Ethylene oligomerization by tridentate cobalt complexes bearing pendant donor modified α-diimine ligands

Bahuleyan, Bijal Kottukkal; Ahn, In Yong; Appukuttan, Vinukrishnan; Lee, So Hyun; Ha, Chang‐Sik; Kim, Il; Suh, Hongsuk

doi:10.1007/s13233-010-0710-y

Cited by 9 publications

(3 citation statements)

References 9 publications

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“…As an important industrial raw material, α-olefin is widely used in the synthesis of detergents, plasticizers, lubricating oils, fine chemicals, linear low-density polyethylene (LLDPE) and monomers of copolymerization [1][2][3][4]. The main technologies of producing α-olefin are wax cracking method, gas method and ethylene oligomerization method.…”

Section: Introductionmentioning

confidence: 99%

Synthesis and ethylene oligomerization behavior of trinuclear nickel complex with phosphorus dendrimer

et al. 2021

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A phosphorus dendrimer with multiple amino groups was synthesized via a two-step reaction with phosphonitrilic chloride trimer and 4-acetamidophenol. The trinuclear nickel complex was subsequently prepared with the phosphorus dendrimer and nickel chloride hexahydrate as starting materials. The structures of the phosphorus dendrimer and the trinuclear nickel complex were characterized by physicochemical and spectroscopic methods. The trinuclear nickel complex based on the phosphorus dendrimer was evaluated as catalyst precursor for ethylene oligomerization using methylaluminoxane (MAO) as an activator. Under the conditions of 0.5 h, 0.9 MPa, 25 °C and Al/Ni molar ratio of 700, the catalytic activity of the trinuclear nickel complex showed a maximum value of 2.31 × 10 5 g/(mol Ni h), and the oligomerization products were mainly low-carbon olefins (C 4 and C 6 ). The ligand structure and the coordination mode showed notable variations in the catalytic activities and the product distribution due to the influence of electronic and steric effects. The catalytic activity of the nickel complex based on the ligand with an aryl backbone was superior to the nickel complex based on the ligand with an alkyl backbone.

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Section: Introductionmentioning

confidence: 99%

Synthesis and ethylene oligomerization behavior of trinuclear nickel complex with phosphorus dendrimer

et al. 2021

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“…They are used for copolymerization with ethylene for the purpose of obtaining low-and high-density linear polyethylene and for the preparation of detergents and synthetic lubricants [12,14,41,48,54,61,62]. They can also be used in the production of surfactants, agents for enhanced oil recovery, corrosion inhibitors, high-performance lubricating oils, linear alkylbenzenes, oxo-synthesis alcohols, a-olefin sulfonates, oil additives, and as drilling fluids [1,3,6,28,35,51,59]. The worldwide growth rate of LAOs production between 1980 and 1990 amounted to 10-15 wt% per year.…”

Section: Introductionmentioning

confidence: 99%

A kinetic model for ethylene oligomerization using zirconium/aluminum- and nickel/zinc-based catalyst systems in a batch reactor

et al. 2014

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The aim of this work is to develop a kinetic model of the oligomerization of ethylene to linear alpha olefins (LAOs) for zirconium/aluminum and nickel/zinc catalyst systems. The development of such model helps in the study of the behavior of industrial LAOs reactors as well as in the optimization of their operation. The kinetic model was developed based on a four-step mechanism: site activation, initiation and propagation, chain transfer and site deactivation. A novel stochastic optimization algorithm, Intelligent Firefly Algorithm, was used to obtain the kinetic model parameters that best fit the available experimental data that were obtained from published sources. The values of the kinetic parameters were obtained for the developed kinetic models for two catalyst systems. The performance of the model with the estimated parameters was tested against the experimental data. The proposed kinetic model predicts the product distribution for the zirconium/aluminum catalyst system with suitable accuracy. The model can also predict the product distribution for the nickel/zinc catalyst system with good accuracy for all products. As expected, the accuracy of the model to predict the concentration of the higher carbon products decreases with the carbon number. Keywords Ethylene Á Oligomerization Á Modeling Á Zirconium/aluminum catalyst Á Nickel/zinc catalyst Abbreviation Notation A Pre-exponential factor C CAT Catalyst concentration, mol/l C CAT k Active catalyst concentration, mol/l C CAT k ÁM Complex active catalyst/ethylene concentration, mol/l C decy Moles of deactivated catalysts, mol C M Concentration of ethylene monomer, mol/l C M k Concentration of active ethylene monomer, mol/l C M k ÁTEA Concentration of complex active ethylene monomer/co-catalyst, mol/l C P 0 Concentration of active site, mol/l C P i Concentration of living polymers, mol/l C P k i Concentration of active living polymers, mol/l C P k i ÁTEA Concentration of complex active living polymers/co-catalyst, mol/l C TEA Co-catalyst concentration, mol/l C TEA k Active co-catalyst concentration, mol/l C TEA k ÁCAT Complex active co-catalyst/catalyst concentration, mol/l C TEA k 1 ÁCAT Complex active co-catalyst/catalyst concentration-catalyst, mol/l D Moles of dead oligomer, mol E Activation energy, cal/mol k 1 Rate constant of active site k 2 Rate constant of chain initiation k 3 Rate constant of chain propagation k 4 Rate constant of chain transfer k 5 Rate constant of deactivation k ?1 Rate constant of attachment of the catalyst in the site activation k-1 Rate constant of detachment of the catalyst in the site activation

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“…[22,23] are applied to olefin polymerization. The products obtained using such catalysts can be changed from polyethylene (PE) to oligomers by tuning the steric and electronic properties of the ligands [24]. Bulky complexes can produce high-molecular-weight branched PE, without the addition of α-olefin comonomers, in the presence of methylaluminoxane (MAO).…”

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Recent progress in immobilization of late-transition-metal complexes with diimine ligands for olefin polymerization

Jiang

et al. 2013

Chin. Sci. Bull.

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Late-transition-metal (LTM) catalysts are a family of very flexible ethylene polymerization catalysts because their catalytic performance can be easily adjusted by modifying the ligand structure. Their less oxyphilicity character, which may promote the production of copolymers from ethylene and polar comonomers, is another aspect that attracts much attention in both academic and industrial fields. The immobilization of LTM catalysts on spherical supports is a crucial step prior to their use in the industrial processes of gas-phase or slurry polymerizations. This paper reviews recent developments in supported LTM catalysts for olefin polymerization, and summarizes loading methods and mechanisms of the immobilization of LTM catalysts on inorganic, organic, and inorganic-organic materials, and the effects of immobilization on catalytic activity, polymerization mechanism, and polymer morphology. [22,23] are applied to olefin polymerization. The products obtained using such catalysts can be changed from polyethylene (PE) to oligomers by tuning the steric and electronic properties of the ligands [24]. Bulky complexes can produce high-molecular-weight branched PE, without the addition of α-olefin comonomers, in the presence of methylaluminoxane (MAO). Some bulky catalysts with special backbone such as camphyl and acenaphthyl show highly thermal stability and good control ability for olefin polymerization [25]. Late transition-metals are more suitable for the copolymerization of ethylene with commercial polar olefins because of their better tolerance of polar functional groups. Only amorphous polymers can be obtained if the polymerization is catalyzed by homogeneous catalysts, inevitably leading to reactor fouling in industrial units. To meet the requirements of continuous industrial gas-phase or slurry polymerization units, a crucial step for the industrialization of LMT catalysts is the immobilization of such catalysts on spherical supports to obtain morphologically uniform polymer particles. late-transition-metal complexes, diimine, immobilization, olefin polymerization

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Ethylene oligomerization by tridentate cobalt complexes bearing pendant donor modified α-diimine ligands

Cited by 9 publications

References 9 publications

Synthesis and ethylene oligomerization behavior of trinuclear nickel complex with phosphorus dendrimer

Synthesis and ethylene oligomerization behavior of trinuclear nickel complex with phosphorus dendrimer

A kinetic model for ethylene oligomerization using zirconium/aluminum- and nickel/zinc-based catalyst systems in a batch reactor

Recent progress in immobilization of late-transition-metal complexes with diimine ligands for olefin polymerization

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