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• W2801589399 abstract "ABSTRACT Vinylsilanes CH 2 CHSiR 3 (R = Me, NMe 2 , OMe, OTMS) copolymerize with ethylene rapidly in the presence of catalytic amounts of [Cp′ 2 ZrMe][MeB(C 6 F 5 ) 3 ] (Cp′ = η 5 ‐C 5 Me 5 ) ( I ) to give high molecular weight silyl‐functionalized polyethylene. The molecular weight of the polymer can be controlled by varying the comonomer concentration as well as the reaction temperature. Relatively low molecular weight polymer was produced at a higher silyl monomer concentration and a higher polymerization temperature. The incorporation of silyl monomer in the polymer is in the range of 0.1‐ 6.0%. On the other hands, catalysts [Cp 2 ZrMe][MeB(C 6 F 5 ) 3 ] (Cp′ = η 5 ‐C 5 H 5 ) ( II ) and [Cp″ 2 ZrMe][MeB(C 6 F 5 ) 3 ] (Cp″ = η 5 ‐1,2‐C 5 Me 2 H 3 ) ( III ) show much lower activity. With the use of more coordinatively unsaturated constrained geometry catalysts (CGC), Me 2 Si(η 5 ‐C 5 Me 4 )(N t Bu)MMe][MeB(C 6 F 5 ) 3 ] ( IV , M = Zr; V , M = Ti), the silyl monomer incorporation in the polymer was increased to 40%. The Ti catalyst is more active and produces polymer with a higher molecular weight with a higher silyl monomer incorporation at 23 °C. The copolymerization of vinyltrimethylsilane with propylene was also investigated with these catalysts, yielding high silyl‐functionalized propylene copolymer/oligmer. The microstructure of the copolymers/oligomers has been thoroughly investigated by 1D and 2D NMR techniques ( 1 H, 13 C, NOE, DEPT, HETCOR, and FLOCK). The results show that the backbone of the copolymers/oligomers is essentially random. Several termination pathways have been identified. In particular, two unsaturated silyl terminations, cis and/or trans‐TMSCHCH, were identified with the constrained geometry catalysts. Their formation was rationalized based on transition state models. It was found that occasional 1,2‐insertion of either propylene or vinyltrimethylsilane into the chain propagation process has a high probability serving as the trigger for polymer chain termination via β‐H elimination. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2018 , 56 , 1308–1321" @default.
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• W2801589399 date "2018-04-17" @default.
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• W2801589399 title "Silyl-functionalized polyolefins via co-polymerization of vinylsilanes with ethylene or propylene catalyzed by group IV metallocene complexes" @default.
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• W2801589399 doi "https://doi.org/10.1002/pola.29012" @default.
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