Copolymerization of propylene and disubstituted diallylsilanes involving intramolecular cyclization with stereoselective zirconocene catalysts

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Abstract

The copolymerization of propylene and disubstituted diallylsilanes [(CH2 =CH-CH2-)2R2Si (R = CH 3 or C6H5)] was investigated with isoselective and syndioselective zirconocene catalysts with methylaluminoxane as a cocatalyst. The syndioselective catalyst showed a higher reactivity for disubstituted diallylsilanes than the isoselective catalysts. Diallyldimethylsilane was incorporated into the polymer chain via cyclization insertion preferentially and formed 3,5-disubstituted dimethylsilacyclohexane units in the polypropylene main chain. In the copolymerization with diallyldiphenylsilane, diallyldiphenylsilane was copolymerized via both cyclization insertion and 1,2-insertion, which formed a pendant allyl group. The structures of isolated silacyclohexane units, determined by 13C NMR and distortionless enhancement by polarization transfer spectroscopy, proved that the 1,2-insertion of diallylsilanes proceeded with enantiomorphic site control; however, the diastereoselectivity of the cyclization reaction was independent of the stereoselectivity of the catalysts used, and cis-silacyclohexane units were mainly formed.

Original languageEnglish
Pages (from-to)6083-6093
Number of pages11
JournalJournal of Polymer Science, Part A: Polymer Chemistry
Volume44
Issue number20
DOIs
Publication statusPublished - 2006 Oct 15

Fingerprint

Cyclization
Copolymerization
Propylene
Catalysts
Stereoselectivity
Polypropylenes
Polymers
Nuclear magnetic resonance
Spectroscopy
Polarization
propylene
Zirconocene dichloride

Keywords

  • Copolymerization
  • Disubstituted diallylsilane
  • Metallocene catalysts
  • Poly (propylene) (PP)
  • Propylene

ASJC Scopus subject areas

  • Polymers and Plastics
  • Materials Chemistry

Cite this

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title = "Copolymerization of propylene and disubstituted diallylsilanes involving intramolecular cyclization with stereoselective zirconocene catalysts",
abstract = "The copolymerization of propylene and disubstituted diallylsilanes [(CH2 =CH-CH2-)2R2Si (R = CH 3 or C6H5)] was investigated with isoselective and syndioselective zirconocene catalysts with methylaluminoxane as a cocatalyst. The syndioselective catalyst showed a higher reactivity for disubstituted diallylsilanes than the isoselective catalysts. Diallyldimethylsilane was incorporated into the polymer chain via cyclization insertion preferentially and formed 3,5-disubstituted dimethylsilacyclohexane units in the polypropylene main chain. In the copolymerization with diallyldiphenylsilane, diallyldiphenylsilane was copolymerized via both cyclization insertion and 1,2-insertion, which formed a pendant allyl group. The structures of isolated silacyclohexane units, determined by 13C NMR and distortionless enhancement by polarization transfer spectroscopy, proved that the 1,2-insertion of diallylsilanes proceeded with enantiomorphic site control; however, the diastereoselectivity of the cyclization reaction was independent of the stereoselectivity of the catalysts used, and cis-silacyclohexane units were mainly formed.",
keywords = "Copolymerization, Disubstituted diallylsilane, Metallocene catalysts, Poly (propylene) (PP), Propylene",
author = "Naofumi Naga",
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N2 - The copolymerization of propylene and disubstituted diallylsilanes [(CH2 =CH-CH2-)2R2Si (R = CH 3 or C6H5)] was investigated with isoselective and syndioselective zirconocene catalysts with methylaluminoxane as a cocatalyst. The syndioselective catalyst showed a higher reactivity for disubstituted diallylsilanes than the isoselective catalysts. Diallyldimethylsilane was incorporated into the polymer chain via cyclization insertion preferentially and formed 3,5-disubstituted dimethylsilacyclohexane units in the polypropylene main chain. In the copolymerization with diallyldiphenylsilane, diallyldiphenylsilane was copolymerized via both cyclization insertion and 1,2-insertion, which formed a pendant allyl group. The structures of isolated silacyclohexane units, determined by 13C NMR and distortionless enhancement by polarization transfer spectroscopy, proved that the 1,2-insertion of diallylsilanes proceeded with enantiomorphic site control; however, the diastereoselectivity of the cyclization reaction was independent of the stereoselectivity of the catalysts used, and cis-silacyclohexane units were mainly formed.

AB - The copolymerization of propylene and disubstituted diallylsilanes [(CH2 =CH-CH2-)2R2Si (R = CH 3 or C6H5)] was investigated with isoselective and syndioselective zirconocene catalysts with methylaluminoxane as a cocatalyst. The syndioselective catalyst showed a higher reactivity for disubstituted diallylsilanes than the isoselective catalysts. Diallyldimethylsilane was incorporated into the polymer chain via cyclization insertion preferentially and formed 3,5-disubstituted dimethylsilacyclohexane units in the polypropylene main chain. In the copolymerization with diallyldiphenylsilane, diallyldiphenylsilane was copolymerized via both cyclization insertion and 1,2-insertion, which formed a pendant allyl group. The structures of isolated silacyclohexane units, determined by 13C NMR and distortionless enhancement by polarization transfer spectroscopy, proved that the 1,2-insertion of diallylsilanes proceeded with enantiomorphic site control; however, the diastereoselectivity of the cyclization reaction was independent of the stereoselectivity of the catalysts used, and cis-silacyclohexane units were mainly formed.

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KW - Propylene

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