ESR study of radicals obtained from vinylalkoxysilanes and their adducts with branched fluoroalkenes

ESR spectra of radicals obtained by abstracting a hydrogen atom from methylvinyldimethoxysilane and methylvinyldiethoxysilane through the action of thetert-butoxy radical were studied. It was shown that the radicals appearing react with branched fluorinated olefins to give relatively stable radical adducts.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 3, pp. 538–540, March, 1994.     

Controlled copolymerization of vinyl acetate with 1‐alkenes and their fluoro derivatives by degenerative transfer

The degenerative transfer copolymerization of vinyl acetate with ethene and higher 1‐alkenes, as well as their fluoro derivatives (R_fCH?CH₂), under mild conditions was carried out using AIBN as the initiator and ethyl iodoacetate as the control agent. The obtained random copolymers were fairly high in alkene content, with high molecular weights and relatively narrow polydispersities. The quasi‐living nature of the copolymerization allowed the synthesis of a block terpolymer by sequential addition of two different 1‐alkene comonomers to a vinyl acetate copolymerization system. The fluorinated side chains of vinyl acetate/fluoro alkene copolymers segregate toward the air‐side of thin films, resulting in advancing water contact angle as high as 114°. 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 3728–3736, 2005     

Alternating polyester/fluoroalkene copolymers: Combining high hydrophobicity with degradability

2‐Methylene‐1,3‐dioxepane (MDO) was copolymerized with fluoroalkenes (R_fCH?CH₂) using azobis(isobutyronitrile) AIBN as an initiator. NMR spectroscopy confirmed that the obtained polymers are effectively alternating copolymers of caprolactone and fluoroalkene. Angle resolved XPS of copolymer films revealed that the outer layers have higher CF_x:COO ratio relative to the subsurface, indicating that the perfluoroalkyl tails segregate to the air‐side, thereby presenting a hydrophobic surface with water contact angle as high as 130°. Blends of this material with polycaprolactone and polycarbonate polymers also form hydrophobic films. In the presence of trifluoroacetic acid, the copolymer undergoes complete degradation through hydrolysis. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 1225–1232, 2006