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浙江大学学报(工学版)
J4  2011, Vol. 45 Issue (10): 1855-1861    DOI: 10.3785/j.issn.1008-973X.2011.10.026
化学与生物工程、环境工程     
乙酰丙酮铁/双亚胺基吡啶体系催化乙烯齐聚研究
秦伟, 张乐天, 历伟, 王靖岱, 阳永荣, 蒋斌波
浙江大学 化学工程与生物工程学系,化学工程联合国家重点实验室,浙江 杭州 310027
Iron (Ⅲ) acetylacetonate and bis(imino)pyridyl ligand catalyst
system for ethylene oligomerization
QIN Wei, ZHANG Le-tian, LI Wei, WANG Jing-dai,
YANG Yong-rong, JIANG Bin-bo
State Key Laboratory of Chemical Engineering, Department of Chemical and Biological Engineering,
Zhejiang University, Hangzhou 310027, China
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摘要：

为了研究乙酰丙酮铁(Fe(acac)3)与双亚胺基吡啶类配体组成催化体系的乙烯齐聚行为,合成由乙酰丙酮铁和3种不同结构双亚胺基吡啶配体组成的催化体系.通过比较研究3种含不同取代基配体的催化体系的乙烯齐聚性能,发现配体取代基结构与齐聚活性和齐聚产物分布有很大的关系,合适的取代基位阻及电子效应是决定催化体系活性和产物分布的重要因素.反应温度对催化体系活性和产物分布具有较大影响,随着反应温度的升高,齐聚活性降低,齐聚产物分布向低碳数方向移动；随着n(Al)∶n(Fe)从500增加到3 000,齐聚活性先迅速增加,在n(Al)∶n(Fe)=2 000左右时达到最大,然后呈现下降的趋势,n(Al)∶n(Fe)对齐聚产物的分布基本没有影响.
Abstract:

Three iron acetylacetonate complexes ligated with different bis(imino)pyridyl ligands were synthesized in order to analyze the oligomerization behavior of iron acetylacetonate and bis(imino)pyridyl ligands catalyst system. In comparison on the oligomerization behavior of three different substituented catalysts, catalytic activities and distribution of oligomers for bis(imino) pyridyl iron acetylacetonate complexes were greatly influenced by the structures of the ligands. The proper steric and electronic effect of the substituents were the main factors responsible for the catalytic behavior. Meanwhile, the reaction temperature significantly affected catalytic activities and oligomer distribution. The activities rapidly decreased with the increase of reaction temperature, and more lowmolecularweight products were produced. With the Al/Fe molar ratio increasing from 500 to 3 000, catalytic activities rapidly increased at first, and reached the highest activities at n(Al)/n(Fe)=2 000, then decreased slowly. The distribution of the obtained oligomers was almost invariant with the Al/Fe molar ratio.
出版日期: 2011-10-01
:  TQ 316.31  
基金资助:

国家自然科学基金资助项目（20776124）；国家“863”高技术研究发展计划资助项目（2007AA030208）；中央高校基本科研业务费专项资金资助项目（2009QNA4028）.
通讯作者: 蒋斌波,男,副教授.     E-mail: jiangbb@zju.edu.cn
作者简介: 秦伟(1985—),男,硕士生,从事烯烃齐聚和聚合的研究.E-mail: qw@zju.edu.cn
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引用本文:

秦伟, 张乐天, 历伟, 王靖岱, 阳永荣, 蒋斌波. 乙酰丙酮铁/双亚胺基吡啶体系催化乙烯齐聚研究[J]. J4, 2011, 45(10): 1855-1861.

QIN Wei, ZHANG Le-tian, LI Wei, WANG Jing-dai, YANG Yong-rong, JIANG Bin-bo. Iron (Ⅲ) acetylacetonate and bis(imino)pyridyl ligand catalyst
system for ethylene oligomerization. J4, 2011, 45(10): 1855-1861.

链接本文:

https://www.zjujournals.com/eng/CN/10.3785/j.issn.1008-973X.2011.10.026    或    https://www.zjujournals.com/eng/CN/Y2011/V45/I10/1855

［1］ 姜涛,阎卫东,刘力新. α烯烃的生产和应用进展［J］.化工进展,2001,20(3): 17-23.
JIANG Tao, YAN Weidong, LIU Lixin, et al. Applications for alphaolefins and its production processes ［J］. Chemical Industry and Engineering Progress, 2001, 20(3): 17-23.
［2］ 曹军,张宝军,李明远,等.乙烯齐聚均相铬系催化剂的研究进展［J］.石油化工，2007,36(3): 304-309.
CAO Jun, ZHANG Baojun, LI Mingyuan, et al. Progress in research of ethylene oligomerization by chromiumbased homogeneous catalyst ［J］. Petrochemical Technology, 2007, 36(3): 304-309.
［3］ KILLIAN C M, JOHNSON L K, BROOKHART M. Preparation of linear alphaOlefins using cationic nickel (II) alphadiimine catalysts ［J］. Organometallics, 1997, 16(10): 2005-2007.
［4］ 介素云,张树,孙文华.乙烯齐聚催化剂的研究进展［J］.石油化工,2006,35(3): 295-300.
JIE Suyun, ZHANG Shu, SUN Wenhua. Progress on research of catalysts for ethylene oligomerization ［J］. Petrochemical Technology, 2006, 35(3): 295-300.
［5］ ROGERS J S, BAZAN G C, SPERRY C K. Ethoxyboratabenzene zirconium complexes: catalysts for αolefin production ［J］. Journal of the American Chemical Society, 1997, 119(39): 9305-9306.
［6］ SMALL B L, BROOKHART M. Ironbased catalysts with exceptionally high activities and selectivities for oligomerization of ethylene to linear alphaolefins ［J］. Journal of the American Chemical Society, 1998, 120(28): 7143-7144.
［7］ BRITOVSEK G, MASTROIANNI S, SOLAN G A, et al. Oligomerisation of ethylene by bis(imino)pyridyliron and cobalt complexes ［J］. Chemistry: A European Journal, 2000, 6(12): 2221-2231.
［8］ BIANCHINI C, GIAMBASTIANI G, RIOS I G, et al. Ethylene oligomerization, homopolymerization and copolymerization by iron and cobalt catalysts with 2,6(bisorganylimino) pyridyl ligands ［J］. Coordination Chemistry Reviews, 2006, 250(11/12): 1391-1418.
［9］ BIANCHINI C, GIAMBASTIANI G, RIOS I G, et al. Synthesis of a new polydentate ligand obtained by coupling 2,6bis(imino)pyridine and (imino)pyridine moieties and its use in ethylene oligomerization in conjunction with iron(II) and cobalt(II) bishalides ［J］. Organometallics, 2007, 26(20): 5066-5078.
［10］ GAO R, LI Y, WANG F S, et al. 2Benzoxazolyl6［1(arylimino)ethyl］ pyridyliron(II) chlorides as ethylene oligomerization catalysts ［J］. European Journal of Inorganic Chemistry, 2009(27): 4149-4156.
［11］ HAO P, CHEN Y J, XIAO T, et al. Iron (III) complexes bearing 2(benzimidazole)6(1aryliminoethyl) pyridines: Synthesis, characterization and their catalytic behaviors towards ethylene oligomerization and polymerization ［J］. Journal of Organometallic Chemistry, 2009, 695(1): 90-95.
［12］ BIANCHINI C, GIAMBASTIANI G, LUCONI L, et al. Olefin oligomerization, homopolymerization and copolymerization by late transition metals supported by (imino) pyridine ligands ［J］. Coordination Chemistry Reviews, 2009, 254(6): 431-455.
［13］ 张志成,柯毓才,吕英莹,等.一种吡啶二亚胺类铁催化剂的合成及乙烯低聚研究［J］.高分子学报,2005(2): 191-196.
ZHANG Zhicheng, KE Yucai, LV Yingying, et al. Synthesis of a novel bis(imino)pyridyl iron complex and its application in oligomerization of ethylene ［J］. Acta Polymerica Sinica, 2005(2): 191-196.
［14］ 宁英男,刘晓瑜,王力搏,等.新型铁配合物/MAO催化乙烯低聚［J］.化工进展,2006,25(6): 680-683.
NING Yingnan, LIU Xiaoyu, WANG Libo, et al. Ethylene oligomerization catalyzed by novel iron complex/MAO ［J］. Chemical Industry and Engineering Progress, 2006, 25(6): 680-683.
［15］ BRITOVSEK G, CLENTSMITH G, GIBSON V C, et al. The nature of the active site in bis(imino)pyridine iron ethylene polymerisation catalysts ［J］. Catalysis Communications, 2002, 3(5): 207-211.
［16］ SWIFT H E, BOZIK J E, WU C Y. Specific catalysis with iron coordination complexes ［J］. Journal of Catalysis, 1970, 17(3): 331-340.
［17］ ZHANG Z Y, ZHANG H J, MA H M, et al. A novel iron catalyst for the polymerization of butadiene ［J］. Journal of Molecular Catalysis, 1982, 17(1): 65-76.

［18］ WANG L C, REN H, SUN J Q. Fe (acac)3bis (imino) pyridine/MAO: a new

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