Preparation of Silica-Supported Bis(imino)pyridyl Iron(II) and Cobalt(II) Catalysts for Ethylene Polymerization

Kim, Il; Han, Byeong Heui; Ha, Chang‐Sik; Kim, Jae-Kon; Suh, Hongsuk

doi:10.1021/ma0347060

Cited by 59 publications

(39 citation statements)

References 14 publications

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“…a Only original reports given Table 2 (continued) [2,6-(ArN=CMe) 2 -4-R-C 5 H 2 N] ( 1 R = t -butyl [55] ), allyl [69] , O( ω -alkenyl) [57,58] , benzyl [69] , Cl [56] , 2-methyl-2-phenylpropyl [69] ) in which the 4-position of the central pyridine unit in 1 can be varied; this latter site also being used to facilitate the linking of two bis(imino)pyridine units [54] .…”

Section: Ligand Preparationmentioning

confidence: 99%

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Iron-Based and Cobalt-Based Olefin Polymerisation Catalysts

Gibson¹,

Solan²

2008

Topics in Organometallic Chemistry

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This chapter describes the brief history of iron or cobalt catalysts for olefin polymerisation and oligomerisation. Since the discovery in 1998 that 2,6-bis(imino)pyridine iron and cobalt halides, on activation with MAO, can convert ethylene to highly linear polyethylene, numerous reports have been concerned with ligand modification, mechanisms for precatalyst activation, identifying the active species and understanding the mode of propagation/chain transfer. In addition, heterogenisation of this class of catalysts, their incorporation into macrocycles/ polymers and their use in reactor blending/tandem catalysis has seen some important developments; alternative ligand architectures that can support active iron and cobalt catalysts are also discussed as are different types of olefinic monomer.

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Section: Ligand Preparationmentioning

confidence: 99%

“…The 4-position on the central pyridyl ring has also been employed as the site for supporting iron catalysts [57,58,137] . For example, Kim et al have used the 4-substituted O -allyl group in 1 (Ar = 2,6-Me 2 C 6 H 3 ) as a means of generating silica-supported iron and cobalt systems ( 39 ) ( Scheme 12 ) [58] .…”

Section: Supported Catalystsmentioning

confidence: 99%

Iron-Based and Cobalt-Based Olefin Polymerisation Catalysts

Gibson¹,

Solan²

2008

Topics in Organometallic Chemistry

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“…They then prepared a novel series of supported LTM catalysts by coordination reactions of metal compounds with ligands attached to SiO 2 . The metal active center loading of the supported catalyst was 45.9 mg-Fe/gcatalyst, about four times higher than that obtained by Kaul et al [34] and Kim et al [35]. Kim and coworkers [37] used three methods to immobilize Ni-based α-diimine catalysts on nonporous SiO 2 covalently, without using any lengthy conventional processes.…”

Section: Late-transition-metal Catalysts Immobilized On Sio 2 Supportsmentioning

confidence: 87%

“…With the aim of achieving higher loadings of active centers in SiO 2 -supported catalysts reported in previous studies [34,35], Zheng et al [36] modified the diimine ligands by hydrosilylation of bis(imino)pyridyl containing an allyl group with dichloromethylsilane to introduce Si-Cl endgroups; these end-groups could react with -OH groups on the SiO 2 surface. They then prepared a novel series of supported LTM catalysts by coordination reactions of metal compounds with ligands attached to SiO 2 .…”

Section: Late-transition-metal Catalysts Immobilized On Sio 2 Supportsmentioning

confidence: 99%

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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“…Despite the success of this new approach to the synthesis of branched polyethylenes by homogeneous late transition metal catalysts, the extension of this technique to heterogeneous polymerization catalyst will allow us to implement the late transition metal catalysts in existing industrial processes and to improve the morphology of branched polyethylene. Inorganic oxide SiO 2 has been used as catalyst supports due to their high surface area and good morphology [5][6][7][8][9]. MgCl 2 is also a good support for preparation of highly efficient the late transition metal catalysts [10][11][12][13][14][15].…”

Section: Introductionmentioning

confidence: 99%

Polymerization of ethylene using a nickel α-diimine complex covalently supported SiO2-MgCl2 bisupport

Jiang

Xiao

2011

E-Polymers

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Bisupported catalyst for ethylene polymerization was prepared by mixing alcohol solution of MgCl 2 with pretreated SiO 2 in heptane, the prepared bisupport was modified by treatment with alkyl aluminum compounds, and further treatment with bis(4-(4-amine-3,5-diisopropylbenzyl)-2,6-diisopropylphenylimino) acenaphthene NiBr 2 (abbreviaed as NiLBr 2 ) solution. The most significant feature of the supported catalyst is that it polymerizes ethylene with high activities in the presence of inexpensive general alkylaluminum compounds. According to the results of high temperature GPC, the number-average molecular weights of the polymers ranged from 2.15×10 5 to 9.27×10 5 and the polydispersities ranged from 3.12 to 4.23. By modulating the polymerization temperatures, the products of different and good morphologies were obtained. The resultant PE was confirmed by 13 C NMR to contain significant amounts of not only methyl but also ethyl, propyl, butyl,amyl, and long branches (longer than six carbons).

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Preparation of Silica-Supported Bis(imino)pyridyl Iron(II) and Cobalt(II) Catalysts for Ethylene Polymerization

Cited by 59 publications

References 14 publications

Iron-Based and Cobalt-Based Olefin Polymerisation Catalysts

Iron-Based and Cobalt-Based Olefin Polymerisation Catalysts

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

Polymerization of ethylene using a nickel α-diimine complex covalently supported SiO2-MgCl2 bisupport

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