Vinylidene fluoride (VDF)-based copolymers bearing pendant phosphonic acid function for potential application as anticorrosion coatings were synthesized via free radical copolymerization of VDF with a new phosphorus containing 2-trifluoromethacrylate monomer, (dimethoxyphosphoryl)methyl 2-(trifluoromethyl)acrylate (MAF-DMP). MAF-DMP was prepared from 2-trifluoromethacrylic acid in 60% overall yield. Radical copolymerizations of VDF with MAF-DMP initiated by tert-amyl peroxy-2-ethylhexanoate at varying ([VDF]/[MAF-DMP]) feed ratios led to several poly(VDF-co-MAF-DMP) copolymers having different molar percentages of VDF (79-96%) and number-average molecular weights (M's) up to ca. 10 000 g mol in fair yields (47-53%). Determination of the composition and microstructure of all the synthesized copolymers was done by H andF NMR spectroscopies. The monomer reactivity ratios of this new VDF/MAF-DMP pair were also determined (r = 0.76 ± 0.34 and r = 0 at 74 °C). The resulting poly(VDF-co-MAF-DMP) copolymers exhibited high melting temperature (162-171 °C, with respect to the VDF content), and the degree of crystallinity reached up to 51%. Finally, the pendant dimethyl phosphonate ester groups of the synthesized poly(VDF-co-MAF-DMP) copolymer were quantitatively hydrolyzed, giving rise to novel phosphonic acid-functionalized PVDF (PVDF-PA). In comparison to hydrophobic poly(VDF-co-MAF-DMP) copolymers (the water contact angle, WCA, was 98°), the hydrophilic character of the PVDF-PA was found to be surprisingly rather pronounced, exhibiting low WCA (15°). Finally, steel plates coated with PVDF-PA displayed satisfactory anticorrosion properties under simulated seawater environment.

Several strategies to synthesize fluorinated (co)polymers containing phosphorus groups and their applications are reviewed. First, original fluoromonomers bearing phosphorus atoms are supplied from relevant routes. They may possess fluorinated atoms linked to the ethylenic carbon atoms with different structures, such as F 2 CCF-or H 2 CC(CF 3 )-and a phosphonated ω-function adjacent to an aliphatic or aromatic linker, while other monomers display a difluoromethylene dialkylphosphonate end group such as -CF 2 −P(O)(OR) 2 . Then, fluorinated copolymers were obtained according to various pathways: (i) by radical homopolymerization of monomers containing both fluorine and phosphorus atoms, (ii) by direct radical copolymerization of fluoromonomers and phosphorus-based monomers, or (iii) by chemical modification of fluorinated copolymers with phosphorus-based reactants. Conventional radical and controlled (or reversible deactivation radical polymerization, RDRP) copolymerization have also been explored. As for the chemical change of halogenated polymers, either conventional organic reactions (e.g., Arbuzov reaction from a chlorine, iodine, or bromine atom) or radiation grafting with specific monomers led to graft copolymers composed of a fluorinated backbone and phosphonated grafts. This second part also details aliphatic and aromatic fluorophosphorous copolymers in which dialkylphosphonates or phosphonic acids are reported. Finally, since fluorine and phosphorus atoms bring complementary relevant properties (low refractive index and dielectric constants, chemical inertness, high electrochemical, soils, and heat resistances, electroattractivity from fluorine atoms and high acidity, complexation, anticorrosion, flame retardant, and biomedical properties from phosphorus ones), synergetic characteristics have been targeted. These properties allow such fluoro-phosphorus (co)polymers to be used as novel materials involved in various applications such as polymer exchange membranes for fuel cells, self-etching adhesives for dental materials, adhesion promoters, flame retardants, polymer blends, and anticorrosive coatings.

Solid polymer electrolytes with high ionic conductivity have been prepared from a microphase separated fluorinated copolymer bearing cyclocarbonate side groups.

Vinylidene fluoride (VDF)-based copolymers bearing pendant trialkoxysilane groups for potential applications for coatings were synthesized via a free radical copolymerization of VDF with functional 2-trifluoromethyl acrylate cyclic carbonate monomer (MAF-cyCB), followed by introduction of silane pendant groups. MAF-cyCB was prepared from 2-trifluoromethacrylic acid with 70% overall yield. Radical copolymerization of VDF with MAF-cyCB initiated by tert-amyl peroxy-2-ethylhexanoate at varying [VDF]0/[MAF-cyCB]0 ratios led to several poly­(VDF-co-MAF-cyCB) copolymers having different molar percentages of VDF (77–96%). The average molecular weights (M ns) reached up to 19 000 g mol–1 in fair to good yields (45–74%). Compositions and microstructures of all synthesized copolymers were achieved by 1H and 19F NMR spectroscopies. The resulting poly­(VDF-co-MAF-cyCB) copolymers exhibited moderately high melting temperature (131–161 °C, with respect to the VDF content) while the degree of crystallinity, which reached up to 34%, decreased with increasing MAF-cyCB. Then, the pendant cyclic carbonate ester groups of the synthesized poly­(VDF-co-MAF-cyCB) copolymers were quantitatively converted into novel triethoxysilane-functionalized PVDF, which could be further hydrolyzed under acidic conditions into trihydroxysilane-functionalized PVDF. Finally, steel plates were coated with the silylated PVDF and displayed improved adhesion properties compared to those of pristine PVDF.

A study of the copolymerization kinetics of vinylidene fluoride with tert-butyl 2-trifluoromethyl acrylate: a suitable pair for the synthesis of alternating fluorinated copolymers.

Vinylidene fluoride (VDF)-based copolymers bearing pendant perfluoroalkyl ether groups for potential application in gel polymer electrolytes were synthesized via conventional radical copolymerization of VDF with a 2trifluoromethacrylate monomer bearing pendant perfluoroalkyl ether groups [2,3,3,3-tetrafluoro-2-[1,1,2,3,3,3-hexafluoro-2-(perfluoropropoxy)propoxy]propyl 2-(trifluoromethyl)acrylate (MAF-PFE)]. Two kinds of initiators (hydrogenated and a perfluorinated highly branched persistent radical that released CF 3• radical from 80 °C) were used. Molar masses ranged between 35 000 and ca. 50 000 g•mol −1 . The synthesized poly(VDF-co-MAF-PFE) copolymers were evaluated in gel polymer electrolytes based on ionic liquids. With this aim, the poly(VDF-co-MAF-PFE) copolymers were mixed with lithium bis(trifluoromethanesulfonyl)imide and the ionic liquid 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide. Homogeneous gels with conductivity values at room temperature reaching up to 3 × 10 −3 S•cm −1 were obtained, while the transference number of lithium ions was 0.12 at 40 °C. Finally, such electrolytes displayed an electrochemical stability window between 1.5 and 4.4 V as determined by cyclic voltamperometry measurements.

The radical copolymerisation of vinylidene fluoride (VDF) with vinyl dimethyl phosphonate (VDMP) initiated by various kinds of initiators is presented.

Novel triethoxysilane and dimethyl phosphonate functional vinylidene fluoride (VDF)-containing terpolymers, for potential applications in Eu ion extraction from water, were produced by conventional radical terpolymerization of VDF with vinyltriethoxylsilane (VTEOS) and vinyldimethylphosphonate (VDMP). Although initial attempts for the copolymerization of VTEOS and VDMP failed, the successful terpolymerization was initiated by peroxide to lead to multiple poly(VDF-ter-VDMP-ter-VTEOS) terpolymers, that had different molar percentages of VDF (70–90 mol.%), VTEOS (5–20 mol.%) and VDMP (10 mol.%) in 50–80% yields. The obtained terpolymers were characterized by 1H, 19F, 29Si and 31P NMR spectroscopies. The crosslinking of such resulting poly(VDF-ter-VDMP-ter-VTEOS) terpolymers was achieved by hydrolysis and condensation (sol–gel process) of the triethoxysilane groups in acidic media, to obtain a 3D network, which was analyzed by solid state 29Si and 31P NMR spectroscopies, TGA and DSC. The thermal stability of the terpolymers was moderately high (up to 300 °C under air), whereas they display a slight increase in their crystallinity-rate from 9.7% to 12.1% after crosslinking. Finally, the dimethyl phosphonate functions were hydrolyzed into phosphonic acid successfully, and the europium ion extraction capacity of terpolymer was studied. The results demonstrated a very high removal capacity of Eu(III) ions from water, up to a total removal at low concentrations.