Homo- and copolymers of hexafluoroisopropyl methacrylate and alpha-fluoroacrylate with alkyl vinyl ethers: Microstructure and thermal properties

A study is reported, dealing with the microstructure and thermal behavior o f the homopolymers of 1,1,1,3,3,3-hexafluoroisopropyl methacrylate (HFIM) a nd 1, 1,1,3,3,3-hexafluoroisopropyl alpha -fluoroacrylate (HFIFA), as well as of their copolymers with various vinyl ethers. The aim of this work was a better understanding of the role that fluorine content and distribution-f irst in the monomer and then along the ensuring macromolecular chain-play i n determining the polymerizability of the selected vinyl monomers, and the final properties of the polymeric material. Primary (n-butyl, isobutyl, 2-e thylhexyl), secondary (cyclohexyl), and tertiary (tert-butyl) vinyl ethers were employed as the comonomers. A general tendency towards comonomer alter nation was observed upon radical initiated copolymerization with HFIFA. On the other hand, the relatively more electron-rich HFIM did not usually yiel d strictly alternating sequences, unless the bulky tert-butyl vinyl ether w as employed. The incorporation of electron-rich vinyl ether monomers within a partially fluorinated polymeric chain by simple radical initiated proces s was considered particularly interesting in view of the possible applicati on of these materials as water-repellent protective coatings. In this case, the fluorinated units should provide the low energy surface (water repelle ncy) and, possibly, photo- and thermostability, whereas the vinyl ether cou nits should grant improved adhesion and adequate film-forming properties. ( C) 2000 John Wiley & Sons, Inc.