Synthesis of polyolefins containing silacycloalkane units in the main chain, 1 copolymerization of ethylene and disubstituted diallylsilanes involving intramolecular cyclization with zirconocene catalysts

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Abstract

Copolymerizations of ethylene and disubstituted diallylsilanes (CH 2=CH-CH2)2R2Si (R = CH3, C6H5) have been investigated with various zirconocene catalysts using methylaluminoxane as a cocatalyst. The bridged stereospecific catalysts showed a higher reactivity for disubstituted diallylsilanes than the non-bridged aspecific catalysts, Disubstituted diallylsilanes were incorporated into the polymer chain via cyclization insertion preferentially, and formed 3,5-disubstituted silacyclohexane units in the polyethylene main chain. A zirconocene catalyst, dimethylsilylenebis(indenyl)zirconium dichloride, produced a copolymer containing pendant ullyl groups derived from the 1,2-insertion of diallyldiphenylsilane without cyclization.

Original languageEnglish
Pages (from-to)1959-1966
Number of pages8
JournalMacromolecular Chemistry and Physics
Volume206
Issue number19
DOIs
Publication statusPublished - 2005 Oct 6

Fingerprint

Cyclization
Polyolefins
copolymerization
Copolymerization
Ethylene
ethylene
catalysts
Catalysts
synthesis
insertion
methylidyne
dichlorides
Polyethylene
Zirconium
Polyethylenes
polyethylenes
copolymers
Polymers
Copolymers
reactivity

Keywords

  • Copolymerization
  • Disubstituted diallylsilane
  • Ethylene
  • Zircnocene

ASJC Scopus subject areas

  • Polymers and Plastics
  • Materials Chemistry
  • Organic Chemistry
  • Physical and Theoretical Chemistry

Cite this

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title = "Synthesis of polyolefins containing silacycloalkane units in the main chain, 1 copolymerization of ethylene and disubstituted diallylsilanes involving intramolecular cyclization with zirconocene catalysts",
abstract = "Copolymerizations of ethylene and disubstituted diallylsilanes (CH 2=CH-CH2)2R2Si (R = CH3, C6H5) have been investigated with various zirconocene catalysts using methylaluminoxane as a cocatalyst. The bridged stereospecific catalysts showed a higher reactivity for disubstituted diallylsilanes than the non-bridged aspecific catalysts, Disubstituted diallylsilanes were incorporated into the polymer chain via cyclization insertion preferentially, and formed 3,5-disubstituted silacyclohexane units in the polyethylene main chain. A zirconocene catalyst, dimethylsilylenebis(indenyl)zirconium dichloride, produced a copolymer containing pendant ullyl groups derived from the 1,2-insertion of diallyldiphenylsilane without cyclization.",
keywords = "Copolymerization, Disubstituted diallylsilane, Ethylene, Zircnocene",
author = "Naofumi Naga",
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TY - JOUR

T1 - Synthesis of polyolefins containing silacycloalkane units in the main chain, 1 copolymerization of ethylene and disubstituted diallylsilanes involving intramolecular cyclization with zirconocene catalysts

AU - Naga, Naofumi

PY - 2005/10/6

Y1 - 2005/10/6

N2 - Copolymerizations of ethylene and disubstituted diallylsilanes (CH 2=CH-CH2)2R2Si (R = CH3, C6H5) have been investigated with various zirconocene catalysts using methylaluminoxane as a cocatalyst. The bridged stereospecific catalysts showed a higher reactivity for disubstituted diallylsilanes than the non-bridged aspecific catalysts, Disubstituted diallylsilanes were incorporated into the polymer chain via cyclization insertion preferentially, and formed 3,5-disubstituted silacyclohexane units in the polyethylene main chain. A zirconocene catalyst, dimethylsilylenebis(indenyl)zirconium dichloride, produced a copolymer containing pendant ullyl groups derived from the 1,2-insertion of diallyldiphenylsilane without cyclization.

AB - Copolymerizations of ethylene and disubstituted diallylsilanes (CH 2=CH-CH2)2R2Si (R = CH3, C6H5) have been investigated with various zirconocene catalysts using methylaluminoxane as a cocatalyst. The bridged stereospecific catalysts showed a higher reactivity for disubstituted diallylsilanes than the non-bridged aspecific catalysts, Disubstituted diallylsilanes were incorporated into the polymer chain via cyclization insertion preferentially, and formed 3,5-disubstituted silacyclohexane units in the polyethylene main chain. A zirconocene catalyst, dimethylsilylenebis(indenyl)zirconium dichloride, produced a copolymer containing pendant ullyl groups derived from the 1,2-insertion of diallyldiphenylsilane without cyclization.

KW - Copolymerization

KW - Disubstituted diallylsilane

KW - Ethylene

KW - Zircnocene

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