Homo- and Copolymers of HexafluoroisopropylMethacrylate and a-Fluoroacrylate with Alkyl Vinyl Ethers:Microstructure and Thermal Properties

STRACT: A study is reported, dealing with the microstructure and thermal behavior of the homopolymers of 1,1,1,3,3,3-hexafluoroisopropyl methacrylate (HFIM) and 1,1,1,3,3,3-hexafluoroisopropyl a-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--first in the monomer and then along the ensuring macromolecular chain--play in determining the polymerizability of the selected vinyl monomers, and the final properties of the polymeric material. Primary (n-butyl, isobutyl, 2-ethylhexyl), secondary (cyclohexyl), and tertiary (tert-butyl) vinyl ethers were employed as the comonomers.Ageneral tendency towards comonomer alternation was observed upon radical initiated copolymerization with HFIFA. On the other hand, the relatively more electron-rich HFIM did not usually yield strictly alternating sequences, unless the bulky tert-butyl vinyl ether was employed. The incorporation of electron-rich vinyl ether monomers within a partially fluorinated polymeric chain by simple radical initiated process was considered particularly interesting in view of the possible application of these materials as water-repellent protective coatings. In this case, the fluorinated units should provide the low energy surface (water repellency) and, possibly, photo- and thermostability, whereas the vinyl ether counits should grant improved adhesion and adequate film-forming properties.