两相体系内PNPCr（Ⅲ）MAO催化乙烯齐聚.pdfVIP

第 65 卷 第 9 期 化 工 学 报 Vol.65 No.9 2014 年 9 月 CIESC Journal September 2014 两相体系内PNP/Cr(Ⅲ)/MAO 催化乙烯齐聚 王媚，时鹏飞，陈延辉，姜涛 （天津科技大学材料科学与化学工程学院，天津 300457 ） 摘要：通过 1-n-丁基-3- 甲基咪唑六氟磷酸盐离子液体([BMIM][PF ])/环己烷构建了液/液两相体系。研究了两相体 6 系内反应温度、Al/Cr 摩尔比、离子液体浓度等因素对异丙基双膦胺配体(PNP)/Cr(Ⅲ)/ 甲基铝氧烷(MAO)催化乙烯 齐聚性能的影响。研究结果表明：与均相催化体系相比，两相体系内 PNP/Cr(Ⅲ)/MAO 催化乙烯由四聚变为三聚， 1-C6 的选择性最高达到97.40% 。齐聚产物存在于有机溶剂相，催化剂溶解在离子液体相，便于产物与催化剂的分 离及催化剂的循环使用。 关键词：催化；乙烯；齐聚；配合物；离子液体 DOI ：10.3969/j.issn.0438-1157.2014.09.024 中图分类号：TQ 316 文献标志码：A 文章编号：0438—1157 （2014 ）09—3485—05 Ethylene oligomerization catalyzed by PNP/Cr(Ⅲ)/MAO in biphase systems WANG Mei, SHI Pengfei, CHEN Yanhui, JIANG Tao （Material Science and Chemical Engineering Institute , Tianjin University of Science and Technology, Tianjin 300457, China ） Abstract: 1-n-Butyl-3-methylimidazolium hexafluorophosphate ([BMIM][PF6])/cyclohexane biphasic system was used for studying performance of ethylene oligomerization catalyzed by diphosphinoamine ligand (PNP)/Cr(Ⅲ)/ methylaluminoxane(MAO). The effect of reaction temperature, molar ratio of Al/Cr and ionic liquid concentration on catalytic activity and product distribution was investigated. The results showed that compared with homogeneous catalysis system, the action of catalytic active center in biphase systems changed from ethylene tetramerization to ethylene trimerization. = 1-C selectivity was up to 97.40%. The product existed in the organic 6 solvent while the catalyst w