Metal-free synthesis of alternating silylether-carbosilane copolymers using unsaturated ketones

We report metal-free B(C6F5)3-catalysed hydrosilylation polymerization for alternating silylether-carbosilane copolymers. The reaction was carried out at room temperature using bis(dimethylsilyl)benzene and cyclic and aliphatic unsaturated ketones. It was found that 1,4-conjugation on the unsaturated ketone monomers is important for undergoing hydrosilylation-based polymerization on both C 00000000 00000000 00000000 00000000 11111111 00000000 11111111 00000000 00000000 00000000 O and CC groups. The obtained polymers were characterized by high molecular weight (Mw = 4.23 x 104, PDI = 2.0), tunable Tg (ranging from -7 to 27 degrees C) and good thermal stability (above 280 degrees C). Hydrolysis of silylether linkages with an HCl catalyst was demonstrated, revealing an alternating arrangement, which was supported by monitoring the polymerization processes with 1H NMR measurements. Metal-free B(C6F5)3-catalysed hydrosilylation polymerization was demonstrated at room temperature for alternating silylether-carbosilane copolymer synthesis using bis(dimethylsilyl)benzene and alpha,beta-unsaturated ketones.