Copolymerization and oligomerization by transition metal catalysts

Alternating copolymerization of diolefins and olefins is possible by controlling the coordination site and the coordination ability with alkylvanadium halide as catalyst prepared at extremely low temperature. Alternating structure of the isoprene-propylene copolymer is established by nuclear magnetic resonance spectroscopy and ozonolysis analysis and the alternating addition of isoprene at the 4,1-position and of propylene at the α,β-position is proposed. The model reaction indicates that the π-allylvanadium bond prefers propylene, whereas the ethylvanadium bond prefers butadiene. However, the selectivity is lowered with bulky α-olefins. Acetylene is also copolymerized with nickel catalyst to give random copolymers possessing active methylene groups available for drying oil. Controlling the amount and acidity of the protic component added to Ni⁰, cyclo-, or linear oligomers of butadiene and the 1,3-1,2 adduct of butadiene are prepared selectively. Also, the addition of amine or alcohol to butadiene is successful. The reaction occurs through a π-allyl nickel intermediate and the reaction is extended to π-allyl exchange reactions.     

过渡金属磷化物催化剂综述

过渡金属磷化物催化剂具有特殊的晶体结构,在催化加氢脱硫、加氢脱氮及电化学制氢反应中具有优异的催化活性。主要简述过渡金属磷化物催化剂的结构、制备方法和应用。多金属、复合多功能型过渡金属磷化物催化剂将在催化制氢反应中受到更多的关注。     

Supramolecular transition metal catalysts in two-phase systems

The concept of covalently connecting a catalytically active transition metal center with a water-soluble receptor (host molecule) makes a new type of supramolecular catalysis possible in which the features of molecular recognition, phase transfer catalysis and transition metal catalysis are combined in a single system. The first examples of this principle make use of the commercially available β-cyclodextrin (β-CD) as the receptor and rhodium complexes of diphosphanes as the catalytically active center, these being covalently connected to one another via a spacer. In competitive hydrogenation of certain olefins unusual degrees of substrate selectivity based on the molecular recognition are observed, not possible by conventional transition metal catalysts. The two-phase (H₂O/organic) hydrogenation of nitro-aromatics also is a smooth process with these supramolecular catalysts. They also constitute an unusually active catalyst system for the selective hydroformylation of higher olefins such as 1-octene in a two-phase system.     

Recent transition metal catalysts for syndiotactic polystyrene

Syndiotactic polystyrene has attracted much interest in scientific and industrial research after its first synthesis in 1985 and has led to a fast commercialization of this polymer. The catalyst systems used for this coordination polymerization of styrene are a key point in this development to provide high polymerization activities and syndiotacticities of the polymers obtained.This literature review gives a comprehensive overview on the recent transition metal catalysts comprising the literature since about 2000 and especially on the transition metal complexes investigated in the syndiospecific homopolymerization of styrene. It includes the polymerization activity of the catalysts, the syndiotacticity of the polymers received as well as the discussion of the relationships between catalyst structure and polymerization activity. The complex-coordination mechanism of the syndiospecific polymerization of styrene is summarized in general at the beginning.The review of the recent transition metal catalysts for the syndiospecific styrene polymerization includes transition metal complexes, cocatalysts (methylaluminoxanes and boron compounds), activators and chain transfer agents, and supported and heterogenized catalysts. Transition metal complexes contain group 4 transition metal complexes (mono- and bis-cyclopentadienyl complexes, metal complexes of other ring systems such as indenyl, fluorenyl and other complexes, di- and multi-nuclear complexes, and non-metallocene complexes), and metal complexes of other transition metals (groups 8–10, rare earth metals, and others). The chapter on mono-cyclopentadienyl complexes demonstrates an overview on the investigations using unsubstituted cyclopentadienyl and pentamethylcyclopentadienyl complexes, on the influence of the variation of the structure of the cyclopentadienyl ligand, and on the effect of the variation of ancillary complex ligands besides cyclopentadienyl.This summary also considers recent developments in the preparation of new transition metal complexes based on the synthesis of completely novel π-ligands of the half-metallocenes, the success in attaining high syndiospecificities with transition metal complexes based on rare earth metals, the coordination polymerization in aqueous systems, the syndiospecific living polymerization, and new activators for the catalysts, with regard to syndiotactic polystyrenes.     

Relative activity of transition metal catalysts in coal liquefaction

The catalytic activity of transition metals in coal liquefaction was studied and compared. Impregnation of coal with transition metals significantly increased oil production and asphaltene and preasphaltene conversion in coal liquefaction. Overall, coal conversion increased marginally and hydrocarbon gas production decreased slightly with metals. Iron impregnation was more active than cobalt, nickel, and molybdenum in preasphaltene conversion, whereas the other metals were more active than iron in asphaltene conversion. Hydrogen consumption decreased with all metals. The quality of generated solvent decreased with iron, but increased with other metals. Significant benefits were observed by using iron and molybdenum together; simultaneous impregnation of coal with iron and molybdenum significantly increased coal, asphaltene, and preasphaltene conversion, as well as oil production compared to individual metals. In addition, a mixture of iron and molybdenum decreased hydrocarbon gas production and increased hydrogen consumption and the quality of generated solvent over iron alone.     

Polymerization of N-substituted 2-propynamides with transition metal catalysts

Summary Polymerization of N-substituted 2-propynamides proceeded in the presence of Pd(II) catalysts such as [Pd(CH₃CN)₄](BF₄)₂, PdCl₂(PhCN)₂-n-BuLi, and PdCl₂(nbd)-n-BuLi. The molecular weights of the obtained polymers ranged 8,500 to 14,000, depending on the catalysts. From the ¹H NMR spectra, these polymers were found to have alternating double bonds in the main chain. Received: 25 December 2000/Revised version: 17 January 2001/Accepted: 19 January 2001     

Miniemulsion polymers as solid support for transition metal catalysts

A pentadentate salen-type ligand was immobilized in a poly[(styrene)]-co-(butyl acrylate)] matrix by miniemulsion polymerization. The obtained polymer beads revealed a particle size of 50 nm in the dry state by transmission electron microscopy. Dynamic light scattering experiments in methanol and water showed a solvent-dependent average particle size with a mean particle diameter of up to 233 nm in methanol. These results provide valuable insights for the optimization of macromolecular oxidation catalysts and their future use as enzyme-like entities in aqueous media. The particle stability was demonstrated over a wide pH range (3-11) by gel permeation chromatography, and initial results for the metal ion binding ability were obtained.     

Few layer graphene synthesis on transition metal ferrite catalysts

Development of cheap, green and up scalable production methods for graphene is one of the most challenging problems in its manufacture on an industrial scale. We report here a large scale substrate-free fluidized bed catalytic chemical vapour deposition (FB-CCVD) process for few layer graphene (FLG) powder production that uses a crystalline oxide catalyst of the general formula A_xB_3−xO₄, wherein the FLG layer thickness and domain sizes can be varied. A and B can be chosen from a list of transition elements including Co, Fe, Ni, Mn, Cu and Zn. The best results in terms of activity and selectivity are obtained for the Co_xFe_3−xO₄ system. We also investigated the reaction mechanism using in situ EXAFS and Raman spectroscopy, and electron tomography. Since FB-CCVD processes are already used for industrial scale production of carbon nanotubes, this process should enable the large scale production of free standing FLG in the near future.     

树枝状桥联过渡金属催化剂的合成、表征与性能

以1.0代聚酰胺-胺(PAMAM)与水杨醛为原料,通过席夫碱反应合成一类新型树枝状水杨醛亚胺配体,并进一步与铜、锌、镍络合得到3种树枝状桥联过渡金属催化剂;采用元素分析、红外光谱、核磁共振光谱和紫外光谱分析手段对树枝状配体及树枝状桥联催化剂的结构进行了表征,同时考察了催化剂对分解双氧水反应的催化性能.结果表明,树枝状配...     

乙烯聚合用树枝状过渡金属催化剂研究进展

树枝状过渡金属催化剂是在树枝状大分子上负载上过渡金属活性中心,因此,此类催化剂既具有树枝状大分子特有的艺术结构,同时还具有过渡金属配合物的功能化性能,使其两者能够协同发挥作用,兼具均相和非均相催化体系的特点,在催化烯烃聚合方面具有较高的催化活性和良好的催化稳定性,近年来备受关注,催化乙烯聚合就是其中的研究热点之一。本文按其过渡金属活性中心进行分类,综述了近年来国内外树枝状过渡金属催化剂在这乙烯聚合方面的进展,阐述了多种树枝状效应产生的原因,并且对乙烯聚合用树枝状过渡金属催化剂的发展前景进行了展望。     

Sonogashira偶联反应的过渡金属催化剂研究进展

Sonogashira偶联反应是形成新的C—C键及炔基化的最有效方法之一,金属催化剂在其中起着重要的催化作用。综述了近年来Sonogashira偶联反应中新发展起来的过渡金属催化剂,重点介绍了新型钯类催化剂在绿色化中的应用,以及其它过渡金属催化剂在Sonogashira偶联反应中的应用。指出Pd/C催化剂有望成为Sonogashira反应工业化应用的生力军,并且,水的存在、合适的催化体系以及碱体系等反应条件的选择对改善反应的环境亲和性具有重要意义。     

过渡金属多相催化剂催化的分子氧选择性氧化邻二醇研究进展

邻二醇选择性氧化断键生成醛、酮和羧酸是重要和基本的有机反应,氧化剂通常采用化学计量的高碘酸盐或四乙酸铅,无论从经济还是环保的角度考虑,这些传统方法都有违绿色化工的发展理念。理论上以分子氧为氧化剂选择性氧化邻二醇断键的副产物只有水,而且分子氧廉价易得,因而具有环境友好和经济可行的双重优势。经过多年探索,人们已发展了多个基于不同过渡金属为活性组分的多相催化剂或催化体系用于分子氧选择性氧化邻二醇断键反应,如钌、金、锰、钴,为未来广泛应用奠定了基础。本文将按贵金属和非贵金属分类综述此类催化剂及相关反应工艺的研究进展,并指出该领域的发展方向     

烯烃聚合后过渡金属催化剂的研究进展

综述了烯烃聚合后过渡金属催化剂的主要进展,提出了有待研究的问题,展望了后过渡金属催化剂在烯烃聚合中的应用。     

Silica–alumina-supported transition metal sulphide catalysts for deep hydrodesulphurization

Deep hydrodesulphurization (HDS) of dibenzothiophene (DBT) and gas-oil has been carried out on amorphous-silica–alumina (ASA)-supported transition metal sulphides (TMS) under conditions which approach industrial practice. The activity and selectivity of the binary Ni-, Ru- and Pd-promoted Mo catalysts were compared with the monometallic ones (Ru, Ir, Pd, Ni, Mo on ASA). For both HDS of DBT and gas-oil, the observed activity trends were similar; thus, all catalysts were more active with model feed than with gas-oil, and less active than commercial CoMo/Al₂O₃. The binary catalysts showed larger activity than monometallic ones, with Ni–Mo catalyst being more effective than Ru–Mo or Pd–Mo. For Ni–Mo sample, the X-ray photoelectron and temperature-programmed reduction techniques confirmed that incorporation of Mo minimises metal–support interaction, although the formation of nickel hydrosilicate was not prevented. The consecutive impregnation of calcined Mo/ASA catalyst with precursor solution followed by calcination enhances molybdenum surface exposure in binary samples. As a consequence, the temperature of reduction of MoO₃ to molybdenum suboxides is decreased.     

新型后过渡金属烯烃催化剂的研究进展

综述了近年来－系列新型α－二亚胺型后过渡金属（Ni、Pd、Fe、Co）催化剂在烯烃聚合、极性单体共聚、烯烃齐聚、环烯烃加成聚合、烯烃活性聚合和聚烯烃纳米复合物等方面的最新进展。系统地阐述了不同的中心过渡金属离子、α－二亚胺骨架、骨架上的取代基和不同的聚合条件（温度、压力）分别对催化剂的聚合活性、聚烯烃支化率、聚合物分子量和分子量分布以及聚合产物的性质等影响，并且简要说明了这一类催化剂的制备方法和新特点。     

后过渡金属烯烃聚合催化剂的研究进展

综述了以后过渡金属 (Ni,Pd ,Fe和Co)络合物为主催化剂的烯烃聚合催化剂的发现、沿革及研究进展 ,包括催化剂的合成、结构、性能、催化烯烃聚合机理等。     

Effect of transition metal catalysts on the microstructure of carbide-derived carbon

Carbon materials with different microstructure can be produced by a carbide-derived carbon (CDC) approach varying the carbide precursor and the reaction conditions for the selective etching of the metal. CDC was produced using biomorphic TiC and SiC ceramics derived from paper preforms by a chemical vapor infiltration and reaction technique. In this work the effect of transition metal salt catalysts such as Ru(III), Fe(II), Fe(III) or Ru(III)/Fe(III) on the chlorination process at temperatures in the range 600-1200 °C as well as on the microstructure of the resulting carbon was investigated. The produced CDC was characterized by its degree of order and pore structure using Raman spectroscopy, high resolution transmission electron microscopy and low temperature nitrogen adsorption. A higher etching rate as well as a higher degree of order at lower reaction temperatures was observed if a catalytically active metal was present during the chlorination process. This effect was mostly pronounced in the case of a Ru(III)/Fe(III) bimetallic catalyst. The higher degree of order of the carbon is associated with an increased amount of mesopores and with a decrease in specific surface area. Therefore, the CDC processing in the presence of catalysts offers another way to produce ordered carbon structures at lower temperatures.     

Catalytic growth of semiconductor micro- and nano-crystals using transition metal catalysts

The catalytic reaction concept was introduced in the growth of semiconductor micro- and nano-crystals. It was found that gallium nitride (GaN) micro- and nano-crystal structures, carbon nanaotubes, and silicon carbide (SiC) nanostructures could be efficiently grown using transition metal catalysts. The use of Ni catalyst enhanced the growth rate and crystallinity of GaN micro-crystals. At 1,100 ‡C, the growth rate of GaN micro-crystals grown in the presence of Ni catalyst was over nine times higher than that in the absence of the catalyst. The crystal quality of the GaN microcrystals was almost comparable to that of bulk GaN. Good quality GaN nanowires was also grown over Ni catalyst loaded on Si wafer. The nanowires had 6H hexagonal structure and their diameter was in the range of 30–50 nm. Multiwall nanotubes (MWNTs) were grown over 20Fe : 20Ni : 60Al₂O₃ catalyst. However, single wall nanotubes (SWNTs) were grown over 15Co : 15Mo : 70MgO catalyst. This result showed that the structure of CNTs could be controlled by the selection of catalysts. The average diameters of MWNTs and SWNTs were 20 and 10 nm, respectively. SiC nanorod crystals were prepared by the reaction of catalytically grown CNTs with tetrametysilane. Structural and optical properties of the catalytically grown semiconductor micro- and nano-crystals were characterized using various analytic techniques. This paper is dedicated to Professor Wha Young Lee on the occasion of his retirement from Seoul National University.     

Thermal and crystallization behaviors of polyethylene blends synthesized by binary late transition metal catalysts combinations

A series of reactor blends of linear and branched polyethylenes have been prepared, in the presence of modified methylaluminoxane, using a combination of 2,6‐bis[1‐(2,6‐dimethyphenylimino) pyridyl]‐cobalt(II) dichloride ( 1 ), known as an active catalyst for producing linear polyethylene, and [1,4‐bis(2,6‐diidopropylphenyl)] acenaphthene diimine nickel(II) dibromide ( 2 ), which is active for the production of branched polyethylene. The polymerizations were performed at various levels of catalyst feed ratio at 10 bar. The linear correlation between catalyst activity and concentration of catalyst 2 suggested that the catalysts performed independently from each other. The weight‐average molecular weights , crystalline structures, and phase structures of the blends were investigated, using a combination of gel permeation chromatography, differential scanning calorimetry, wide‐angle X‐ray diffraction, and small angle X‐ray scattering techniques. It was found that the polymerization activities and MWs and crystallization rate of the polymers took decreasing tendency with the increase of the catalyst 2 ratios, while melting temperatures (T_m), crystalline temperatures (T_c), and crystalline degrees took decreasing tendency. Long period was distinctly influenced by the amorphous component concentration. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 4188–4198, 2007