过渡金属络合物催化乙烯齐聚

综述了乙烯齐聚的最新成果,重点阐述了用于乙烯齐聚的新型催化剂,讨论了烯烃高聚与齐聚催化剂的关系,烯烃高聚与齐聚的反应机理相同,。差别主要在于烯烃插入与β－H消除反应的速率,第IV副族金属络合物主要催化乙烯齐聚,第Ⅲ副族金属主要催化乙烯高聚,改变茂金属催化体系的助催化剂和反应条件可得到齐聚产物,选择体积较小配体的第Ⅷ族金属络合物,有利于β－H消除得到齐聚产物。     

新型高效 Br(o)nsted 酸性离子液体催化剂体系催化烯烃齐聚反应

烯烃齐聚是重要的化工反应之一, 是指低碳烯烃在催化剂存在下发生聚合反应, 生成一个或多个单体重复相连的化合物过程. 烯烃齐聚反应是一种碳链增长过程, 是生成线性α-烯烃的重要过程. 齐聚反应主要生成单体的二聚、三聚、四聚或五聚物等低聚体, 发生反应的单体主要是低碳烯烃如乙烯、丙烯、正丁烯和异丁烯等. 烯烃齐聚产物应用十分广泛, 可以用于合成环境友好的液体燃料、长链烷烃润滑油、表面活性剂、增塑剂、汽油柴油添加剂等重要化工产品, 同时齐聚产物本身亦是重要的化工中间体和化学试剂. 烯烃齐聚反应研究的重点内容是开发新颖高效的催化剂, 以满足不同需要, 而应用 Br(o)nsted 酸性功能化离子液体作为催化剂用于齐聚反应的报道较少.本文考察了新型高效催化剂体系 (Br(o)nsted 酸性离子液体作为主催化剂, 三辛基甲基氯化铵作为助剂) 对烯烃齐聚反应的催化性能. 合成的 Br(o)nsted 酸性离子液体通过红外光谱、紫外可见光谱、1H 核磁共振和13C 核磁共振等进行系列表征,并进一步分析其结构与酸度的关系. 结果表明, 在相同的反应条件下, Br(o)nsted 酸性离子液体[HIMBs]HSO4对烯烃齐聚反应具有最好的催化活性. 本文考察了不同离子液体、离子液体用量、不同助剂、助剂用量、反应时间、反应压力、反应温度和不同溶剂等因素对反应的影响, 得到了最佳反应条件: 催化剂体系为[HIMBs]HSO4与三辛基甲基氯化铵, [HIMBs]HSO4/异丁烯摩尔比为25%, [HIMBs]HSO4/助剂 (三辛基甲基氯化铵)摩尔比为20:1 , 140 ℃, 8 h, 反应起始压力为2.0 MPa, 无添加溶剂 (离子液体本身作催化剂和溶剂). 在最佳反应条件下对反应物进行了拓展, 并研究了催化剂体系的循环使用情况. 在最佳反应条件下, 异丁烯齐聚反应中反应物转化率为 83.21%, 三聚物选择性高达 35.80%, 二聚物选择性为52.02%, 四聚物选择性为 3.14%. 结果表明, 本文提出的催化剂体系对烯烃齐聚反应具有较好的催化性能. 同时, 催化剂体系可以通过静置分层与产物分离, 并进行循环使用. 根据以往的报道和反应产物分布, 推测了烯烃齐聚反应机理. 烯烃齐聚反应为酸催化反应, 生成碳正离子中间体进行碳链增长, 生成齐聚产物.     

新型高效Br?nsted酸性离子液体催化剂体系催化烯烃齐聚反应（英文）

烯烃齐聚是重要的化工反应之一,是指低碳烯烃在催化剂存在下发生聚合反应,生成一个或多个单体重复相连的化合物过程.烯烃齐聚反应是一种碳链增长过程,是生成线性α-烯烃的重要过程.齐聚反应主要生成单体的二聚、三聚、四聚或五聚物等低聚体,发生反应的单体主要是低碳烯烃如乙烯、丙烯、正丁烯和异丁烯等.烯烃齐聚产物应用十分广泛,可以用于合成环境友好的液体燃料、长链烷烃润滑油、表面活性剂、增塑剂、汽油柴油添加剂等重要化工产品,同时齐聚产物本身亦是重要的化工中间体和化学试剂.烯烃齐聚反应研究的重点内容是开发新颖高效的催化剂,以满足不同需要,而应用Br?nsted酸性功能化离子液体作为催化剂用于齐聚反应的报道较少.本文考察了新型高效催化剂体系(Br?nsted酸性离子液体作为主催化剂,三辛基甲基氯化铵作为助剂)对烯烃齐聚反应的催化性能.合成的Br?nsted酸性离子液体通过红外光谱、紫外可见光谱、~1H核磁共振和~(13)C核磁共振等进行系列表征,并进一步分析其结构与酸度的关系.结果表明,在相同的反应条件下,Br?nsted酸性离子液体[HIMBs]HSO_4对烯烃齐聚反应具有最好的催化活性.本文考察了不同离子液体、离子液体用量、不同助剂、助剂用量、反应时间、反应压力、反应温度和不同溶剂等因素对反应的影响,得到了最佳反应条件:催化剂体系为[HIMBs]HSO_4与三辛基甲基氯化铵,[HIMBs]HSO4/异丁烯摩尔比为25%,[HIMBs]HSO_4/助剂(三辛基甲基氯化铵)摩尔比为20:1,140 ℃,8 h,反应起始压力为2.0 MPa,无添加溶剂(离子液体本身作催化剂和溶剂).在最佳反应条件下对反应物进行了拓展,并研究了催化剂体系的循环使用情况.在最佳反应条件下,异丁烯齐聚反应中反应物转化率为83.21%,三聚物选择性高达35.80%,二聚物选择性为52.02%,四聚物选择性为3.14%.结果表明,本文提出的催化剂体系对烯烃齐聚反应具有较好的催化性能.同时,催化剂体系可以通过静置分层与产物分离,并进行循环使用.根据以往的报道和反应产物分布,推测了烯烃齐聚反应机理.烯烃齐聚反应为酸催化反应,生成碳正离子中间体进行碳链增长,生成齐聚产物.     

镍系催化剂乙烯齐聚制线性α—烯烃

镍系催化剂乙烯齐聚制线性α－烯烃刘东兵李达刚（中国科学院兰州化学物理研究所兰州７３００００）关键词乙烯齐聚反应镍配合物α－烯烃催化反应分类号Ｏ６４３．３２乙烯齐聚制得的α－烯烃是具有偶碳数的端基烯烃，在工业上可用作聚乙烯共聚单体及合成洗涤剂、润滑油等...     

NiSO_4／γ－Al_2O_3对低级烯烃齐聚反应的催化作用

用ＮａＯＨ和ＣＯ中毒法、ＥＳＲ检测等方法研究了ＮｉＳＯ４／γ－Ａｌ２Ｏ３催化剂上乙烯、丙烯和１－丁烯齐聚反应的催化作用．结果表明：催化剂的酸性对烯烃的齐聚反应起重要作用，并且反应活性主要与Ｈｏ－３．０的酸中心有关，乙烯二聚反应是通过配位催化进行的，其活性中心是Ｎｉ＋，丙烯齐聚是通过Ｎｉ＋上的配位催化和酸催化进行的，而１－丁烯齐聚则是通过酸催化机理进行     

多相催化乙烯齐聚制α-烯烃的研究(I)

以金属离子交换型中孔分子筛MZSM 5、MZSM 5P为催化剂,在中压条件下对多相催化乙烯齐聚反应进行了探索性研究.结果表明,系列催化剂对乙烯的反应活性较NaZSM 5有显著的提高,但对目标产物α 烯烃的选择性差.对MZSM 5经表面修饰后的系列催化剂MZSM 5P,反应活性降低,而目标产物α 烯烃的选择性有所提高.这说明采用适宜的有机碱对离子交换型分子筛催化剂MZSM 5进行表面修饰是提高离子交换型分子筛催化剂乙烯齐聚反应选择性的一个有效方法.     

乙烯齐聚过程生成癸烯的催化体系研究进展

癸烯作为有机合成的基础原料,是现代化工生产中不可或缺且用量逐年增加的长链烯烃之一,目前工业上还没有一条采用乙烯齐聚法直接生产癸烯的工艺路线。乙烯通过齐聚反应可以制备长链烯烃,本文针对乙烯齐聚生成癸烯的反应,详细地阐述了国内外Cr催化体系的研究现状和取得的研究成果,包括催化剂的结构对产物癸烯选择性的影响、乙烯齐聚过程中发生乙烯、己烯共聚生成癸烯的聚合反应机理等;同时阐述了用于乙烯齐聚反应的Ni催化体系的研究现状,包括催化剂的结构与癸烯选择性之间的关系,配体树枝状大分子的结构对癸烯选择性的影响等。此外,还介绍了Fe、Ti、Zr等其他催化体系在催化乙烯齐聚生成癸烯方面所取得的研究进展,目的是为开发癸烯催化剂提供理论依据。     

NiSO/r-Al2O3对低级烯烃齐聚反应的催化作用

用ＮａＯＨ和ＣＯ中毒法，ＥＳＲ检测等方法研究了ＮｉＳＯ４／ｒ－Ａｌ２Ｏ３催化剂上乙烯，丙烯和１－丁烯齐聚反应的催化作用。结果表明：催化剂的酸性对烯烃的齐聚反应起重要作用，并且反应活性主要与Ｈｏ≤－３．０的酸中心有关；乙烯二聚反应是通过配位催化进行的，其活性中心是Ｎｉ＋，丙烯聚是Ｎｉ＋上的配位催化和酸催化进行的，而１－丁烯齐聚则是通过酸催化机理进行。     

Ni/γ-Al_2O_3催化剂上丙烯齐聚反应研究——Ⅰ.性能研究和机理初探

丙烯齐聚产物,特别是三、四聚产物是合成洗涤剂、增塑剂、表面活性剂、润滑油添加剂等精细化工产品的重要原料。目前,工业上该反应主要采用美国UOP公司开发的固体磷酸催化剂。该催化剂的主要缺点是易泥化结块,堵塞管道。故开发新型丙烯齐聚催化剂并进行相应的理论研究具有重要意义。1984年,美国专利报导了用镍盐负载在γ-Al_2O_3上的催化剂,用于烯烃二聚具有较高的催化活性,但将其用于低碳烯烃三、四聚反应的研究尚未见到。本文考察了Ni/γ-Al_2O_3催化剂用于丙烯三、四聚反应的催化性能,并初步探讨了其催化反应机理。     

六氟代戊二酮合镍/乙氧基二乙基铝催化丙烯的线性齐聚

丙烯二聚和齐聚生成高碳直链烯烃的研究已经引起人们的注意.Keim使用单组份催化剂六氟代戊二酮、1,5-环辛二烯镍络合物、Jones使用双组份催化剂β-戊二酮合镍/乙氧基二乙基铝、作者使用六氟代戊二酮合镍/三异丁基铝催化丙烯齐聚反应,都得到了直链烯烃含量较高的丙烯齐聚物.但是,上述各体系的催化剂活性相差很大.本文简要报道以甲苯为溶剂,六氟代戊二酮合镍/乙氧基二乙基铝〔简称(Hfacac)_2Ni/Et_2AlOEt〕为催化剂的丙烯齐聚反应的规律.     

多氮螯合配位后过渡金属络合物烯烃聚合催化剂

A2二亚胺镍、钯络合物和吡啶二亚胺铁、钴络合物是近几年来发现的新一代烯烃均相聚合后过渡金属催化剂。这类催化剂具有活性高、选择性易调变、聚合物性质可控制的特点, 尤其是对官能团中的杂原子的稳定性方面优于前过渡金属催化剂。本文将近年来的有关报道归纳为4 个方面进行评述: 络合物的合成和结构; 配体结构因素对络合物催化性能的影响; 催化烯烃高聚、齐聚和共聚以及催化反应机理。     

Experimental evidence for large ring metallacycle intermediates in polyethylene chain growth using homogeneous chromium catalysts

Deuterio-ethylene labeling studies on two homogeneous chromium ethylene oligomerization catalysts show that chain propagation proceeds via metallacyclic intermediates; reactions performed in the presence of 1-nonene show no incorporation of the higher olefin, strongly implicating the involvement of large ring metallacycles.     

Selective ethylene oligomerization: Recent advances in chromium catalysis and mechanistic investigations

Selective production of linear α-olefins is of significant commercial interest. Recently discovered catalytic systems based on titanium, tantalum, and chromium show remarkable selectivity and productivity for the oligomerization of ethylene to 1-hexene or 1-octene. Chromium-based catalysts are the most selective and active and show the highest structural diversity. This paper discusses the most recent advances in chromium chemistry related to selective olefin oligomerization. Aspects regarding ligand design, catalyst generation, selectivity for different products, and reaction mechanism are presented. Isotopic labeling protocols designed to distinguish between various mechanisms of catalysis are reviewed.     

Neutral nickel oligo- and polymerization catalysts: the importance of alkyl phosphine intermediates in chain termination

An unconventional chain termination reaction has been explored for the SHOP (Shell higher olefin process)-type, anilinotropone, and salicylaldiminato nickel-based oligo- and polymerization catalysts by using density functional theory (DFT). Starting from the tetracoordinate alkyl phosphine complex, the termination reaction was found to involve a rearrangement of the alkyl chain to form a pentacoordinate β-agostic complex, β-hydride elimination, and olefinic chain dissociation and to compete with propagation at sufficiently high phosphine concentration and/or basicity. It provides the first complete and convincing mechanistic rationale for the decreasing chain lengths observed upon increasing phosphine concentration and basicity. The unconventional reaction was found to be a major termination pathway for the SHOP-type catalyst and is very unlikely to lead to branching and olefin isomerization, which is critical for explaining why the SHOP catalyst, in contrast to the anilinotropone and salicylaldiminato catalysts, tends to lead to the oligomerization of ethylene to form linear α-olefins. Based on our results we have proposed a new and extended catalytic cycle for the SHOP-type ethylene oligomerization catalyst. Finally, the importance of the new termination reaction for the SHOP-type catalyst suggests that this reaction may also operate with other ethylene oligomerization nickel catalysts. This prediction was confirmed for a pyrazolonatophosphine catalyst, for which the new termination route was found to be even more facile, which explains the short oligomers produced by this catalyst.     

Ethylene homopolymerization with P,O-chelated nickel catalysts

Abstraction of phosphine from the nickel(II) P, O-chelated complexes, Ni[Ph₂PCH?C(Ph)O] (Ph)(PPh₃), and related species converts them from olefin oligomerization to olefin polymerization catalysts. Phosphine acceptors such as Rh(acetylacetonate)(C₂H₄)₂ or Ni(1,5-cyclooctadiene)₂ are most effective. Alternatively, nickel complexes in which the phosphine ligand is replaced with weakly coordinated pyridine can be prepared. These active, homogeneous catalysts can be tuned to give either low or high molecular weight, linear low or high density polyethylene. Depending on the diluent, the same catalytic complex can be used as heterogeneous or homogeneous catalyst. They are tolerant of oxygenated, hydroxylic, or polar molecules that would poison normal early transition metal-based Ziegler-Natta catalysts. In fact, the polymerizations can be run in solvents such as ethanol or acetone, but hydrocarbon solvents are preferred.     

烯烃聚合钯催化剂研究进展

综述了烯烃聚合钯催化剂的研究进展,烯烃聚合钯催化剂的配体类型有膦配体、氮配体、碳配体、氧配体、氮-氧配体、膦-氧配体、氮-膦配体等。与齐格勒-纳塔催化剂和茂金属催化剂相比,烯烃聚合钯催化剂具有高催化活性、单活性中心和良好的分子剪裁性等优点,可在分子层次上实现烯烃聚合的分子设计与组装;与铁、钴、镍等后过渡金属催化剂相比,烯烃聚合钯催化剂具有反应条件较温和、催化活性和立体选择性较高的优势。     

Chemistry of olefin polymerization reactions with chromium‐based catalysts

Detailed GC analysis of oligomers formed in ethylene homopolymerization reactions, ethylene/1‐hexene copolymerization reactions, and homo‐oligomerization reactions of 1‐hexene and 1‐octene in the presence of a chromium oxide and an organochromium catalyst is carried out. A combination of these data with the analysis of ¹³C NMR and IR spectra of the respective high molecular weight polymerization products indicates that the standard olefin polymerization mechanism, according to which the starting chain end of each polymer molecule is saturated and the terminal chain end is a C?C bond (in the absence of hydrogen in the polymerization reactions), is also applicable to olefin polymerization reactions with both types of chromium‐based catalysts. The mechanism of active center formation and polymerization is proposed for the reactions. Two additional features of the polymerization reactions, co‐trimerization of olefins over chromium oxide catalysts and formation of methyl branches in polyethylene chains in the presence of organochromium catalysts, also find confirmation in the GC analysis. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 5330–5347, 2008     

Advances in late transition metal catalysts for olefin polymerization/oligomerizarion

In this review article, we have consolidated our recent studies on late transition metal catalysts (mainly Fe, Co) for olefin polymerization/oligomerization. A series of bisiminopyridyl Co(II) and Fe(II) complexes were synthesized. These catalysts when activated with MAO in aromatic or aliphatic hydrocarbon solvents, oligomerize or polymerize ethylene to α-olefins or high molecular weight polymers with exceptionally high activities and selectivities. The electronic and steric effects of allyloxy and benzyloxy substituted bisiminopyridyl Fe(II) and Co(II) complexes were also investigated. The influence of catalyst structure and temperature on the polymerization activity, thermal properties and molecular weight were discussed. The effects of heterogenization of these catalysts on silica and modified SBA-15 were analyzed. The polymerization of polar monomers such as vinyl ethers and methyl methacrylate was tested and no specific trends in activity and polymer molecular weight with changes in steric bulkiness around the metal center were observed with the same catalyst system.     

双核茂金属催化剂催化聚合反应进展

综述了双核茂金属化合物的研究进展及其在烯烃和极性单体聚合方面的应用及双核茂金属化合物的合成及性能研究；并对双核催化剂的作用机理、催化剂结构与性能的关系也做了介绍。     

新型后过渡金属烯烃聚合催化剂－－镍系烯烃聚合催化剂

镍系烯烃聚合催化剂是近年来受到广泛关注的一类新型催化剂，是配位催化研究的热点之一。这类催化剂具有高催化活性、单活性中心和良好的分子剪栽性，可以在分子层次上实现烯烃聚合的分子设计与组装。本文介绍了镍系烯烃聚合催化剂的发展和研究概况，并评述了聚合特性及最新研究进展。