Synthesis of poly(vinyl ether)s with perfluoroalkyl pendant groups

Abstract 2‐Perfluoro(alkyl)ethyl vinyl ethers, F(CF2)nCH2CH2OCHCH2, (n = 6 or 8), were synthesized and polymerized by means of cationic initiators (HI/ZnI2 and CF3SO3H/(CH3)2S). The perfluorohexyl‐substituted poly(vinyl ether) is completely amorphous. The polymer with perfluorooctyl segments shows side chain crystallization with a disordering transition. For the corresponding perfluorooctyl monomer a liquid‐crystalline phase was observed before melting. Copolymerization experiments of the flurocarbon‐segmented monomers with a vinyl ether containing a cyanobiphenyl group in the side chain did not give homogeneous copolymers. This is attributed to the slower rate of polymerization of the fluorinated vinyl ethers as compared with the liquid‐crystalline comonomer.