Photopolymerization of maleimide perfluoropolyalkylethers without a photoinitiator

Abstract

Perfluoropolyalkylethers derived from hexafluoropropylene oxide were functionalized with maleimide groups. Irradiated by UV‐light, the new maleimide macromonomers demonstrated very fast polymerization kinetics with a curing time as fast as 8 s. The effect on photopolymerization of different features such as the molecular weight of the fluorinated chain and the chain length of the hydrogenated spacer were studied, as well as the influence of the type of photoinitiator and the presence of air. Thermal and surface properties of the UV‐cured polymers were examined and were typical to fluoropolymers in view of water–oil repellent coatings. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019, 57, 699–707

Vinyl ethers and epoxides photoinduced copolymerization with perfluoropolyalkylether monomers

“…3 and 4 , it seems that the length of the hydrogenated spacer between the PFPAE chains and the reactive end-groups of the fluorinated comonomers has an influence on reactivity. Similar behaviors were observed and studied for both living cationic [ 23 , 40 , 48 ] and radical [ 49 , 50 ] photopolymerization. This effect was observed in the photoinduced polymerization of the macromonomers studied in [ 24 ]: the long-fluorinated chain decreased the monomer reactivity by an electron withdrawing effect, lowering the nucleophilicity of the functional group.…”

“…Therefore, the rate constant of the reaction, the gel point, and the final conversion were found dependent on the distance between the fluorinated segment and the reactive vinyl ether/epoxide groups. In our case, a clear correlation between reactivity and structural parameters is not present: probably, phase separation phenomena have an influence on the photopolymerization behavior of the copolymers [ 49 , 51 ]. As the length of the alkyl spacing segments decreases, a greater segregation between the hydrogenated and the fluorinated monomers can occur.…”

Perfluoropolyalkylether Maleimides for Protection From Oxygen Inhibition and Surface Modification of Photoinitiator-Free UV-Cured Polymers

“…The fluorinated monomaleimide MMI (see structure in Figure 1) was synthesized as previously reported (Bonneaud et al, 2019) by esterification of Krytox R Methylene Alcohol, kindly provided by Chemours Company (Wilmington, Delaware, USA).…”

“…The monofunctional fluorinated monomaleimide (MMI) containing hexafluoropropyleneoxide units was synthesized as reported in a previous paper (Bonneaud et al, 2019). Two telechelic difunctional bismaleimides (BMI C5 and BMI C10) were obtained by esterification reaction of maleimidocarboxylic acids of different molecular weight with a commercial fluorinated diol HO-RF-OH, where RF (reported in Figure 1) is a fluorinated chain based on -(CF 2 O)-, -(CF 2 CF 2 O)-.…”

“…MMI reaction was studied previously (Bonneaud et al, 2019): it was reported that MMI is a highly reactive monomer with a quantitative conversion observed even in 8 s in the absence of air and in 40 s in the presence of air (see also Having low viscosity, it could be easily coated on glass as a film and under irradiation exhibited high reactivity, giving rise to a linear polymer. As expected, also BMI C5 and BMI C10 were reactive even in the absence of a photoinitiator.…”