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; C_nF_2n+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