Functionalized halogenated polymer and process for its preparation

Abstract

The present invention relates to a process for preparing a functionalized halogenated polymer comprising the steps of: a) supplying a halogenated polymer A1 comprising monomeric units M1 comprising at least one halogen atom, preferably fluorine, and monomeric units M2 comprising at least one carbon-carbon double bond –C(R1)=C(R2)-; b) contacting said halogenated polymer A1 with a thiolate compound B of formula RS- in the presence of a peroxide compound C to form a polymer A2 comprising monomeric units M3 of formula –CH(R1)-C(R2)(SR)- and said monomeric units M1 comprising at least one halogen atom, preferably fluorine, ; R1 and R2 being independently selected from the group consisting of H, C1-C5 alkyl, C1-C5 halogen-alkyl, F, Br, I and Cl; R being an optionally functionalized hydrocarbon substituent.

Description

Title of the invention: Functionalized halogenated polymer and method for preparing it Technical field of the invention

[0001] The present invention relates to a process for preparing a functionalized halogenated polymer. The present invention also relates to the use of the functionalized halogenated polymer thus prepared in the field of batteries or fuel cells. Technological background of the invention

[0002] Halogenated polymers are widely used in many technical fields due to their unique properties in terms of thermal stability, chemical inertness, and mechanical properties. They can therefore be used in the fields of aeronautics, engineering, the automotive or chemical industries, or in insulating materials.

[0003] Polyvinylidene fluoride (PVDF) is particularly preferred in many application areas such as piezoelectric materials, energy storage, and water treatment. PVDF can be prepared by suspension or emulsion processes. Depending on the process used, PVDF may exhibit a different molecular structure and different reactivity towards other monomers. This structural difference, as well as any functionalization of the polymer chain, can have a significant impact on the intended technological applications.

[0004] Emulsion polymerization is characterized by its high productivity and yields branched products, and the incorporation of functional monomers can be complex. PVDF functionalization can also be achieved using plasma treatment and electron beam irradiation approaches. However, certain technical limitations, such as industrialization and repeatability, can be challenging.

[0005] There is therefore a need for a new method of preparing halogenated polymer that is simple, efficient and has a limited environmental impact. Summary of the invention

[0006] According to a first aspect, the present invention provides a process for preparing a functionalized halogenated polymer comprising the steps of: a. Supply of a halogenated polymer Al comprising monomeric units M1 comprising at least one halogen atom, preferably fluorine, and monomeric units M2 comprising at least one carbon-2 double bond carbon -C(R')=C(R2)- ; b. Contacting said halogenated polymer Al with a thiolate compound B of formula RS in the presence of a peroxide compound C to form a polymer A2 comprising monomeric units M3 of formula -CH(R')-C(R2 )(SR)- and said monomeric units Ml comprising at least one halogen atom, preferably fluorine; R1 and R2 being independently of each other selected from the group consisting of H, C1-C5 alkyl, C1-C5 (per)halogenoalkyl, F, Br, I and Cl; R being an optionally functionalized hydrocarbon substituent.

[0007] It has been surprisingly observed that a halogenated polymer can be easily functionalized under mild operating conditions with a good functionalization incorporation yield.

[0008] According to a preferred embodiment, the halogenated polymer Al is obtained by a dehydrohalogenation reaction of a halogenated polymer A comprising monomers Ml comprising at least one halogen atom, preferably fluorine, and monomeric units M4 of formula -CH(R')-C(R2)(X)- in which X is a halogen and R1 and R2 are as defined in the present invention.

[0009] According to a preferred embodiment, the thiolate compound B of formula RS is obtained by reaction between a compound of formula RSH and a base.

[0010] According to a preferred embodiment, the base is selected from the group consisting of LiOH, NaOH, KOH, CsOH, RbOH, Mg(OH)2, Ca(OH)2, N(CnH2n+1)3 with n being an integer from 1 to 10, N,N-Diisopropylethylamine, morpholine, pyridine, pyrrolidine, Piperidine, piperazine, 4-Methylmorpholine, N,N-Diisopropylethylamine, 1,8-Diazabicyclo(5.4.0)undec-7-ene, 6-(Dibutylamino)-1,8-diazabicyclo[5.4.0]undec-7-ene, 1,8-Diazabicyclo[5.4.0]undec-7-ene bonded to polystyrene, 1,5,7-Triazabicyclo[4.4.0]dec-5-ene, 7-Methyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene, 1,1,3,3-Tetramethylguanidine, 2-tert-Butyl-1,1,3,3-tetramethylguanidine, 1,5,7-Triazabicyclo[4.4.0]dec-5-ene linked to polystyrene, 1,4-Diazabicyclo[2.2.2]octane, Quinuclidine, 1,5-Diazabicyclo(4.3.0)non-5-ene, 2,6-Di-tert-butylpyridine, 2,8,9-Trimethyl-2,5,8,9-tetraza-1-phosphabicyclo[3.3.3]undecane, Cyclodi-phosphazane, Lithium diisopropylamide, sodium diisopropylamide, potassium diiso-propylamide, magnésium diisopropylamide, calcium diisopropylamide, rubidium diisopropylamide, lithium bis(trimethylsilyl)amide, sodium bis(trimethylsilyl)amide, potassium bis(trimethylsilyl)amide, magnésium bis(trimethylsilyl)amide, calcium bis(trimethylsilyl)amide, rubidium bis(trimethylsilyl)amide, lithium tetramethylpi-peridide, sodium tetramethylpiperidide, potassium tetramethylpiperidide, magnésium . tetramethylpiperidide, calcium tetramethylpiperidide, rubidium tetramethylpiperidide, [18-crown-6]-KHF2, KHF2, N,N’-diisopropylimidazonium, bifluorure, tetrabuty-lammonium, N(CnH2n+i)4 OH- avec n étant un entier de 1 à 10.

[0011] Selon un mode de réalisation préféré, le composé peroxyde C est sélectionné parmi les peroxydes organiques, percarbonates, perborates et hydroperoxydes.

[0012] According to a preferred embodiment, the thiolate compound B has the formula RS in which R is selected from the group of substituents consisting of Ci-Ci8 alkyl, C2-C18 alkenyl, C4-Ci8 cycloalkenyl, C3-C[8 cycloalkyl, C6-Ci8 aryl, polyalkylene glycol, said substituent optionally bearing one or more functional groups of the formula -F, -OR', -OC(O)R', -CN, -NR'2, -O-Si(OR')3, -Si(R')3, -SO3 R', -OP(O)(OR')2, -P(O)(OR)2, -C(O)OR', -C(O)R', -C(O)-S-R', -C(O)-NR'2, -NR'3+ in which R' is independently selected for each substituent of the functional group from the group consisting of H, Ci_Ci8 alkyl, C2 C,8 alkenyl, C4_Ci8 cycloalkenyl, C3_Ci8 cycloalkyl, C6-Ci8 aryl, polyalkylene glycol.

[0013] According to a preferred embodiment, said monomeric units Ml are derived from a monomer selected from the group consisting of vinyl bromide, vinyl iodide, vinyl chloride, vinylidene chloride, tetrachloroethylene, hexachloropropene, tetrachloropropene, trichloropropene, dichloropropene, difluoropropene, fluoropropene, vinylidene fluoride, vinyl fluoride, hexafluoropropene, tetrafluoroethylene, chlorotrifluoroethylene, trifluoroethylene, 2,3,3,3-tetrafluoropropene, E / Zl,3,3,3-tetrafluoropropene, 3,3,3-trifluoropropene, (E / Z)-l-chloro-2,3,3,3-tetrafluoropropene, 1,2,3,3,3-pentafluoropropene, (E / Z)-l-chloro-3,3,3-trifluoropropene, 2-chloro-3,3,3-trifluoropropene, and mixtures thereof.

[0014] According to a preferred embodiment, step b) is carried out in the presence of a solvent selected from the group consisting of water, acetone, dimethyl sulfoxide, di-methylformamide, N,N-dimethylacetamide, l-methyl-2-pyrrolidone, isobutyl methyl ketone and dihydrolevoglucosenone.

[0015] According to another aspect, the present invention provides a functionalized halogenated polymer comprising monomeric units M3 of formula -CH(R')-C(R2)(SR)- and monomeric units Ml comprising at least one halogen atom, preferably fluorine, with R, R1 and R2 as defined in this application.

[0016] According to a preferred embodiment, the molar content of the monomeric units M3 is between 0.01 and 5%, preferably between 0.05 and 2%, in particular between 0.1 and 1% in said polymer.

[0017] According to another aspect, the present invention provides an electrode binder comprising said halogenated polymer functionalized according to the present invention.

[0018] According to another aspect, the present invention provides an electrode comprising said functionalized halogenated polymer according to the present invention.

[0019] According to another aspect, the present invention provides a battery comprising said electrode according to the present invention.

[0020] According to another aspect, the present invention relates to the use of said halogenated polymer functionalized according to the present invention in the preparation of a conductive polymer, a solid electrolyte for fuel cells, a hydrophilic coating, a hydrophobic coating, or a UV-absorbing coating. Detailed description of the invention Step a) Al polymer

[0021] According to a first aspect, the present invention relates to a process for preparing a functionalized halogenated polymer. Said process comprises a step a) of supplying a halogenated polymer Al comprising monomeric units M1 comprising at least one halogen atom, preferably fluorine, and monomeric units M2 comprising at least one carbon-carbon double bond -C(R')=C(R2)-•

[0022] According to a preferred embodiment, in the monomeric units M2 the substituents R1 and R2 are independently selected from the group consisting of H, Ci-C5 alkyl, Ci-C5 (per)halogenoalkyl, F, Br, I and Cl. Preferably, the substituents R1 and R2 are independently selected from the group consisting of F, CF3, Cl and H.

[0023] According to a preferred embodiment, the monomeric units Ml have the formula -C(Y1)(Y2)-C(Y3)(Y4)- in which Y1, Y2, Y3, and Y4 are independently selected from the group consisting of H, Ci-C5 alkyl, Ci-C5 (per)halogenoalkyl, F, Br, I, and Cl; preferably independently selected from the group consisting of F, CF3, Br, I, Cl, and H, provided that the substituents Y1, Y2, Y3, and Y4 are not simultaneously H or Ci-C5 alkyl. The term Ci-C5 (per)halogenoalkyl refers to alkyl compounds comprising from 1 to 5 carbon atoms and at least one halogen atom.

[0024] Advantageously, the monomeric units Ml are derived from a monomer selected from the group consisting of vinyl bromide, vinyl iodide, vinyl chloride, vinylidene chloride, tetrachloroethylene, hexachloropropene, tetrachloropropene, trichloropropene, dichloropropene, difluoropropene, fluoropropene, vinylidene fluoride, vinyl fluoride, hexafluoropropene, tetrafluoroethylene, chlorotrifluoroethylene, trifluoroethylene, 2,3,3,3-tetrafluoropropene, E / Zl,3,3,3-tetrafluoropropene, 3,3,3-trifluoropropene, (E / Z)-l-chloro-2,3,3,3-tetrafluoropropene, 1,2,3,3,3-pentafluoropropene, (E / Z)-l-chloro-3,3,3-trifluoropropene, 2-chloro-3,3,3-trifluoropropene, and mixtures thereof.

[0025] Preferably, the monomeric units Ml are derived from a monomer selected from the group consisting of vinylidene fluoride, vinyl fluoride, tetrafluoroethylene, chlorotrifluoroethylene, trifluoroethylene, and mixtures thereof. In particular, the monomeric units Ml are derived from vinylidene fluoride.

[0026] In a preferred embodiment, the halogenated polymer Al comprises monomeric units Ml derived from vinylidene fluoride and monomeric units M2 comprising at least one carbon-carbon double bond -C(R')=C(R2)- with R1 and R2 as defined above. In this embodiment, the halogenated polymer Al may also comprise monomeric units Ml' derived from a comonomer compatible with vinylidene fluoride. The comonomers compatible with vinylidene fluoride may be halogenated (fluorinated, chlorinated, brominated, or iodinated) or non-halogenated. Examples of suitable comonomers include vinyl chloride, vinyl iodide, vinyl bromide, vinyl fluoride, tetrafluoroethylene, trifluoroethylene, hexafluoropropene, trifluoropropenes, particularly 3,3,3-trifluoropropene, tetrafluoropropenes, particularly 2,3,3,3-tetrafluoropropene or 1,3,3,3-tetrafluoropropene, hexafluoroisobutylene, and perfluorobutylethylene.pentafluoropropenes and in particular 1,1,3,3,3-pentafluoropropene or 1,2,3,3,3-pentafluoropropene, perfluoroalkylvinyl ethers and in particular those of general formula Rf-O-CF=CF2, Rf being an alkyl group, preferably at Cl to C4 (preferred examples being perfluoropropylvinyl ether and perfluoromethylvinyl ether), alkylvinyl ethers and in particular those of general formula Rf-O-CH=CH2, Rf being an alkyl group, preferably at Cl to C4 (preferred examples being propylvinyl ether and methylvinyl ether), vinyl alkanolates and in particular those of general formula Rf-C(O)-O-CH=CH2, Rf being an alkyl group, preferably at Cl to C4, in particular vinyl acetate. The comonomer compatible with vinylidene fluoride may contain a chlorine, bromine, or iodine atom. In particular, it may be chosen from bromotrifluoroethylene, chlorofluoroethylene,Chlorotrifluoroethylene and chlorotrifluoropropene. Chlorofluoroethylene can refer to either 1-chloro-1-fluoroethylene or 1-chloro-2-fluoroethylene. The 1-chloro-1-fluoroethylene isomer is preferred. Chlorotrifluoropropene is preferably 1-chloro-3,3,3-trifluoropropene or 2-chloro-3,3,3-trifluoropropene.

[0027] The halogenated polymer Al may also comprise monomeric units bearing at least one of the following functional groups: carboxylic acid, carboxylic acid anhydride, carboxylic acid esters, epoxy groups (such as glycidyl), amide, hydroxyl, carbonyl, mercapto, sulfide, oxazoline, phenolic, ester, ether, siloxane, sulfonic, sulfuric, phosphoric, or phosphonic. The functional group is introduced by a chemical reaction, which may be grafting or copolymerization of the vinylidene fluoride (VDF) monomer with a monomer bearing at least one of said functional groups and a vinyl group capable of copolymerizing with the VDF monomer, according to techniques well known to those skilled in the art. In one embodiment, the units bearing the carboxylic acid functional group further comprise a heteroatom selected from oxygen, sulfur, nitrogen, and phosphorus.The functional group content of said halogenated polymer Al may preferably be at least 0.01 mol%, preferably at least 0.1 mol%, and at most 15 mol%, preferably at most 10 mol%.

[0028] In particular, the halogenated polymer Al may also comprise monomeric units Ml” derived from (meth)acrylic acid selected from the group consisting of acrylic acid, methacrylic acid, hydroxyethyl(meth)acrylate, hydroxy-droxypropyl(meth)acrylate, hydroxyethylhexyl(meth)acrylate, styrene, vinylene carbonate, vinyl carbamate, N-vinyl acetamide, vinyl methacrylate, l-vinyl-2-pyrrolidone and methyl methacrylate, the Ci-Ci8 esters of acrylic acid or methacrylic acid; or a mixture thereof.

[0029] Thus, in a particular embodiment, the halogenated polymer Al comprises monomeric units M1 derived from vinylidene fluoride, monomeric units M2 comprising at least one carbon-carbon double bond -C(R')=C(R2)- with R1 and R2 as defined above, and optionally monomeric units M1' as defined above, monomeric units M1" as defined above, or a mixture of the two. More particularly, the halogenated polymer Al comprises monomeric units M1 derived from vinylidene fluoride, monomeric units M2 comprising at least one carbon-carbon double bond -C(R*)=C(R2)- with R1 and R2 as defined above, and optionally monomeric units M1' derived from a monomer selected from the group consisting of tetrafluoroethylene, trifluoroethylene, vinyl acetate, methyl vinyl ether, chlorotrifluoroethylene and hexafluoropropene or a mixture thereof,and monomeric units Ml” derived from a monomer selected from the group consisting of acrylic acid, methacrylic acid, hydroxyethyl(meth)acrylate, hydroxypropyl(meth)acrylate, hydroxyethylhexyl(meth)acrylate, styrene, vinylene carbonate, vinyl carbamate, N-vinyl acetamide, vinyl methacrylate, l-vinyl-2-pyrrolidone and methyl methacrylate, the Ci-Ci8 esters of acrylic acid or methacrylic acid, or a mixture thereof; or a mixture of the , monomeric units Ml' and Ml”. Polymer A

[0030] According to a preferred embodiment, said halogenated polymer Al is obtained by a dehydrohalogenation reaction of a halogenated polymer A. Said halogenated polymer A thus comprises monomers M1 as defined above and monomeric units M4 of formula -CH(R')-C(R2)(X)- in which X is a halogen and R1 and R2 are as defined above. Preferably, X is F or Cl, in particular X is F. The dehydrohalogenation reaction eliminates a compound HX from the monomeric units M4 to form the monomeric units M2 as described above.

[0031] As in the Al polymer above, in the A polymer, the monomeric units Ml are of formula -C(Y1)(Y2)-C(Y3)(Y4)- in which Y1, Y2, Y3 and Y4 are independently of each other selected from the group consisting of H, Ci-C5 alkyl, C1-C5 (per)halogenoalkyl, F, Br, I and Cl; preferably independently of each other selected from the group consisting of F, CF3, Br, I, Cl and H, provided that the substituents Y1, Y2, Y3 and Y4 are not simultaneously H or C1-C5 alkyl.

[0032] Advantageously, the monomeric units Ml are derived from a monomer selected from the group consisting of vinyl bromide, vinyl iodide, vinyl chloride, vinylidene chloride, tetrachloroethylene, hexachloropropene, tetrachloropropene, trichloropropene, dichloropropene, difluoropropene, fluoropropene, vinylidene fluoride, vinyl fluoride, hexafluoropropene, tetrafluoroethylene, chlorotrifluoroethylene, trifluoroethylene, 2,3,3,3-tetrafluoropropene, E / Zl,3,3,3-tetrafluoropropene, 3,3,3-trifluoropropene, (E / Z)-l-chloro-2,3,3,3-tetrafluoropropene, 1,2,3,3,3-pentafluoropropene, (E / Z)-l-chloro-3,3,3-trifluoropropene, 2-chloro-3,3,3-trifluoropropene, and mixtures thereof.

[0033] Preferably, the monomeric units Ml are derived from a monomer selected from the group consisting of vinylidene fluoride, vinyl fluoride, tetrafluoroethylene, chlorotrifluoroethylene, trifluoroethylene, and mixtures thereof. In particular, the monomeric units Ml are derived from vinylidene fluoride.

[0034] In a preferred embodiment, the halogenated polymer A comprises monomeric units M1 derived from vinylidene fluoride and monomeric units M4 of formula -CH(R')-C(R2)(X)- in which X is a halogen and R1 and R2 are as defined above. In this embodiment, the halogenated polymer A may also include monomeric units Ml' derived from a comonomer compatible with vinylidene fluoride. Vinylidene fluoride compatible comonomers can be halogenated (fluorinated, chlorinated, brominated, or iodinated) or non-halogenated. Examples of suitable comonomers include vinyl chloride, vinyl iodide, vinyl bromide, vinyl fluoride, tetrafluoroethylene, trifluoroethylene, hexafluoropropene, trifluoropropenes, particularly 3,3,3-trifluoropropene, tetrafluoropropenes, particularly 2,3,3,3-tetrafluoropropene or 1,3,3,3-tetrafluoropropene, hexafluoroisobutylene, perfluorobutylethylene, pentafluoropropenes, particularly 1,1,3,3,3-pentafluoropropene or 1,2,3,3,3-pentafluoropropene, perfluoroalkyl vinyl ethers, particularly those of general formula Rf-O-CF=CF2, Rf being an alkyl group, preferably at C4 (preferred examples being perfluoropropyl vinyl ether and perfluoromethyl vinyl ether),Alkyl vinyl ethers, particularly those with the general formula Rf-O-CH=CH2, where Rf is an alkyl group, preferably at the C4-Cl position (preferred examples being propyl vinyl ether and methyl vinyl ether), and vinyl alkanolates, particularly those with the general formula Rf-C(O)-O-CH=CH2, where Rf is an alkyl group, preferably at the C4-Cl position, especially vinyl acetate, are suitable for this purpose. The comonomer compatible with vinylidene fluoride may contain a chlorine, bromine, or iodine atom. It may be selected from bromotrifluoroethylene, chlorofluoroethylene, chlorotrifluoroethylene, and chlorotrifluoropropene. Chlorofluoroethylene may refer to either 1-chloro-1-fluoroethylene or 1-chloro-2-fluoroethylene. The 1-chloro-1-fluoroethylene isomer is preferred. Chlorotrifluoropropene is preferably l-chloro-3,3,3-trifluoropropene or 2-chloro-3,3,3-trifluoropropene.

[0035] The halogenated polymer A may also comprise monomeric units bearing at least one of the following functional groups: carboxylic acid, carboxylic acid anhydride, carboxylic acid esters, epoxy groups (such as glycidyl), amide, hydroxyl, carbonyl, mercapto, sulfide, oxazoline, phenolic, ester, ether, siloxane, sulfonic, sulfuric, phosphoric, or phosphonic. The functional group is introduced by a chemical reaction, which may be grafting or copolymerization of the vinylidene fluoride (VDF) monomer with a monomer bearing at least one of said functional groups and a vinyl group capable of copolymerizing with the VDF monomer, according to techniques well known to those skilled in the art. In one embodiment, the units bearing the carboxylic acid functional group further comprise a heteroatom selected from oxygen, sulfur, nitrogen, and phosphorus.The functional group content of said halogenated polymer A may preferably be at least 0.01 mol%, preferably at least 0.1 mol%, and at most 15 mol%, preferably at most 10 mol%.

[0036] In particular, the halogenated polymer A may also include monomeric units Ml” derived from (meth)acrylic acid selected from the group consisting of acrylic acid, methacrylic acid, hydroxyethyl(meth)acrylate, hydroxy-droxypropyl(meth)acrylate, hydroxyethylhexyl(meth)acrylate, styrene, vinylene carbonate, vinyl carbamate, N-vinyl acetamide, vinyl methacrylate, l-vinyl-2-pyrrolidone and methyl methacrylate, the Ci-Ci8 esters of acrylic acid or methacrylic acid; or a mixture thereof.

[0037] Thus, in a particular embodiment, the halogenated polymer A comprises monomeric units Ml derived from vinylidene fluoride, monomeric units M4 of formula -CH(R')-C(R2)(X)- in which X is a halogen and R1 and R2 are as defined above and optionally monomeric units Ml' as defined above, monomeric units Ml” as defined above; or a mixture of the two.

[0038] More particularly, the halogenated polymer A comprises monomeric units Ml derived from vinylidene fluoride, monomeric units M4 of formula -CH(R* )-C(R2)(X)- in which X is a halogen and R1 and R2 are as defined above and optionally monomeric units Ml' derived from a monomer selected from the group consisting of tetrafluoroethylene, trifluoroethylene, vinyl acetate, methyl vinyl ether, chlorotrifluoroethylene and hexafluoropropene or a mixture thereof, and monomeric units Ml” derived from a monomer selected from the group consisting of acrylic acid, methacrylic acid, hydroxyethyl(meth)acrylate, hydroxypropyl(meth)acrylate, hydroxyethylhexyl(meth)acrylate, styrene, vinylene carbonate, vinyl carbamate, N-vinyl acetamide, vinyl methacrylate, l-vinyl-2-pyrrolidone and methyl methacrylate, CrCi8 esters of acrylic acid or methacrylic acid, or a mixture thereof;or a mixture of the monomeric units Ml' and Ml”.;

[0039] In these different particular embodiments, X is preferably F or Cl, in particular X is F.

[0040] The polymer Al is preferably prepared by dehydrofluorination of polymer A. The dehydrofluorination step is carried out in the presence of an alkali hydroxide or alkaline earth hydroxide base; for example, NaOH or KOH, according to techniques known to those skilled in the art. The base can be used in the form of an aqueous solution with a concentration of 10 to 80% by weight, based on the total weight of the solution. This step is preferably carried out at a temperature of 15°C to 80°C. This step can also be carried out in the presence of a solvent, for example, an alcohol or water, or a mixture of the two. Step b)

[0041] In step b) of the present process, said halogenated polymer Al is brought into contact with a thiolate compound B of formula RS in the presence of a peroxide compound C. Peroxide compound C

[0042] According to a preferred embodiment, said peroxide compound C is selected from organic peroxides, percarbonates, perborates, and hydroperoxides. For example, among the perborates, sodium perborate, potassium perborate, or lithium perborate may be cited. For example, among the percarbonates, sodium percarbonate, potassium percarbonate, or lithium percarbonate may be cited.For example, among the organic peroxides and hydroperoxides, we can mention H2O2; bis-acylperoxides of formula (Rf-C(O)-O)2 with Rf being Ci-Cio (per)haloalkyl, Ci-Cio (per)fluoropolyoxyalkylene in particular bis-trichloroacetyl peroxide and bis-dichlorofluoroacetyl peroxide; dialkylperoxides of formula (RH-O)2 with RH being Ci-Cio alkyl, in particular diterbutylperoxide (DTBP); sodium or potassium persulfate; sodium or potassium perphosphate; dialkyl peroxydicarbonates in which the alkyl group has from 1 to 8 carbon atoms such as di-n-propyl-peroxydicarbonate or diisopropylperoxydicarbonate; alkyl peroxyesters such as tert-amylperoxypivalate or tert-butylperoxyisobutirate. .

[0043] In particular, the peroxide compound C is H2O2. Indeed, the use of hydrogen peroxide avoids the presence of organic impurities or additional processing steps such as precipitation or extractions in the presence of organic solvents, which are energy-intensive. This type of impurity can affect performance in certain electronic applications. The use of hydrogen peroxide also avoids the presence of potentially toxic or flammable organic solvents. Thiolate compound B

[0044] As mentioned above, the thiolate compound B has the formula RS. Preferably, this is obtained by reaction between a compound of formula RSH and a base.

[0045] Preferably, said base may be selected from the group consisting of LiOH, NaOH, KOH, CsOH, RbOH, Mg(OH)2, Ca(OH)2, N(CnH2n+l)3 with n being an integer from 1 to 10, N,N-Diisopropylethylamine, morpholine, pyridine, pyrrolidine, Pi-peridine, piperazine, 4-Methylmorpholine, N,N-Diisopropylethylamine, 1,8-Diazabicyclo(5.4.0)undec-7-ene, 6-(Dibutylamino)-1,8-diazabicyclo[5.4.0]undec-7-ene, 1,8-Diazabicyclo[5.4.0]undec-7-ene bonded to polystyrene, 1,5,7-Triazabicyclo[4.4.0]dec-5-ene, 7-Methyl-l,5,7-triazabicyclo[4.4.0]dec-5-ene, 1,1,3,3-Tetramethylguanidine, 2-tert-Butyl-1,1,3,3-tetramethylguanidine, l,5,7-Triazabicyclo[4.4.0]dec-5-ene bonded to polystyrene, 1,4-Diazabicyclo [2.2.2] octane, Quinuclidine, 1,5-Diazabicyclo(4.3.0)non-5-ene, 2,6-Di-tert-butylpyridine, 2,8,9-Trimethyl-2,5,8,9-tetraza-l-phosphabicyclo[3.3.3]undecane, Cyclodi-phosphazane, Lithium diisopropylamide, sodium diisopropylamide, potassium diiso-propylamide, magnésium diisopropylamide, calcium diisopropylamide, rubidium diisopropylamide, lithium bis(trimethylsilyl)amide, sodium bis(trimethylsilyl)amide, potassium bis(trimethylsilyl)amide, magnésium bis(trimethylsilyl)amide, calcium bis(trimethylsilyl)amide, rubidium bis(trimethylsilyl)amide, lithium tetramethylpi-peridide, sodium tetramethylpiperidide, potassium tetramethylpiperidide, magnésium tetramethylpiperidide, calcium tetramethylpiperidide, rubidium tetramethylpiperidide, [18-crown-6]-KHF2, KHF2, N,N’-diisopropylimidazonium, bifluorure, tetrabuty-lammonium, N(CnH2n+l)4 OH- avec n étant un entier de 1 à 10.

[0046] In the thiolate compound B, as in the compound of formula RSH from which it is derived, the substituent R is a hydrocarbon. The term hydrocarbon refers to a substituent comprising from 1 to 150 carbon atoms, preferably from 1 to 75 carbon atoms, in particular from 1 to 30 carbon atoms.

[0047] Advantageously, the substituent R is selected from the group of substituents consisting of Ci_Ci8 alkyl, C2_Ci8 alkenyl, C4_Ci8 cycloalkenyl, C3_Ci8 cycloalkyl, C6-Ci8 aryl, polyalkylene glycol, said substituent optionally bearing one or more functional groups of formula -F, -OR', -OC(O)R', -CN, -NR'2, -O-Si(OR')3, -Si(R')3, -SO3R', -OP(O)(OR')2, -P(O)(OR)2, -C(O)OR', -C(O)R', -C(O)-S-R', -C(O)-NR'2, -NR'3+ in which R' is independently selected for each substituent of the functional group from the group consisting of H, Ci_Ci8 alkyl, C2-Ci8 alkenyl, C4-C[8 cycloalkenyl, C3-Ci8 cycloalkyl, C6-Ci8 aryl and polyalkylene glycol.

[0048] Preferably, the substituent R is selected from the group of substituents consisting of Ci_Ci5 alkyl, C2 Ci5 alkenyl, C4 Ci5 cycloalkenyl, C3 Ci5 cycloalkyl, C6 Ci5 aryl, polyalkylene glycol, said substituent optionally bearing one or more functional groups of the formula -F, -OR', -OC(O)R', -CN, -NR'2, -O-Si(OR')3, -Si(R')3, -SO3R', -OP(O)(OR')2, -P(O)(OR)2, -C(O)OR', -C(O)R', -C(O)-S-R', -C(O)-NR'2, -NR'3+ in which R' is independently selected for each substituent of the functional group from the group consisting of H, Ci_Ci5 alkyl, C2 Ci5 alkenyl, C4-Ci5 cycloalkenyl, C3-Ci5cycloalkyl, C6-Ci5 aryl and polyalkylene glycol.

[0049] More preferably, the substituent R is selected from the group of substituents consisting of C1-C1 alkyl, C2-C1 alkyl, C4-C1 alkyl, C3-C1 alkyl, C6-C1 aryl, polyalkylene glycol, said substituent being optionally bearing one or more functional groups of formula -F, -OR', -OC(O)R', -CN, -NR'2, -O-Si(OR')3, -Si(R')3, -SO3R', -OP(O)(OR')2, -P(O)(OR)2, -C(O)OR', -C(O)R', -C(O)-S-R', -C(O)-NR'2, -NR'3+ in which R' is independently selected for each substituent of the functional group from the group consisting of H, Ci_Ci0 alkyl, C2_Ci0 alkenyl, C4_Ci0 cycloalkenyl, C3_Ci0 cycloalkyl, C6-Ci0 aryl and polyalkylene glycol.

[0050] In particular, the substituent R is selected from the group of substituents consisting of C5-alkyl, C2-alkyl, C4-cycloalkenyl, C3-cycloalkyl, C6-aryl, and polyalkylene glycol, said substituent optionally bearing one or more functional groups of the formula -F, -OR', -OC(O)R', -CN, -NR'2, -O-Si(OR')3, -Si(R')3, -SO3R', -OP(O)(OR')2, -P(O)(OR)2, -C(O)OR', -C(O)R', -C(O)-S-R', -C(O)-NR'2, and -NR'3+, in which R' is independently selected for each substituent of the functional group from the group consisting of H, C, C5-alkyl, C2-alkyl, C4-alkyl, C5-cycloalkyl, C6-aryl, and C5-cycloalkyl. cycloalkenyl, C3-C5 cycloalkyl, C6 aryl and polyalkylene glycol.

[0051] More particularly, the substituent R is selected from the group of substituents consisting of Ci C5 alkyl, C6 aryl, polyalkylene glycol, said substituent optionally bearing one or more functional groups of formula -F, -OR', -OC(O)R', -CN, -NR'2, -O-Si(OR')3, -Si(R')3, -SO3R', -OP(O)(OR')2, -P(O)(OR)2, -C(O)OR', -C(O)R', -C(O)-S-R', -C(O)-NR'2, -NR'3+ in which R' is independently selected for each substituent of the functional group from the group consisting of H, Ci C5 alkyl, C2 C5 alkenyl, C4 C5 cycloalkenyl, C3 C5 cycloalkyl, C6 aryl and polyalkylene glycol.

[0052] Preferably, the substituent R is selected from the group of substituents consisting of C, C5 alkyl, C6 aryl, polyalkylene glycol, said substituent optionally bearing one or more functional groups of formula -F, -OR', -OC(O)R', -CN, -NR'2, -C(O)OR', -C(O)R', -C(O)-NR'2, -NR'3+ in which R' is independently selected for each substituent of the functional group from the group consisting of H, C, C5 alkyl, C2 C5 alkenyl, C4 C2 cycloalkenyl, C3_C5cycloalkyl, C6 aryl and polyalkylene glycol.

[0053] In this application, the term polyalkylene glycol refers in particular to compounds of the formula -CH2CH2(OCH2CH2)n-OCH3 or -CH2CH2O(CH2CH2O)n-CH3 or -CH2CH2C(O)NH-CH2CH2O-(CH2CH2O)CH3 or -(CH2CH2O)n-CH2CO2H or -CH2CH2(OCH2CH2)n-OCH2CH2SH or -(CH2CH2O)n-CH2CH2CO2H or to compounds comprising randomly or blockly distributed polyethylene glycol -(CH2CH2O)n and / or polypropylene glycol (OCH(CH3)CH2)n units; or any of the above formulas in which one or more hydrogen atoms are substituted by a fluorine atom; with n an integer from 1 to 100, advantageously from 1 to 75, of Preferencely from 1 to 50, more preferably from 1 to 25, in particular from 1 to 10. Polyalkylene glycol can be functionalized by a group of the formula -Y2-C(Y1)-C(R10)=C(R8)(R9), -Y2-CH2-C(R10)=C(R8)(R9), -Y2-C(R10)=C(R8)(R9) or -Y2-C6H4-C(R10)=C(R8)(R9), in which R8, R9 and R10 are independently selected from each other from the group consisting of H, F, Cl, Br, I, Ci-C5 alkyl; and Y1 and Y2 are independently selected from each other from O and S. Preferably, R8, R9 and R10 are independently selected from each other from the group consisting of H, F, Cl, Ci-C5 alkyl. In particular, R8, R9 and R10 are independently selected from the group consisting of H, F and Ci-C3 alkyl. Implementation of step b)

[0054] Preferably, step b) of the present process is carried out in the presence of a solvent. This solvent may be an organic solvent suitable for solubilizing compounds B and C. Alternatively, the solvent may be water. Thus, without limitation, the solvent may be selected from the group consisting of water, acetone, dimethyl sulfoxide, dimethylformamide, N,N-dimethylacetamide, l-methyl-2-pyrrolidone, isobutyl methyl ketone, and dihydrolevoglucosenone. Preferably, the solvent is water. This avoids organic impurities that would necessitate additional purification steps.

[0055] According to a preferred embodiment, step b) is carried out at a temperature of 10°C to 80°C, preferably from 10°C to 50°C.

[0056] According to a particular embodiment, step b) is carried out in the presence of a thiolate compound B as described above in the presence of hydrogen peroxide (H2O2) and water. Since both thiolate compound B and hydrogen peroxide are soluble in water, this allows for the combination of additional advantages, even though the process can be carried out with good yields using other peroxide compounds (C) or in another solvent. The particularly preferred use of H2O2 and water makes it possible to carry out the process at a temperature of 10°C to 50°C with good yields without the use of potentially flammable or toxic organic solvents, under environmentally friendly conditions, and without requiring excessive energy consumption.

[0057] The use of thiolate compound B in step b) rather than its thiol precursor (RSH) facilitates the polymer functionalization reaction. Indeed, it has been surprisingly observed that thiolate compound B is much more readily activated by peroxide compound C, particularly H2O2, compared to the thiol precursor. The functionalization of the halogenated polymer Al is thus facilitated by implementing step b) of the present process compared to a step using a thiol derivative. Polymer A2

[0058] As mentioned above, the implementation of step b) allows the formation of a halogenated polymer A2. Said polymer A2 comprises monomeric units M3 of formula -CH(R')-C(R2)(SR)- and said monomeric units M1 comprising at least one halogen atom, preferably of fluorine; R, R1 and R2 being as defined above.

[0059] According to a preferred embodiment, the monomeric units Ml are of formula -C(Y1)(Y2)-C(Y3)(Y4)- in which Y1, Y2, Y3 and Y4 are independently of each other selected from the group consisting of H, Ci-C5 alkyl, Ci-C5 (per)halogenoalkyl, F, Br, I and Cl; preferably independently of each other selected from the group consisting of F, CF3, Cl, Br, I and H; provided that the substituents Y1, Y2, Y3 and Y4 are not simultaneously H or Ci-C5 alkyl.

[0060] Advantageously, the monomeric units Ml are derived from a monomer selected from the group consisting of vinyl bromide, vinyl iodide, vinyl chloride, vinylidene chloride, tetrachloroethylene, hexachloropropene, tetrachloropropene, trichloropropene, dichloropropene, difluoropropene, fluoropropene, vinylidene fluoride, vinyl fluoride, hexafluoropropene, tetrafluoroethylene, chlorotrifluoroethylene, trifluoroethylene, 2,3,3,3-tetrafluoropropene, E / Zl,3,3,3-tetrafluoropropene, 3,3,3-trifluoropropene, (E / Z)-l-chloro-2,3,3,3-tetrafluoropropene, 1,2,3,3,3-pentafluoropropene, (E / Z)-l-chloro-3,3,3-trifluoropropene, 2-chloro-3,3,3-trifluoropropene, and mixtures thereof.

[0061] Preferably, the monomeric units Ml are derived from a monomer selected from the group consisting of vinylidene fluoride, vinyl fluoride, tetrafluoroethylene, chlorotrifluoroethylene, trifluoroethylene, and mixtures thereof. In particular, the monomeric units Ml are derived from vinylidene fluoride.

[0062] In a preferred embodiment, the halogenated polymer A2 comprises monomeric units M1 derived from vinylidene fluoride and monomeric units M3 of the formula -CH(R')-C(R2)(SR)- with R, R1, and R2 as defined above in this application. In this embodiment, the halogenated polymer A2 may also comprise monomeric units M1' derived from a comonomer compatible with vinylidene fluoride. Comonomers compatible with vinylidene fluoride may be halogenated (fluorinated, chlorinated, brominated, or iodinated) or non-halogenated. Examples of suitable comonomers include, for example, vinyl chloride, vinyl iodide, vinyl bromide, vinyl fluoride, tetrafluoroethylene, trifluoroethylene, hexafluoropropene, trifluoropropenes, and in particular the 3,3,3-Trifluoropropene, tetrafluoropropenes, particularly 2,3,3,3-tetrafluoropropene or 1,3,3,3-tetrafluoropropene, hexafluoroisobutylene, perfluorobutylethylene, pentafluoropropenes, particularly 1,1,3,3,3-pentafluoropropene or 1,2,3,3,3-pentafluoropropene, perfluoroalkylvinyl ethers, particularly those of general formula Rf-O-CF=CF2, Rf being an alkyl group, preferably at C4 (preferred examples being perfluoropropylvinyl ether and perfluoromethylvinyl ether), alkylvinyl ethers, particularly those of general formula Rf-O-CH=CH2, Rf being an alkyl group, preferably at C4 (preferred examples being propylvinyl ether and methylvinyl ether), alkanolates of vinyl, and in particular those with the general formula Rf-C(0)-0-CH=CH2, where Rf is an alkyl group, preferably at the C4-Cl position, especially vinyl acetate. The comonomer compatible with vinylidene fluoride may contain a chlorine, bromine, or iodine atom.It can in particular be chosen from bromotrifluoroethylene, chlorofluoroethylene, chlorotrifluoroethylene, and chlorotrifluoropropene. Chlorofluoroethylene can refer to either 1-chloro-1-fluoroethylene or 1-chloro-2-fluoroethylene. The 1-chloro-1-fluoroethylene isomer is preferred. Chlorotrifluoropropene is preferably 1-chloro-3,3,3-trifluoropropene or 2-chloro-3,3,3-trifluoropropene.

[0063] The halogenated polymer A2 may also comprise monomeric units bearing at least one of the following functional groups: carboxylic acid, carboxylic acid anhydride, carboxylic acid esters, epoxy groups (such as glycidyl), amide, hydroxyl, carbonyl, mercapto, sulfide, oxazoline, phenolic, ester, ether, siloxane, sulfonic, sulfuric, phosphoric, or phosphonic. The functional group is introduced by a chemical reaction, which may be grafting or copolymerization of the vinylidene fluoride (VDF) monomer with a monomer bearing at least one of said functional groups and a vinyl group capable of copolymerizing with the VDF monomer, according to techniques well known to those skilled in the art. In one embodiment, the units bearing the carboxylic acid functional group further comprise a heteroatom selected from oxygen, sulfur, nitrogen, and phosphorus.The functional group content of said halogenated polymer A2 may preferably be at least 0.01 mol%, preferably at least 0.1 mol%, and at most 15 mol%, preferably at most 10 mol%.

[0064] In particular, the halogenated polymer A2 may also comprise monomeric units Ml” derived from (meth)acrylic acid selected from the group consisting of acrylic acid, methacrylic acid, hydroxyethyl(meth)acrylate, hydroxypropyl(meth)acrylate, hydroxyethylhexyl(meth)acrylate, styrene, vinylene carbonate, vinyl carbamate, N-vinyl acetamide, vinyl methacrylate, l-vinyl-2-pyrrolidone and methyl methacrylate, the Ci-Ci8 esters of the acid acrylic or methacrylic acid; or a mixture of these.

[0065] Thus, in a particular embodiment, the halogenated polymer A2 comprises monomeric units Ml derived from vinylidene fluoride, monomeric units M3 of formula -CH(R')-C(R2)(SR)- with R, R1 and R2 as defined above and optionally monomeric units Ml' as defined above, monomeric units Ml” as defined above; or a mixture of the two.

[0066] More particularly, the halogenated polymer A2 comprises monomeric units M1 derived from vinylidene fluoride, monomeric units M3 of formula -CH(R*)-C(R2)(SR)- with R, R1, and R2 as defined above, and optionally monomeric units M1' derived from a monomer selected from the group consisting of tetrafluoroethylene, trifluoroethylene, vinyl acetate, methyl vinyl ether, chlorotrifluoroethylene, and hexafluoropropene, or a mixture thereof, and monomeric units M1” derived from a monomer selected from the group consisting of acrylic acid, methacrylic acid, hydroxyethyl(meth)acrylate, hydroxypropyl(meth)acrylate, hydroxyethylhexyl(meth)acrylate, styrene, vinylene carbonate, vinyl carbamate, N-vinyl acetamide, vinyl methacrylate, and l-vinyl-2-pyrrolidone and methyl methacrylate, the Ci-Ci8 esters of acrylic acid or methacrylic acid; or a mixture of these;or a mixture of the monomeric units Ml' and Ml”.;

[0067] Preferably, the molar content of the monomeric units M3 in said polymer A2 is between 0.01 and 5%, preferably between 0.05 and 2%, in particular between 0.1 and 1%. Use

[0068] The polymer A2 as described in this application can be used in numerous applications. Thus, said polymer A2 can be used as a binder for electrodes (cathode or anode). According to another aspect of the present invention, an electrode comprising said polymer A2 is provided. According to another aspect, a battery comprising said electrode is also provided.

[0069] According to another aspect, said polymer A2 can be used in the preparation of a conductive polymer, a solid electrolyte for fuel cells, a hydrophilic coating, a hydrophobic coating or a UV-absorbing coating. Examples

[0070] Preparation of a dehydrofluorinated poly(vinylidene fluoride)

[0071] Example 1

[0072] 5 g of Kynar® 741 PVDF powder are stirred in 55 ml of a 10% ethanol solution in water. To this mixture, 2.5 ml of a 50 wt% NaOH solution in water are added. The ingredients are added and the reaction mixture is stirred for 24 hours at room temperature. A decolorization of the powder is observed, indicating that the dehydrofluorination reaction has taken place (from white to brown or black). The dehydrofluorinated PVDF is isolated by filtration and washed with water until a colorless filtrate is obtained. The dehydrofluorinated PVDF is then dried at 50°C for 24 hours.

[0073] Example 2

[0074] Example 1 is reproduced using 18 ml of a 50% NaOH solution in water.

[0075] Example 3

[0076] Example 2 is reproduced with the addition of 0.05g of sodium dodecyl sulfate in addition to the 18 ml of a 50% NaOH solution in water.

[0077] In each of Examples 1 to 3, a dehydrofluorinated PVDF is obtained. The PVDF thus obtained comprises monomeric units M1 of formula -CH2CF2- and monomeric units M2 of formula -CH=CF-. Functionalization of the dehydrofluorinated PVDF

[0078] Example 4 (comparative - no compound C)

[0079] 4.5 ml of trimethylamine are added to a 2.85 ml solution of methyl- 2-Mercaptopropionate (thiolate compound B) is dissolved in 20 mL of water and mixed until completely soluble. To this mixture, 2 g of dehydrofluorinated PVDF, 40 mL of water, 10 mL of tert-butanol, and 0.03 g of sodium dodecyl sulfate are added while stirring. A homogeneous dispersion is obtained. No decolorization is observed after 30 hours of reaction, indicating no functionalization of the PVDF.

[0080] Example 5 (comparative - no compound B)

[0081] 1.4 ml of triethylamine are added to 20 ml of water. To this mixture, 2 g of PVDF Dehydrofluorinated compound, 40 mL of water, and 10 mL of ethanol are added while stirring. A homogeneous dispersion is obtained. After 10 minutes of stirring, 0.2 mL of a 35% wt. hydrogen peroxide (H₂O₂) solution is added to the reaction mixture. No decolorization is observed after 30 hours of reaction, indicating the absence of PVDF functionalization.

[0082] Example 6 (invention)

[0083] 1.4 ml of triethylamine are added to a 1.4 ml methyl- 2-mercaptopropionate (CH3OC(O)CH(CH3)SH) is dissolved to form the thiolate compound B, CH3OC(O)CH(CH3)S, in 20 mL of water and mixed until completely dissolved. To this mixture, 2 g of dehydrofluorinated PVDF, 40 mL of water, and 10 mL of ethanol are added while stirring. A homogeneous dispersion is obtained. After 10 minutes of stirring, 0.2 mL of a 35% wt. H2O2 solution is added to the reaction mixture. Rapid decolorization occurs, forming a white powder. After 24 hours, the dispersion is filtered and washed with water until a colorless filtrate is obtained. The PVDF polymer thus obtained comprises monomeric units M1 of formula -CH2 CF2- and monomeric units M3 of formula -CHa(F)-C(H)(SR)- with R = -CH(CH3)(C(O)OCH3).

[0084] The powder is characterized by 'H NMR (Bruker Avance III 400 with a 5mm BBFO+ probe). The sample is dissolved in (CD3)2CO or (CD3)2SO. A quadruplet doublet is observed at 4.56 ppm characteristic of the hydrogen Ha of the following monomeric unit M3 -CHa(F)-C(H)(SR)- with R = -CH(CH3)(C(O)OCH3).

Claims

Demands

1. A process for preparing a functionalized halogenated polymer comprising the steps of: a. Providing a halogenated polymer Al comprising monomeric units M1 comprising at least one halogen atom, preferably fluorine, and monomeric units M2 comprising at least one carbon-carbon double bond -C(R')=C(R2)-; b. Contacting said halogenated polymer Al with a thiolate compound B of formula RS in the presence of a peroxide compound C to form a polymer A2 comprising monomeric units M3 of formula -CH(R')-C(R2)(SR)- and said monomeric units M1 comprising at least one halogen atom, preferably fluorine; R1 and R2 being independently selected from the group consisting of H, Ci-C5 alkyl, Ci-C5 (per)halogenoalkyl, F, Br, I and Cl; R being an optionally functionalized hydrocarbon substituent.

2. A process according to the preceding claim characterized in that the halogenated polymer Al is obtained by a dehydrohalogenation reaction of a halogenated polymer A comprising monomers M1 comprising at least one halogen atom, preferably fluorine, and monomeric units M4 of formula -CH(R')-C(R2)(X)- in which X is a halogen and R1 and R2 are as defined in claim 1.

3. A process according to any one of the preceding claims characterized in that the thiolate compound B of formula RS is obtained by reaction between a compound of formula RSH and a base.

4. A process according to the preceding claim characterized in that the base is selected from the group consisting of LiOH, NaOH, KOH, CsOH, RbOH, Mg(OH)2, Ca(OH)2, N(CnH2n+1)3 with n being an integer from 1 to 10, N,N-Diisopropylethylamine, morpholine, pyridine, pyrrolidine, Piperidine, piperazine, 4-Methylmorpholine, N,N-Diisopropylethylamine, 1,8-Diazabicyclo(5.4.0)undec-7-ene, 6-(Dibutylamino)-1,8-diazabicyclo[5.4.0]undec-7-ene,

5.

6.

7. l,8-Diazabicyclo[5.4.0]undec-7-ene bonded to polystyrene, l,5,7-Triazabicyclo[4.4.0]dec-5-ene, 7-Methyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene, 1,1,3,3-Tetramethylguanidine, 2-tert-Butyl-1,1,3,3-tetramethylguanidine, 1,5,7-Triazabicyclo[4.4.0]dec-5-ene linked to polystyrene, 1,4-Diazabicyclo[2.2.2]octane, Quinuclidine, 1,5-Diazabicyclo(4.3.0)non-5-ene, 2,6-Di-tert-butylpyridine, 2,8,9-Trimethyl-2,5,8,9-tetraza-1-phosphabicyclo[3.3.3]undecane, Cy-clodiphosphazane, Lithium diisopropylamide, sodium diisopropylamide, potassium diisopropylamide, magnésium diisopropylamide, calcium diisopropylamide, rubidium diisopropylamide, lithium bis(trimethylsilyl)amide, sodium bis(trimethylsilyl)amide, potassium bis(trimethylsilyl)amide, magnésium bis(trimethylsilyl)amide, calcium bis(trimethylsilyl)amide, rubidium bis(trimethylsilyl)amide, lithium te-tramethylpiperidide, sodium tetramethylpiperidide, potassium tetrame-thylpiperidide, magnésium tetramethylpiperidide, calcium tetramethylpiperidide, rubidium tetramethylpiperidide, [18-crown-6]-KHF2, KHF2, N,N’-diisopropylimidazonium, bifluorure, tetrabutylammonium, N(CnH 2n+i)4 OH- avec n étant un entier de 1 à 10. A process according to any one of the preceding claims characterized in that the peroxide compound C is selected from organic peroxides, percarbonates, perborates and hydroperoxides. A process according to any one of the preceding claims, characterized in that the thiolate compound B has the formula RS in which R is selected from the group of substituents consisting of C1-C18 alkyl, C2-Ci8 alkenyl, C4-Ci8 cycloalkenyl, C3-Ci8 cycloalkyl, C6-Ci8 aryl, polyalkylene glycol, said substituent optionally bearing one or more functional groups of the formula -F, -OR', -OC(O)R', -CN, -NR'2, -O-Si(OR')3, -Si(R')3, -SO3R', -OP(O)(OR')2, -P(O)(OR)2, -C(O)OR', -C(O)R', -C(O)-S-R', -C(O)-NR'2, -NR'3+ in which R' is independently selected for each substituent of the functional group from the group consisting of H, Ci_Ci8 alkyl, C2_Ci8 alkenyl, C4_Ci8 cycloalkenyl, C3 Ci8 cycloalkyl, C6-Ci8 aryl, polyalkylene glycol. A process according to any one of the preceding claims, characterized in that said monomeric units Ml are derived from a monomer selected from the group consisting of vinyl bromide, vinyl iodide, vinyl chloride, vinylidene chloride, tetrachloroethylene, hexachloropropene, tetrachloropropene, trichloropropene, dichloropropene, difluoropropene, fluoropropene, vinylidene fluoride, vinyl fluoride, hexafluoropropene, tetrafluoroethylene, chlorotrifluoroethylene, trifluoroethylene, 2,3,3,3-tetrafluoropropene, E / Z-1,3,3,3-tetrafluoropropene, 3,3,3-trifluoropropene, (E / Z)-l-chloro-2,3,3,3-tetrafluoropropene, 1,2,3,3,3-pentafluoropropene, (E / Z)-l-chloro-3,3,3-trifluoropropene, 2-chloro-3,3,3-trifluoropropene, and mixtures thereof.

8. A process according to any one of the preceding claims characterized in that step b) is carried out in the presence of a solvent selected from the group consisting of water, acetone, dimethyl sulfoxide, dimethylformamide, N,N-dimethylacetamide, l-methyl-2-pyrrolidone, isobutyl methyl ketone and dihydrolevoglu-cosenone.

9. Electrode binder comprising a functionalized halogenated polymer A2 comprising monomeric units M3 of formula -CH(R')-C(R2)(SR)- and monomeric units M1 comprising at least one halogen atom, preferably fluorine, with R, R1 and R2 as defined in any one of the preceding claims 1 or 6; preferably the molar content of the monomeric units M3 is between 0.01 and 5%, preferably between 0.05 and 2%, in particular between 0.1 and 1% in said polymer.

10. Electrode comprising a functionalized halogenated polymer A2 comprising monomeric units M3 of formula -CH(R')-C(R2)(SR)- and monomeric units M1 comprising at least one halogen atom, preferably fluorine, with R, R1 and R2 as defined in any one of the preceding claims 1 or 6; preferably the molar content of the monomeric units M3 is between 0.01 and 5%, preferably between 0.05 and 2%, in particular between 0.1 and 1% in said polymer.

11.

12. Battery comprising said electrode according to the preceding claim. Use of a functionalized halogenated polymer A2 comprising monomeric units M3 of formula -CH(R')-C(R2)(SR)- and monomeric units M1 comprising at least one halogen atom, preferably fluorine, with R, R1 and R2 as defined in any one of the preceding claims 1 or 6 in the preparation of a solid electrolyte for fuel cells, of a hy- coating drophile, a hydrophobic coating or a UV-absorbing coating; preferably the molar content of the M3 monomeric units is between 0.01 and 5%, preferably between 0.05 and 2%, in particular between 0.1 and 1% in said polymer.

13. Functionalized halogenated polymer A2 comprising monomeric units M3 of formula -CH(R')-C(R2)(SR)- and monomeric units M1 comprising at least one halogen atom, preferably fluorine, with R, R1 and R2 as defined in any one of the preceding claims 1 or 6; and characterized in that the molar content of the monomeric units M3 is between 0.01 and 1% in said polymer.