Photochemical Stability of Partially Fluorinated Acrylic Protective Coatings. 2. Copolymers of 1H,1H,2H,2H-Perfluorodecyl Methacrylate with Unfluorinated Acrylic Esters

Abstract

The photochemical stability of a series of copolymers of 1H,1H,2H,2H-perfluorodecyl methacrylate (XFDMA) with acrylic or methacrylic unfluorinated esters has been investigated under artificial solar light irradiation. Molecular and chemical changes induced by the light treatment were monitored by weight loss and gel content determination, size exclusion chromatography, and Fourier transform infrared spectroscopy. In XFDMA/methyl acrylate the degradation mainly occurs on the tertiary position of the acrylic units, followed by extensive chain scissions. In the copolymers with butyl acrylate, butyl methacrylate, and lauryl methacrylate, the XFDMA units are not affected by oxidative degradation reaction, and the mechanism of degradation is influenced by the specific reactivity of the unfluorinated comonomer. For these samples the principal degradation effect is the cross-linking of the polymer structure promoted by radicals formed on the alkyl side groups, and it is only partially attenuated by the fluorinated units.

Random Copolymer Films with Molecular‐Scale Compositional Heterogeneities that Interfere with Protein Adsorption

“…Monomer pairs of highly contrasting solubility typically lack a common solvent, making synthesis very difficult and limiting the achievable hydrophilic contrast between comonomers. [18][19][20][21] Second, when such polymers can be synthesized, they are very difficult to cast as the smooth, thin films required both for practical application and for characterization of protein interaction. The copolymerization of hydrophilic acrylates and methacrylates with perfluorinated alkyl acrylates and methacrylates has been reported, but efforts to cast them as a thin film resulted in extremely rough and nonuniform surfaces.…”

Compositional analysis of fluorinated and unfluorinated acrylic copolymers

“…The series of partially fluorinated (meth)acrylic homoand copolymers used as references (see below) were prepared by free radical polymerization in solution or in bulk using AIBN as initiator. Experimental details were already published elsewhere [15][16][17]19]. Around 100 mm thick films for infrared analysis or pyrolysis experiments were prepared by evaporation of the lattices at room temperature up to constant weight values.…”

“…Within a comprehensive investigation on the durability of a series of acrylic products, both commercial resins [13,14] and newly synthesized polymers [15][16][17], potentially usable for the protection and consolidation of monuments and stone surfaces we have also carried out the necessary preliminary compositional analyses, whose most significant results are reported in this work. The monomeric components of a series of acrylic lattices containing fluorinated and unfluorinated monomeric units of different nature were determined by high temperature pyrolysis with direct analysis of volatile products of thermal degradation through a coupled system (pyrolysis-gas chromatography/mass spectrometry, Py-GC/MS), taking into account the pathways of thermal decomposition of acrylic and/or methacrylic homo-and copolymers [18].…”

Synthesis and reactivity of a fluorinated N-alkylmaleimide towards free-radical grafting and polymerization reactions

“…Chromatographic and spectroscopic techniques were used to monitor the chemical evolution during up to 2000 h of irradiation [13][14][15][16].…”