Direct Precise Functional Group Introduction into Polyolefins: Efficient Incorporation of Vinyltrialkylsilanes in Ethylene Copolymerizations by Nonbridged Half-Titanocenes

Nomura, Kotohiro; Kakinuki, Kenichi; Fujiki, Michiya; Itagaki, Koji

doi:10.1021/ma8020757

Cited by 37 publications

(34 citation statements)

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“…[41][42][43][44][45] In particular, 4-methylcyclohexene (4-MeCHE) and 1-methylcyclopentene (1-MeCPE) copolymers have been synthesized recently with nonbridged half-titanocenes containing anionic donor ligands of type, Cp'TiX2(Y) (Cp' = cyclopentadienyl group, Y = aryloxo, ketimide, phosphinimide etc.) [46].…”

Section: Microstructural Analysis Of Poly(ethylene-co-4-mechche) and mentioning

confidence: 99%

Microstructure of Copolymers of Norbornene Based on Assignments of 13C NMR Spectra: Evolution of a Methodology

2018

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An overview of the methodologies to elucidate the microstructure of copolymers of ethylene and cyclic olefins through 13 C Nuclear magnetic resonance (NMR) analysis is given. 13 C NMR spectra of these copolymers are quite complex because of the presence of stereogenic carbons in the monomer unit and of the fact that chemical shifts of these copolymers do not obey straightforward additive rules. We illustrate how it is possible to assign 13 C NMR spectra of cyclic olefin-based copolymers by selecting the proper tools, which include synthesis of copolymers with different comonomer content and by catalysts with different symmetries, the use of one-or two-dimensional NMR techniques. The consideration of conformational characteristics of copolymer chain, as well as the exploitation of all the peak areas of the spectra by accounting for the stoichoimetric requirements of the copolymer chain and the best fitting of a set of linear equation was obtained. The examples presented include the assignments of the complex spectra of poly(ethylene-co-norbornene (E-co-N), poly(propylene-co-norbornene (P-co-N) copolymers, poly(ethylene-co-4-Me-cyclohexane)s, poly(ethylene-co-1-Me-cyclopentane)s, and poly(E-ter-N-ter-1,4-hexadiene) and the elucidation of their microstructures.

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Section: Microstructural Analysis Of Poly(ethylene-co-4-mechche) and mentioning

confidence: 99%

Microstructure of Copolymers of Norbornene Based on Assignments of 13C NMR Spectra: Evolution of a Methodology

2018

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“…This is because ATMS also plays the role of chain transfer reagent due to a favored bhydrogen elimination after bulky ATMS insertion (Previous reports for polymerization of ATMS by metallocenes [160,161]). The copolymerization with ATMS by Cp*TiCl 2 (O-2,6-i Pr 2 C 6 H 3 ) (2a) proceeded efficiently, affording high molecular weight copolymers with uniform molecular weight distributions (Scheme 2.8, Table 2.7) [162,163]. The activity by 2a increased upon increasing the initial ATMS concentration and/or ethylene pressure.…”

Section: Copolymerization Of Tert-butylethylene A-olefins Containingmentioning

confidence: 99%

Olefin Polymerization with Half-Metallocene Catalysts

Nomura

Liu

2014

Organometallic Reactions and Polymerization

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In this chapter, recent development of half-sandwich titanium complexes containing anionic donor ligands as the catalyst precursors for olefin polymerization has been described. These catalysts display unique characteristics especially for synthesis of new ethylene copolymers by incorporation of new monomers that are very difficult or impossible to be incorporated in ethylene copolymerization by conventional Ziegler-Natta and ordinary metallocene catalysts. Both cyclopentadienyl fragment and anionic donor ligand play an essential key role for both the catalytic activity and the comonomer incorporation in the copolymerization.

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“…Later, we found that the copolymerization by the constrained geometry catalyst (2) also proceeded efficiently [49]. The attempted copolymerization using Cp 2 ZrCl 2 -MAO catalyst afforded linear polyethylene with low catalytic activity [48].…”

Section: Efficient Introduction Of Functional Group Into Polyolefins mentioning

confidence: 97%

“…possessed high molecular weights with uniform molecular weight distributions [48]. Complex 7 exhibited both higher catalytic activities and better VTMS incorporations than 1: efficient synthesis of high molecular weight 1-x SiR' 3 x R' = Me, Et MAO copolymers with uniform compositions could be achieved by adopting 7, although both the activity and the M n values decreased upon increasing the VTMS contents.…”

Section: Efficient Introduction Of Functional Group Into Polyolefins mentioning

confidence: 99%

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A Greener Approach for Synthesis of Functionalized Polyolefins by Introducing Reactive Functionality into Ethylene Copolymers

Apisuk¹,

Tsutsumi²,

Kim³

et al. 2014

GSC

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Direct Precise Functional Group Introduction into Polyolefins: Efficient Incorporation of Vinyltrialkylsilanes in Ethylene Copolymerizations by Nonbridged Half-Titanocenes

Cited by 37 publications

References 50 publications

Microstructure of Copolymers of Norbornene Based on Assignments of 13C NMR Spectra: Evolution of a Methodology

Microstructure of Copolymers of Norbornene Based on Assignments of 13C NMR Spectra: Evolution of a Methodology

Olefin Polymerization with Half-Metallocene Catalysts

A Greener Approach for Synthesis of Functionalized Polyolefins by Introducing Reactive Functionality into Ethylene Copolymers

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