Alkenylsilane effects on organotitanium-catalyzed ethylene polymerization. Toward simultaneous polyolefin branch and functional group introduction.
The comonomer 5-hexenylsilane is introduced into organotitanium-mediated ethylene polymerizations to produce silane-terminated ethylene/5-hexenylsilane copolymers. The resulting polymers were characterized by (1)H and (13)C NMR, GPC, and DSC. High activities (up to 10(7) g polymer/(mol Ti.atm ethylene.h)) and narrow polydispersities are observed in the polymerization/chain transfer process. Ethylene/5-hexenylsilane copolymer molecular weights are found to be inversely proportional to 5-hexenylsilane concentration, supporting a silanolytic chain transfer mechanism. Control experiments indicate that chain transfer mechanism by 5-hexenylsilane is significantly more efficient than that of n-hexylsilane for organotitanium-mediated ethylene polymerization. The present study represents the first case in which a functionalized comonomer is efficiently used to effect both propagation and chain transfer chemistry during olefin polymerization.[1]References
- Alkenylsilane effects on organotitanium-catalyzed ethylene polymerization. Toward simultaneous polyolefin branch and functional group introduction. Amin, S.B., Marks, T.J. J. Am. Chem. Soc. (2006) [Pubmed]
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