Novel Partially Fluorinated Copolymers: Evidence of the Effect of Fluorine on the Reactivity of the Unfluorinated Comonomer Units

Abstract

Summary: A conventional free‐radical polymerization of vinyl or propenyl ethers with acrylic or methacrylic monomers with fluorine substitution either in the main chain or in the ester groups has permitted us to obtain a series of copolymers with substantially different fluorine contents and distributions to be obtained. Such copolymers were considered as model compounds to offer new valuable insights as to the influence of fluorinated moieties on the overall stability and, more specifically, on their reactivity with atmospheric oxygen under environmental‐like conditions. Depending on the relative position of the fluorine atoms with respect to the common active center of oxidation, the influence ranges from a simple slowing down of the process to a complete redirection towards an otherwise secondary mechanism of oxidation.FT‐IR spectra of the carbonyl region of three novel fluorinated copolymers after oxidation.imageFT‐IR spectra of the carbonyl region of three novel fluorinated copolymers after oxidation.

Synthesis and characterization of fluorine‐containing polyacrylate latex with core–shell structure by UV‐initiated seeded emulsion polymerization

“…Furthermore, fluorine exhibits concentration gradient from the film–air interface to the film–glass interface. The XPS results are consistent with those reported in the literatures,37, 38 and in good agreement with the CA measurements.…”

Copolymers of Isopropenyl Alkyl Ethers with Fluorinated Acrylates and Fluoroacrylates: Influence of Fluorine on Their Thermal, Photochemical, and Hydrolytic Stability

“…This was somehow expected in the case of the not homopropagating EFMA, 29 although the conversion of a similar copolymerization with BVE was reported to be significantly higher. 18 Apparently, the bulkiness of the R-methyl group of BPE and of the neighboring -CF 2from the alternating EFMA plays a particularly important role in slowing down the copolymerization.…”

“…The syntheses of the copolymers of BPE with HFIMA and HFIFA have been reported elsewhere. 18 HFIFA/DPE. HFIFA (0.27 g, 1.1mmol), DPE (0.22 g, 1.1 mmol), AIBN (5.41 mg, 3.3 × 10 -5 mol), and 0.1 mL of dry THF to achieve miscibility were stirred under a nitrogen atmosphere at 60 °C for 72 h. After cooling at room temperature the solid product was dissolved in acetone, precipitated in methanol, and dried to constant weight to give 0.42 g of polymer (86% yield).…”

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].…”