Synthesis of fluorosilicone having highly fluorinated alkyl side chains based on the hydrosilylation of fluorinated olefins with polyhydromethylsiloxane

Hydrosilylation of fluorinated olefins with polyhydromethylsiloxane (PHMS) in the presence of a platinum catalyst was investigated to synthesize fluorosilicone having highly fluorinated alkyl side chains (R-f; CnF2n+1-). The hydrosilylation of 3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-heptadecafluoro-1-decene (C8F17CH=CH2) (1) with poly(dimethylsiloxane-co-hydromethylsiloxane) [(CH3)(3)SiO[-(H)CH3SiO-](8)[-(CH3)(2) SiO-](18)Si(CH3)(3)] (4) converted the hydrogen bonded to silicons into the 3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-heptadecafluorodecyl group or fluorine bonded to silicons in the ratio of about 52:48, and the formation of the byproduct C8F17C7F15==CHCH3 (8) was observed. The hydroliylation of 7,7,8,8,9,9,10,10,11,11,12,12,13,13,14,14,14-heptadecafluoro-4-oxa-l-tetradecene (CgF17CH2,CH2,OCH2CH==CH2) (2) with 4 converted the hydrogen bonded to silicons into the 7,7,8,8,9,9,10,10,11,11,12,12,13,13,14,14,14-heptadeca-fluoro-4-oxa-tetradocyI group bonded to silicons, but an excess amount of 2 was required to complete the reaction because the isomerization of 2 occurred in part to form C8F17CH2CH2OCH==CHCH3 (9). The hydrosilylation of 4,4,5,5,6,6,7,7,8,8,9,9, 10,10,11,11,11-heptadecafluoro-l-undecene (C8F17CH2CH==CH2) (3) with 4 converted the hydrogen bonded to silicons into the 4,4,5,5,6,6,7,7,8,8,9,9,10,10,11,11-heptadecafluoroundecyl group bonded to silicons. This type of fluorinated olefin was successfully applied to the hydrosilylation with other PHMS's that involved a homopolymer of PHMS and a cyclic PHMS. (C) 2002 Wiley Periodicals, Inc.