Synthesis and characterization of perfluorinated acrylate–methyl methacrylate copolymers

Abstract

A novel perfluorinated acrylic monomer 3,5-bis(perfluorobenzyloxy)benzyl acrylate (FM) with perfluorinated aromatic units was synthesized with 3,5-bis(perfluorobenzyl)oxybenzyl alcohol, acryloyl chloride, and triethylamine. Copolymers of FM monomer with methyl methacrylate (MMA) were prepared via free-radical polymerization at 80 C in toluene with 2,2 0 -azobisisobutyronitrile as the initiator. The obtained copolymers were characterized by 1 H-NMR and gel permeation chromatography. The monomer reactivity ratios for the monomer pair were calculated with the extended Kelen-Tüdos method. The reactivity ratios were found to be r 1 ¼ 0.38 for FM, r 2 ¼ 1.11 for MMA, and r 1 r 2 < 1 for the pair FM-MMA. This shows that the system proceeded as random copolymerization. The thermal behavior of the copolymers was investigated by thermogravimetric analysis and differential scanning calorimetry (DSC). The copolymers had only one glass-transition temperature, which changed from 46 to 78 C depending on the copolymer composition. Melting endotherms were not observed in the DSC traces; this indicated that all of the copolymers were completely amorphous. Copolymer films were prepared by spin coating, and contact angle measurements of water and ethylene glycol on the films indicated a high degree of hydrophobicity.

Homopolymerization and synthesis of a new methacrylate monomer bearing a boron side group: characterization and determination of monomer reactivity ratios with styrene

“…26 Oxygen was removed by nitrogen via applying a vacuum using three freeze pumps. The reaction tube was immersed into a silicon oil bath, preheated to 80 • C. After the desired time, the tube was removed from the bath and cooled rapidly down to ambient temperature, and the reaction mixture was diluted with THF.…”

“…The polymerizations were performed by general copolymerization method as mentioned in our previous work in a dry Schlenk tube charged with determined amounts of monomers (BAc and styrene), 2 mL of toluene, and AIBN (2.5 mol % of total monomer). 26 Oxygen was removed by nitrogen via applying a vacuum using three freeze pumps. The reaction tube was immersed into a silicon oil bath, preheated to 80 • C. After the desired time, the tube was removed from the bath and cooled rapidly down to ambient temperature, and the reaction mixture was diluted with THF.…”

Polycarboxylate superplasticizers of acrylic acid–isobutylene polyethylene glycol copolymers: monomer reactivity ratios, copolymerization behavior and performance

“…A controlled/living photopolymerization of styrene (St) and acrylic acid (AA) was performed at room temperature under UV irradiation, and the monomer reactivity ratios were calculated by the methods of Mayo-Lewis [15], Kelen-Tüdös [11], and YBR [16]. In addition to the above-mentioned methods and means, the methods of Joshi-Joshi [17], extended Kelen-Tüdös [18], Tidwell-Mortimer [19], and error-in-variable [13] and the means of UV-vis [20], 13 C NMR [21], 1 H NMR [22][23][24], 19 F NMR [25], FTIR [26,27], elementary analysis [28], and elemental microanalysis [29] are appropriate for the determination of the monomer reactivity ratios at low conversions. In general, based on terminal copolymerization equation, determination of monomer reactivity ratios needs instantaneous mole fractions of monomers in the copolymer and unreacted and instantaneous monomer concentrations [15].…”

Controlled synthesis of amphiphilic graft copolymer for superhydrophobic electrospun fibres with effective surface fluorine enrichment: the role of electric field and solvent

“…[1][2][3] As is known, bres of large specic surface area can be achieved via an electrospinning technique which is notable as a versatile method for generating bres with diameters in the range of nanometers to a few microns. 7,8 And, the in situ low surface-energy modication during the electrospinning process is the most attractive strategy for fabricating superhydrophobic uorinated electrospun bres. Generally, uoropolymers are the preferential selection in fabricating superhydrophobic electrospun bres because of their extremely low surface free energy as well as the excellent properties such as oxygen resistance, acid and alkali resistance, and corrosion resistance derived from the contained highly electronegative uorine atoms.…”

“…Generally, uoropolymers are the preferential selection in fabricating superhydrophobic electrospun bres because of their extremely low surface free energy as well as the excellent properties such as oxygen resistance, acid and alkali resistance, and corrosion resistance derived from the contained highly electronegative uorine atoms. 7,8 And, the in situ low surface-energy modication during the electrospinning process is the most attractive strategy for fabricating superhydrophobic uorinated electrospun bres.…”