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

Abstract

The homopolymer of butyl isopropenyl ether (pBPE) and a series of homo-and copolymers of BPE and decyl isopropenyl ether (DPE) with acrylates and methacrylates fluorinated on the vinyl and/or the alkoxy group were synthesized by cationic (pBPE) or free-radical process. The three structurally analogous 1,1,1,3,3,3-hexafluoroisopropyl methacrylate (HFIMA), 1,1,1,3,3,3-hexafluoroisopropyl 2-fluoroacrylate (HFIFA), and isopropyl 2-fluoroacrylate (IFA) as well as ethyl 3,3-difluoro-2-methylpropenoate (EFMA) were used as the fluorinated comonomers. The thermal properties and aging behavior of the copolymers were correlated to their structure and particularly to the protective action of the fluorinated moieties against photooxidative and acidcatalyzed hydrolytic degradation triggered by the labile side chains of the BPE units. Depending on their distance from the primary center of photooxidation, the fluorinated groups can either slow down or largely modify the degradation pathway, as shown by the dominant cross-linking in the strictly alternating HFIFA/BPE which outweighs the prevailing chain fragmentation of the other copolymers.

Preparation and characterization of fluorinated acrylate copolymer latexes by miniemulsion polymerization under microwave irradiation

“…Acrylic polymers with fluorine-containing groups or perfluoroalkyl groups, in particular, can provide the material with low surface energies and the acrylic groups ensure that the polymers can adhere well to various substrates [3,4]. Therefore, fluorinated polyacrylate latexes have been used progressively in a wide range of applications such as biomaterials, microelectronics, antifogging, and antifouling applications [5][6][7], especially as surface coatings for textile, paper and leather, because their presence can introduce a number of unique physical and chemical surface properties [1,8]. Many fluorinated or perfluorinated (meth)acrylate monomers have been studied with regard to the synthesis of copolymers with conventional acrylate in aqueous emulsions by radical polymerization methods [1,[5][6][7][8][9][10].…”

Synthesis and Performance of Novel Fluorinated Acrylate Polymers: Preparation and Reactivity of Short Perfluoroalkyl Group Containing Monomers

“…1 , and a liter of sodium iodide were dissolved in acetone (25 mL). The reaction continued for 24 h under reflux until complete conversion and then cooled to room temperature and purified.…”

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].…”