非茂金属催化剂的合成及其聚合反应动力学  

Synthesis of non-metallocene catalysts and their polymerization kinetics

作　　者：吴为果 张艺镡 王梦雪[1] 米普科[1] 许胜[1] 

机构地区：[1]华东理工大学材料科学与工程学院 上海市先进聚合物材料重点实验室,上海200237

出　　处：《石油化工》2017年第2期183-189,共7页Petrochemical Technology

基　　金：中国石油科技创新基金项目(2014D-5006-0504)

摘　　要：以配体2,2’-硫代(4,6-二氯苯酚)与不同的钛化合物合成了4种均相非茂金属催化剂,利用^(1)H NMR,MS,^(13)C NMR等方法分析了配体、催化剂以及聚合产物的结构,通过非茂金属催化剂催化乙烯聚合测定了聚合反应体系的相关动力学参数,考察了温度和压力对聚合反应速率的影响。实验结果表明,以倍半乙基氯化铝为助催化剂催化乙烯聚合时,聚合反应速率很高。催化剂Ⅰ(钛酸四丁酯与2,2’-硫代(4,6-二氯苯酚)合成)制得的聚乙烯中的支链含量很低,约占聚乙烯的0.103%。催化剂Ⅰ的动力学曲线为缓升平稳型,聚合反应级数为1.099,接近1级反应。随聚合温度的升高,聚合反应速率逐渐增大。非茂金属催化剂催化乙烯聚合反应的表观活化能为37.49 k J/mol。A series of homogeneous non-metallocene catalysts were synthesized from titanium compounds and 2, 2＇-thiobis（4, 6-dichlorophenol） as ligands. The kinetics of ethylene polymerization with the catalysts was investigated and the kinetics parameters were obtained. The ligands, catalysts and obtained polymers were characterized by means of 1H NMR, MS and 13C NMR. The effects of pressure and temperature on the polymerization were discussed. It was showed that, when ethylaluminum sesquichloride was used as the co-catalyst, the reaction rate of the ethylene polymerization was very high. The branching degree of the obtained polymers was very low about 0.103%. The kinetics curve of catalyst I was slowly and stably rising, and the polymerization reaction order was 1.099, approaching a pseudo first order reaction. With the polymerization temperature rise, the polymerization rate increased gradually. The apparent activation energy of the polymerization with the non-metalloeene catalysts was 37.49 kJ/mol.

关 键 词：非茂金属催化剂 倍半乙基氯化铝 乙烯聚合 聚合动力学 

分 类 号：TQ426.92[化学工程]