膦胺铬和双膦铬催化乙烯选择性齐聚研究进展

乙烯选择性齐聚制备线性α-烯烃是在学术界和工业界均受到高度重视,具有目标产物选择性高、产品易分离和经济效益显著等特点。铬系配合物催化剂在催化乙烯选择性齐聚反应中综合性能较好,有良好的发展和应用前景。近年来的研究表明,配体结构对催化剂性能有重要影响;反应体系中通入H 2可以改善齐聚产物的分布并抑制低聚物的生成;开发不以甲基铝氧烷为助催化剂的催化体系可降低催化剂成本;而乙烯选择齐聚机理及金属中心氧化态对催化剂的设计有重要的指导意义。本文主要从以上几个方面介绍了膦胺铬和双膦铬配合物在催化乙烯选择性齐聚中的研究进展,分析了目前乙烯选择性四聚工业化急需解决的问题,展望了该领域未来的发展方向。     

地方城市空间要素规划建设时序研究:以清代台湾省为例*

Cr/PNP催化乙烯选择性齐聚反应制短链线性α-烯烃(LAOs)技术是近年来发展极为迅速的研究方向,其中关于反应微观机理的研究对高性能催化剂设计和研发具有重要意义.通过使用量子化学计算与实验相结合的方法,可以获得对催化反应过程更为深刻的认识.我们主要从理论计算研究的角度,总结了铬系催化剂催化乙烯选择性齐聚研究中取得的最新成果.主要内容包括反应过程中催化剂的氧化态[Cr(Ⅰ/Ⅲ) vs Cr(Ⅱ/Ⅳ)],反应路径中单乙烯和双乙烯配位的竞争,配体的空间结构和电子效应,自然键轨道理论(NBO)以及H_2效应对催化体系的影响等.     

Cr/PNP催化乙烯选择性三/四聚反应的量子化学研究进展

Cr/PNP催化乙烯选择性齐聚反应制短链线性α-烯烃(LAOs)技术是近年来发展极为迅速的研究方向,其中关于反应微观机理的研究对高性能催化剂设计和研发具有重要意义.通过使用量子化学计算与实验相结合的方法,可以获得对催化反应过程更为深刻的认识.我们主要从理论计算研究的角度,总结了铬系催化剂催化乙烯选择性齐聚研究中取得的最...     

乙烯反应中的铁配合物催化剂：从概念到产业化

聚烯烃的核心是催化剂,地球上丰度最高的过渡元素铁的配合物在催化乙烯反应中展示了优异性能,本文综述了用于乙烯低聚与聚合的铁配合物催化剂的最新进展.通过调控所用配体的电子效应和空间位阻可以实现乙烯催化性能与所得聚合物微观结构的控制;铁催化剂具有独特的优势,不仅实现α-烯烃制备,而且可以制备高度线性聚乙烯包括制备窄分布的聚乙烯蜡.铁催化剂未来将在高附加值聚乙烯有巨大应用潜力.     

镍二亚胺配合物/烷基铝催化乙烯聚合

直链低碳α-烯烃是生产线性低密度聚乙烯的共聚单体及合成高级润滑油和一些精细化学品的中间体，通过乙烯齐聚反应生成直链α-烯烃是目前工业上重要的生产方法，近几年来使乙烯齐聚成α-烯烃的含二或三齿配体后过渡金属催化剂的催化特性受到人们很大的关注。     

基于[PNP]配体的铬催化剂体系选择性催化乙烯齐聚的研究进展

乙烯选择性三聚和四聚催化反应为制备1-己烯和1-辛烯提供了重要途径.在报道和披露的众多结构和组成的催化剂体系中,我们选择[PNP]配位骨架的铬催化剂体系,对其发展和应用进行了综述.论文以结构与催化性能的关联性为主线,阐述[PNP]骨架以及N和P上取代基的电子和立体空间效应对催化性能的影响.从目前的研究态势来看,[PNP]配位骨架的铬催化剂体系在乙烯选择性齐聚生产1-辛烯等线性α-烯烃方面具有发展潜力.     

镍系催化剂选择性催化乙烯二聚研究进展

1-丁烯和2-丁烯是重要的有机合成原料,可以通过金属催化剂选择性催化乙烯二聚合成丁烯.乙烯选择性二聚合成丁烯的催化剂通常有镍催化体系、钒催化体系、钨催化体系、铁或钴催化体系、钽催化体系以及钛催化体系等.近年来镍系催化剂催化乙烯选择性二聚取得了很大的进展,本论文对近年来镍系催化剂催化乙烯选择性二聚进行了综述.主要概述了[...     

一种新型亚胺基吡啶铁配合物和茂金属复配催化乙烯原位共聚制备LLDPE

20世纪80年代中期,Kissin等人^[1]首先采用了乙烯二聚催化剂和传统Ziegler-Natta催化剂组成双功能催化体系,催化乙烯原位聚合制备短支链线性低密度聚乙烯(LLDPE)．由于该方法具有不需要另外加入α-烯烃的特点,近年来受到人们的重视．胡友良^[2-4]等人用乙烯二聚催化剂Ti-     

均相Cr系催化剂催化乙烯选择性齐聚反应机理研究进展

线性α-烯烃是一类重要的化工原料,均相Cr系催化剂催化乙烯选择性齐聚制备特定的α-烯烃是近年来得到迅速发展的一个重要的研究方向,其中催化反应机理的研究对新型高效催化剂的研发具有重要的指导作用.综述了示踪原子、预制催化剂前驱体、EPR-XAS、密度泛函理论(DFT)计算等方法在乙烯选择性齐聚的反应路径和金属中心价态研究中的应用,总结了该催化反应机理研究中取得的最新成果,从方法学角度对各位学者的研究进行了比较与讨论,并在此基础上提出了双核Cr金属环机理研究的新观点,对进一步的研究方向进行了展望.     

同核双金属烯烃聚合催化剂

与单核金属配合物催化剂相比,双核金属配合物催化剂所具的双金属活性中心对烯烃聚合催化活性和所得聚合物的性能(包括聚合物微结构、分子量大小和分子量分布)产生了重要影响。本文综述了双金属配合物作为均相催化剂催化乙烯聚合及共聚合的最新研究,归纳思路包括不同的金属类型,即基于前过渡金属(Zr, Ti, Hf) 和后过渡金属(Ni, Fe, Co) 的双核金属组合; 不同的配体化合物,即CGC配体、酚氧亚胺配体、氮杂环胺配体、α-二亚胺和亚胺吡啶配体等。这些研究表明,前过渡金属催化剂不仅解决了乙烯自聚还实现了乙烯与α-烯烃共聚;后过渡金属催化剂高效催化乙烯自聚合,其中铁和钴催化剂获得高度线性聚乙烯,镍催化剂则产生多支链聚乙烯。     

Ethylene tetramerization: a new route to produce 1-octene in exceptionally high selectivities

Linear alpha-olefins, such as 1-hexene and 1-octene, are important comonomers in the production of linear low-density polyethylene (LLDPE). The conventional method of producing 1-hexene and 1-octene is by oligomerization of ethylene, which yields a wide spectrum of linear alpha-olefins (LAOs). While there exists several processes for producing 1-hexene via ethylene trimerization, a similar route for the selective production of 1-octene has so far been elusive. We now, for the first time, report an unprecedented ethylene tetramerization reaction that produces 1-octene in selectivities exceeding 70%, using an aluminoxane-activated chromium/((R2)2P)2NR1 catalyst system.     

Effects of halide in homogeneous Cr(III)/PNP/MAO catalytic systems for ethylene tetramerization toward 1-octene

In homogeneous Cr(III)/methylaluminoxane/cyclopentyl-bisphosphineamine (PNP)/halide ethylene tetramerization catalyst systems, the effects of halide on the 1-octene formation selectivity and the catalytic activity were investigated. The comparative studies showed that both 1-octene formation selectivity and catalytic activity of the four-member catalytic systems containing dichloromethane were higher than those of containing trichloromethane and tetrachoromethane. 1,1,2-Trichloroethane showed much higher 1-octene formation selectivity improvement than 1,1,1-trichloroethane. The improvement of chloride on 1-octene formation selectivity and catalytic activity was much better than that of a corresponding bromide. So we can draw a conclusion that the steric hindrance, the molecular stability, the halides group configuration, and the types of the halides are important factors for ethylene tetramerization toward 1-octene. Some specific interaction modes of halogen groups with active Cr species in the catalytic cycle are proposed to explain the 1-octene selectivity improvement effects of halide in the ethylene tetramerization reaction.     

Cyclic Alkyl Amino Carbene (CAAC) Ruthenium Complexes as Remarkably Active Catalysts for Ethenolysis

An expanded family of ruthenium‐based metathesis catalysts bearing cyclic alkyl amino carbene (CAAC) ligands was prepared. These catalysts exhibited exceptional activity in the ethenolysis of the seed‐oil derivative methyl oleate. In many cases, catalyst turnover numbers (TONs) of more than 100 000 were achieved, at a catalyst loading of only 3 ppm. Remarkably, the most active catalyst system was able to achieve a TON of 340 000, at a catalyst loading of only 1 ppm. This is the first time a series of metathesis catalysts has exhibited such high performance in cross‐metathesis reactions employing ethylene gas, with activities sufficient to render ethenolysis applicable to the industrial‐scale production of linear α‐olefins (LAOs) and other terminal‐olefin products.     

Density functional studies on chromium catalyzed ethylene trimerization

Mechanism of ethylene trimerization using chromium catalyst is investigated using density functional methods. Recent experimental results indicate Cr-based homogeneous catalysts to follow metallacycle pathway in ethylene tri-, teta- and oligomerization reactions. Given the importance of chlorinated Cr-based active catalysts in these reactions, we have used “bare” minimal ligands like Cl^? and considered catalytic cycles with neutral or cationic intermediates starting with [Cr(II)Cl₂(ethylene)₂] and [Cr(II)Cl(ethylene)₂]⁺, respectively. We have compared both ‘Cossee’ and the ‘metallacycle’ mechanisms on these model systems utilizing density functional computations at B3LYP/LANL2DZ(d,p) level. The metallacycle mechanism with cationic Cr(II)–Cr(IV) intermediates is found to be the most favored path, with oxidative coupling of two coordinated ethylene to form the chromacyclopentane being the rate determining step (RDS). We also found that with neutral intermediates the Cossee pathway rather than the metallacycle mechanism is followed. Thus in spite of the simplicity of using just Cl^? as ligand in the model catalytic intermediates, our computational results match remarkably well with many recent and important experimental findings.     

The use of bis(diphenylphosphino)amines with N-aryl functionalities in selective ethylene tri- and tetramerisation

A systematic study was conducted on the Cr catalysed tri- and tetramerisation of ethylene using bis(diphenylphosphino)amine ligands with N-aryl functionality. This study revealed that the oligomerisation reaction product selectivity is primarily dependent on the structure and size of the N-aryl groups.

Addition of sufficient steric bulk to the N-phenyl group via ortho-alkyl substitution increased the combined 1-hexene and 1-octene selectivity (overall alpha selectivity) to above 82% at an overall 1-octene selectivity of 56%. The introduction of a single carbon spacer between the N-atom and the aryl-moiety, as well as the addition of branching on this carbon, resulted in further selectivity improvements, achieving an overall 1-octene selectivity of 64% and an overall alpha selectivity of 84%. This was obtained at catalyst productivities in excess of 1,000,000 g/g Cr/h.     

Ring-opening polymerizations of cyclic olefins

A ziegler-type catalyst system consisting of tungsten hexachloride and alkyl or aryl tin compounds was found to polymerize cyclopentene and other cyclic olefins through a ring-opening mechanism. This catalyst system also polymerized α-olefins such as ethylene and 1-octene. An attempt was made to copolymerize cyclopentene and ethylene. Other catalyst systems were also employed for ring-opening polymerizations with limited success.     

Catalytic oligomerization of ethylene to higher linear alpha-olefins promoted by the cationic group 4 [(eta 5-Cp-(CMe2-bridge)-Ph)MII(ethylene)2]+ (M = Ti, Zr, Hf) active catalysts: a density functional investigation of the influence of the metal on the catalytic activity and selectivity

A detailed theoretical analysis is presented of the catalytic abilities of heavier group 4 (M = Zr, Hf) metals for linear ethylene oligomerization with the cationic [(eta(5)-C(5)H(4)-(CMe(2)-bridge)-C(6)H(5))M(IV)(CH(3))(2)](+) complex as precatalyst, employing a gradient-corrected DFT method. The parent Ti system has been reported as a highly selective catalyst for ethylene trimerization. The mechanism involving metallacycle intermediates, originally proposed by Briggs and Jolly, has been supported by the present study to be operative for the investigated class of group 4 catalysts. Metallacycle growth through bimolecular ethylene uptake and subsequent insertion is likely to occur at uniform rates for larger cycles that are furthermore comparable for Ti, Zr, and Hf catalysts. Ethylene insertion into the two smallest five- and seven-membered cycles is found to become accelerated for Zr and Hf catalysts, which is due to geometrical factors. In contrast, electronic effects act to raise the barrier for metallacycle decomposition, affording alpha-olefins upon descending group 4. This process is furthermore predicted to be kinetically more difficult for larger metallacycles. The oligomer distribution of the Zr-mediated reaction is likely to comprise predominantly 1-hexene together with 1-octene, while 1-butene and alpha-olefins of chain lengths C(10)-C(18) should occur only in negligible portions. A similar composition of alpha-olefins having C(6)-C(18) chain lengths is indicated for the Hf catalysts, but with long-chain oligomers and polymers as the prevalent fraction. Between the group 4 catalysts of the investigated type, the Zr system appears as the most promising candidate having catalytic potential for production of 1-octene, although not selectively. The influence of temperature to modulate the oligomer product composition has been evaluated.