Synthesis of hybrid fluorinated silicones. I. Influence of the spacer between the silicon atom and the fluorinated chain in the preparation and the thermal properties of hybrid homopolymers

The synthesis of fluorinated hybrid silicones prepared in three steps from H₂C CH—C₆F₁₂ CH CH₂(I) and H₂C CHCH₂—C₆F₁₂—CH₂CH CH₂(II) is presented. First, both hydrosilylations of chlorodimethylsilane with these nonconjugated dienes were carried out in the presence of the Speier's catalyst leading to the expected bis-chlorosilane in excellent yield from (II) but giving a rearranged by-product from (I). However, a similar reaction from (I) initiated by a peroxide produced the expected bis-chlorosilane selectively. Second, these chlorosilanes were quantitatively hydrolyzed into the corresponding α,ω-bis silanols, whatever the spacer between the fluorinated group and the silicon atom. Finally, the polycondensations of these bis silanols were performed in the presence of an amine/acid adduct catalyst. Interestingly, the dihydroxysilane produced from (I) reacts much quicker than the other one. Moreover, thermal properties (T_g, T_dec) were investigated and compared to those of commercially available fluorosilicones or mentioned in the literature and show improvement of the behavior of these fluorosilicones at low and high temperatures. © 1996 John Wiley & Sons, Inc.