titanium or zirconium on the catalytic activity and polymer molecular weight were also investigated.The experimental results show that the activity of the catalysts reached 105-106 g/(mol M·h);and the catalyst C5 has the highest catalytic activity of 1.23×10^6 g/(mol Zr·h).However,the C4 could keep higher catalytic activity when the molar ratio of Al/Ti was lower to 50∶1,and the molecular weight of the polymer was higher to 1.11×10^6.It is also found that the catalyst could effectively catalyze the copolymerization of ethylene with 1-octene and the insertion rate of 1-octene could reach to 10.65%(molar fraction).