Syntheses of poly(siloxane)-supported zirconocene catalysts and application to olefin polymerizations

Arai, Takashi; Uozumi, Toshiya; Soga, Kazuo

doi:10.1002/(sici)1099-0518(199802)36:3<421::aid-pola6>3.0.co;2-u

Cited by 23 publications

(6 citation statements)

References 2 publications

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“…Generally speaking, the toluene soluble catalysts display higher activities to give polyethene with slightly lower M w . Since we used a mixture of mesoand rac-isomers of Ind 2 SiCl 2 in the catalyst preparation for convenience, the polyethenes produced here showed considerably broad molar mass distributions (M w /M n ) as reported previously 18) . It was found that the activities of these catalysts drastically increase when rising the polymerization temperature from 40 up to 70 8 C. To test the stability of the active species more precisely, the polymerization of ethene was carried out at 100 and 120 19) .…”

Section: Resultssupporting

confidence: 58%

Synthesis of metallocene catalysts supported on poly[p-(silylene)phenylene] derivatives for the application to olefin polymerizations

Uozumi

Sano

Soga³

1999

Macromol. Chem. Phys.

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The polymeric [Ind 2 Si(C 6 H 4 )] n and [Ind 2 Si(C 6 H 4 ) 2 ] m compounds (Ind = indenyl) were synthesized via the condensation reaction of bisindenyldichlorosilane and p-dilithiobenzene or p-dilithiobiphenyl, and the supported-type zirconocene catalysts were prepared by reacting them with zirconium tetrachloride. The content of zirconium in the catalysts is much higher than that in the metallocene catalysts supported by inorganic compounds. Polymerizations of ethene and propene were conducted with them using methylaluminoxane (MAO) or ordinary alkylaluminiums as cocatalysts and toluene as the solvent. The catalysts combined with MAO display very high activities especially for the ethene polymerization. From the polymerization at high temperatures, it was found that the active species are markedly stabilized, probably due to the rigid backbones of the carriers. The activity of the catalysts activated with ordinary alkylaluminiums is far less as compared with those activated with MAO.

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Section: Resultssupporting

confidence: 58%

Synthesis of metallocene catalysts supported on poly[p-(silylene)phenylene] derivatives for the application to olefin polymerizations

Uozumi

Sano

Soga³

1999

Macromol. Chem. Phys.

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“…In this way, Soga and co-workers [6,7] have elaborated well-defined poly(siloxane)s containing aromatic substituents (indenyl, fluorenyl, etc.) and have used the latter as carriers and as ligands of zirconocene catalysts.…”

Section: Introductionmentioning

confidence: 99%

Functionalized Star‐Like Polystyrenes as Organic Supports of a Tridentate Bis(imino)pyridinyliron/Aluminic Derivative Catalytic System for Ethylene Polymerization

Bouilhac

Cloutet

Cramail

et al. 2005

Macromol. Rapid Commun.

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Summary: Star‐like polystyrenes composed of a microgel core with arms functionalized with a few hydroxy‐ or methoxy‐ended ethylene oxide units were used as organic supports for a tridentate bis(imino)pyridinyliron catalyst towards ethylene polymerization. When used as supports of 2,6‐bis[1‐2,6(diisopropylphenyl)imino]ethylpyridynyl iron dichloride in the presence of various alkylaluminium compounds, the supported catalysts enabled the production, with a high catalytic activity, of polyethylene beads of a spherical morphology and high bulk density. A good control of the polyethylene molar mass distribution could also be achieved, which was explained by a lowering of the transfer reaction to the aluminium derivative, as compared to homogeneous conditions.SEM image of PE particles prepared in the presence of trimethylaluminium supported on a PS microgel with an iron catalyst (TMA/Fe = 800).imageSEM image of PE particles prepared in the presence of trimethylaluminium supported on a PS microgel with an iron catalyst (TMA/Fe = 800).

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“…[3][4][5] The reports on the use of polysiloxanes as catalyst supports are very scarce. [6][7][8] Polysiloxanes are known for their extreme flexibility, which may be advantageous, as the chain may easily adopt optimal conformation for catalytic centers to participate in the reaction. Polysiloxanes are also chemically and thermally stable and highly soluble in many organic solvents.…”

Section: Introductionmentioning

confidence: 99%

Soluble Alkylthiopolysiloxane-Supported Palladium Catalysts for the Heck Reaction

Cypryk

Pośpiech

Strzelec³

et al. 2009

Phosphorus, Sulfur, and Silicon and the Related Elements

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Soluble polysiloxanes with 2-butylthioethyl side groups have been used as support for palladium(II) catalyst. Catalytic activity of such immobilized palladium complex was tested in a model Heck reaction. The activity of the complex in terms of yield and turnover number was comparable to that of PdCl 2 (PhCN) 2 . Polysiloxanesupported catalyst shows good stability and low leaching, and its catalytic activity maintained practically unchanged through five catalytic cycles. According to XPS analysis, palladium in the complex with polysiloxane containing thioether groups appears as Pd(II).

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Syntheses of poly(siloxane)-supported zirconocene catalysts and application to olefin polymerizations

Cited by 23 publications

References 2 publications

Synthesis of metallocene catalysts supported on poly[p-(silylene)phenylene] derivatives for the application to olefin polymerizations

Synthesis of metallocene catalysts supported on poly[p-(silylene)phenylene] derivatives for the application to olefin polymerizations

Functionalized Star‐Like Polystyrenes as Organic Supports of a Tridentate Bis(imino)pyridinyliron/Aluminic Derivative Catalytic System for Ethylene Polymerization

Soluble Alkylthiopolysiloxane-Supported Palladium Catalysts for the Heck Reaction

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