Reactive polymers incorporating silyl enol ether groups. 3 - Incorporation of alpha,beta-bis(siloxy)vinylene units into the backbone of vinyl polymers by free-radical (co)polymerization of 2,3-bis(trialkylsiloxy)butadienes

Mayne, V.;Penelle, J.
(1998) Macromolecular Chemistry and Physics — Vol. 199, n° 10, p. 2173-2178 (1998)

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  • Mayne, V.
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  • Penelle, J.
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Abstract
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 free-radical 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 H-1 and C-13 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 alpha,beta-bis(trialkylsiloxy)vinylene functional group. Monomer reactivity ratios r(1) and r(2) at 60 degrees C were determined from copolymer composition curves obtained at low conversions and are compared with values obtained for other 1,2-butadienyl systems.
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Mayne, V., & Penelle, J. (1998). Reactive polymers incorporating silyl enol ether groups. 3 - Incorporation of alpha,beta-bis(siloxy)vinylene units into the backbone of vinyl polymers by free-radical (co)polymerization of 2,3-bis(trialkylsiloxy)butadienes. Macromolecular Chemistry and Physics, 199(10), 2173-2178. https://hdl.handle.net/2078.5/141441 (Original work published 1998)