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

Abstract

AbstractHydrosilylation of fluorinated olefins with polyhydromethylsiloxane (PHMS) in the presence of a platinum catalyst was investigated to synthesize fluorosilicone having highly fluorinated alkyl side chains (Rf; 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)3SiO[(H)CH3SiO]8[(CH3)2 SiO]18Si(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 C7F15CFCHCH3 (8) was observed. The hydrosilylation of 7,7,8,8,9,9,10,10,11,11,12,12,13,13,14,14,14‐heptadecafluoro‐4‐oxa‐1‐tetradecene (C8F17CH2CH2OCH2CH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‐heptadecafluoro‐4‐oxa‐tetradocyl 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‐1‐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. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 3120–3128, 2002