Ethylene oligomerization catalyzed by PNP/Cr(Ⅲ)/MAO in biphase systems

doi:10.3969/j.issn.0438-1157.2014.09.024

Abstract

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. selectivity was up to 97.40%. The product existed in the organic solvent while the catalyst was dissolved in ionic liquids, which made the separation of product and recycle of catalyst easy.

Key words: catalysis, ethylene, oligomerization, complexes, ionic liquid

摘要： 通过1-n-丁基-3-甲基咪唑六氟磷酸盐离子液体（[BMIM][PF₆]）/环己烷构建了液/液两相体系。研究了两相体系内反应温度、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，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

CLC Number:

TQ316

WANG Mei, SHI Pengfei, CHEN Yanhui, JIANG Tao. Ethylene oligomerization catalyzed by PNP/Cr(Ⅲ)/MAO in biphase systems[J]. CIESC Journal, 2014, 65(9): 3485-3489.

王媚, 时鹏飞, 陈延辉, 姜涛. 两相体系内PNP/Cr（Ⅲ）/MAO催化乙烯齐聚[J]. 化工学报, 2014, 65(9): 3485-3489.

References 20

[1]	PERP Report. Alpha Olefins(02/03-4) [M]. New York: Nexant. Chem. Systems, 2004
[2]	Jiang Tao, Zhang Sai, Jiang Xingliang, Yang Chaofeng, Niu Bo, Ning Yingnan. The effect of N-aryl PNP ligands on the selective ethylene tetramerization using Cr(Ⅲ)/PNP/MAO [J]. Journal of Molecular Catalysis A: Chemical, 2008, 279 (1): 90-93
[3]	Wass D F. Olefin trimerisation using a catalyst comprising a source of chromium,molybdenum or tungsten and a ligand containing at least one phosphorous,arsenic or anti-mony atom bound to at least one (hetero)hydrocarbyl group [P]: UK, WO, 02/004119. 2002-01-17
[4]	Bollmann A, Blann K, Dixon J T, Hess F M, Killian E, Maumela H, McGuinness D S, Morgan D H, Neveling A, Otto S, Overett M, Slawin A M Z, Wasserscheid P, Kuhlmann S. Ethylene tetramerization: a new route to produce 1-octene in exceptionally high selectivities [J]. J. Am. Chem. Soc., 2004, 126 (45): 14712-14713
[5]	Mao Guoliang, Ning Yingnan, Hu Wenbo, Li Shanming, Song Xianfeng, Niu Bo, Jiang Tao. Synthesis of a novel triple-site diphosphinoamine (PNP) ligand and its applications in ethylene tetramerization [J]. Chinese Science Bulletin, 2008, 53 (22): 3511-3515
[6]	Chen Hongxia, Liu Xiaoyu, Hu Wenbo, Ning Yingnan, Jiang Tao. Effects of halide in homogeneous Cr(Ⅲ)/PNP/MAO catalytic systems for ethylene tetramerization toward 1-octene [J]. Journal of Molecular Catalysis A: Chemical, 2007, 270 (1): 273-277
[7]	Jiang Tao, Huang Zhijun, Luo Mingjian, Chen Hongxia, Ning Yingnan. Preparation of ethylene/1-octene copolymers from ethylene stock with tandem catalytic system [J]. Journal of Applied Polymer Science, 2008, 107 (5): 3071-3075
[8]	Chauvin Y, Gilbert B, Guibard I. Catalytic dimerization of alkenes by nickel complexes in organochloroaluminate molten salts [J]. Chem. Soc.,Chem .Commun.,1990: 1715-1716
[9]	Einloft S, Dietrich F K, Dupont J. Selective two-phase catalytic ethylene dimerization by Ni(Ⅱ) complexes/ AlEtCl2 dissolved in organoaluminate ionic liquids [J]. Polyhedron, 1996, 15 (19) : 3257-3259
[10]	Wasserscheid P, Goedon C M, Hilgers C, Muldoon M J, Dunkin I R. Ionic liquids :polar,but weakly coordinating solvents for the first biphasic oligomerisation of ethene to higher-olefins with cationic Ni complexes [J]. Chem. Commun., 2001 (13): 1186-1187
[11]	Bollmann A, Blann K, Dixon J T, Hess F M, Killian E, Maumela H, Mcguinness D S, Morgan D H, Neveling A, Otto S, Overett M, Slawin A M Z, Wasserscheid P, Kuhlmann S. Ethylene tetramerization: a new route to produce 1-octene in exceptionally high selectivities [J]. J. Am. Chem. Soc., 2004, 126 (45): 14712-14713
[12]	Dzyuba S V, Bartsch R A. Efficient synthesis of 1-alkyl(aralkyl)-3- methyl(ethyl)-imidazolium halides: precursors for room temperature ionic liquids [J]. J. Heterocyl. Chem., 2001, 38: 265-268
[13]	Wioletta Ochedzan-Siod?ak, Katarzyna Dziubek, Dawid Siod?ak. Biphasic ethylene polymerisation using 1-n-alkyl-3-methylimidazolium tetrachloroaluminate ionic liquid as a medium of the Cp2TiCl2 titanocene catalyst [J]. European Polymer Journal, 2008, 44 (11): 3608-3614
[14]	Jiang Tao, Chen Hongxia, Ning Yingnan, Chen Wei. Preparation of 1-octene by ethylene tetramerization with high selectivity [J]. Chin. Sci. Bull., 2006, 51 (5): 521-523
[15]	Kuhlmann S, Dixon J T, Haumann M, Morgan D H, Ofili J, Spuhl O, Taccardo N, Wasserscheid P. Influence of elevated temperature and pressure on the chromium-catalysed tetramerisation of ethylene [J]. Adv. Synth. Catal., 2006, 348 (10/11): 1200-1206
[16]	Wasserscheid P, Hilgers C, Keim W. Ionic liquids-weakly-coordinating solvents for the biphasic ethylene oligomerization to α-olefins using cationic Ni-complexes [J]. Journal of Molecular Catalysis A: Chemical, 2004, 214 (1): 83-90
[17]	Peitz S, Aluri B R, Peulecke N, Muller B H, Wohl A, Muller W, Hazmi M, Mosa F M, Rosenthal U. An alternative mechanistic concept for homogeneous selective ethylene oligomerization of chromium-based catalysts: binuclear metallacycles as a reason for 1-octene selectivity [J]. Chemistry-A European Journal, 2010, 16 (26): 7670-7676
[18]	Shaikh Y, Gurnham J, Albahily K, Gambarotta S, Korobkov I. Aminophosphine-based chromium catalysts for selective ethylene tetramerization [J]. Organometallics, 2012, 31 (21): 7427-7433
[19]	Cotton F A, Walter R A. Multiple Bonds Between Metal Atoms [M]. 2nd ed. Clarendon: Oxford, 1993
[20]	Sharma Anu Prava. Palladium complexes of diphosphazane and related ligands [D]. Pietermaritzburg: University of Natal, 2001