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Reactive polymers incorporating silyl enol ether groups, 3 . Incorporation of α,β‐bis(siloxy)vinylene units into the backbone of vinyl polymers by free‐radical (co)polymerization of 2,3‐bis(trialkylsiloxy)butadienes
Author(s) -
Mayné Véronique,
Penelle Jacques
Publication year - 1998
Publication title -
macromolecular chemistry and physics
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.57
H-Index - 112
eISSN - 1521-3935
pISSN - 1022-1352
DOI - 10.1002/(sici)1521-3935(19981001)199:10<2173::aid-macp2173>3.0.co;2-h
Subject(s) - polymer chemistry , monomer , copolymer , chemistry , methyl methacrylate , reactivity (psychology) , radical polymerization , polymer , substituent , vinyl ether , steric effects , polymerization , methacrylate , organic chemistry , medicine , alternative medicine , pathology
2,3‐Bis(trimethylsiloxy)butadiene ( 1 ) and 2,3‐bis( tert ‐butyldimethylsiloxy)butadiene ( 2 ) have been homopolymerized and copolymerized with styrene (St) and methyl methacrylate (MMA) under freeradical conditions. Comparison of initial rates and molecular weights with polymerizations conducted under identical experimental conditions on monosubstituted analogs, 2‐trimethysiloxybutadiene ( 3 ) and 2‐( tert ‐butyldimethylsiloxy)butadiene ( 4 ), demonstrated that the second substituent does not decrease the polymerizability significantly despite the additional steric hindrance introduced in the monomer. Extensive 1 H and 13 C NMR characterization of the polymers demonstrated that the main incorporation mode is of the 1,4‐type, allowing more than 95% of the butadienyl subunit to be incorporated in the main chain as an α,β‐bis(trialkylsiloxy)vinylene functional group. Monomer reactivity ratios r 1 and r 2 at 60°C were determined from copolymer composition curves obtained at low conversions and are compared with values obtained for other 1,2‐butadienyl systems.