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

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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.

元の言語English
ページ(範囲)6083-6093
ページ数11
ジャーナルJournal of Polymer Science, Part A: Polymer Chemistry
44
発行部数20
DOI
出版物ステータスPublished - 2006 10 15

ASJC Scopus subject areas

  • Polymers and Plastics
  • Organic Chemistry
  • Materials Chemistry

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