Synthesis and catalytic performance in ethylene and 1-octene polymerization of chlorotitanium(IV) silsesquioxane complexes. Effect of increasing ligand denticity and type of nonreactive organic substituents

Although homogeneous catalysts provide high performance and selectivity, the difficulty of separation and recycling of these catalysts has bothered the scientific community worldwide. Therefore, the demand for heterogeneous catalysts that possess the advantages of homogeneous ones, with ease of separation and recyclability remains a topic of major impact. The oligomeric catalyst synthesized in this work was characterized using elemental analysis, Fourier transform infrared, 13 C NMR, 29 Si NMR and energy-dispersive X-ray spectroscopies, X-ray diffraction, thermogravimetric analysis, scanning electron microscopy and Brunauer-Emmett-Teller analysis and compared to its homogeneous counterpart [W(CO) 3 Br 2 (ATC)] in the epoxidation of 1-octene, cyclooctene, (S)-limonene, cis-3-hexen-1-ol, trans-3hexen-1-ol and styrene. The results showed that the percentage conversion for the homogeneous species [W(CO) 3 Br 2 (ATC)] was slightly higher than for the oligomeric catalyst (POSS-ATC-[W(CO) 3 Br 2 ]). Furthermore, the selectivity for epoxide of the oligomeric catalyst was greater than that of the homogeneous catalyst by about 25% when (S)-limonene was used. Great conversions (yields) of products were obtained with a wide range of substrates and the catalyst was recycled many times without any substantial loss of its catalytic activity.

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Synthesis, characterization and catalytic application of a new organometallic oligomer based on polyhedral oligomeric silsesquioxane

Vieira

Silva

Furlani

et al. 2017

Applied Organom Chemis

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Heptanuclear Cage Cu^II‐Silsesquioxanes: Synthesis, Structure and Catalytic Activity

et al. 2018

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Two prismatic phenyl-(PhSiO 1.5 ) 14 (CuO) 7 (1, 29 % yield) and methyl-(MeSiO 1.5 ) 14 (CuO) 7 (2, 19 % yield) heptacoppersilsesquioxanes were obtained by the interaction of Cu,Na-based cage silsesquioxanes [(RSiO 1.5 ) 12 (CuO) 4 (NaO 0.5 ) 4 ] (R = Ph, Me) with 4,4′-bipyridine and pyrazine, respectively, acting as "silent witness" ligands. Unusual molecular topologies of both compounds 1 and 2, which are the first representatives of [a] Nesmeyanov Institute of Organoelement Compounds,

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Synthesis and catalytic properties for olefin polymerization of new vanadium complexes containing silsesquioxane ligands with different denticity

Białek

Pochwała

Franczyk

et al. 2017

Polymer International

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A series of new vanadium‐silsesquioxanes (2a − 2d) was prepared by reacting VCl4 with not fully condensed silsesquioxanes (having from one to four silanol groups) and evaluated as pre‐catalysts in olefin polymerization. The activation of 2a − 2d with EtAlCl2 generated highly active catalysts for ethylene polymerization, yielding high molar mass polymers with narrow dispersity. Ultra‐high molar mass polyethylenes, Mw up to 4 × 106 g mol−1, were obtained with methylaluminoxane and Al(iBu)3/[Ph3C][B(C6F5)4] as activators. Upon treatment with methylaluminoxane and boron compounds, all vanadium pre‐catalysts were active in 1‐octene polymerization as well, and produced isotactic‐rich poly(1‐octene)s with moderate monomer conversion (up to 23%). The polymerization parameters were optimized and the effect of the silsesquioxane structure on the catalytic activity and polymer properties was studied. © 2017 Society of Chemical Industry

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Synthesis and catalytic performance in ethylene and 1-octene polymerization of chlorotitanium(IV) silsesquioxane complexes. Effect of increasing ligand denticity and type of nonreactive organic substituents

Cited by 7 publications

References 34 publications

Synthesis, characterization and catalytic application of a new organometallic oligomer based on polyhedral oligomeric silsesquioxane

Synthesis, characterization and catalytic application of a new organometallic oligomer based on polyhedral oligomeric silsesquioxane

Heptanuclear Cage Cu^II‐Silsesquioxanes: Synthesis, Structure and Catalytic Activity

Synthesis and catalytic properties for olefin polymerization of new vanadium complexes containing silsesquioxane ligands with different denticity

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Synthesis and catalytic performance in ethylene and 1-octene polymerization of chlorotitanium(IV) silsesquioxane complexes. Effect of increasing ligand denticity and type of nonreactive organic substituents

Cited by 7 publications

References 34 publications

Synthesis, characterization and catalytic application of a new organometallic oligomer based on polyhedral oligomeric silsesquioxane

Synthesis, characterization and catalytic application of a new organometallic oligomer based on polyhedral oligomeric silsesquioxane

Heptanuclear Cage CuII‐Silsesquioxanes: Synthesis, Structure and Catalytic Activity

Synthesis and catalytic properties for olefin polymerization of new vanadium complexes containing silsesquioxane ligands with different denticity

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Heptanuclear Cage Cu^II‐Silsesquioxanes: Synthesis, Structure and Catalytic Activity