Synthesis and characterization of original functional polymers of tetrafluoroethylene and 4,5,5‐trifluoro‐4‐ene pentyl acetate

Abstract

The bulk radical copolymerization of tetrafluoroethylene (TFE) with 4,5,5trifluoro-4-ene pentyl acetate (FAc), initiated by tert-butyl peroxypivalate to synthesize original, functionalized fluorinated poly(TFE-co-FAc), was investigated. FAc monomer was prepared from a five-step process. The copolymerization was carried out in batch at different initial monomer molar ratios ([TFE] o /[FAc] o ranging from 95/5 to 10/90 mol %) and at different initiator concentrations (ranging between 0.075 and 1.100 mol % about the monomers) at 70°C. All the experiments revealed the production of fluorooligomers as evidenced by an allylic-transfer reaction from FAc. The microstructure of these copolymers (i.e., the molar percentage of both monomers in the copolymers) was assessed by 19 F NMR spectroscopy. From the kinetics of copolymerization, two key characteristics were determined. First, the reaction order to the initiator (being 1.07) and that of FAc monomer (0.85) showed a heterogeneous character of the copolymerization and monomolecular chain-transfer reaction to FAc. Second, from the Tidwell and Mortimer method, the reactivity ratios of both comonomers were determined, showing a tendency to alternance in a wide range of initial monomeric ratios (30/70 -70/30): r FAc ϭ 0.20 Ϯ 0.26 and r TFE ϭ 0.18 Ϯ 0.15. Alfrey and Price's Q and e values of FAc were calculated by Greenley's technique [Q FAc ϭ 0.098 (from Q TFE ϭ 0.032) and e FAc ϭ 1.23 (vs e TFE ϭ 1.63)], indicating that FAc is a strong electron-withdrawing monomer as TFE. The normalized monomer-diad and triad fractions as a function of the polymer composition were obtained from the comonomer sequence-distribution procedure. The average molecular weights and molecular weight distributions as well as the thermal properties (glass-transition temperature and decomposition temperature) of the fluorocopolymers were assessed and are discussed.

Original SF5-Containing Fluorinated Copolymers Based on Vinylidene Fluoride

“…In addition the solution polymerization used leads to lower molecular weights in contrast to polymerizations carried out in aqueous media (such as emulsion, miniemulsion, or suspension) that result in higher molecular weights (as for poly(VDF- co -HFP) copolymers). ,,7c,9a …”

Hyperbranched fluoropolymer and linear poly(ethylene glycol) based amphiphilic crosslinked networks as efficient antifouling coatings: An insight into the surface compositions, topographies, and morphologies

“…Fluoropolymers [1][2][3][4][5][6][7][8][9][10][11][12][13][14] have been the focus of extensive research in the development of minimally adhesive surfaces because of their low surface energy, low wettability, and chemical stability, which have also led to studies of their utility as potential antifouling materials for marine applications, [15][16][17][18][19][20] among other things. [21][22][23][24] It has been established that fouling by marine organisms upon surfaces such as ship hulls involves a process by which the organism secretes an adhesive protein or glycoprotein, either of a hydrophobic 25 or hydrophilic nature, 26,27 depending on the fouling species, that provides for binding to the surface through various modes of interaction, including chemical bonding, electrostatic interaction, diffusion, and mechanical interlocking. 28 In this regard, it becomes imperative that any coating formulated for preventing both soft and hard fouling present a surface that can simultaneously defeat all the modes of interaction between the fouling organism and the surface.…”

Radical Copolymerization of α‐Trifluoromethylacrylic Acid with Vinylidene Fluoride and Vinylidene Fluoride/Hexafluoropropene

“…[11] Such fluoropolymers can be synthesized by radical copolymerization of VDF with other fluoroalkenes, leading to statistic copolymers. [9,10,12,13] However, the copolymers of VDF and hexafluoroisobutylene [14,15] (commercialized by the Allied Company under the trade mark of CMX 1 ), and methyl trifluoroacrylate/VDF [16] are alternating copolymers. As a matter of fact, VDF was copolymerized with various fluorinated monomers functionalized by hydroxyl, [17][18][19][20] acetoxy, [19] carboxy, [21] thioacetoxy, [21,22] sulfonyl fluoride, [23][24][25][26][27] nitrile, [28,29] bromine [30][31][32][33][34] or perfluoro groups.…”