FR3160697A1 - Functionalized vinyl acetate, process for its preparation and use thereof - Google Patents

Abstract

The present invention relates to a functionalized vinyl acetate compound and its use in various applications.

Description

Functionalized vinyl acetate, process for its preparation and use thereof

The present invention relates to functionalized vinyl acetate compounds and the preparation and use thereof in various applications. In particular, the obtained compounds can be used as a monomer or comonomer for the preparation of electrode binder or separator. More specifically, the compounds can be used to prepare a halogenated polymer, such as poly(vinylidene fluoride), which is functionalized.

Technological background of the invention

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, automotive or chemical industry or in insulating materials.

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

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 by plasma treatment and electron beam irradiation approaches. However, some technical limitations such as industrialization and repeatability can be difficult.

There is therefore a need for a new method for preparing halogenated polymers that is simple, efficient and has limited environmental impact.

According to a first aspect, the present invention relates to a compound of formula (I)

wherein R ¹ , R ² , R ³ , R ⁵ , R ⁶ , R ⁷ are independently of each other selected from the group consisting of H and C ₁ -C ₅ alkyl;

X is selected from the group consisting of C _1- C ₁₈ alkyl, C _2- C ₁₈ alkenyl, C _4- C ₁₈ cycloalkenyl, C _3- C ₁₈ cycloalkyl, C ₆ -C ₁₈ aryl, polyalkylene glycol, optionally carrying one or more functional groups selected from the group consisting of -F, –OR', -OC(O)R', -C(O)OR', -CN, -NR' ₂ , -O-Si(OR') ₃ , -Si(R') ₃ , -SO ₃ R', -OP(O)(OR') ₂ , -P(O)(OR) ₂ , -C(O)R', -C(O)-S-R', -C(O)-NR' ₂ , -NR' ₃ ⁺ wherein R' is independently selected for each substituent of the functional group from the group consisting of H, C _1- C ₁₈ alkyl, C _2- C ₁₈ alkenyl, C _4- C ₁₈ cycloalkenyl, C _3- C ₁₈ cycloalkyl and C ₆ -C ₁₈ aryl;

Y is selected from the group F, Cl, Br, I, -CN, -OR’’, -C(O)OR’’, -SO₃R’’, C(O)Cl, -O-Si(OR’’)₃, -If(R’’)₃, -O-P(O)(OR’’)₂, -P(O)(OR’’)₂, -C(O)R’’, -C(O)-S-R’’, -C(O)-NR’’₂with R’’ selected from the group consisting of H, C_1-C₁₈alkyl, C_2-C₁₈alkenyl, C_4-C₁₈cycloalkenyl, C_3-C₁₈cycloalkyl and C₆-C₁₈aryl.

According to a preferred embodiment, in the compound of formula (I) R ¹ , R ² , R ³ , R ⁵ , R ⁶ , R ⁷ are independently of each other selected from the group consisting of H, C ₁ -C ₃ alkyl;

X is selected from the group consisting of C_1-C₁₀alkyl, C_2-C₁₀alkenyl, C_4-C₁₀cycloalkenyl, C_3-C₁₀cycloalkyl, C₆-C₁₀aryl, polyalkylene glycol, optionally carrying one or more functional groups selected from the group consisting of -F, –OR’, -O-C(O)R’, -C(O)OR’, -CN, -NR’₂, -O-Si(OR’)₃, -Si(R’)₃, -SO₃R’, -O-P(O)(OR’)₂, -P(O)(OR)₂, -C(O)R’, -C(O)-S-R’, -C(O)-NR’₂, -NR’₃ ⁺wherein R’ is independently selected for each substituent of the functional group from the group consisting of H, C_1-C₁₀alkyl, C_2-C₁₀alkenyl, C_4-C₁₀cycloalkenyl, C_3-C₁₀cycloalkyl and C₆-C₁₀aryl; Y is selected from the group F, Cl, Br, I, -CN, -OR’’, -C(O)OR’’, -SO₃R’’, C(O)Cl, -O-Si(OR’’)₃, -If(R’’)₃, -O-P(O)(OR’’)₂, -P(O)(OR’’)₂, -C(O)R’’, -C(O)-S-R’’, -C(O)-NR’’₂with R’’ selected from the group consisting of H, C_1-C₁₀alkyl, C_1-C₁₀alkyl, C_2-C₁₀alkenyl, C_4-C₁₀cycloalkenyl, C_3-C₁₀cycloalkyl and C₆-C₁₀aryl.

According to a preferred embodiment, said compound is of formula (Ia)

in which

R ¹ , R ² , R ³ , R ⁵ , R ⁶ , R ⁷ are independently of each other selected from the group consisting of H and C ₁ -C ₃ alkyl;

R ⁸ and R ⁹ are, independently of each other and independently for each of the n units, selected from the group consisting of H, C _1- C _{1 0} alkyl, C _2- C _{1 0} alkenyl, C _4- C _{1 0} cycloalkenyl, C _3- C ₁₀ cycloalkyl, C ₆ -C _{1 0} aryl, polyalkylene glycol, optionally carrying one or more functional groups selected from the group consisting of -F, -OR', -OC(O)R', -C(O)OR', -CN, -NR' ₂ , -O-Si(OR') ₃ , -Si(R') ₃ , -SO ₃ R', -OP(O)(OR') ₂ , -P(O)(OR) ₂ , -C(O)R', -C(O)-S-R', -C(O)-NR' ₂ , -NR' ₃ ⁺ wherein R' is independently selected for each substituent of the functional group from the group consisting of H, C _1- C _{1 0} alkyl, C _2- C _{1 0} alkenyl, C _4- C _{1 0} cycloalkenyl, C _3- C _{1 0} cycloalkyl and C ₆ -C _{1 0} aryl;

n is an integer from 1 to 15, preferably from 1 to 10, in particular from 1 to 5, more particularly from 2 to 5;

Y is selected from the group F, Cl, Br, I, -CN, -OR’’, -C(O)OR’’, -SO₃R’’, C(O)Cl, -O-Si(OR’’)₃, -If(R’’)₃, -O-P(O)(OR’’)₂, -P(O)(OR’’)₂, -C(O)R’’, -C(O)-S-R’’, -C(O)-NR’’₂with R’’ selected from the group consisting of H, C_1-C_{1 0}alkyl, C_1-C_{1 0}alkyl, C_2-C_{1 0}alkenyl, C_4-C_{1 0}cycloalkenyl, C_3-C_{1 0}cycloalkyl and C₆-C_{1 0}aryl.

According to a preferred embodiment, said compound is of formula (Ia)

in which

R ¹ , R ² , R ³ , R ⁵ , R ⁶ , R ⁷ are independently of each other selected from the group consisting of H and C ₁ -C ₃ alkyl;

R ⁸ and R ⁹ are, independently of each other and independently for each of the n units, selected from the group consisting of H, C _1- C ₅ alkyl, C _3- C ₁₀ cycloalkyl, C ₆ -C ₁₀ aryl, optionally carrying one or more functional groups selected from the group consisting of -F, -OR', -OC(O)R', -C(O)OR', -CN, -NR' ₂ , -O-Si(OR') ₃ , -Si(R') ₃ , -SO ₃ R', -OP(O)(OR') ₂ , -P(O)(OR) ₂ , -C(O)R', -C(O)-S-R', -C(O)-NR' ₂ , -NR' ₃ ⁺ wherein R' is independently selected for each substituent of the functional group from the group consisting of H, C _1- C ₁₀ alkyl, C _2- C ₁₀ alkenyl, C _4- C ₁₀ cycloalkenyl, C _3- C ₁₀ cycloalkyl and C ₆ -C ₁₀ aryl;

n is an integer from 1 to 15, preferably from 1 to 10, in particular from 1 to 5, more particularly from 2 to 5;

Y is selected from the group -CN, -C(O)OR’’, -SO₃R’’, -O-P(O)(OR’’)₂, -P(O)(OR’’)₂, - with R’’ selected from the group consisting of H, C_1-C₁₀alkyl, C_2-C₁₀alkenyl, C_4-C₁₀cycloalkenyl, C_3-C₁₀cycloalkyl and C₆-C₁₀aryl.

According to a preferred embodiment, said compound is of formula (Ia)

in which

R ¹ , R ² , R ³ , R ⁵ , R ⁶ , R ⁷ are independently of each other selected from the group consisting of H and C ₁ -C ₃ alkyl;

R ⁸ and R ⁹ are, independently of each other and independently for each of the n units, selected from the group consisting of H, C _1- C ₅ alkyl, C _3- C ₁₀ cycloalkyl, C ₆ -C ₁₀ aryl, optionally carrying one or more functional groups selected from the group consisting of -F, -OR', -OC(O)R', -C(O)OR', -CN, -NR' ₂ , -O-Si(OR') ₃ , -Si(R') ₃ , -SO ₃ R', -OP(O)(OR') ₂ , -P(O)(OR) ₂ , -C(O)R', -C(O)-S-R', -C(O)-NR' ₂ , -NR' ₃ ⁺ wherein R' is independently selected for each substituent of the functional group from the group consisting of H, C _1- C ₁₀ alkyl, C _2- C ₁₀ alkenyl, C _4- C ₁₀ cycloalkenyl, C _3- C ₁₀ cycloalkyl, C ₆ -C ₁₀ aryl; preferably R' is independently selected for each substituent of the functional group from the group consisting of H and C _1- C ₃ alkyl;

n is an integer from 1 to 15, preferably from 1 to 10, in particular from 1 to 5, more particularly from 2 to 5;

Y is selected from the group -C(O)OR’’, -SO₃R’’, -O-P(O)(OR’’)₂, -P(O)(OR’’)₂, - with R’’ selected from the group consisting of H and C_1-C₃alkyl; preferably R’’ is H.

According to another aspect, the present invention relates to a process for preparing the compound of formula (I), (Ia) as described in the present application comprising a step a) of reaction between a compound of formula (IIa)

and a thiol compound of formula (IIb) Y-X-SH in the presence of a base;

in which

R ¹ , R ² , R ³ , R ⁵ , R ⁶ , R ⁷ are independently of each other selected from the group consisting of H and C ₁ -C ₅ alkyl;

X is selected from the group consisting of C _1- C ₁₈ alkyl, C _2- C ₁₈ alkenyl, C _4- C ₁₈ cycloalkenyl, C _3- C ₁₈ cycloalkyl, C ₆ -C ₁₈ aryl, polyalkylene glycol, optionally carrying one or more functional groups selected from the group consisting of -F, –OR', -OC(O)R', -C(O)OR', -CN, -NR' ₂ , -O-Si(OR') ₃ , -Si(R') ₃ , -SO ₃ R', -OP(O)(OR') ₂ , -P(O)(OR) ₂ , -C(O)R', -C(O)-S-R', -C(O)-NR' ₂ , -NR' ₃ ⁺ wherein R' is independently selected for each substituent of the functional group from the group consisting of H, C _1- C ₁₈ alkyl, C _2- C ₁₈ alkenyl, C _4- C ₁₈ cycloalkenyl, C _3- C ₁₈ cycloalkyl and C ₆ -C ₁₈ aryl;

Y is selected from the group F, Cl, Br, I, -CN, -OR’’, -C(O)OR’’, -SO₃R’’, C(O)Cl, -O-Si(OR’’)₃, -If(R’’)₃, -O-P(O)(OR’’)₂, -P(O)(OR’’)₂, -C(O)R’’, -C(O)-S-R’’, -C(O)-NR’’₂with R’’ selected from the group consisting of H, C_1-C₁₈alkyl, C_2-C₁₈alkenyl, C_4-C₁₈cycloalkenyl, C_3-C₁₈cycloalkyl and C₆-C₁₈aryl; to form the compound of formula (I).

According to a preferred embodiment, the thiol compound is of formula (IIb')

R ⁸ and R ⁹ are, independently of each other and independently for each of the n units, selected from the group consisting of H, C _1- C ₁₀ alkyl, C _2- C ₁₀ alkenyl, C _4- C ₁₀ cycloalkenyl, C _3- C ₁₀ cycloalkyl, C ₆ -C ₁₀ aryl, polyalkylene glycol, optionally carrying one or more functional groups selected from the group consisting of -F, -OR', -OC(O)R', -C(O)OR', -CN, -NR' ₂ , -O-Si(OR') ₃ , -Si(R') ₃ , -SO ₃ R', -OP(O)(OR') ₂ , -P(O)(OR) ₂ , -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, C _1- C ₁₀ alkyl, C _2- C ₁₀ alkenyl, C _4- C ₁₀ cycloalkenyl, C _3- C ₁₀ cycloalkyl and C ₆ -C ₁₀ aryl;

n is an integer from 1 to 15, preferably from 1 to 10, in particular from 1 to 5, more particularly from 2 to 5;

Y is selected from the group F, Cl, Br, I, -CN, -OR’’, -C(O)OR’’, -SO₃R’’, C(O)Cl, -O-Si(OR’’)₃, -If(R’’)₃, -O-P(O)(OR’’)₂, -P(O)(OR’’)₂, -C(O)R’’, -C(O)-S-R’’, -C(O)-NR’’₂with R’’ selected from the group consisting of H, C_1-C₁₀alkyl, C_1-C₁₀alkyl, C_2-C₁₀alkenyl, C_4-C₁₀cycloalkenyl, C_3-C₁₀cycloalkyl and C₆-C₁₀aryl; to form the compound of formula (Ia).

According to a preferred embodiment, said base is selected from the group consisting of LiOH, NaOH, KOH, CsOH, RbOH, Mg(OH)2, Ca(OH)2, N(C _m H _2m+1 ) ₃ with m 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, triethylenediamine, 6-(Dibutylamino)-1,8-diazabicyclo[5.4.0]undec-7-ene, 1,8-Diazabicyclo[5.4.0]undec-7-ene bound 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, Cyclodiphosphazane, Lithium diisopropylamide, sodium diisopropylamide, potassium diisopropylamide, magnesium diisopropylamide, calcium diisopropylamide, rubidium diisopropylamide, lithium bis(trimethylsilyl)amide, sodium bis(trimethylsilyl)amide, potassium bis(trimethylsilyl)amide, magnesium bis(trimethylsilyl)amide, calcium bis(trimethylsilyl)amide, rubidium bis(trimethylsilyl)amide, lithium tetramethylpiperidide, sodium tetramethylpiperidide, potassium tetramethylpiperidide, magnesium tetramethylpiperidide, calcium tetramethylpiperidide, rubidium tetramethylpiperidide, [18-crown-6]-KHF2, KHF2, N,N'-diisopropylimidazonium, bifluoride, tetrabutylammonium, N(C _m H _2m+1 )4 OH- with m being an integer from 1 to 10.

According to a preferred embodiment, in step a), the molar content of said base is from 1 mol to 500 mol per 100 mol of said compound (IIb) or (IIb').

According to a preferred embodiment, step a) is carried out under an atmosphere containing less than 10 molar oxygen, preferably step a) is carried out under a nitrogen atmosphere.

According to another aspect, the present invention relates to a polymerP 0comprising monomeric units derived from a fluorinated monomerM 0 comprising a C=C double bond and at least one fluorine atom and monomeric units derived from the compound of formula (I) according to the present invention.

According to another aspect, the present invention relates to a composition comprising a fluorinated polymer P1 and a polymer P2 comprising monomeric units derived from the compound of formula (I) according to the present invention.

According to another aspect, the present invention relates to an electrode binder comprising said polymer according to the present invention or said composition according to the present invention.

According to another aspect, the present invention relates to a separator comprising said polymer according to the present invention or said composition according to the present invention.

According to another aspect, the present invention relates to an electrode comprising an active material, a binder according to the present invention and optionally a conductive agent.

According to a preferred embodiment, said electrode is a positive electrode and the active material is selected from the group consisting of LiCoO ₂ , Li(Ni, Co, AI)O ₂ , Li _{(1+ x),} Ni _a Mn _b Co _c (x represents a real number of 0 or more, a = 0.9, 0.8, 0.6, 0.5, or 1/3, b = 0.05, 0.1, 0.2, 0.3, or 1/3, c = 0.05, 0.1, 0.2, or 1/3), LiNiO ₂ , LiMn ₂ O ₄ , LiCoMnO ₄ , Li ₃ NiMn ₃ O ₃ , Li ₃ Fe ₂ (PO ₄ ) ₃ , Li ₃ V ₂ (PO ₄ ) ₃ , a spinel Li Mn substituted by a different element having a composition represented by Li _1+x Mn _2-xy M _y O ₄ , M representing at least one metal selected from Al, Mg, Co, Fe, Ni, and Zn, x and y independently representing a real number between 0 and 2, lithium titanate Li _x TiO _y – x and y independently representing a real number between 0 and 2, and a lithium metal phosphate having a composition represented by LiMPO ₄ , M representing Fe, Mn, Co, or Ni.

According to another preferred embodiment, said electrode is a negative electrode and the active material is selected from the group consisting of a lithium alloy, lithium metal, a metal oxide, a carbon material such as graphite or hard carbon, silicon, silicone, a silicon alloy and Li ₄ Ti ₅ O ₁₂ .

According to another aspect, the present invention relates to a Li-ion secondary battery comprising a positive electrode, a negative electrode and a separator; said separator being according to the present invention and/or one of said electrodes being according to the present invention.

According to another aspect, the present invention relates to the use of the compound according to the present invention or the polymer according to the present invention or the composition according to the present invention in the preparation of a conductive polymer, a solid electrolyte for fuel cells, paints, cables, wires, anti-corrosion equipment for the chemical industry, coatings for construction or architecture.

Detailed description of the invention

The present invention relates to functionalized vinyl acetate compounds. The present invention provides an efficient and simple process for preparing these compounds via a thiol-ene reaction. The process is carried out without a metal catalyst with volatile reagents, thus facilitating purification. The compound thus synthesized is of significant interest in applications related to batteries and more generally to energy storage.

Compound of formula (I)

According to a first aspect, the present invention provides a functionalized vinyl acetate compound. According to one embodiment, the present invention relates to a compound of formula (I)

wherein R ¹ , R ² , R ³ , R ⁵ , R ⁶ , R ⁷ are independently of each other selected from the group consisting of H and C ₁ -C ₅ alkyl;

X is selected from the group consisting of C _1- C ₁₈ alkyl, C _2- C ₁₈ alkenyl, C _4- C ₁₈ cycloalkenyl, C _3- C ₁₈ cycloalkyl, C ₆ -C ₁₈ aryl, polyalkylene glycol, optionally carrying one or more functional groups selected from the group consisting of -F, –OR', -OC(O)R', -C(O)OR', -CN, -NR' ₂ , -O-Si(OR') ₃ , -Si(R') ₃ , -SO ₃ R', -OP(O)(OR') ₂ , -P(O)(OR) ₂ , -C(O)R', -C(O)-S-R', -C(O)-NR' ₂ , -NR' ₃ ⁺ wherein R' is independently selected for each substituent of the functional group from the group consisting of H, C _1- C ₁₈ alkyl, C _2- C ₁₈ alkenyl, C _4- C ₁₈ cycloalkenyl, C _3- C ₁₈ cycloalkyl and C ₆ -C ₁₈ aryl;

Y is selected from the group F, Cl, Br, I, -CN, -OR’’, -C(O)OR’’, -SO₃R’’, C(O)Cl, -O-Si(OR’’)₃, -If(R’’)₃, -O-P(O)(OR’’)₂, -P(O)(OR’’)₂, -C(O)R’’, -C(O)-S-R’’, -C(O)-NR’’₂with R’’ selected from the group consisting of H, C_1-C₁₈alkyl, C_2-C₁₈alkenyl, C_4-C₁₈cycloalkenyl, C_3-C₁₈cycloalkyl and C₆-C₁₈aryl.

Advantageously, said compound is of formula (I) in which R ¹ , R ² , R ³ , R ⁵ , R ⁶ , R ⁷ are independently of each other selected from the group consisting of H and C ₁ -C ₃ alkyl;

X is selected from the group consisting of C_1-C₁₀alkyl, C_2-C₁₀alkenyl, C_4-C₁₀cycloalkenyl, C_3-C₁₀cycloalkyl, C₆-C₁₀aryl, polyalkylene glycol, optionally carrying one or more functional groups selected from the group consisting of -F, –OR’, -O-C(O)R’, -C(O)OR’, -CN, -NR’₂, -O-Si(OR’)₃, -Si(R’)₃, -SO₃R’, -O-P(O)(OR’)₂, -P(O)(OR)₂, -C(O)R’, -C(O)-S-R’, -C(O)-NR’₂, -NR’₃ ⁺wherein R’ is independently selected for each substituent of the functional group from the group consisting of H, C_1-C₁₀alkyl, C_2-C₁₀alkenyl, C_4-C₁₀cycloalkenyl, C_3-C₁₀cycloalkyl, C₆-C₁₀aryl; Y is selected from the group F, Cl, Br, I, -CN, -OR’’, -C(O)OR’’, -SO₃R’’, C(O)Cl, -O-Si(OR’’)₃, -If(R’’)₃, -O-P(O)(OR’’)₂, -P(O)(OR’’)₂, -C(O)R’’, -C(O)-S-R’’ and -C(O)-NR’’₂with R’’ selected from the group consisting of H, C_1-C₁₀alkyl, C_2-C₁₀alkenyl, C_4-C₁₀cycloalkenyl, C_3-C₁₀cycloalkyl and C₆-C₁₀aryl.

Preferably, said compound is of formula (I) in which R ¹ , R ² , R ³ , R ⁵ , R ⁶ , R ⁷ are independently of each other selected from the group consisting of H, C ₁ -C ₃ alkyl;

X is selected from the group consisting of C_1-C₁₀alkyl, C₆-C₁₀aryl, polyalkylene glycol, optionally carrying one or more functional groups selected from the group consisting of -F, –OR’, -O-C(O)R’, -C(O)OR’, -CN, -NR’₂, -O-Si(OR’)₃, -Si(R’)₃, -SO₃R’, -O-P(O)(OR’)₂, -P(O)(OR)₂, -C(O)R’, -C(O)-S-R’, -C(O)-NR’₂, -NR’₃ ⁺wherein R’ is independently selected for each substituent of the functional group from the group consisting of H, C_1-C₁₀alkyl, C_2-C₁₀alkenyl, C_4-C₁₀cycloalkenyl, C_3-C₁₀cycloalkyl and C₆-C₁₀aryl; Y is selected from the group F, Cl, Br, I, -CN, -OR’’, -C(O)OR’’, -SO₃R’’, C(O)Cl, -O-Si(OR’’)₃, -If(R’’)₃, -O-P(O)(OR’’)₂, -P(O)(OR’’)₂, -C(O)R’’, -C(O)-S-R’’, -C(O)-NR’’₂with R’’ selected from the group consisting of H, C_1-C₁₀alkyl and C₆-C₁₀aryl.

More preferably, said compound is of formula (I) in which R ¹ , R ² , R ³ , R ⁵ , R ⁶ , R ⁷ are independently of each other selected from the group consisting of H, C ₁ -C ₃ alkyl;

X is selected from the group consisting of C_1-C₅alkyl, polyalkylene glycol, optionally carrying one or more functional groups selected from the group consisting of -F, –OR’, -O-C(O)R’, -C(O)OR’, -CN, -NR’₂, -O-Si(OR’)₃, -Si(R’)₃, -SO₃R’, -O-P(O)(OR’)₂, -P(O)(OR)₂, -C(O)R’, -C(O)-S-R’, -C(O)-NR’₂, -NR’₃ ⁺wherein R’ is independently selected for each substituent of the functional group from the group consisting of H, C_1-C₁₀alkyl, C_2-C₁₀alkenyl, C_4-C₁₀cycloalkenyl, C_3-C₁₀cycloalkyl and C₆-C₁₀aryl; Y is selected from the group F, Cl, Br, I, -CN, -OR’’, -C(O)OR’’, -SO₃R’’, C(O)Cl, -O-Si(OR’’)₃, -If(R’’)₃, -O-P(O)(OR’’)₂, -P(O)(OR’’)₂, -C(O)R’’, -C(O)-S-R’’, -C(O)-NR’’₂with R’’ selected from the group consisting of H, C_1-C₅alkyl and C₆-C₁₀aryl.

According to a preferred embodiment, the group X is an alkyl radical of CR ⁸ R ⁹ units. Thus, said compound of formula (I) is of formula (Ia)

in which

R ¹ , R ² , R ³ , R ⁵ , R ⁶ , R ⁷ are independently of each other selected from the group consisting of H and C ₁ -C ₃ alkyl;

R ⁸ and R ⁹ are, independently of each other and independently for each of the n units, selected from the group consisting of H, C _1- C _{1 0} alkyl, C _2- C _{1 0} alkenyl, C _4- C _{1 0} cycloalkenyl, C _3- C ₁₀ cycloalkyl, C ₆ -C _{1 0} aryl, polyalkylene glycol, optionally carrying one or more functional groups selected from the group consisting of -F, -OR', -OC(O)R', -C(O)OR', -CN, -NR' ₂ , -O-Si(OR') ₃ , -Si(R') ₃ , -SO ₃ R', -OP(O)(OR') ₂ , -P(O)(OR) ₂ , -C(O)R', -C(O)-S-R', -C(O)-NR' ₂ , -NR' ₃ ⁺ wherein R' is independently selected for each substituent of the functional group from the group consisting of H, C _1- C _{1 0} alkyl, C _2- C _{1 0} alkenyl, C _4- C _{1 0} cycloalkenyl, C _3- C _{1 0} cycloalkyl and C ₆ -C _{1 0} aryl;

n is an integer from 1 to 15, preferably from 1 to 10, in particular from 1 to 5, more particularly from 2 to 5;

Y is selected from the group F, Cl, Br, I, -CN, -OR’’, -C(O)OR’’, -SO₃R’’, C(O)Cl, -O-Si(OR’’)₃, -If(R’’)₃, -O-P(O)(OR’’)₂, -P(O)(OR’’)₂, -C(O)R’’, -C(O)-S-R’’, -C(O)-NR’’₂with R’’ selected from the group consisting of H, C_1-C_{1 0}alkyl, C_1-C_{1 0}alkyl, C_2-C_{1 0}alkenyl, C_4-C_{1 0}cycloalkenyl, C_3-C_{1 0}cycloalkyl and C₆-C_{1 0}aryl.

According to a preferred embodiment, said compound is of formula (Ia)

in which

R ¹ , R ² , R ³ , R ⁵ , R ⁶ , R ⁷ are independently of each other selected from the group consisting of H and C ₁ -C ₃ alkyl;

R ⁸ and R ⁹ are, independently of each other and independently for each of the n units, selected from the group consisting of H, C _1- C ₅ alkyl, C _3- C ₁₀ cycloalkyl, C ₆ -C ₁₀ aryl, optionally carrying one or more functional groups selected from the group consisting of -F, -OR', -OC(O)R', -C(O)OR', -CN, -NR' ₂ , -O-Si(OR') ₃ , -Si(R') ₃ , -SO ₃ R', -OP(O)(OR') ₂ , -P(O)(OR) ₂ , -C(O)R', -C(O)-S-R', -C(O)-NR' ₂ , -NR' ₃ ⁺ wherein R' is independently selected for each substituent of the functional group from the group consisting of H, C _1- C ₁₀ alkyl, C _2- C ₁₀ alkenyl, C _4- C ₁₀ cycloalkenyl, C _3- C ₁₀ cycloalkyl and C ₆ -C ₁₀ aryl;

n is an integer from 1 to 15, preferably from 1 to 10, in particular from 1 to 5, more particularly from 2 to 5;

Y is selected from the group -CN, -C(O)OR’’, -SO₃R’’, -O-P(O)(OR’’)₂, -P(O)(OR’’)₂, - with R’’ selected from the group consisting of H, C_1-C₁₀alkyl, C_2-C₁₀alkenyl, C_4-C₁₀cycloalkenyl, C_3-C₁₀cycloalkyl and C₆-C₁₀aryl.

Advantageously, said compound is of formula (Ia)

in which

R ¹ , R ² , R ³ , R ⁵ , R ⁶ , R ⁷ are independently of each other selected from the group consisting of H and C ₁ -C ₃ alkyl;

R ⁸ and R ⁹ are, independently of each other and independently for each of the n units, selected from the group consisting of H, C _1- C ₅ alkyl, C _3- C ₁₀ cycloalkyl, C ₆ -C ₁₀ aryl, optionally carrying one or more functional groups selected from the group consisting of -F, -OR', -OC(O)R', -C(O)OR', -CN, -NR' ₂ , -O-Si(OR') ₃ , -Si(R') ₃ , -SO ₃ R', -OP(O)(OR') ₂ , -P(O)(OR) ₂ , -C(O)R', -C(O)-S-R', -C(O)-NR' ₂ , -NR' ₃ ⁺ wherein R' is independently selected for each substituent of the functional group from the group consisting of H, C _1- C ₁₀ alkyl, C _2- C ₁₀ alkenyl, C _4- C ₁₀ cycloalkenyl, C _3- C ₁₀ cycloalkyl, C ₆ -C ₁₀ aryl; preferably R' is independently selected for each substituent of the functional group from the group consisting of H and C _1- C ₃ alkyl;

n is an integer from 1 to 15, preferably from 1 to 10, in particular from 1 to 5, more particularly from 2 to 5;

Y is selected from the group -C(O)OR’’, -SO₃R’’, -O-P(O)(OR’’)₂, -P(O)(OR’’)₂, - with R’’ selected from the group consisting of H and C_1-C₃alkyl; preferably R’’ is H.

Preferably, said compound is of formula (Ia)

in which

R ¹ , R ² , R ³ , R ⁵ , R ⁶ , R ⁷ are independently of each other selected from the group consisting of H and C ₁ -C ₃ alkyl;

R ⁸ and R ⁹ are, independently of each other and independently for each of the n units, selected from the group consisting of H, C _1- C ₅ alkyl, C ₆ -C ₁₀ aryl, optionally carrying one or more functional groups selected from the group consisting of -F, -OR', -OC(O)R', -C(O)OR', -CN, -NR' ₂ , -O-Si(OR') ₃ , -Si(R') ₃ , -SO ₃ R', -OP(O)(OR') ₂ , -P(O)(OR) ₂ , -C(O)R', -C(O)-S-R', -C(O)-NR' ₂ , -NR' ₃ ⁺ wherein R' is independently selected for each substituent of the functional group from the group consisting of H, C _1- C ₁₀ alkyl, C ₆ -C ₁₀ aryl ; preferably R' is independently selected for each substituent of the functional group from the group consisting of H and C _1- C ₃ alkyl;

n is an integer from 1 to 15, preferably from 1 to 10, in particular from 1 to 5, more particularly from 2 to 5;

Y is selected from the group -C(O)OR’’, -SO₃R’’, -O-P(O)(OR’’)₂, -P(O)(OR’’)₂, - with R’’ selected from the group consisting of H and C_1-C₃alkyl; preferably R’’ is H.

More preferably, said compound is of formula (Ia)

in which

R ¹ , R ² , R ³ , R ⁵ , R ⁶ , R ⁷ are independently of each other selected from the group consisting of H and C ₁ -C ₃ alkyl;

R ⁸ and R ⁹ are, independently of each other and independently for each of the n units, selected from the group consisting of H and C _1- C ₅ alkyl optionally carrying one or more functional groups selected from the group consisting of -F, -OR', -OC(O)R', -C(O)OR', -CN, -NR' ₂ , -O-Si(OR') ₃ , -Si(R') ₃ , -SO ₃ R', -OP(O)(OR') ₂ , -P(O)(OR) ₂ , -C(O)R', -C(O)-S-R', -C(O)-NR' ₂ , -NR' ₃ ⁺ wherein R' is independently selected for each substituent of the functional group from the group consisting of H, C _1- C ₁₀ alkyl, C ₆ -C ₁₀ aryl; preferably R' is independently selected for each substituent of the functional group from the group consisting of H and C _1- C ₃ alkyl;

n is an integer from 1 to 15, preferably from 1 to 10, in particular from 1 to 5, more particularly from 2 to 5;

Y is selected from the group -C(O)OR’’, -SO₃R’’, -O-P(O)(OR’’)₂, -P(O)(OR’’)₂, - with R’’ selected from the group consisting of H and C_1-C₃alkyl; preferably R’’ is H.

In particular, said compound is of formula (Ia)

in which

R ¹ , R ² , R ³ , R ⁵ , R ⁶ , R ⁷ are independently of each other selected from the group consisting of H and C ₁ -C ₃ alkyl;

R ⁸ and R ⁹ are, independently of each other and independently for each of the n units, selected from the group consisting of H, C _1- C ₅ alkyl optionally carrying one or more functional groups selected from the group consisting of -F, -OR', -OC(O)R', -C(O)OR', -SO ₃ R', -OP(O)(OR') ₂ , -P(O)(OR) ₂ , -C(O)R', -C(O)-S-R' wherein R' is independently selected for each substituent of the functional group from the group consisting of H, C _1- C ₁₀ alkyl, C ₆ -C ₁₀ aryl; preferably R' is independently selected for each substituent of the functional group from the group consisting of H and C _1- C ₃ alkyl;

n is an integer from 1 to 15, preferably from 1 to 10, in particular from 1 to 5, more particularly from 2 to 5;

Y is selected from the group -C(O)OR’’, -SO₃R’’, -O-P(O)(OR’’)₂, -P(O)(OR’’)₂, - with R’’ selected from the group consisting of H and C_1-C₃alkyl; preferably R’’ is H.

More particularly, said compound is of formula (Ia)

in which

R ¹ , R ² , R ³ , R ⁵ , R ⁶ , R ⁷ are independently of each other selected from the group consisting of H and C ₁ -C ₃ alkyl, preferably R ¹ , R ² , R ³ , R ⁵ , R ⁶ , R ⁷ are H;

R ⁸ and R ⁹ are, independently of each other and independently for each of the n units, selected from the group consisting of H, C _1- C ₃ alkyl optionally carrying one or more functional groups selected from the group consisting of -OR', -OC(O)R', -C(O)OR', -SO ₃ R', -OP(O)(OR') ₂ , -P(O)(OR) ₂ in which R' is independently selected for each substituent of the functional group from the group consisting of H, C _1- C ₁₀ alkyl, C ₆ -C ₁₀ aryl; preferably R' is independently selected for each substituent of the functional group from the group consisting of H and C _1- C ₃ alkyl; in particular R' is H;

n is an integer from 1 to 5, preferably from 2 to 5;

Y is selected from the group -C(O)OR’’, -SO₃R’’, -O-P(O)(OR’’)₂, -P(O)(OR’’)₂, - with R’’ selected from the group consisting of H and C_1-C₃alkyl; preferably R’’ is H.

Process for the preparation of the compound of formula (I)

According to another aspect, the present invention relates to a process for preparing compounds of formula (I), preferably (Ia) as described in the present application. Said process comprises a step a) of reaction between a compound of formula (IIa)

and a thiol compound of formula (IIb) Y-X-SH in the presence of a base;

in which

R ¹ , R ² , R ³ , R ⁵ , R ⁶ , R ⁷ are independently of each other selected from the group consisting of H and C ₁ -C ₅ alkyl;

X is selected from the group consisting of C_1-C₁₈alkyl, C_2-C₁₈alkenyl, C_4-C₁₈cycloalkenyl, C_3-C₁₈cycloalkyl, C₆-C₁₈aryl, polyalkylene glycol, optionally carrying one or more functional groups selected from the group consisting of -F, –OR’, -O-C(O)R’, -C(O)OR’, -CN, -NR’₂, -O-Si(OR’)₃, -Si(R’)₃, -SO₃R’, -O-P(O)(OR’)₂, -P(O)(OR)₂, -C(O)R’, -C(O)-S-R’, -C(O)-NR’₂ and -NR’₃ ⁺wherein R’ is independently selected for each substituent of the functional group from the group consisting of H, C_1-C₁₈alkyl, C_2-C₁₈alkenyl, C_4-C₁₈cycloalkenyl, C_3-C₁₈cycloalkyl and C₆-C₁₈aryl;

Y is selected from the group F, Cl, Br, I, -CN, -OR’’, -C(O)OR’’, -SO₃R’’, C(O)Cl, -O-Si(OR’’)₃, -If(R’’)₃, -O-P(O)(OR’’)₂, -P(O)(OR’’)₂, -C(O)R’’, -C(O)-S-R’’, -C(O)-NR’’₂with R’’ selected from the group consisting of H, C_1-C₁₈alkyl, C_2-C₁₈alkenyl, C_4-C₁₈cycloalkenyl, C_3-C₁₈cycloalkyl, C₆-C₁₈aryl; to form the compound of formula (I).

Advantageously, in the compound of formula (IIa), R ¹ , R ² , R ³ , R ⁵ , R ⁶ , R ⁷ are independently of each other selected from the group consisting of H and C ₁ -C ₃ alkyl.

Advantageously, in the compound of formula (IIb), X is selected from the group consisting of C_1-C₁₀alkyl, C_2-C₁₀alkenyl, C_4-C₁₀cycloalkenyl, C_3-C₁₀cycloalkyl, C₆-C₁₀aryl, polyalkylene glycol, optionally carrying one or more functional groups selected from the group consisting of -F, –OR’, -O-C(O)R’, -C(O)OR’, -CN, -NR’₂, -O-Si(OR’)₃, -Si(R’)₃, -SO₃R’, -O-P(O)(OR’)₂, -P(O)(OR)₂, -C(O)R’, -C(O)-S-R’, -C(O)-NR’₂, -NR’₃ ⁺wherein R’ is independently selected for each substituent of the functional group from the group consisting of H, C_1-C₁₀alkyl, C_2-C₁₀alkenyl, C_4-C₁₀cycloalkenyl, C_3-C₁₀cycloalkyl, C₆-C₁₀aryl; Y is selected from the group F, Cl, Br, I, -CN, -OR’’, -C(O)OR’’, -SO₃R’’, C(O)Cl, -O-Si(OR’’)₃, -If(R’’)₃, -O-P(O)(OR’’)₂, -P(O)(OR’’)₂, -C(O)R’’, -C(O)-S-R’’ and -C(O)-NR’’₂with R’’ selected from the group consisting of H, C_1-C₁₀alkyl, C_2-C₁₀alkenyl, C_4-C₁₀cycloalkenyl, C_3-C₁₀cycloalkyl and C₆-C₁₀aryl.

Preferably, in the compound of formula (IIa), R¹, R², R³, R⁵, R⁶, R⁷are independently selected from the group consisting of H and C₁-C₃alkyl; and in the compound of formula (IIb), X is selected from the group consisting of C_1-C₁₀alkyl, C₆-C₁₀aryl, polyalkylene glycol, optionally carrying one or more functional groups selected from the group consisting of -F, –OR’, -O-C(O)R’, -C(O)OR’, -CN, -NR’₂, -O-Si(OR’)₃, -Si(R’)₃, -SO₃R’, -O-P(O)(OR’)₂, -P(O)(OR)₂, -C(O)R’, -C(O)-S-R’, -C(O)-NR’₂, -NR’₃ ⁺wherein R’ is independently selected for each substituent of the functional group from the group consisting of H, C_1-C₁₀alkyl, C_2-C₁₀alkenyl, C_4-C₁₀cycloalkenyl, C_3-C₁₀cycloalkyl and C₆-C₁₀aryl; Y is selected from the group F, Cl, Br, I, -CN, -OR’’, -C(O)OR’’, -SO₃R’’, C(O)Cl, -O-Si(OR’’)₃, -If(R’’)₃, -O-P(O)(OR’’)₂, -P(O)(OR’’)₂, -C(O)R’’, -C(O)-S-R’’, -C(O)-NR’’₂with R’’ selected from the group consisting of H, C_1-C₁₀alkyl and C₆-C₁₀aryl.

More preferably, in the compound of formula (IIa), R¹, R², R³, R⁵, R⁶, R⁷are independently selected from the group consisting of H, C₁-C₃alkyl; and in the compound of formula (IIb), X is selected from the group consisting of C_1-C₅alkyl, polyalkylene glycol, optionally carrying one or more functional groups selected from the group consisting of -F, –OR’, -O-C(O)R’, -C(O)OR’, -CN, -NR’₂, -O-Si(OR’)₃, -Si(R’)₃, -SO₃R’, -O-P(O)(OR’)₂, -P(O)(OR)₂, -C(O)R’, -C(O)-S-R’, -C(O)-NR’₂, -NR’₃ ⁺wherein R’ is independently selected for each substituent of the functional group from the group consisting of H, C_1-C₁₀alkyl, C_2-C₁₀alkenyl, C_4-C₁₀cycloalkenyl, C_3-C₁₀cycloalkyl and C₆-C₁₀aryl; Y is selected from the group F, Cl, Br, I, -CN, -OR’’, -C(O)OR’’, -SO₃R’’, C(O)Cl, -O-Si(OR’’)₃, -If(R’’)₃, -O-P(O)(OR’’)₂, -P(O)(OR’’)₂, -C(O)R’’, -C(O)-S-R’’, -C(O)-NR’’₂with R’’ selected from the group consisting of H, C_1-C₅alkyl and C₆-C₁₀aryl.

According to a preferred embodiment, the group X is an alkyl radical of CR ⁸ R ⁹ units.

Thus, according to a preferred embodiment, the thiol compound used in the present process, in step a), is of formula (IIb')

in which R ⁸ and R ⁹ are, independently of each other and independently for each of the n units, selected from the group consisting of H, C _1- C ₁₀ alkyl, C _2- C ₁₀ alkenyl, C _4- C ₁₀ cycloalkenyl, C _3- C ₁₀ cycloalkyl, C ₆ -C ₁₀ aryl, polyalkylene glycol, optionally carrying one or more functional groups selected from the group consisting of -F, -OR', -OC(O)R', -C(O)OR', -CN, -NR' ₂ , -O-Si(OR') ₃ , -Si(R') ₃ , -SO ₃ R', -OP(O)(OR') ₂ , -P(O)(OR) ₂ , -C(O)R', -C(O)-S-R', -C(O)-NR' ₂ , -NR' ₃ ⁺ wherein R' is independently selected for each substituent of the functional group from the group consisting of H, C _1- C ₁₀ alkyl, C _2- C ₁₀ alkenyl, C _4- C ₁₀ cycloalkenyl, C _3- C ₁₀ cycloalkyl, C ₆ -C ₁₀ aryl;

n is an integer from 1 to 15, preferably from 1 to 10, in particular from 1 to 5, more particularly from 2 to 5;

Y is selected from the group F, Cl, Br, I, -CN, -OR’’, -C(O)OR’’, -SO₃R’’, C(O)Cl, -O-Si(OR’’)₃, -If(R’’)₃, -O-P(O)(OR’’)₂, -P(O)(OR’’)₂, -C(O)R’’, -C(O)-S-R’’, -C(O)-NR’’₂with R’’ selected from the group consisting of H, C_1-C₁₀alkyl, C_1-C₁₀alkyl, C_2-C₁₀alkenyl, C_4-C₁₀cycloalkenyl, C_3-C₁₀cycloalkyl, C₆-C₁₀aryl; to form the compound of formula (Ia).

Advantageously, in compound (IIa), R¹, R², R³, R⁵, R⁶, R⁷are independently selected from the group consisting of H and C₁-C₃alkyl; and in the compound (IIb’) R⁸and R⁹are, independently of each other and independently for each of the units n, selected from the group consisting of H, C_1-C₅alkyl, C_3-C₁₀cycloalkyl, C₆-C₁₀aryl, optionally carrying one or more functional groups selected from the group consisting of -F, -OR’, -O-C(O)R’, -C(O)OR’, -CN, -NR’₂, -O-Si(OR’)₃, -Si(R’)₃, -SO₃R’, -O-P(O)(OR’)₂, -P(O)(OR)₂, -C(O)R’, -C(O)-S-R’, -C(O)-NR’₂, -NR’₃ ⁺wherein R’ is independently selected for each substituent of the functional group from the group consisting of H, C_1-C₁₀alkyl, C_2-C₁₀alkenyl, C_4-C₁₀cycloalkenyl, C_3-C₁₀cycloalkyl and C₆-C₁₀aryl; n is an integer from 1 to 15, preferably from 1 to 10, in particular from 1 to 5, more particularly from 2 to 5; Y is selected from the group -CN, -C(O)OR’’, -SO₃R’’, -O-P(O)(OR’’)₂, -P(O)(OR’’)₂, - with R’’ selected from the group consisting of H, C_1-C₁₀alkyl, C_2-C₁₀alkenyl, C_4-C₁₀cycloalkenyl, C_3-C₁₀cycloalkyl and C₆-C₁₀aryl.

Preferably, in compound (IIa), R¹, R², R³, R⁵, R⁶, R⁷are independently selected from the group consisting of H and C₁-C₃alkyl; and in compound (IIb’), R⁸and R⁹are, independently of each other and independently for each of the units n, selected from the group consisting of H, C_1-C₅alkyl, C_3-C₁₀cycloalkyl, C₆-C₁₀aryl, optionally carrying one or more functional groups selected from the group consisting of -F, -OR’, -O-C(O)R’, -C(O)OR’, -CN, -NR’₂, -O-Si(OR’)₃, -Si(R’)₃, -SO₃R’, -O-P(O)(OR’)₂, -P(O)(OR)₂, -C(O)R’, -C(O)-S-R’, -C(O)-NR’₂, -NR’₃ ⁺wherein R’ is independently selected for each substituent of the functional group from the group consisting of H, C_1-C₁₀alkyl, C_2-C₁₀alkenyl, C_4-C₁₀cycloalkenyl, C_3-C₁₀cycloalkyl, C₆-C₁₀aryl; preferably R’ is independently selected for each substituent of the functional group from the group consisting of H and C_1-C₃alkyl; n is an integer from 1 to 15, preferably from 1 to 10, in particular from 1 to 5, more particularly from 2 to 5; Y is selected from the group -C(O)OR’’, -SO₃R’’, -O-P(O)(OR’’)₂, -P(O)(OR’’)₂, - with R’’ selected from the group consisting of H and C_1-C₃alkyl; preferably R’’ is H.

More preferably, in compound (IIa), R¹, R², R³, R⁵, R⁶, R⁷are independently selected from the group consisting of H and C₁-C₃alkyl; and in the compound (IIb’) R⁸and R⁹are, independently of each other and independently for each of the units n, selected from the group consisting of H, C_1-C₅alkyl, C₆-C₁₀aryl, optionally carrying one or more functional groups selected from the group consisting of -F, -OR’, -O-C(O)R’, -C(O)OR’, -CN, -NR’₂, -O-Si(OR’)₃, -Si(R’)₃, -SO₃R’, -O-P(O)(OR’)₂, -P(O)(OR)₂, -C(O)R’, -C(O)-S-R’, -C(O)-NR’₂, -NR’₃ ⁺wherein R’ is independently selected for each substituent of the functional group from the group consisting of H, C_1-C₁₀alkyl, C₆-C₁₀aryl; preferably R’ is independently selected for each substituent of the functional group from the group consisting of H and C_1-C₃alkyl; n is an integer from 1 to 15, preferably from 1 to 10, in particular from 1 to 5, more particularly from 2 to 5; Y is selected from the group -C(O)OR’’, -SO₃R’’, -O-P(O)(OR’’)₂, -P(O)(OR’’)₂, - with R’’ selected from the group consisting of H and C_1-C₃alkyl; preferably R’’ is H.

In particular, in said compound is of formula (IIa) R¹, R², R³, R⁵, R⁶, R⁷are independently selected from the group consisting of H and C₁-C₃alkyl; and in said compound (IIb’) R⁸and R⁹are, independently of each other and independently for each of the units n, selected from the group consisting of H and C_1-C₅alkyl optionally carrying one or more functional groups selected from the group consisting of -F, -OR’, -O-C(O)R’, -C(O)OR’, -CN, -NR’₂, -O-Si(OR’)₃, -Si(R’)₃, -SO₃R’, -O-P(O)(OR’)₂, -P(O)(OR)₂, -C(O)R’, -C(O)-S-R’, -C(O)-NR’₂, -NR’₃ ⁺wherein R’ is independently selected for each substituent of the functional group from the group consisting of H, C_1-C₁₀alkyl, C₆-C₁₀aryl; preferably R’ is independently selected for each substituent of the functional group from the group consisting of H and C_1-C₃alkyl; n is an integer from 1 to 15, preferably from 1 to 10, in particular from 1 to 5, more particularly from 2 to 5; Y is selected from the group -C(O)OR’’, -SO₃R’’, -O-P(O)(OR’’)₂, -P(O)(OR’’)₂, - with R’’ selected from the group consisting of H and C_1-C₃alkyl; preferably R’’ is H.

More particularly, in said compound is of formula (IIa), R¹, R², R³, R⁵, R⁶, R⁷are independently selected from the group consisting of H and C₁-C₃alkyl; and in said compound (IIb’) R⁸and R⁹are, independently of each other and independently for each of the units n, selected from the group consisting of H, C_1-C₅alkyl optionally carrying one or more functional groups selected from the group consisting of -F, -OR’, -O-C(O)R’, -C(O)OR’, -SO₃R’, -O-P(O)(OR’)₂, -P(O)(OR)₂, -C(O)R’, -C(O)-S-R’ wherein R’ is independently selected for each substituent of the functional group from the group consisting of H, C_1-C₁₀alkyl, C₆-C₁₀aryl; preferably R’ is independently selected for each substituent of the functional group from the group consisting of H and C_1-C₃alkyl; n is an integer from 1 to 15, preferably from 1 to 10, in particular from 1 to 5, more particularly from 2 to 5; Y is selected from the group -C(O)OR’’, -SO₃R’’, -O-P(O)(OR’’)₂, -P(O)(OR’’)₂, - with R’’ selected from the group consisting of H and C_1-C₃alkyl; preferably R’’ is H.

Preferably, in said compound is of formula (IIa), R ¹ , R ² , R ³ , R ⁵ , R ⁶ , R ⁷ are independently of each other selected from the group consisting of H and C ₁ -C ₃ alkyl, preferably R ¹ , R ² , R ³ , R ⁵ , R ⁶ , R ⁷ are H; and in said compound (IIb'), R ⁸ and R ⁹ are, independently of each other and independently for each of the n units, selected from the group consisting of H, C _1- C ₃ alkyl optionally carrying one or more functional groups selected from the group consisting of -OR', -OC(O)R', -C(O)OR', -SO ₃ R', -OP(O)(OR') ₂ , -P(O)(OR) ₂ in which R' is independently selected for each substituent of the functional group from the group consisting of H, C _1- C ₁₀ alkyl, C ₆ -C ₁₀ aryl; preferably R' is independently selected for each substituent of the functional group from the group consisting of H and C _1- C ₃ alkyl; in particular R' is H;

n is an integer from 1 to 5, preferably from 2 to 5; Y is selected from the group -C(O)OR’’, -SO₃R’’, -O-P(O)(OR’’)₂, -P(O)(OR’’)₂, - with R’’ selected from the group consisting of H and C_1-C₃alkyl; preferably R’’ is H.

As mentioned above, step a) is carried out in the presence of a base.

Preferably, said base is selected from the group consisting of LiOH, NaOH, KOH, CsOH, RbOH, Mg(OH) ₂ , Ca(OH) ₂ , N(C _m H _2m+1 ) ₃ with m 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, triethylenediamine, 6-(Dibutylamino)-1,8-diazabicyclo[5.4.0]undec-7-ene, 1,8-Diazabicyclo[5.4.0]undec-7-ene bound 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, Cyclodiphosphazane, Lithium diisopropylamide, sodium diisopropylamide, potassium diisopropylamide, magnesium diisopropylamide, calcium diisopropylamide, rubidium diisopropylamide, lithium bis(trimethylsilyl)amide, sodium bis(trimethylsilyl)amide, potassium bis(trimethylsilyl)amide, magnesium bis(trimethylsilyl)amide, calcium bis(trimethylsilyl)amide, rubidium bis(trimethylsilyl)amide, lithium tetramethylpiperidide, sodium tetramethylpiperidide, potassium tetramethylpiperidide, magnesium tetramethylpiperidide, calcium tetramethylpiperidide, rubidium tetramethylpiperidide, [18-crown-6]-KHF2, KHF2, N,N'-diisopropylimidazonium, bifluoride, tetrabutylammonium, N(C _m H _2m+1 )4 OH- with m being an integer from 1 to 10. In particular, said base is selected from the group consisting of LiOH, NaOH, KOH, CsOH, RbOH, Mg(OH) ₂ , Ca(OH) ₂ , N(C _m H _2m+1 ) ₃ with m being an integer from 1 to 5, N,N-Diisopropylethylamine, morpholine, pyridine, pyrrolidine, Piperidine, piperazine, 4-Methylmorpholine, N,N-Diisopropylethylamine, 1,8-Diazabicyclo(5.4.0)undec-7-ene, triethylenediamine, 6-(Dibutylamino)-1,8-diazabicyclo[5.4.0]undec-7-ene, 1,8-Diazabicyclo[5.4.0]undec-7-ene bound to polystyrene. Said base can be used in excess, at stoichiometry or in deficiency relative to the amount of thiol compound (IIb) or (IIb'). Thus, in step a), the molar content of said base is advantageously greater than 1 mol per 100 mol of said thiol compound (IIb) or (IIb'), preferably greater than 5 mol, more preferably greater than 10 mol, in particular greater than 50 mol, more particularly greater than 100 mol per 100 mol of said compound (IIb) or (IIb'). Preferably, in step a), the molar content of said base is advantageously greater than 150 mol, preferably greater than 200 mol, more preferably greater than 250 mol, in particular greater than 300 mol per 100 mol of said thiol compound (IIb) or (IIb').

In step a), the molar content of said base may also be from 1 mol to 500 mol, advantageously from 50 to 500 mol, preferably from 100 to 500 mol, more preferably from 200 to 500 mol, in particular from 250 mol to 500 mol, more particularly 300 mol per 100 mol of said thiol compound (IIb) or (IIb').

Preferably, step a) is carried out without solvent.

The temperature at which step a) is carried out is not particularly limiting. Step a) may be carried out at a temperature of 15°C to 90°C, preferably 20°C to 40°C.

Step a) can be carried out under ambient atmosphere or under controlled atmosphere. Step a) can be carried out under controlled atmosphere to limit the formation of a disulfide compound resulting from the reaction on itself of the thiol compound (IIb) or (IIb'). Thus, step a) can be carried out under atmosphere containing less than 10 mol% of oxygen, preferably step a) is carried out under nitrogen atmosphere.

Polymer P0

According to another aspect, the present invention provides a polymerP0comprises monomeric units derived from a fluorinated monomerM 0 comprising a C=C double bond and at least one fluorine atom and monomeric units derived from the compound of formula (I) according to the present invention. Preferably, said polymerP0comprises monomeric units derived from a fluorinated monomerM 0 comprising a C=C double bond and at least one fluorine atom and monomeric units derived from the compound of formula (Ia) according to the present invention.

According to a preferred embodiment, the molar content of monomeric units derived from the compound of formula (I) or (Ia) according to the present invention in the polymer P0 is between 0.01 and 10 mol%, advantageously between 0.05 and 9 mol%, preferably between 0.1 and 8 mol%, more preferably between 0.1 and 7 mol%, in particular between 0.1 and 6 mol%, more particularly between 0.1 and 5 mol%, preferably between 0.1 and 4 mol%, preferably between 0.1 and 3 mol%, particularly preferably between 0.1 and 2 mol%.

Said fluorinated monomer M 0 is preferably selected from the group consisting of vinylidene fluoride, vinyl fluoride, trifluoroethylene, chlorotrifluoroethylene, 1,2-difluoroethylene, tetrafluoroethylene, hexafluoropropylene, perfluoro(alkyl vinyl) ethers, perfluoro(1,3-dioxole), perfluoro(2,2-dimethyl-1,3-dioxole), the monomer of formula CF ₂ =CFOCF ₂ CF(CF ₃ )OCF ₂ CF ₂ X in which X is SO ₂ F, CO ₂ H, CH ₂ OH, CH ₂ OCN or CH ₂ OPO ₃ H, the monomer of formula CF ₂ =CFOCF ₂ CF ₂ SO ₂ F, the monomer of formula F(CF ₂ )nCH ₂ OCF=CF ₂ in which n is 1, 2, 3, 4 or 5, the monomer of formula R ¹ CH ₂ OCF=CF ₂ in in which R ¹ is hydrogen or F(CF ₂ )m and m is 1, 2, 3 or 4, the monomer of formula R ² OCF=CH ₂ in which R ² is F(CF ₂ )p and p is 1, 2, 3 or 4, perfluorobutyl ethylene, trifluoropropene, tetrafluoropropene, hexafluoroisobutylene, perfluorobutylethylene, pentafluoropropene, bromotrifluoroethylene, chlorofluoroethylene, chlorotrifluoropropene, 2-trifluoromethyl-3,3,3-trifluoro-1-propene.

Preferably, said fluorinated monomer M 0 is selected from the group consisting of vinylidene fluoride, vinyl fluoride, trifluoroethylene, chlorotrifluoroethylene, 1,2-difluoroethylene, tetrafluoroethylene, hexafluoropropylene, perfluoro(alkyl vinyl) ethers, perfluoro(1,3-dioxole), perfluoro(2,2-dimethyl-1,3-dioxole), the monomer of formula CF ₂ =CFOCF ₂ CF(CF ₃ )OCF ₂ CF ₂ X in which X is SO ₂ F, CO ₂ H, CH ₂ OH, CH ₂ OCN or CH ₂ OPO ₃ H, the monomer of formula CF ₂ =CFOCF ₂ CF ₂ SO ₂ F, the monomer of formula F(CF ₂ )nCH ₂ OCF=CF ₂ in which n is 1, 2, 3, 4 or 5, the monomer of formula R ¹ CH ₂ OCF=CF ₂ in in which R ¹ is hydrogen or F(CF ₂ )m and m is 1, 2, 3 or 4, the monomer of formula R ² OCF=CH ₂ in which R ² is F(CF ₂ )p and p is 1, 2, 3 or 4.

More preferably, said fluorinated monomer M 0 is selected from the group consisting of vinylidene fluoride, vinyl fluoride, trifluoroethylene, chlorotrifluoroethylene, 1,2-difluoroethylene, tetrafluoroethylene, hexafluoropropylene.

In particular, said fluorinated monomer M 0 is vinylidene fluoride.

Said polymer P0 may also contain monomeric units derived from a monomer M 0 ' . Said monomer M 0 ' is copolymerizable with said fluorinated monomer M 0 or the compound (I) according to the invention to form a polymer P 0 comprising monomeric units derived from the fluorinated monomer M 0 , monomeric units derived from the compound of formula (I) according to the present invention and monomeric units derived from the monomer M 0 ' .

According to a preferred embodiment, said monomer M 0 ' is different from the monomer M 0 and is selected from the group consisting of vinylidene fluoride, vinyl fluoride, trifluoroethylene, chlorotrifluoroethylene, 1,2-difluoroethylene, tetrafluoroethylene, hexafluoropropylene, perfluoro(alkyl vinyl) ethers, perfluoro(1,3-dioxole), perfluoro(2,2-dimethyl-1,3-dioxole), the monomer of formula CF ₂ =CFOCF ₂ CF(CF ₃ )OCF ₂ CF ₂ X in which X is SO ₂ F, CO ₂ H, CH ₂ OH, CH ₂ OCN or CH ₂ OPO ₃ H, the monomer of formula CF ₂ =CFOCF ₂ CF ₂ SO ₂ F, the monomer of formula F(CF ₂ )nCH ₂ OCF=CF ₂ in which n is 1, 2, 3, 4 or 5, the monomer of formula R ¹ CH ₂ OCF=CF ₂ in which R ¹ is hydrogen or F(CF ₂ )m and m is 1, 2, 3 or 4, the monomer of formula R ² OCF=CH ₂ in which R ² is F(CF ₂ )p and p is 1, 2, 3 or 4, perfluorobutyl ethylene, trifluoropropene, tetrafluoropropene, hexafluoroisobutylene, perfluorobutylethylene, pentafluoropropene, bromotrifluoroethylene, chlorofluoroethylene, chlorotrifluoropropene, 2-trifluoromethyl-3,3,3-trifluoro-1-propene.

According to a preferred embodiment, said fluorinated monomer M 0 is vinylidene fluoride and said monomer M 0 ' is selected from the group consisting of vinyl fluoride, trifluoroethylene, chlorotrifluoroethylene, 1,2-difluoroethylene, tetrafluoroethylene, hexafluoropropylene, perfluoro(alkyl vinyl) ethers, perfluoro(1,3-dioxole), perfluoro(2,2-dimethyl-1,3-dioxole), the monomer of formula CF ₂ =CFOCF ₂ CF(CF ₃ )OCF ₂ CF ₂ X in which X is SO ₂ F, CO ₂ H, CH ₂ OH, CH ₂ OCN or CH ₂ OPO ₃ H, the monomer of formula CF ₂ =CFOCF ₂ CF ₂ SO ₂ F, the monomer of formula F(CF ₂ )nCH ₂ OCF=CF ₂ in which n is 1, 2, 3, 4 or 5, the monomer of formula R ¹ CH ₂ OCF=CF ₂ in which R ¹ is hydrogen or F(CF ₂ )m and m is 1, 2, 3 or 4, the monomer of formula R ² OCF=CH ₂ in which R ² is F(CF ₂ )p and p is 1, 2, 3 or 4, perfluorobutyl ethylene, trifluoropropene, tetrafluoropropene, hexafluoroisobutylene, perfluorobutylethylene, pentafluoropropene, bromotrifluoroethylene, chlorofluoroethylene, chlorotrifluoropropene, 2-trifluoromethyl-3,3,3-trifluoro-1-propene.

According to a particular embodiment, said fluorinated monomer M 0 is vinylidene fluoride and said monomer M 0 ' is selected from the group consisting of trifluoroethylene, chlorotrifluoroethylene, tetrafluoroethylene, hexafluoropropylene, perfluoro(alkyl vinyl) ethers, perfluoro(1,3-dioxole), perfluoro(2,2-dimethyl-1,3-dioxole), the monomer of formula CF ₂ =CFOCF ₂ CF(CF ₃ )OCF ₂ CF ₂ X in which X is SO ₂ F, CO ₂ H, CH ₂ OH, CH ₂ OCN or CH ₂ OPO ₃ H, the monomer of formula CF ₂ =CFOCF ₂ CF ₂ SO ₂ F, the monomer of formula F(CF ₂ )nCH ₂ OCF=CF ₂ in which n is 1, 2, 3, 4 or 5, the monomer of formula R ¹ CH ₂ OCF=CF ₂ in which R ¹ is hydrogen or F(CF ₂ )m and m is 1, 2, 3 or 4, the monomer of formula R ² OCF=CH ₂ in which R ² is F(CF ₂ )p and p is 1, 2, 3 or 4, perfluorobutylethylene.

According to a particular embodiment, said fluorinated monomer M 0 is vinylidene fluoride and said monomer M 0 ' is selected from the group consisting of trifluoroethylene, chlorotrifluoroethylene, tetrafluoroethylene, hexafluoropropylene and perfluoro(alkyl vinyl) ethers. The perfluoro(alkyl vinyl) ether is for example perfluoro(methyl vinyl) ether, perfluoro(ethyl vinyl) ether, perfluoro(propyl vinyl) ether or perfluoro(butyl vinyl) ether.

Said polymer P0 may also contain monomeric units derived from a monomer M 0 ' ' . Said monomer M 0 '' is copolymerizable with said fluorinated monomer M 0 or the compound (I) according to the invention to form a polymer P 0 comprising monomeric units derived from the fluorinated monomer M 0 , monomeric units derived from the compound of formula (I) according to the present invention and monomeric units derived from the monomer M 0 '' .

Optionally, said monomer M 0 '' is also copolymerizable with said monomer M 0 ' to form a polymer P 0 comprising monomeric units derived from the fluorinated monomer M 0 , monomeric units derived from the monomer M 0 ' , monomeric units derived from the monomer M 0 '' and monomeric units derived from the compound of formula (I) according to the present invention.

According to one embodiment, said monomer M 0 '' is of formula (Ia) R ¹ R ² C=C(R ³ )C(O)R in which the substituents R ¹ , R ² and R ³ are, independently of each other, selected from the group consisting of H and C ₁ -C ₅ alkyl; R is selected from the group consisting of –NHC(CH ₃ ) ₂ CH ₂ C(O)CH ₃ or –OR' with R' selected from the group consisting of H and C ₁ -C ₁₈ alkyl optionally substituted by one or more groups –OH, -CO ₂ H, -SO ₃ H, -PO ₃ H, -OC(O)R'', -C(O)O-R'' or a five- or ten-membered heterocycle comprising at least one nitrogen atom in its ring chain; R'' being selected from the group consisting of C ₁ -C ₆ alkyl or C ₆ -C ₁₂ aryl optionally substituted by one or more group(s) –OH, -CO ₂ H, -SO ₃ H, -PO ₃ H.

Said monomerM 0 ''can therefore be of formula (Ia) R¹R²C=C(R³)C(O)R in which the substituents R¹, R²and R³are, independently of each other, selected from the group consisting of H and C₁-C₅alkyl; R is selected from the group consisting of –NHC(CH₃)₂CH₂C(O)CH₃or –OR’ with R’ selected from the group consisting of H and C₁-C₁₈alkyl optionally substituted by one or more –OH, -CO group(s)₂H, -SO₃H, -PO₃H, -OC(O)R’’, -C(O)O-R’’ or a five- or ten-membered heterocycle comprising at least one nitrogen atom in its ring chain; R’’ being selected from the group consisting of C₁-C₆alkyl or C₆-C₁₂aryl optionally substituted by one or more –OH, -CO group(s)₂H, -SO₃H, -PO₃H. Said heterocycle may be saturated or unsaturated or aromatic. Said heterocycle may be monocyclic or bicyclic. Said heterocycle may be a pyrrole, pyrrolidine, pyridine, piperidine, pyrimidine, pyrazine, 1,4-dihydropyridine, indole, oxindole, isatin, quinoline, isoquinoline, quinazoline, imidazoline, pyrazolidine, 2-pyrrolidone, deltalactam, succinimide, 2-imidazolidinone, 4-imidazolidinone ring. Said heterocycle may be substituted by one or more C groups₁-C₅alkyl. As mentioned above, the C₁-C₁₈alkyl is optionally substituted by said heterocycle. The latter may be linked to the alkyl chain by the nitrogen atom or any other atom forming the heterocycle. Preferably the heterocycle is 2-pyrrolidone, delta-lactam, succinimide, 2-imidazolidinone, 4-imidazolidinone. Advantageously, said monomerM 0 '' can be of formula (Ia) R¹R²C=C(R³)C(O)R in which the substituents R¹, R²and R³are independently selected from the group consisting of H and C₁-C₅alkyl; R is -OR’ with R’ selected from the group consisting of H and C₁-C₁₈alkyl optionally substituted by one or more –OH, -CO group(s)₂H, -SO₃H, -PO₃H, -OC(O)R’’, -C(O)O-R’’ or a five- or ten-membered heterocycle comprising at least one nitrogen atom in its ring chain; R’’ being selected from the group consisting of C₁-C₆alkyl or C₆-C₁₂aryl optionally substituted by one or more –OH, -CO group(s)₂H, -SO₃H, -PO₃H. Preferably, the heterocycle is as defined above, in particular the heterocycle is 2-pyrrolidone, deltalactam, succinimide, 2-imidazolidinone, 4-imidazolidinone. Said substituent R' may be selected from the group consisting of H, methyl, ethyl, propyl, n-butyl, isobutyl, t-butyl, n-dodecyl, amyl, isoamyl, hexyl, 2-ethylhexyl, lauryl, n-octyl, hydroxyethyl, hydroxybutyl, hydroxypropyl, 2-pyrrolidone, deltalactam, succinimide, 2-imidazolidinone, 4-imidazolidinone ethyl substituted by a ureido group. Preferably, said monomerM 0 ''is of formula (Ia) R¹R²C=C(R³)C(O)R in which the substituents R¹and R²are H; R³ is H or CH₃; R is -OR’ with R’ selected from the group consisting of H and C₁-C₁₈alkyl optionally substituted by one or more –OH, -CO group(s)₂H, -SO₃H, -PO₃H, -OC(O)R’’, -C(O)O-R’’; R’’ being selected from the group consisting of C₁-C₆alkyl or C₆-C₁₂aryl optionally substituted by one or more –OH, -CO group(s)₂H, -SO₃H, -PO₃H. More preferably, said monomerM 0 ''is of formula (Ia) R¹R²C=C(R³)C(O)R in which the substituents R¹and R²are H; R³ is H or CH₃; R is -OR’ with R’ selected from the group consisting of H and C₁-C_{1 5}alkyl optionally substituted by one or more –OH, -CO group(s)₂H, -SO₃H, -PO₃H, -OC(O)R’’, -C(O)O-R’’; R’’ being selected from the group consisting of C₁-C₆alkyl or C₆-C₁₂aryl optionally substituted by one or more –OH, -CO group(s)₂H, -SO₃H, -PO₃H. In particular, said monomerM 0 ''is of formula (Ia) R¹R²C=C(R³)C(O)R in which the substituents R¹and R²are H; R³ is H or CH₃; R is -OR’ with R’ selected from the group consisting of H and C₁-C_{1 0}alkyl optionally substituted by one or more –OH, -CO group(s)₂H, -SO₃H, -PO₃H, -OC(O)R’’, -C(O)O-R’’; R’’ being selected from the group consisting of C₁-C₆alkyl or C₆-C₁₂aryl optionally substituted by one or more –OH, -CO group(s)₂H, -SO₃H, -PO₃H. More particularly, said monomerM 0 ''may be acrylic acid, methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, isobutyl acrylate, t-butyl acrylate, n-dodecyl acrylate, amyl acrylate, isoamyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, diacetone acrylamide, lauryl acrylate, n-octyl acrylate, hydroxypropyl methacrylate, hydroxybutyl methacrylate, hydroxyethyl methacrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, methyl acrylic acid, methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, methacrylate isobutyl methacrylate, t-butyl methacrylate, n-dodecyl methacrylate, amyl methacrylate, isoamyl methacrylate, hexyl methacrylate, 2-ethylhexyl methacrylate, lauryl methacrylate, n-octyl methacrylate, ureido methacrylate, monomers of formula CH₂=CH(CO₂CH₂CH₂CO₂H), CH₂=CH(CO₂CH₂CH₂-O-C(O)-CH₂CH₂CO₂H), CH₂=CH(CO₂CH₂CH₂CH₂-O-C(O)-CH₂CH₂CO₂H), CH₂=CH(CO₂CH(CH₃)CH₂-O-C(O)-CH₂CH₂CO₂H), CH₂=CH(CO₂CH₂CH₂-O-C(O)-C₆H₄CO₂H), CH₂=CH(CO₂CH₂CH₂CH₂CH(CO₂H)CH₂CH₂CO₂H); and mixtures thereof. Among these, said monomerM 0 ''with an alkyl group having 1 to 8 carbon atoms is preferred, and an alkyl group having 1 to 5 carbon atoms is more preferable. Said fluoropolymerP 0may comprise one or more monomeric units derived from a monomerM 0 ''as defined herein, for exampleM 0 ''may be a mixture of methyl methacrylate, acrylic acid and methacrylic acid and the polymerP 0may thus include, for example, monomeric units derived from methyl methacrylate, methacrylic acid and acrylic acid.

Composition

According to another aspect, the present invention relates to a composition comprising a fluoropolymer P1 and a polymer P2 comprising monomeric units derived from the compound of formula (I).

Said fluorinated polymer P1 may be a homopolymer derived from the fluorinated monomer M1 or a polymer derived from the fluorinated monomer M1 , from the monomer M1' and/or from the monomer M1'' .

Thus, said fluorinated polymer P1 comprises monomeric units derived from a fluorinated monomer M1 selected from the group consisting of vinyl fluoride, vinylidene fluoride, trifluoroethylene, chlorotrifluoroethylene, 1,2-difluoroethylene, tetrafluoroethylene, hexafluoropropylene, perfluoro(alkyl vinyl) ethers such as perfluoro(methyl vinyl) ether (PMVE), perfluoro(ethyl vinyl) ether (PEVE) and perfluoro(propyl vinyl) ether (PPVE); perfluoro(1,3-dioxole); perfluoro(2,2-dimethyl-1,3-dioxole); the product of formula CF ₂ =CFOCF ₂ CF(CF ₃ )OCF ₂ CF ₂ X in which X is SO ₂ F, CO ₂ H, CH ₂ OH, CH ₂ OCN or CH ₂ OPO ₃ H; the product of formula CF ₂ =CFOCF ₂ CF ₂ SO ₂ F; the product of formula F(CF ₂ )nCH ₂ OCF=CF ₂ in which n is 1, 2, 3, 4 or 5; the product of formula R ¹ CH ₂ OCF=CF ₂ in which R ¹ is hydrogen or F(CF ₂ )m and m is 1, 2, 3 or 4; the product of formula R ² OCF=CH ₂ in which R ² is F(CF ₂ )p and p is 1, 2, 3 or 4; perfluorobutyl ethylene (PFBE); trifluoropropene, tetrafluoropropene, hexafluoroisobutylene, perfluorobutylethylene, pentafluoropropene, bromotrifluoroethylene, chlorofluoroethylene, chlorotrifluoropropene and 2-trifluoromethyl-3,3,3-trifluoro-1-propene or a mixture thereof. Preferably, said fluorinated monomer M 1 is selected from the group consisting of vinylidene fluoride, vinyl fluoride, trifluoroethylene, chlorotrifluoroethylene, 1,2-difluoroethylene, tetrafluoroethylene, hexafluoropropylene, perfluoro(alkyl vinyl) ethers, perfluoro(1,3-dioxole), perfluoro(2,2-dimethyl-1,3-dioxole), the monomer of formula CF ₂ =CFOCF ₂ CF(CF ₃ )OCF ₂ CF ₂ X in which X is SO ₂ F, CO ₂ H, CH ₂ OH, CH ₂ OCN or CH ₂ OPO ₃ H, the monomer of formula CF ₂ =CFOCF ₂ CF ₂ SO ₂ F, the monomer of formula F(CF ₂ )nCH ₂ OCF=CF ₂ in which n is 1, 2, 3, 4 or 5, the monomer of formula R ¹ CH ₂ OCF=CF ₂ in in which R ¹ is hydrogen or F(CF ₂ )m and m is 1, 2, 3 or 4, the monomer of formula R ² OCF=CH ₂ in which R ² is F(CF ₂ )p and p is 1, 2, 3 or 4. More preferably, said fluorinated monomer M 1 is selected from the group consisting of vinylidene fluoride, vinyl fluoride, trifluoroethylene, chlorotrifluoroethylene, 1,2-difluoroethylene, tetrafluoroethylene, hexafluoropropylene. In particular, said fluorinated monomer M 1 is vinylidene fluoride.

According to a preferred embodiment, said fluorinated polymer P1 may be a homopolymer of vinylidene fluoride.

According to another preferred embodiment, the fluoropolymer P1 also comprises monomeric units derived from a monomer M1' or a monomer M1'' as described below or a mixture of the two.

According to a preferred embodiment, the fluoropolymer P1 also comprises monomeric units derived from a monomer M1' selected from the group consisting of vinyl fluoride; trifluoroethylene (VF ₃ ); chlorotrifluoroethylene (CTFE); 1,2-difluoroethylene; tetrafluoroethylene (TFE); hexafluoropropylene (HFP); perfluoro(alkyl vinyl) ethers such as perfluoro(methyl vinyl) ether (PMVE), perfluoro(ethyl vinyl) ether (PEVE) and perfluoro(propyl vinyl) ether (PPVE); perfluoro(1,3-dioxole); perfluoro(2,2-dimethyl-1,3-dioxole) (PDD); the product of formula CF ₂ =CFOCF ₂ CF(CF ₃ )OCF ₂ CF ₂ X in which X is SO ₂ F, CO ₂ H, CH ₂ OH, CH ₂ OCN or CH ₂ OPO ₃ H; the product of formula CF ₂ =CFOCF ₂ CF ₂ SO ₂ F; the product of formula F(CF ₂ )nCH ₂ OCF=CF ₂ in which n is 1, 2, 3, 4 or 5; the product of formula R ¹ CH ₂ OCF=CF ₂ in which R ¹ is hydrogen or F(CF ₂ )m and m is 1, 2, 3 or 4; the product of formula R ² OCF=CH ₂ in which R ² is F(CF ₂ )p and p is 1, 2, 3 or 4; perfluorobutyl ethylene (PFBE); trifluoropropene, tetrafluoropropene, hexafluoroisobutylene, perfluorobutylethylene, pentafluoropropene, bromotrifluoroethylene, chlorofluoroethylene, chlorotrifluoropropene and 2-trifluoromethyl-3,3,3-trifluoro-1-propene or a mixture thereof; or optionally monomeric units derived from a monomer M1'' of formula (Ia) R ¹ R ² C=C(R ³ )C(O)R in which the substituents R ¹ , R ² and R ³ are, independently of each other, selected from the group consisting of H and C ₁ -C ₅ alkyl; R is selected from the group consisting of –NHC(CH ₃ ) ₂ CH ₂ C(O)CH ₃ or –OR' with R' selected from the group consisting of H and C ₁ -C ₁₈ alkyl optionally substituted by one or more groups –OH, -CO ₂ H, -SO ₃ H, -PO ₃ H, -OC(O)R'', -C(O)O-R'' or a five- or ten-membered heterocycle comprising at least one nitrogen atom in its ring chain; R'' being selected from the group consisting of C ₁ -C ₆ alkyl or C ₆ -C ₁₂ aryl optionally substituted by one or more group(s) –OH, -CO ₂ H, -SO ₃ H, -PO ₃ H; or a mixture of monomeric units derived from said monomer M1'' and M1' .

Preferably, said monomer M 1' is selected from the group consisting of vinyl fluoride, trifluoroethylene, chlorotrifluoroethylene, 1,2-difluoroethylene, tetrafluoroethylene, hexafluoropropylene, perfluoro(alkyl vinyl) ethers, perfluoro(1,3-dioxole), perfluoro(2,2-dimethyl-1,3-dioxole), the monomer of formula CF ₂ =CFOCF ₂ CF(CF ₃ )OCF ₂ CF ₂ X in which X is SO ₂ F, CO ₂ H, CH ₂ OH, CH ₂ OCN or CH ₂ OPO ₃ H, the monomer of formula CF ₂ =CFOCF ₂ CF ₂ SO ₂ F, the monomer of formula F(CF ₂ )nCH ₂ OCF=CF ₂ in which n is 1, 2, 3, 4 or 5, the monomer of formula R ¹ CH ₂ OCF=CF ₂ in which R ¹ is hydrogen or F(CF ₂ )m and m is 1, 2, 3 or 4, the monomer of formula R ² OCF=CH ₂ in which R ² is F(CF ₂ )p and p is 1, 2, 3 or 4, perfluorobutyl ethylene, trifluoropropene, tetrafluoropropene, hexafluoroisobutylene, perfluorobutylethylene, pentafluoropropene, bromotrifluoroethylene, chlorofluoroethylene, chlorotrifluoropropene, 2-trifluoromethyl-3,3,3-trifluoro-1-propene. More preferably, said monomer M 1' is selected from the group consisting of trifluoroethylene, chlorotrifluoroethylene, tetrafluoroethylene, hexafluoropropylene, perfluoro(alkyl vinyl) ethers, perfluoro(1,3-dioxole), perfluoro(2,2-dimethyl-1,3-dioxole), the monomer of formula CF ₂ =CFOCF ₂ CF(CF ₃ )OCF ₂ CF ₂ X in which X is SO ₂ F, CO ₂ H, CH ₂ OH, CH ₂ OCN or CH ₂ OPO ₃ H, the monomer of formula CF ₂ =CFOCF ₂ CF ₂ SO ₂ F, the monomer of formula F(CF ₂ )nCH ₂ OCF=CF ₂ in which n is 1, 2, 3, 4 or 5, the monomer of formula R ¹ CH ₂ OCF=CF ₂ in which R ¹ is hydrogen or F(CF ₂ )m and m is 1, 2, 3 or 4, the monomer of formula R ² OCF=CH ₂ in which R ² is F(CF ₂ )p and p is 1, 2, 3 or 4, perfluorobutylethylene.

Preferably, said monomerM 1''is of formula (Ia) R¹R²C=C(R³)C(O)R in which the substituents R¹, R²and R³are, independently of each other, selected from the group consisting of H and C₁-C₅alkyl; R is selected from the group consisting of –NHC(CH₃)₂CH₂C(O)CH₃or –OR’ with R’ selected from the group consisting of H and C₁-C₁₈alkyl optionally substituted by one or more –OH, -CO group(s)₂H, -SO₃H, -PO₃H, -OC(O)R’’, -C(O)O-R’’ or a five- or ten-membered heterocycle comprising at least one nitrogen atom in its ring chain; R’’ being selected from the group consisting of C₁-C₆alkyl or C₆-C₁₂aryl optionally substituted by one or more –OH, -CO group(s)₂H, -SO₃H, -PO₃H. Said heterocycle may be saturated or unsaturated or aromatic. Said heterocycle may be monocyclic or bicyclic. Said heterocycle may be a pyrrole, pyrrolidine, pyridine, piperidine, pyrimidine, pyrazine, 1,4-dihydropyridine, indole, oxindole, isatin, quinoline, isoquinoline, quinazoline, imidazoline, pyrazolidine, 2-pyrrolidone, deltalactam, succinimide, 2-imidazolidinone, 4-imidazolidinone ring. Said heterocycle may be substituted by one or more C groups₁-C₅alkyl. As mentioned above, the C₁-C₁₈alkyl is optionally substituted by said heterocycle. The latter may be linked to the alkyl chain by the nitrogen atom or any other atom forming the heterocycle. Preferably the heterocycle is 2-pyrrolidone, delta-lactam, succinimide, 2-imidazolidinone, 4-imidazolidinone. More preferably, said monomerM 1'' can be of formula (Ia) R¹R²C=C(R³)C(O)R in which the substituents R¹, R²and R³are independently selected from the group consisting of H and C₁-C₅alkyl; R is -OR’ with R’ selected from the group consisting of H and C₁-C₁₈alkyl optionally substituted by one or more –OH, -CO group(s)₂H, -SO₃H, -PO₃H, -OC(O)R’’, -C(O)O-R’’ or a five- or ten-membered heterocycle comprising at least one nitrogen atom in its ring chain; R’’ being selected from the group consisting of C₁-C₆alkyl or C₆-C₁₂aryl optionally substituted by one or more –OH, -CO group(s)₂H, -SO₃H, -PO₃H. Preferably, the heterocycle is as defined above, in particular the heterocycle is 2-pyrrolidone, deltalactam, succinimide, 2-imidazolidinone, 4-imidazolidinone. Said substituent R' may be selected from the group consisting of H, methyl, ethyl, propyl, n-butyl, isobutyl, t-butyl, n-dodecyl, amyl, isoamyl, hexyl, 2-ethylhexyl, lauryl, n-octyl, hydroxyethyl, hydroxybutyl, hydroxypropyl, 2-pyrrolidone, deltalactam, succinimide, 2-imidazolidinone, 4-imidazolidinone ethyl substituted by a ureido group. In particular, said monomerM 1''is of formula (Ia) R¹R²C=C(R³)C(O)R in which the substituents R¹and R²are H; R³ is H or CH₃; R is -OR’ with R’ selected from the group consisting of H and C₁-C₁₈alkyl optionally substituted by one or more –OH, -CO group(s)₂H, -SO₃H, -PO₃H, -OC(O)R’’, -C(O)O-R’’; R’’ being selected from the group consisting of C₁-C₆alkyl or C₆-C₁₂aryl optionally substituted by one or more –OH, -CO group(s)₂H, -SO₃H, -PO₃H. More preferably, said monomerM 1''is of formula (Ia) R¹R²C=C(R³)C(O)R in which the substituents R¹and R²are H; R³ is H or CH₃; R is -OR’ with R’ selected from the group consisting of H and C₁-C_{1 5}alkyl optionally substituted by one or more –OH, -CO group(s)₂H, -SO₃H, -PO₃H, -OC(O)R’’, -C(O)O-R’’; R’’ being selected from the group consisting of C₁-C₆alkyl or C₆-C₁₂aryl optionally substituted by one or more –OH, -CO group(s)₂H, -SO₃H, -PO₃H. More particularly, said monomerM 1''is of formula (Ia) R¹R²C=C(R³)C(O)R in which the substituents R¹and R²are H; R³ is H or CH₃; R is -OR’ with R’ selected from the group consisting of H and C₁-C_{1 0}alkyl optionally substituted by one or more –OH, -CO group(s)₂H, -SO₃H, -PO₃H, -OC(O)R’’, -C(O)O-R’’; R’’ being selected from the group consisting of C₁-C₆alkyl or C₆-C₁₂aryl optionally substituted by one or more –OH, -CO group(s)₂H, -SO₃H, -PO₃H. Thus, said monomerM 1''may be acrylic acid, methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, isobutyl acrylate, t-butyl acrylate, n-dodecyl acrylate, amyl acrylate, isoamyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, diacetone acrylamide, lauryl acrylate, n-octyl acrylate, hydroxypropyl methacrylate, hydroxybutyl methacrylate, hydroxyethyl methacrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, methyl acrylic acid, methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, methacrylate isobutyl methacrylate, t-butyl methacrylate, n-dodecyl methacrylate, amyl methacrylate, isoamyl methacrylate, hexyl methacrylate, 2-ethylhexyl methacrylate, lauryl methacrylate, n-octyl methacrylate, ureido methacrylate, monomers of formula CH₂=CH(CO₂CH₂CH₂CO₂H), CH₂=CH(CO₂CH₂CH₂-O-C(O)-CH₂CH₂CO₂H), CH₂=CH(CO₂CH₂CH₂CH₂-O-C(O)-CH₂CH₂CO₂H), CH₂=CH(CO₂CH(CH₃)CH₂-O-C(O)-CH₂CH₂CO₂H), CH₂=CH(CO₂CH₂CH₂-O-C(O)-C₆H₄CO₂H), CH₂=CH(CO₂CH₂CH₂CH₂CH(CO₂H)CH₂CH₂CO₂H); and mixtures thereof. Among these, said monomerM 1''with an alkyl group having 1 to 8 carbon atoms is preferred, and an alkyl group having 1 to 5 carbon atoms is more preferable. Said fluoropolymerP 1may comprise one or more monomeric units derived from a monomerM 1''as defined herein, for exampleM 1''may be a mixture of methyl methacrylate, acrylic acid and methacrylic acid and fluoropolymerP1may thus include, for example, monomeric units derived from methyl methacrylate, methacrylic acid and acrylic acid.

Generally, the fluoropolymer P1 preferably contains at least 50 mol% vinylidene fluoride, advantageously at least 60 mol% vinylidene fluoride, preferably at least 70 mol% vinylidene fluoride. The monomeric units derived from the monomer M1' or M1'' may be present in a content of 1 to 50%, advantageously 2 to 30% by weight relative to the weight of said fluoropolymer P1 .

According to a preferred embodiment, the fluoropolymer P1 is a copolymer of vinylidene fluoride (VDF) and hexafluoropropylene (HFP) (P(VDF-HFP)), having a mass content of hexafluoropropylene monomer units of 2 to 30%, advantageously of 2 to 25%, preferably of 2 to 20%, preferably of 4 to 15% by weight relative to the weight of said fluoropolymer P1 . According to another embodiment, the fluoropolymer P1 is a copolymer of vinylidene fluoride (VDF) and hexafluoropropylene (HFP) (P(VDF-HFP)), having a mass content of hexafluoropropylene monomer units of 10 to 30%, advantageously of 10 to 25% by weight relative to the weight of said fluoropolymer P1 .

According to one embodiment, the fluoropolymer P1 is a copolymer of vinylidene fluoride and tetrafluoroethylene (TFE).

According to one embodiment, the fluoropolymer P1 is a copolymer of vinylidene fluoride and chlorotrifluoroethylene (CTFE).

According to one embodiment, the fluoropolymer P1 is a VDF-TFE-HFP terpolymer. According to one embodiment, the fluoropolymer P1 is a VDF-TrFE-TFE terpolymer (TrFE being trifluoroethylene). In these terpolymers, the mass content of VDF is at least 10%, the comonomers being present in variable proportions.

According to a particular embodiment, the fluoropolymer P1 comprises monomeric units carrying at least one of the following functions: 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, phosphonic. The function is introduced by a chemical reaction which may be grafting, or a copolymerization of the vinylidene fluoride (VDF) monomer with a monomer carrying at least one of said functional groups and a vinyl function capable of copolymerizing with vinylidene fluoride, according to techniques well known to those skilled in the art. Examples of monomers carrying an acid function and copolymerizable with vinylidene fluoride are listed among the monomer M1'' . The content of functional groups in said fluorinated polymer P1 is at least 0.01 mol%, preferably at least 0.1 mol%, and at most 15 mol%, preferably at most 10 mol%.

Thus, said fluorinated polymer P1 may be, for example, a copolymer of vinylidene fluoride and a monomer M 1'' selected from the group consisting of acrylic acid, methacrylic acid, methyl (meth)acrylate, ethyl (meth)acrylate, hydroxyethyl(meth)acrylate, hydroxybutyl(meth)acrylate, hydroxypropyl(meth)acrylate, hydroxyethylhexyl(meth)acrylate and acryloyloxy propylsuccinate. Preferably, the content of monomer M1'' in said polymer P1 is from 0.01% to 5% mol. In this embodiment, at least 40% of the units derived from monomer M1'' are distributed between two vinylidene fluoride units.

The fluoropolymer P1 preferably has a high molecular weight. By high molecular weight, as used herein, is meant a fluoropolymer P1 having a melt viscosity greater than 100 Pa.s, preferably greater than 500 Pa.s, more preferably greater than 1000 Pa.s, according to ASTM D-3835 method measured at 232°C and 100 sec-1.

According to a preferred embodiment, said fluoropolymer P1 is obtained in the form of a latex and the particle size of said fluoropolymer P1 is between 10 nm and 800 nm. The particle size is determined by laser granulometry. A particle size analyzer of the Malvern INSITEC System type is used for the measurement. This is carried out in a dry process by laser diffraction on a powder with a focal length of 100 mm.

According to a preferred embodiment, said fluoropolymer P1 has a solid content of between 10% and 55%, preferably between 10% and 50%, in particular between 10 and 40%.

Said polymer P2 comprises monomeric units derived from the compound of formula (I) according to the present invention. Said polymer P2 may also comprise monomeric units derived from a monomer M2 , M2' , M2'' or a mixture thereof. Said monomer M2 may be selected from the group consisting of vinylidene fluoride, vinyl fluoride, trifluoroethylene, chlorotrifluoroethylene, 1,2-difluoroethylene, tetrafluoroethylene, hexafluoropropylene, perfluoro(alkyl vinyl) ethers, perfluoro(1,3-dioxole), perfluoro(2,2-dimethyl-1,3-dioxole), the monomer of formula CF ₂ =CFOCF ₂ CF(CF ₃ )OCF ₂ CF ₂ X in which X is SO ₂ F, CO ₂ H, CH ₂ OH, CH ₂ OCN or CH ₂ OPO ₃ H, the monomer of formula CF ₂ =CFOCF ₂ CF ₂ SO ₂ F, the monomer of formula F(CF ₂ )nCH ₂ OCF=CF ₂ in which n is 1, 2, 3, 4 or 5, the monomer of formula R ¹ CH ₂ OCF=CF ₂ in which R ¹ is hydrogen or F(CF ₂ )m and m is 1, 2, 3 or 4, the monomer of formula R ² OCF=CH ₂ in which R ² is F(CF ₂ )p and p is 1, 2, 3 or 4, perfluorobutyl ethylene, trifluoropropene, tetrafluoropropene, hexafluoroisobutylene, perfluorobutylethylene, pentafluoropropene, bromotrifluoroethylene, chlorofluoroethylene, chlorotrifluoropropene, 2-trifluoromethyl-3,3,3-trifluoro-1-propene.

Preferably, said fluorinated monomer M2 is selected from the group consisting of vinylidene fluoride, vinyl fluoride, trifluoroethylene, chlorotrifluoroethylene, 1,2-difluoroethylene, tetrafluoroethylene, hexafluoropropylene, perfluoro(alkyl vinyl) ethers, perfluoro(1,3-dioxole), perfluoro(2,2-dimethyl-1,3-dioxole), the monomer of formula CF ₂ =CFOCF ₂ CF(CF ₃ )OCF ₂ CF ₂ X in which X is SO ₂ F, CO ₂ H, CH ₂ OH, CH ₂ OCN or CH ₂ OPO ₃ H, the monomer of formula CF ₂ =CFOCF ₂ CF ₂ SO ₂ F, the monomer of formula F(CF ₂ )nCH ₂ OCF=CF ₂ in which n is 1, 2, 3, 4 or 5, the monomer of formula R ¹ CH ₂ OCF=CF ₂ in which R ¹ is hydrogen or F(CF ₂ )m and m is 1, 2, 3 or 4, the monomer of formula R ² OCF=CH ₂ in which R ² is F(CF ₂ )p and p is 1, 2, 3 or 4.

More preferably, said fluorinated monomer M2 is selected from the group consisting of vinylidene fluoride, vinyl fluoride, trifluoroethylene, chlorotrifluoroethylene, 1,2-difluoroethylene, tetrafluoroethylene, hexafluoropropylene.

In particular, said fluorinated monomer M2 is vinylidene fluoride.

Said monomer M 2' is copolymerizable with said fluorinated monomer M 2 or the compound (I) according to the invention. According to a preferred embodiment, said monomer M 2' is different from monomer M 2 and is selected from the group consisting of vinylidene fluoride, vinyl fluoride, trifluoroethylene, chlorotrifluoroethylene, 1,2-difluoroethylene, tetrafluoroethylene, hexafluoropropylene, perfluoro(alkyl vinyl) ethers, perfluoro(1,3-dioxole), perfluoro(2,2-dimethyl-1,3-dioxole), the monomer of formula CF ₂ =CFOCF ₂ CF(CF ₃ )OCF ₂ CF ₂ X in which X is SO ₂ F, CO ₂ H, CH ₂ OH, CH ₂ OCN or CH ₂ OPO ₃ H, the monomer of formula CF ₂ =CFOCF ₂ CF ₂ SO ₂ F, the monomer of formula F(CF ₂ )nCH ₂ OCF=CF ₂ in which n is 1, 2, 3, 4 or 5, the monomer of formula R ¹ CH ₂ OCF=CF ₂ in which R ¹ is hydrogen or F(CF ₂ )m and m is 1, 2, 3 or 4, the monomer of formula R ² OCF=CH ₂ in which R ² is F(CF ₂ )p and p is 1, 2, 3 or 4, perfluorobutyl ethylene, trifluoropropene, tetrafluoropropene, hexafluoroisobutylene, perfluorobutylethylene, pentafluoropropene, bromotrifluoroethylene, chlorofluoroethylene, chlorotrifluoropropene, 2-trifluoromethyl-3,3,3-trifluoro-1-propene.

According to a preferred embodiment, said fluorinated monomer M 2 is vinylidene fluoride and said monomer M 2' is selected from the group consisting of vinyl fluoride, trifluoroethylene, chlorotrifluoroethylene, 1,2-difluoroethylene, tetrafluoroethylene, hexafluoropropylene, perfluoro(alkyl vinyl) ethers, perfluoro(1,3-dioxole), perfluoro(2,2-dimethyl-1,3-dioxole), the monomer of formula CF ₂ =CFOCF ₂ CF(CF ₃ )OCF ₂ CF ₂ X in which X is SO ₂ F, CO ₂ H, CH ₂ OH, CH ₂ OCN or CH ₂ OPO ₃ H, the monomer of formula CF ₂ =CFOCF ₂ CF ₂ SO ₂ F, the monomer of formula F(CF ₂ )nCH ₂ OCF=CF ₂ in which n is 1, 2, 3, 4 or 5, the monomer of formula R ¹ CH ₂ OCF=CF ₂ in which R ¹ is hydrogen or F(CF ₂ )m and m is 1, 2, 3 or 4, the monomer of formula R ² OCF=CH ₂ in which R ² is F(CF ₂ )p and p is 1, 2, 3 or 4, perfluorobutyl ethylene, trifluoropropene, tetrafluoropropene, hexafluoroisobutylene, perfluorobutylethylene, pentafluoropropene, bromotrifluoroethylene, chlorofluoroethylene, chlorotrifluoropropene, 2-trifluoromethyl-3,3,3-trifluoro-1-propene.

According to a particular embodiment, said fluorinated monomer M 2 is vinylidene fluoride and said monomer M 2' is selected from the group consisting of trifluoroethylene, chlorotrifluoroethylene, tetrafluoroethylene, hexafluoropropylene, perfluoro(alkyl vinyl) ethers, perfluoro(1,3-dioxole), perfluoro(2,2-dimethyl-1,3-dioxole), the monomer of formula CF ₂ =CFOCF ₂ CF(CF ₃ )OCF ₂ CF ₂ X in which X is SO ₂ F, CO ₂ H, CH ₂ OH, CH ₂ OCN or CH ₂ OPO ₃ H, the monomer of formula CF ₂ =CFOCF ₂ CF ₂ SO ₂ F, the monomer of formula F(CF ₂ )nCH ₂ OCF=CF ₂ in which n is 1, 2, 3, 4 or 5, the monomer of formula R ¹ CH ₂ OCF=CF ₂ in in which R ¹ is hydrogen or F(CF ₂ )m and m is 1, 2, 3 or 4, the monomer of formula R ² OCF=CH ₂ in which R ² is F(CF ₂ )p and p is 1, 2, 3 or 4, perfluorobutylethylene.

According to a particular embodiment, said fluorinated monomer M 2 is vinylidene fluoride and said monomer M 2' is selected from the group consisting of trifluoroethylene, chlorotrifluoroethylene, tetrafluoroethylene, hexafluoropropylene and perfluoro(alkyl vinyl) ethers. The perfluoro(alkyl vinyl) ether is for example perfluoro(methyl vinyl) ether, perfluoro(ethyl vinyl) ether, perfluoro(propyl vinyl) ether or perfluoro(butyl vinyl) ether.

Said monomer M 2'' is copolymerizable with said fluorinated monomer M 2 or the compound (I) according to the invention. Optionally, said monomer M 2 '' is also copolymerizable with said monomer M 2' . According to one embodiment, said monomer M 2 '' is of formula (Ia) R ¹ R ² C=C(R ³ )C(O)R in which the substituents R ¹ , R ² and R ³ are, independently of each other, selected from the group consisting of H and C ₁ -C ₅ alkyl; R is selected from the group consisting of –NHC(CH ₃ ) ₂ CH ₂ C(O)CH ₃ or –OR' with R' selected from the group consisting of H and C ₁ -C ₁₈ alkyl optionally substituted with one or more groups –OH, -CO ₂ H, -SO ₃ H, -PO ₃ H, -OC(O)R'', -C(O)O-R'' or a five- or ten-membered heterocycle comprising at least one nitrogen atom in its ring chain; R'' being selected from the group consisting of C ₁ -C ₆ alkyl or C ₆ -C ₁₂ aryl optionally substituted with one or more groups –OH, -CO ₂ H, -SO ₃ H, -PO ₃ H.

Said monomerM 2 ''can therefore be of formula (Ia) R¹R²C=C(R³)C(O)R in which the substituents R¹, R²and R³are, independently of each other, selected from the group consisting of H and C₁-C₅alkyl; R is selected from the group consisting of –NHC(CH₃)₂CH₂C(O)CH₃or –OR’ with R’ selected from the group consisting of H and C₁-C₁₈alkyl optionally substituted by one or more –OH, -CO group(s)₂H, -SO₃H, -PO₃H, -OC(O)R’’, -C(O)O-R’’ or a five- or ten-membered heterocycle comprising at least one nitrogen atom in its ring chain; R’’ being selected from the group consisting of C₁-C₆alkyl or C₆-C₁₂aryl optionally substituted by one or more –OH, -CO group(s)₂H, -SO₃H, -PO₃H. Said heterocycle may be saturated or unsaturated or aromatic. Said heterocycle may be monocyclic or bicyclic. Said heterocycle may be a pyrrole, pyrrolidine, pyridine, piperidine, pyrimidine, pyrazine, 1,4-dihydropyridine, indole, oxindole, isatin, quinoline, isoquinoline, quinazoline, imidazoline, pyrazolidine, 2-pyrrolidone, deltalactam, succinimide, 2-imidazolidinone, 4-imidazolidinone ring. Said heterocycle may be substituted by one or more C groups₁-C₅alkyl. As mentioned above, the C₁-C₁₈alkyl is optionally substituted by said heterocycle. The latter may be linked to the alkyl chain by the nitrogen atom or any other atom forming the heterocycle. Preferably the heterocycle is 2-pyrrolidone, delta-lactam, succinimide, 2-imidazolidinone, 4-imidazolidinone. Advantageously, said monomerM 2 '' can be of formula (Ia) R¹R²C=C(R³)C(O)R in which the substituents R¹, R²and R³are independently selected from the group consisting of H and C₁-C₅alkyl; R is -OR’ with R’ selected from the group consisting of H and C₁-C₁₈alkyl optionally substituted by one or more –OH, -CO group(s)₂H, -SO₃H, -PO₃H, -OC(O)R’’, -C(O)O-R’’ or a five- or ten-membered heterocycle comprising at least one nitrogen atom in its ring chain; R’’ being selected from the group consisting of C₁-C₆alkyl or C₆-C₁₂aryl optionally substituted by one or more –OH, -CO group(s)₂H, -SO₃H, -PO₃H. Preferably, the heterocycle is as defined above, in particular the heterocycle is 2-pyrrolidone, deltalactam, succinimide, 2-imidazolidinone, 4-imidazolidinone. Said substituent R' may be selected from the group consisting of H, methyl, ethyl, propyl, n-butyl, isobutyl, t-butyl, n-dodecyl, amyl, isoamyl, hexyl, 2-ethylhexyl, lauryl, n-octyl, hydroxyethyl, hydroxybutyl, hydroxypropyl, 2-pyrrolidone, deltalactam, succinimide, 2-imidazolidinone, 4-imidazolidinone ethyl substituted by a ureido group. Preferably, said monomerM 2 ''is of formula (Ia) R¹R²C=C(R³)C(O)R in which the substituents R¹and R²are H; R³ is H or CH₃; R is -OR’ with R’ selected from the group consisting of H and C₁-C₁₈alkyl optionally substituted by one or more –OH, -CO group(s)₂H, -SO₃H, -PO₃H, -OC(O)R’’, -C(O)O-R’’; R’’ being selected from the group consisting of C₁-C₆alkyl or C₆-C₁₂aryl optionally substituted by one or more –OH, -CO group(s)₂H, -SO₃H, -PO₃H. More preferably, said monomerM 2 ''is of formula (Ia) R¹R²C=C(R³)C(O)R in which the substituents R¹and R²are H; R³ is H or CH₃; R is -OR’ with R’ selected from the group consisting of H and C₁-C_{1 5}alkyl optionally substituted by one or more –OH, -CO group(s)₂H, -SO₃H, -PO₃H, -OC(O)R’’, -C(O)O-R’’; R’’ being selected from the group consisting of C₁-C₆alkyl or C₆-C₁₂aryl optionally substituted by one or more –OH, -CO group(s)₂H, -SO₃H, -PO₃H. In particular, said monomerM 2 ''is of formula (Ia) R¹R²C=C(R³)C(O)R in which the substituents R¹and R²are H; R³ is H or CH₃; R is -OR’ with R’ selected from the group consisting of H and C₁-C_{1 0}alkyl optionally substituted by one or more –OH, -CO group(s)₂H, -SO₃H, -PO₃H, -OC(O)R’’, -C(O)O-R’’; R’’ being selected from the group consisting of C₁-C₆alkyl or C₆-C₁₂aryl optionally substituted by one or more –OH, -CO group(s)₂H, -SO₃H, -PO₃H. More particularly, said monomerM 2 ''may be acrylic acid, methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, isobutyl acrylate, t-butyl acrylate, n-dodecyl acrylate, amyl acrylate, isoamyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, diacetone acrylamide, lauryl acrylate, n-octyl acrylate, hydroxypropyl methacrylate, hydroxybutyl methacrylate, hydroxyethyl methacrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, methyl acrylic acid, methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, methacrylate isobutyl methacrylate, t-butyl methacrylate, n-dodecyl methacrylate, amyl methacrylate, isoamyl methacrylate, hexyl methacrylate, 2-ethylhexyl methacrylate, lauryl methacrylate, n-octyl methacrylate, ureido methacrylate, monomers of formula CH₂=CH(CO₂CH₂CH₂CO₂H), CH₂=CH(CO₂CH₂CH₂-O-C(O)-CH₂CH₂CO₂H), CH₂=CH(CO₂CH₂CH₂CH₂-O-C(O)-CH₂CH₂CO₂H), CH₂=CH(CO₂CH(CH₃)CH₂-O-C(O)-CH₂CH₂CO₂H), CH₂=CH(CO₂CH₂CH₂-O-C(O)-C₆H₄CO₂H), CH₂=CH(CO₂CH₂CH₂CH₂CH(CO₂H)CH₂CH₂CO₂H); and mixtures thereof. Among these, said monomerM 2 ''with an alkyl group having 1 to 8 carbon atoms is preferred, and an alkyl group having 1 to 5 carbon atoms is more preferable. Said fluoropolymerP 2may comprise one or more monomeric units derived from a monomerM 2''as defined herein, for exampleM 2''may be a mixture of methyl methacrylate, acrylic acid and methacrylic acid and the polymerP 2may thus include, for example, monomeric units derived from methyl methacrylate, methacrylic acid and acrylic acid.

Applications

Said polymer P 0 according to the present invention or said composition according to the present invention can be used in various applications. Thus, said polymer P 0 according to the present invention or said composition according to the present invention can be used as a binder for an electrode (cathode or anode) or as a coating for a separator.

Said polymer P0 according to the present invention or said composition according to the present invention can be used as a binder for an electrode. Thus, according to another aspect, the present invention provides an electrode composition comprising said polymer P0 according to the present invention or said composition according to the present invention, an active material and optionally a conductive agent.

In a preferred embodiment, the electrode composition has the following mass composition:

a. 50% to 99.95% active material, preferably 50% to 99%,

b. 25% to 0% conductive agent, preferably 25% to 0.5%,

c. 25% to 0.05% of said polymer P0 according to the present invention or said composition according to the present invention, preferably 25% to 0.5%,

d. 0% to 5% of at least one additive selected from the group consisting of a plasticizer, an ionic liquid, a dispersing agent for a conductive additive, and a flow aid;

the sum of all these percentages being 100%.

The conductive agents in the electrode are composed of one or more materials that can enhance conductivity. Some examples include carbon blacks such as acetylene black, Ketjen black; carbon fibers, such as carbon nanotube, carbon nanofiber, vapor-grown carbon fiber; metal powders such as SUS powder, and aluminum powder.

Active materials in electrode compositions are materials that are capable of storing and releasing lithium ions.

In a preferred embodiment, said electrode is a negative electrode. In particular, for a negative electrode, said active material is selected from the group consisting of a lithium alloy, lithium metal, a metal oxide, a carbon material such as graphite or hard carbon, silicon, a silicon alloy and Li ₄ Ti ₅ O ₁₂ . The shape of the negative electrode active material is not particularly limited but is preferably particulate.

In another preferred embodiment, said electrode is a positive electrode. Preferably, for a positive electrode, said active material is selected from the group consisting of LiCoO ₂ , Li(Ni, Co, AI)O ₂ , Li _{(1+ x)} Ni _a Mn _b Co _c (x represents a real number of 0 or more, a = 0.9, 0.8, 0.6, 0.5, or 1/3, b = 0.05, 0.1, 0.2, 0.3, or 1/3, c = 0.05, 0.1, 0.2, or 1/3), LiNiO ₂ , LiMn ₂ O ₄ , LiCoMnO ₄ , Li ₃ NiMn ₃ O ₃ , Li ₃ Fe ₂ (PO ₄ ) ₃ , Li ₃ V ₂ (PO ₄ ) ₃ , a spinel Li Mn substituted by a different element having a composition represented by Li _1+x Mn _2-xy M _y O ₄ , M representing at least one metal selected from Al, Mg, Co, Fe, Ni, and Zn, x and y independently representing a real number between 0 and 2, lithium titanate Li _x TiO _y – x and y independently representing a real number between 0 and 2, and a lithium metal phosphate having a composition represented by LiMPO ₄ , M representing Fe, Mn, Co, or Ni. The shape of the positive electrode active material is not particularly limited but is preferably particulate. In addition, the surface of each of the materials described above can be coated. The coating material is not particularly limited as long as it has lithium ion conductivity and contains a material capable of being maintained as a coating layer on the surface of the active material. Examples of the coating material include LiNbO ₃ , Li ₄ Ti ₅ O ₁₂ , and Li ₃ PO ₄ .

Said electrode composition can be deposited on at least one face of a current collector to form said electrode. This deposition can be carried out in the presence of an organic solvent, water, a mixture of both or by a solvent-free process. Said organic solvent can be selected from the group consisting of n-methylpyrrolidone (NMP), dimethylsulfoxide (DMSO), N,N-dimethylformamide (DMF), triethylphosphite (TEP), acetone, cyclopentanone, tetrahydrofuran, methyl ethylketone (MEK), methyl isobutyl ketone (MiBK), ethyl acetate (EA), butyl acetate (BA), ethylene carbonate (EC), propylene carbonate (PC), dimethyl carbonate (DMC), diethyl carbonate (DEC), ethyl methyl carbonate (EMC), gamma-butyrolactone and N-butylpyrrolidone; and mixtures thereof.

According to another aspect of the present invention, a Li-ion battery is provided. Preferably, the Li-ion battery comprises a positive electrode, a negative electrode and a separator, at least one electrode being an electrode according to the present invention. Said battery preferably comprises an electrolyte salt selected from the group consisting of LiCF ₃ SO ₃ , LiPF ₆ , LiClO ₄ , LiBF ₄ , LiB(C ₂ O ₄ ) ₂ , LiN(SO ₂ F) ₂ , LiN(SO ₂ CF ₃ ) ₂ , LiN(SO ₂ C ₂ F ₃ ) ₂ , LiN(SO ₂ C ₂ F ₅ ) ₂ , LiN(SO ₂ F)(SO ₂ CF ₃ ), LiN(SO ₂ F)(SO ₂ C ₂ F ₅ ), LiN(SO ₂ CF ₃ )(SO ₂ C ₂ F ₅ ),LiAsF ₆ , LiBF ₂ C ₂ O ₄ , LiNO ₃ , LiPF3(CF ₂ CF ₃ ) ₃ , LiBETI (Lithium bis(pentafluoroethanesulfonyl)imide), LiTDI (Lithium 4,5-dicyano-2-trifluoromethylimidazole), or a mixture thereof.

According to another aspect of the present invention, said polymer P0 according to the present invention or said composition according to the present invention may be used as a coating in a separator arranged between two electrodes. Said separator according to the present invention comprises a coating comprising, preferably consisting of, said polymer P0 according to the present invention or said composition according to the present invention, optionally arranged on one or both faces of a porous support. In this case, the coating is used to coat the support of a separator, on at least one face, in the form of a monolayer or multilayers. There is no particular limitation in the choice of the support which is coated with the coating of the invention, as long as it is a porous substrate having pores. When it comprises several layers, the coating as described in the present invention is arranged on the external face of the support, that is to say on the face which will first be in contact with the electrolytic composition used in the battery. Advantageously, the application of the coating to the support is carried out by aqueous means or by solvent means. The porous substrate may take the form of a membrane or a fibrous fabric. When the porous substrate is fibrous, it may be a nonwoven web forming a porous web, such as a web obtained by direct spinning or melt-blowing (of the "spunbond" or "melt-blown" type) or electro-spinning. Examples of porous substrates useful in the invention as a support include, but are not limited to: polyolefins, polyethylene terephthalate, polybutylene terephthalate, polyester, polyacetal, polyamide, polycarbonate, polyimide, polyetheretherketone, polyether sulfone, poly(phenylene oxide), poly(phenylene sulfide), polyethylene naphthalene or mixtures thereof. However, other heat-resistant engineering plastics may be used without particular limitation. Nonwoven materials made of natural and synthetic materials may also be used as the substrate of the separator. The porous substrate generally has a thickness of 1 to 50 µm, and are typically membranes obtained by extrusion and stretching (wet or dry process) or cast nonwovens. The porous substrate preferably has a porosity of between 5% and 95%. The average pore size (diameter) is preferably between 0.001 and 50 µm, more preferably between 0.01 and 10 µm. The support can also be aluminum or aluminum coated with a polymer layer.

In addition to said composition, the separator coating may contain inorganic particles that serve to form micropores in the coating (the interstices between inorganic particles). The addition of inorganic particles may also contribute to heat resistance or improve wettability. In one embodiment, said coating comprises from 50 to 99 percent by weight of inorganic particles, based on the weight of the coating. These inorganic particles must be electrochemically stable (not subject to oxidation and/or reduction in the range of voltages used). In addition, powdered inorganic materials preferably have high ionic conductivity. Materials with a low density are preferred over materials with a higher density, since the weight of the produced battery can be reduced. The dielectric constant is preferably equal to or greater than 5. According to one embodiment, said inorganic particles are selected from the group consisting of: BaTiO ₃ , Pb(Zr,Ti)O ₃ , Pb _1-x La _x Zr _y O ₃ (0<x<1, 0<y<1), PbMg ₃ Nb _2/3 O ₃ , PbTiO ₃ , HfO, HfO ₂ , SrTiO ₃ , SnO ₂ , CeO ₂ , MgO, NiO, CaO, ZnO, Y ₂ O ₃ , bohemite (y-AlO(OH)), Al ₂ O ₃ , TiO ₂ , SiC, ZrO ₂ , boron silicate, BaSO ₄ , nano-clays, or mixtures thereof. The separator coating may optionally comprise from 0 to 15% by weight based on the polymer, and preferably 0.1 to 10% by weight of additives, selected from thickeners, pH adjusting agents, anti-settling agents, surfactants, wetting agents, fillers, anti-foaming agents and fugitive or non-fugitive adhesion promoters. The fillers mentioned herein in the additives are different from the inorganic particles mentioned above.

According to another aspect of the present invention, a Li-ion battery is provided. Preferably, the Li-ion battery comprises a positive electrode, a negative electrode and said separator according to the present invention. Said battery preferably comprises an electrolyte salt selected from the group consisting of LiCF ₃ SO ₃ , LiPF ₆ , LiClO ₄ , LiBF ₄ , LiB(C ₂ O ₄ ) ₂ , LiN(SO ₂ F) ₂ , LiN(SO ₂ CF ₃ ) ₂ , LiN(SO ₂ C ₂ F ₃ ) ₂ , LiN(SO ₂ C ₂ F ₅ ) ₂ , LiN(SO ₂ F)(SO ₂ CF ₃ ), LiN(SO ₂ F)(SO ₂ C ₂ F ₅ ), LiN(SO ₂ CF ₃ )(SO ₂ C ₂ F ₅ ),LiAsF ₆ , LiBF ₂ C ₂ O ₄ , LiNO ₃ , LiPF3(CF ₂ CF ₃ ) ₃ , LiBETI (Lithium bis(pentafluoroethanesulfonyl)imide), LiTDI (Lithium 4,5-dicyano-2-trifluoromethylimidazole), or a mixture thereof.

According to another aspect of the present invention, said polymer P0 according to the present invention or said composition according to the present invention can be used in the preparation of a conductive polymer, a solid electrolyte for fuel cells, paints, cables, wires, anti-corrosion equipment for the chemical industry, coatings for construction or architecture. The coating can be a hydrophilic, hydrophobic or UV-absorbing coating. Generally, said polymer P0 according to the present invention or said composition according to the present invention have applications in the field of semiconductors and electronics, oil and gas, automotive, cabling, architecture and building, aerospace, in the chemical industry where the polymer P0 according to the present invention or said composition according to the present invention can be used in production processes, in storage or transport equipment, as an anti-corrosion agent.

Examples

Example 1: Preparation of a compound of formula (I)

In a round-bottomed flask, 7 ml of triethylamine (0.05 mol) was mixed with 1.44 ml of 3-mercaptopropionic acid (0.01 mol), a cloudy and inhomogeneous solution was obtained. To this mixture, 2 ml of vinyl methacrylate (0.01 mol) was added, the reaction medium changed from turbid to a clear phase. After 24 h of stirring, 5 ml of acetic acid and 20 ml of water were poured into the medium, then extraction with 30 ml of ethyl acetate was carried out. The organic medium was separated and dried with MgCl2. Then, the solvent was removed under vacuum at 35 °C. The final product with the formula CH ₂ =CH-OC(O)CH(CH ₃ )CH ₂ SCH ₂ CH ₂ CO ₂ H was isolated as a clear liquid. The product obtained is soluble in water, acetone, DMSO, ethanol, dichloromethane or ethyl acetate. The product is characterized by ¹ H NMR (300 MHz, DMSO d ⁶ ) δ 7.21 (dd 1H), 4.8 (dd 1H), 4.5 (dd, 1H), 2.85 – 2.73 (m, 2H), 2.72 – 2.62 (m, 3H), 2.48 (t, J = 7.0 Hz, 2H), 1.22 – 1.14 (m, 3H).

Example 2: preparation of a polymer P0

A 250 ml high-pressure reactor was flushed with nitrogen. 80 ml of DMSO containing 0.4 g of KPS and 0.4 g of the compound prepared in Example 1 were added to the reactor. After that, it was filled at room temperature (22 ° C) with 22 bar of VDF under stirring in order to saturate the solution well and heated to 90 ° C. An exotherm occurred and the pressure was decreased. When no consumption of VF2 was observed, the reactor was cooled and opened. After precipitation and washing with water, the obtained polymer was characterized by NMR. 1H NMR (300 MHz, DMSO) δ 6.35 (tt, J = 54.9, 4.6 Hz, 1H), 5.51 (m, 1H), 4.10 (t, J = 14.3 Hz, 1H), 3.94 (t, J = 13.7 Hz, 1H), 2.98 – 2.78 (m, 214H), 2.26 (t, J = 14.9 Hz, 34H), 1.78 (t, J = 19.7 Hz, 3H), 1.13 (d, J = 6.2 Hz, 3H), 0.95 (t, J = 7.4 Hz, 1H). The incorporation rate of the compound prepared in Example 1 into the polymer is 0.7 mol% characterized by the shift to 5.51 ppm.

Claims (19)

Compound of formula (I)

in which R¹, R², R³, R⁵, R⁶, R⁷are independently selected from the group consisting of H and C₁-C₅alkyl;
X is selected from the group consisting of C_1-C₁₈alkyl, C_2-C₁₈alkenyl, C_4-C₁₈cycloalkenyl, C_3-C₁₈cycloalkyl, C₆-C₁₈aryl, polyalkylene glycol, optionally carrying one or more functional groups selected from the group consisting of -F, –OR’, -O-C(O)R’, -C(O)OR’, -CN, -NR’₂, -O-Si(OR’)₃, -Si(R’)₃, -SO₃R’, -O-P(O)(OR’)₂, -P(O)(OR)₂, -C(O)R’, -C(O)-S-R’, -C(O)-NR’₂, -NR’₃ ⁺wherein R’ is independently selected for each substituent of the functional group from the group consisting of H, C_1-C₁₈alkyl, C_2-C₁₈alkenyl, C_4-C₁₈cycloalkenyl, C_3-C₁₈cycloalkyl and C₆-C₁₈aryl;
Y is selected from the group F, Cl, Br, I, -CN, -OR’’, -C(O)OR’’, -SO₃R’’, C(O)Cl, -O-Si(OR’’)₃, -If(R’’)₃, -O-P(O)(OR’’)₂, -P(O)(OR’’)₂, -C(O)R’’, -C(O)-S-R’’, -C(O)-NR’’₂with R’’ selected from the group consisting of H, C_1-C₁₈alkyl, C_2-C₁₈alkenyl, C_4-C₁₈cycloalkenyl, C_3-C₁₈cycloalkyl and C₆-C₁₈aryl. Compound of formula (I) according to the preceding claim, characterized in that
R¹, R², R³, R⁵, R⁶, R⁷are independently selected from the group consisting of H and C₁-C₃alkyl;
X is selected from the group consisting of C_1-C_{1 0}alkyl, C_2-C_{1 0}alkenyl, C_4-C_{1 0}cycloalkenyl, C_3-C₁₀cycloalkyl, C₆-C_{1 0}aryl, polyalkylene glycol, optionally carrying one or more functional groups selected from the group consisting of -F, –OR’, -O-C(O)R’, -C(O)OR’, -CN, -NR’₂, -O-Si(OR’)₃, -Si(R’)₃, -SO₃R’, -O-P(O)(OR’)₂, -P(O)(OR)₂, -C(O)R’, -C(O)-S-R’, -C(O)-NR’₂, -NR’₃ ⁺wherein R’ is independently selected for each substituent of the functional group from the group consisting of H, C_1-C_{1 0}alkyl, C_2-C_{1 0}alkenyl, C_4-C_{1 0}cycloalkenyl, C_3-C_{1 0}cycloalkyl and C₆-C_{1 0}aryl;
Y is selected from the group F, Cl, Br, I, -CN, -OR’’, -C(O)OR’’, -SO₃R’’, C(O)Cl, -O-Si(OR’’)₃, -If(R’’)₃, -O-P(O)(OR’’)₂, -P(O)(OR’’)₂, -C(O)R’’, -C(O)-S-R’’, -C(O)-NR’’₂with R’’ selected from the group consisting of H, C_1-C_{1 0}alkyl, C_1-C_{1 0}alkyl, C_2-C_{1 0}alkenyl, C_4-C_{1 0}cycloalkenyl, C_3-C_{1 0}cycloalkyl and C₆-C_{1 0}aryl. Compound according to any one of the preceding claims, characterized in that it is of formula (Ia)

in which
R¹, R², R³, R⁵, R⁶, R⁷are independently selected from the group consisting of H, C₁-C₃alkyl;
R⁸and R⁹are, independently of each other and independently for each of the units n, selected from the group consisting of H, C_1-C_{1 0}alkyl, C_2-C_{1 0}alkenyl, C_4-C_{1 0}cycloalkenyl, C_3-C₁₀cycloalkyl, C₆-C_{1 0}aryl, polyalkylene glycol, optionally carrying one or more functional groups selected from the group consisting of -F, -OR’, -O-C(O)R’, -C(O)OR’, -CN, -NR’₂, -O-Si(OR’)₃, -Si(R’)₃, -SO₃R’, -O-P(O)(OR’)₂, -P(O)(OR)₂, -C(O)R’, -C(O)-S-R’, -C(O)-NR’₂, -NR’₃ ⁺wherein R’ is independently selected for each substituent of the functional group from the group consisting of H, C_1-C_{1 0}alkyl, C_2-C_{1 0}alkenyl, C_4-C_{1 0}cycloalkenyl, C_3-C_{1 0}cycloalkyl and C₆-C_{1 0}aryl;
n is an integer from 1 to 15, preferably from 1 to 10, in particular from 1 to 5, more particularly from 2 to 5;
Y is selected from the group F, Cl, Br, I, -CN, -OR’’, -C(O)OR’’, -SO₃R’’, C(O)Cl, -O-Si(OR’’)₃, -If(R’’)₃, -O-P(O)(OR’’)₂, -P(O)(OR’’)₂, -C(O)R’’, -C(O)-S-R’’, -C(O)-NR’’₂with R’’ selected from the group consisting of H, C_1-C_{1 0}alkyl, C_1-C_{1 0}alkyl, C_2-C_{1 0}alkenyl, C_4-C_{1 0}cycloalkenyl, C_3-C_{1 0}cycloalkyl and C₆-C_{1 0}aryl. Compound according to any one of the preceding claims, characterized in that it is of formula (Ia)

in which
R¹, R², R³, R⁵, R⁶, R⁷are independently selected from the group consisting of H, C₁-C₃alkyl;
R⁸and R⁹are, independently of each other and independently for each of the units n, selected from the group consisting of H, C_1-C₅alkyl, C_3-C₁₀cycloalkyl, C₆-C_{1 0}aryl, optionally carrying one or more functional groups selected from the group consisting of -F, -OR’, -O-C(O)R’, -C(O)OR’, -CN, -NR’₂, -O-Si(OR’)₃, -Si(R’)₃, -SO₃R’, -O-P(O)(OR’)₂, -P(O)(OR)₂, -C(O)R’, -C(O)-S-R’, -C(O)-NR’₂, -NR’₃ ⁺wherein R’ is independently selected for each substituent of the functional group from the group consisting of H, C_1-C_{1 0}alkyl, C_2-C_{1 0}alkenyl, C_4-C_{1 0}cycloalkenyl, C_3-C_{1 0}cycloalkyl and C₆-C_{1 0}aryl;
n is an integer from 1 to 15, preferably from 1 to 10, in particular from 1 to 5, more particularly from 2 to 5;
Y is selected from the group -CN, -C(O)OR’’, -SO₃R’’, -O-P(O)(OR’’)₂, -P(O)(OR’’)₂, - with R’’ selected from the group consisting of H, C_1-C₁₀alkyl, C_2-C₁₀alkenyl, C_4-C₁₀cycloalkenyl, C_3-C₁₀cycloalkyl and C₆-C₁₀aryl. Compound according to any one of the preceding claims, characterized in that it is of formula (Ia)

in which
R¹, R², R³, R⁵, R⁶, R⁷are independently selected from the group consisting of H, C₁-C₃alkyl;
R⁸and R⁹are, independently of each other and independently for each of the units n, selected from the group consisting of H, C_1-C₅alkyl, C_3-C₁₀cycloalkyl, C₆-C_{1 0}aryl, optionally carrying one or more functional groups selected from the group consisting of -F, -OR’, -O-C(O)R’, -C(O)OR’, -CN, -NR’₂, -O-Si(OR’)₃, -Si(R’)₃, -SO₃R’, -O-P(O)(OR’)₂, -P(O)(OR)₂, -C(O)R’, -C(O)-S-R’, -C(O)-NR’₂, -NR’₃ ⁺wherein R’ is independently selected for each substituent of the functional group from the group consisting of H, C_1-C_{1 0}alkyl, C_2-C_{1 0}alkenyl, C_4-C_{1 0}cycloalkenyl, C_3-C_{1 0}cycloalkyl, C₆-C_{1 0}aryl; preferably R’ is independently selected for each substituent of the functional group from the group consisting of H and C_1-C₃alkyl;
n is an integer from 1 to 15, preferably from 1 to 10, in particular from 1 to 5, more particularly from 2 to 5;
Y is selected from the group -C(O)OR’’, -SO₃R’’, -O-P(O)(OR’’)₂, -P(O)(OR’’)₂, - with R’’ selected from the group consisting of H, C_1-C₃alkyl; preferably R’’ is H. Process for preparing the compound according to any one of the preceding claims comprising a step a) of reaction between a compound of formula (IIa)

and a thiol compound of formula (IIb) Y-X-SH in the presence of a base;
in which
R¹, R², R³, R⁵, R⁶, R⁷are independently selected from the group consisting of H, C₁-C₅alkyl;
X is selected from the group consisting of C_1-C₁₈alkyl, C_2-C₁₈alkenyl, C_4-C₁₈cycloalkenyl, C_3-C₁₈cycloalkyl, C₆-C₁₈aryl, polyalkylene glycol, optionally carrying one or more functional groups selected from the group consisting of -F, –OR’, -O-C(O)R’, -C(O)OR’, -CN, -NR’₂, -O-Si(OR’)₃, -Si(R’)₃, -SO₃R’, -O-P(O)(OR’)₂, -P(O)(OR)₂, -C(O)R’, -C(O)-S-R’, -C(O)-NR’₂, -NR’₃ ⁺wherein R’ is independently selected for each substituent of the functional group from the group consisting of H, C_1-C₁₈alkyl, C_2-C₁₈alkenyl, C_4-C₁₈cycloalkenyl, C_3-C₁₈cycloalkyl, C₆-C₁₈aryl;
Y is selected from the group F, Cl, Br, I, -CN, -OR’’, -C(O)OR’’, -SO₃R’’, C(O)Cl, -O-Si(OR’’)₃, -If(R’’)₃, -O-P(O)(OR’’)₂, -P(O)(OR’’)₂, -C(O)R’’, -C(O)-S-R’’, -C(O)-NR’’₂with R’’ selected from the group consisting of H, C_1-C₁₈alkyl, C_2-C₁₈alkenyl, C_4-C₁₈cycloalkenyl, C_3-C₁₈cycloalkyl, C₆-C₁₈aryl; to form the compound of formula (I). Process according to the preceding claim, characterized in that the thiol compound is of formula (IIb’)

R⁸and R⁹are, independently of each other and independently for each of the units n, selected from the group consisting of H, C_1-C_{1 0}alkyl, C_2-C_{1 0}alkenyl, C_4-C_{1 0}cycloalkenyl, C_3-C₁₀cycloalkyl, C₆-C_{1 0}aryl, polyalkylene glycol, optionally carrying one or more functional groups selected from the group consisting of -F, -OR’, -O-C(O)R’, -C(O)OR’, -CN, -NR’₂, -O-Si(OR’)₃, -Si(R’)₃, -SO₃R’, -O-P(O)(OR’)₂, -P(O)(OR)₂, -C(O)R’, -C(O)-S-R’, -C(O)-NR’₂, -NR’₃ ⁺wherein R’ is independently selected for each substituent of the functional group from the group consisting of H, C_1-C_{1 0}alkyl, C_2-C_{1 0}alkenyl, C_4-C_{1 0}cycloalkenyl, C_3-C_{1 0}cycloalkyl, C₆-C_{1 0}aryl;
n is an integer from 1 to 15, preferably from 1 to 10, in particular from 1 to 5, more particularly from 2 to 5;
Y is selected from the group F, Cl, Br, I, -CN, -OR’’, -C(O)OR’’, -SO₃R’’, C(O)Cl, -O-Si(OR’’)₃, -If(R’’)₃, -O-P(O)(OR’’)₂, -P(O)(OR’’)₂, -C(O)R’’, -C(O)-S-R’’, -C(O)-NR’’₂with R’’ selected from the group consisting of H, C_1-C_{1 0}alkyl, C_1-C_{1 0}alkyl, C_2-C_{1 0}alkenyl, C_4-C_{1 0}cycloalkenyl, C_3-C_{1 0}cycloalkyl, C₆-C_{1 0}aryl; to form the compound of formula (Ia). A method according to any one of claims 6 or 7 characterized in that said base is selected from the group consisting of LiOH, NaOH, KOH, CsOH, RbOH, Mg(OH)2, Ca(OH)2, N(C _m H _{2 m +1} ) ₃ with m 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, triethylenediamine, 6-(Dibutylamino)-1,8-diazabicyclo[5.4.0]undec-7-ene, 1,8-Diazabicyclo[5.4.0]undec-7-ene bound 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, Cyclodiphosphazane, Lithium diisopropylamide, sodium diisopropylamide, potassium diisopropylamide, magnesium diisopropylamide, calcium diisopropylamide, rubidium diisopropylamide, lithium bis(trimethylsilyl)amide, sodium bis(trimethylsilyl)amide, potassium bis(trimethylsilyl)amide, magnesium bis(trimethylsilyl)amide, calcium bis(trimethylsilyl)amide, rubidium bis(trimethylsilyl)amide, lithium tetramethylpiperidide, sodium tetramethylpiperidide, potassium tetramethylpiperidide, magnesium tetramethylpiperidide, calcium tetramethylpiperidide, rubidium tetramethylpiperidide, [18-crown-6]-KHF2, KHF2, N,N'-diisopropylimidazonium, bifluoride, tetrabutylammonium, N(C _m H _{2 m +1} )4 OH- with m being an integer from 1 to 10. Process according to any one of claims 6 to 8, characterized in that, in step a), the molar content of said base is from 1 mol to 500 mol per 100 mol of said compound (IIb) or (IIb'). Process according to any one of claims 6 to 9, characterized in that step a) is carried out in an atmosphere containing less than 10 molar oxygen, preferably step a) is carried out in a nitrogen atmosphere. PolymerP0comprising monomeric units derived from a fluorinated monomerM 0 comprising a C=C double bond and at least one fluorine atom and monomeric units derived from the compound of formula (I) according to any one of claims 1 to 5. Composition comprising a fluorinated polymer P1 and a polymer P2 comprising monomeric units derived from the compound of formula (I) according to any one of claims 1 to 5. An electrode binder comprising said polymer according to claim 11 or said composition according to claim 12. Separator comprising said polymer according to claim 11 or said composition according to claim 12. Electrode comprising an active material, a binder according to claim 13 and optionally a conductive agent. Electrode according to the preceding claim, characterized in that said electrode is a positive electrode and the active material is selected from the group consisting of LiCoO₂, Li(Ni, Co, AI)O₂, Li_{(1+ x) ,} Neither_hasMn_bCo_c(x represents a real number of 0 or more, a = 0.9, 0.8, 0.6, 0.5, or 1/3, b = 0.05, 0.1, 0.2, 0.3, or 1/3, c = 0.05, 0.1, 0.2, or 1/3), LiNiO₂, LiMn₂O₄, LiCoMnO₄, Li₃NiMn₃O₃, Li₃Fe₂(PO₄)₃, Li₃V₂(PO₄)₃, a Li Mn spinel substituted by a different element having a composition represented by Li_1+xMn_2-xyM_yO₄, M representing at least one metal chosen from Al, Mg, Co, Fe, Ni, and Zn, x and y independently representing a real number between 0 and 2, lithium titanate Li_xTiO_y– x and y independently representing a real number between 0 and 2, and a lithium metal phosphate having a composition represented by LiMPO₄, M representing Fe, Mn, Co, or Ni. Electrode according to the preceding claim, characterized in that said electrode is a negative electrode and the active material is selected from the group consisting of a lithium alloy, lithium metal, a metal oxide, a carbon material such as graphite or hard carbon, silicon, silicone, a silicon alloy and Li ₄ Ti ₅ O ₁₂ . A Li-ion secondary battery comprising a positive electrode, a negative electrode and a separator; said separator being according to claim 14 and/or one of said electrodes being according to any one of claims 15 to 17. Use of the compound according to any one of claims 1 to 5 or of the polymer according to claim 11 or the composition according to claim 12 in the preparation of a conductive polymer, a solid electrolyte for fuel cells, paints, cables, wires, anti-corrosion equipment for the chemical industry, coatings for construction or architecture.