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

Authors :
Naofumi Naga
Source :
Journal of Polymer Science Part A: Polymer Chemistry. 44:6083-6093
Publication Year :
2006
Publisher :
Wiley, 2006.

Abstract

The copolymerization of propylene and disubstituted diallylsilanes [(CH2 CHCH2)2R2Si (R = CH3 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. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 6083–6093, 2006

Details

ISSN :
10990518 and 0887624X
Volume :
44
Database :
OpenAIRE
Journal :
Journal of Polymer Science Part A: Polymer Chemistry
Accession number :
edsair.doi...........0ae100f231765342997dfe5fa8c5b4d9
Full Text :
https://doi.org/10.1002/pola.21719