Stablized compositions based on fertilizers or pesticides or oxidants

Abstract

The present invention relates to a composition in the form of a powder comprising: a polymer A which is a fluorinated polymer A1, a polyamide A2 or a polyamide-polyether block copolymer A3 or a mixture thereof; and a compound having an oxygen balance of less than 60.

Description

[0001] STABILIZED COMPOSITIONS BASED ON FERTILIZERS OR PESTICIDES OR OXIDANTS

[0002] Technical field of the invention

[0003] The present invention relates to compositions containing compounds having heat release or volume expansion properties under prolonged or unsuitable storage conditions. In particular, the present invention relates to compositions containing energetic or oxidizing compounds such as, for example, fertilizers, herbicides or weedkillers.

[0004] Technological background of the invention

[0005] Ammonium nitrate-based fertilizers are commonly used in agriculture. Although ammonium nitrate is generally a stable compound, the risk of detonation cannot be ruled out, particularly under certain storage conditions. Ammonium nitrates are classified as oxidizers. Detonation is possible in the event of contamination by combustible or incompatible substances, in the event of heating (especially under confinement with continued containment of combustion gases), or in the event of a very violent impact from an object or a shock wave.

[0006] The instability of ammonium nitrates under certain conditions has led in the past to industrial accidents causing a blast effect of great severity, as was the case in Toulouse or more recently in Beirut. Solutions for stabilizing compositions based on ammonium nitrate have been developed. For example, document US 9,630,886 discloses a fertilizer composition comprising ammonium nitrate and an effective amount of a stabilizing material to obtain a specific impulse which is not greater than 13.5 kPa*ms / kg when measured in accordance with a blast propagation test; wherein the stabilizing material comprises hydrocalumite, hydroxyapatite hydrotalcite, and / or apatite, wherein the stabilizing material is at least 12.5% ​​by weight of the total fertilizer composition, wherein the stabilizing material is not more than 35% by weight of the total fertilizer composition.

[0007] Also known from EP 1 292 537 is a process for producing thermally and mechanically stable granulated ammonium nitrate, characterized in that crosslinked metal silicate is dissolved in a fluid consisting essentially of nitric acid in an amount of 1-3% by weight of the ammonium nitrate product, the solution consisting essentially of nitric acid and crosslinked metal silicate is treated with ammonia to form an ammonium nitrate slurry and to neutralize the solution, the ammonium nitrate slurry is dried and granulated.Also known from EP 1 981 830 is a fertilizer comprising ammonium nitrate in the form of a double salt and at least one stabilizing agent wherein said at least one stabilizing agent is selected from the group consisting of MgSO4, CaCOs, MgCOs, dolomite, MgfNOsh, and combinations of two or more thereof, or silicon oxide, thiourea, ammonium tartrate, ammonium oxalate, ammonium sulfamate, and combinations thereof.

[0008] It is also known that ammonium nitrates tend to agglomerate or form lumps under the effect of humidity during storage, which leads to a risk of degranulation and clumping of the fertilizer likely to destabilize the composition. For example, US 3,660,070 discloses a method for preventing the agglomeration of fertilizers by adding a solution comprising polymers such as polyvinyl butyrate. However, it has been found that polymers such as polyvinyl butyrate exhibit inadequate heat behavior given the risks of detonation of the ammonium nitrates.

[0009] There is still a need to provide stable fertilizer, herbicide or weedkiller compositions that limit the risks of detonation of compounds such as ammonium nitrates while avoiding the formation of lumps during their storage.

[0010] Summary of the invention

[0011] According to a first aspect, the present invention provides a composition in powder form comprising a polymer A and a compound B comprising at least one functional group selected from the group consisting of -NO2, NOs", -ON=O, -N=N-, -N =N + N -, NX3 with X being a halogen, -C=NO-, CIOs', CIO4 _ , -OO-, -O3- and -CC MÜ with Mt a transition metal; characterized in that: said polymer A is a fluorinated polymer Al, a polyamide A2 or a polyamide-polyether block copolymer A3 or a mixture thereof, and said compound B has an oxygen balance BO less than 60, said oxygen balance being determined by the formula BO (%) = [1600*(d-2a-(b / 2)] / M in which a, b and d are respectively the number of carbon, hydrogen and oxygen atoms of compound B and M the molar mass of said compound B.

[0012] The use of one of the polymers A as defined in the present invention makes it possible to impact in a versatile manner the behavior of said compound B as defined above, in particular when the latter is subjected to rapid heating. The choice of polymer A in said composition makes it possible to act specifically on the behavior of said compound B depending on the intended applications, for example when the composition is intended for the implementation of a fertilizer, herbicide, energy or weedkiller formulation. According to a preferred embodiment, said polymer A is a polyamide A2 or a polyamide-polyether block copolymer A3 or a mixture thereof. The use of a polymer of the polyamide or polyamide-polyether block copolymer type prevents the release of HF in the event of a reaction during a heat release or a deflagration.

[0013] According to a preferred embodiment, said compound B has a molar mass of less than 1000 g. mol- i

[0014] According to a preferred embodiment, said compound B is selected from the group consisting of a salt of formula M + X _ wherein M is selected from the group consisting of Li, Na, K and NH4; and X is selected from the group consisting of a nitrate anion, a chlorate anion and a perchlorate anion.

[0015] According to a preferred embodiment, said composition also comprises poly(vinyl butyrate).

[0016] According to a preferred embodiment, said polymer A is said fluorinated polymer Al comprising monomeric units derived from vinylidene fluoride and optionally monomeric units of a monomer selected from the group consisting of vinyl fluoride; trifluoroethylene (VF3); chlorotrifluoroethylene (CTFE); 1,2-difluoroethylene; tetrafluoroethylene (TFE); hexafluoropropylene (HFP); perfluoro(alkyl vinyl) ethers such as perfluoro(methylvinyl) ether (PMVE), perfluoro(ethyl vinyl) ether (PEVE) and perfluoro(propylvinyl) ether (PPVE); perfluoro(1,3-dioxole); perfluoro(2,2-dimethyl-1,3-dioxole) (PDD); the product of formula CF2=CFOCF2CF(CF3)OCF2CF2X in which X is SO2F, CO2H, CH2OH, CH2OCN or CH2OPO3H; the product of formula CF2=CFOCF2CF2SC>2F; the product of formula F(CF2)nCH2OCF=CF2 in which n is 1, 2, 3, 4 or 5; the product of formula R 1 CH2OCF=CF2 in which R 1is hydrogen or F(CF2)m and m is 1, 2, 3 or 4; the product of formula R 2 OCF=CH2 in which R 2 is F(CF2)p and p is 1, 2, 3 or 4; perfluorobutyl ethylene (PFBE); 3,3,3-trifluoropropene and 2-trifluoromethyl-3,3,3-trifluoro-l-propene or a mixture thereof.

[0017] According to a preferred embodiment, said fluorinated polymer Al is selected from a homopolymer of vinylidene fluoride or a copolymer comprising monomeric units derived from vinylidene fluoride and monomeric units derived from a monomer selected from the group consisting of trifluoroethylene, chlorotrifluoroethylene, 1,2-difluoroethylene, tetrafluoroethylene, hexafluoropropylene or a mixture thereof.

[0018] According to a preferred embodiment, said fluorinated polymer Al comprises at least 50 mol% of monomeric units derived from vinylidene fluoride.

[0019] According to a preferred embodiment, said polymer A3 is a polyamide-polyether block copolymer is a copolymer with amide units (Bal) and polyether units (Ba2), said amide unit (Bal) corresponding to an aliphatic repeating unit chosen from a unit obtained from at least one amino acid or a unit obtained from at least one lactam, or a unit obtained from the polycondensation:

[0020] - at least one diamine, said diamine being preferably chosen from a linear or branched aliphatic diamine or a mixture thereof, and

[0021] - at least one dicarboxylic acid, said diacid being preferably chosen from: a linear or branched aliphatic diacid, or a mixture thereof, said diamine and said diacid comprising from 4 to 36 carbon atoms, advantageously from 6 to 18 carbon atoms; said polyether units (Ba2) being in particular derived from at least one polyalkylene ether polyol, in particular a polyalkylene ether diol.

[0022] According to a preferred embodiment, the mass content of polymer A in said composition is from 0.1 to 30%, preferably from 1 to 30%, in particular from 1 to 15% based on the total weight of the composition.

[0023] According to a preferred embodiment, the mass content of said compound B in said composition is greater than 65% based on the total weight of the composition.

[0024] According to a preferred embodiment, the mass content of said compound B in said composition is greater than 65% based on the total weight of the composition; and said polymer A is a polyamide A2 or a polyamide-polyether block copolymer A3 or a mixture thereof.

[0025] According to a preferred embodiment, the mass content of said compound B in said composition is at least 80% based on the total weight of the composition; and said polymer A is a fluorinated polymer Al.

[0026] According to a preferred embodiment, said composition consists of said polymer A and said compound B and optionally poly(vinyl butyrate).

[0027] According to another aspect, the present invention relates to the use of a polymer A as a stabilizer of an energetic composition, in particular a weedkiller, herbicide or fertilizer composition, said polymer A being as defined in the present invention, preferably said polymer A is said fluorinated polymer Al, and preferably said composition comprises a compound B as defined in the present invention.

[0028] According to another aspect, the present invention relates to the use of a polymer A for desensitizing or sensitizing an energetic composition, said polymer A being as defined in the present invention and said composition comprising a compound B having heat release properties or volume expansion properties; preferably said compound B is as defined in the present invention. According to a preferred embodiment, the mass content of polymer A in said composition is from 0.1 to 35%, preferably from 1 to 30%, in particular from 1 to 15% based on the total weight of the composition; and preferably the mass content of said compound B in said composition is greater than 65% based on the total weight of the composition. If the amount of polymer B in the composition is not high enough, the overall effectiveness of the composition is reduced by a dilution effect.

[0029] According to a preferred embodiment, the mass content of said compound B in said composition is greater than 65% based on the total weight of the composition; and said polymer A is a polyamide A2 or a polyamide-polyether block copolymer A3 or a mixture thereof; or the mass content of said compound B in said composition is at least 80% based on the total weight of the composition; and said polymer A is a fluorinated polymer Al.According to another aspect, the present invention relates to a method for reducing or increasing the liveliness of response to heat of a composition according to the present invention, preferably said composition is an energetic composition, said method comprising adding a polymer A as defined in the present invention to said energetic composition; the latter comprising a compound B having heat release properties or volume expansion properties; preferably said compound B is as defined in the present invention.

[0030] According to a preferred embodiment, the mass content of polymer A in said composition is from 0.1 to 35%, preferably from 1 to 30%, in particular from 1 to 15% based on the total weight of the composition; and preferably the mass content of said compound B in said composition is greater than 65% based on the total weight of the composition.

[0031] According to a preferred embodiment, the mass content of said compound B in said composition is greater than 65% based on the total weight of the composition; and said polymer A is a polyamide A2 or a polyamide-polyether block copolymer A3 or a mixture thereof; or the mass content of said compound B in said composition is at least 80% based on the total weight of the composition; and said polymer A is a fluorinated polymer Al.

[0032] Brief description of the figures

[0033] Fig. 1 is a graph showing the differential scanning calorimetry of different comparative compositions or according to a particular embodiment of the present invention.

[0034] Fig. 2 is a graph showing the evolution of pressure as a function of temperature for different comparative compositions or according to a particular embodiment of the present invention. Detailed description of the invention

[0035] According to a first aspect of the present invention, a composition in powder form is provided. Said composition comprises a polymer A and a compound B. Preferably, said composition consists of said polymer A and said compound B.

[0036] The mass content of polymer A in said composition may be from 0.1 to 30% based on the total weight of the composition, advantageously from 0.1 to 28% based on the total weight of the composition, preferably from 0.5 to 26% based on the total weight of the composition, more preferably from 1% to 24% based on the total weight of the composition, in particular from 1% to 22% based on the total weight of the composition, more particularly from 1% to 20% based on the total weight of the composition. According to a preferred embodiment, the mass content of polymer A in said composition is from 0.1% to 15%, advantageously from 0.5% to 10%, preferably from 1% to 5% based on the total weight of the composition.

[0037] Preferably, the mass content of compound B in said composition may be from 25% to 99.9% based on the total weight of the composition. According to a preferred embodiment, the mass content of compound B in said composition is from 30% to 99.5%, advantageously from 35% to 99%, preferably from 40% to 99%, more preferably from 50% to 95% based on the total weight of the composition. Preferably, the mass content of compound B in said composition is greater than 65%, advantageously greater than 66%, preferably greater than 67%, more preferably greater than 68%, in particular greater than 69%, more particularly greater than 70% based on the total weight of the composition.The mass content of compound B in said composition may be greater than 71%, advantageously 72%, preferably greater than 73%, more preferably greater than 74%, in particular greater than 75%, more particularly greater than 76%, preferably greater than 77%, advantageously greater than 78%, preferably greater than 79%, more preferably greater than 80%, particularly greater than 81%, more particularly greater than 82% based on the total weight of the composition.Preferably, the mass content of compound B in said composition may be greater than 83%, advantageously 84%, preferably greater than 85%, more preferably greater than 86%, in particular greater than 87%, more particularly greater than 88%, preferably greater than 89%, advantageously more preferably greater than 90% based on the total weight of the composition. When said composition comprises as polymer A, a polyamide A2 or a polyamide-polyether block copolymer A3 or a mixture thereof; the mass content of said compound B in said composition is greater than 65% based on the total weight of the composition. Advantageously, when said composition comprises as polymer A, a polyamide A2 or a polyamide-polyether block copolymer A3 or a mixture thereof; the mass content of said compound B in said composition is greater than 70% based on the total weight of the composition.Preferably, when said composition comprises as polymer A, a polyamide A2 or a polyamide-polyether block copolymer A3 or a mixture thereof; the mass content of said compound B in said composition is greater than 75% based on the total weight of the composition. More preferably, when said composition comprises as polymer A, a polyamide A2 or a polyamide-polyether block copolymer A3 or a mixture thereof; the mass content of said compound B in said composition is greater than 80% based on the total weight of the composition. In particular, when said composition comprises as polymer A, a polyamide A2 or a polyamide-polyether block copolymer A3 or a mixture thereof; the mass content of said compound B in said composition is greater than 85% based on the total weight of the composition.More particularly, when said composition comprises as polymer A, a polyamide A2 or a polyamide-polyether block copolymer A3 or a mixture thereof; the mass content of said compound B in said composition is greater than 90% based on the total weight of the composition. According to a preferred embodiment, when said composition consists of said polymer A1 and said compound B, and optionally poly(vinyl butyrate), the mass content of compound B is according to one of the above mass contents and said polymer A and optionally poly(vinyl butyrate) forms the remainder, i.e. less than 35% by weight or less than 30%, or less than 25% or less than 20% or less than 15% by weight based on the total weight of said composition.

[0038] When said polymer A is a fluorinated polymer Al, the mass content of said compound B in said composition is at least 70% based on the total weight of the composition. Advantageously, when said polymer A is a fluorinated polymer Al, the mass content of said compound B in said composition is at least 75% based on the total weight of the composition. Preferably, when said polymer A is a fluorinated polymer Al, the mass content of said compound B in said composition is at least 80% based on the total weight of the composition. In particular, when said polymer A is a fluorinated polymer Al, the mass content of said compound B in said composition is at least 85% based on the total weight of the composition.According to a preferred embodiment, when said composition consists of said polymer A1 and said compound B, and optionally poly(vinyl butyrate), the mass content of compound B is according to one of the mass contents above and said polymer A and optionally poly(vinyl butyrate) forms the remainder, i.e. less than 30% by weight or less than 25%, or less than 20% or less than 15% by weight based on the total weight of said composition.

[0039] Said composition may be prepared by adding the various constituents in powder form in the desired proportions. Alternatively, one or all of the constituents may be in solution and after mixing them a drying step is carried out to obtain the composition in powder form.

[0040] Depending on the nature of compound B present in said composition, it may be a weedkiller, fertilizer, herbicide or more generally an energetic composition. An energetic composition is understood to mean a composition in which compound B is an energetic material, usually in the form of a solid crystalline powder, which may have heat release or thermal expansion properties depending on the conditions to which the compound is subjected. Such energetic filler materials are notably present in compositions suitable for use in fertilizers, fertilizers, weedkillers, demolition, welding or are, for example, gas-generating materials or pyrotechnic materials.

[0041] In addition, said composition may comprise other constituents such as anti-caking agents, anti-foaming agents, hydrophobic agents or corrosion inhibitors. According to a particular embodiment, said composition comprises in particular polyvinyl butyral, polyvinyl acetate, polybutadiene, polyurethane, thermoplastic elastomers or polysulfides or a mixture thereof.

[0042] Polymer A

[0043] As mentioned above, said composition comprises a polymer A. This may be a fluoropolymer Al, a polyamide A2 or a polyamide-polyether block copolymer A3 or a mixture thereof.

[0044] Fluorinated polymer Al

[0045] According to a preferred embodiment, said fluorinated polymer Al comprises monomeric units derived from a monomer selected from the group consisting of vinylidene fluoride, vinyl fluoride; trifluoroethylene (VF3); chlorotrifluoroethylene (CTFE); 1,2-difluoroethylene; tetrafluoroethylene (TFE); hexafluoropropylene (HFP); perfluoro(alkyl vinyl) ethers such as perfluoro(methylvinyl) ether (PMVE), perfluoro(ethyl vinyl) ether (PEVE) and perfluoro(propylvinyl) ether (PPVE); perfluoro(1,3-dioxole); perfluoro(2,2-dimethyl-1,3-dioxole) (PDD); the product of formula CF2=CFOCF2CF(CF3)OCF2CF2X in which X is SO2F, CO2H, CH2OH, CH2OCN or CH2OPO3H; the product of formula CF2=CFOCF2CF2SC>2F; the product of formula F(CF2)nCH2OCF=CF2 in which n is 1, 2, 3, 4 or 5; the product of formula R 1 CH2OCF=CF2 in which R 1 is hydrogen or F(CF2)m and m is 1, 2, 3 or 4; the product of formula R 2 OCF=CH2 in which R2 is F(CF2)p and p is 1, 2, 3 or 4; perfluorobutyl ethylene (PFBE); 3,3,3-trifluoropropene and 2-trifluoromethyl-3,3,3-trifluoro-l-propene or a mixture thereof.

[0046] According to one embodiment, said fluorinated polymer Al is a homopolymer of vinylidene fluoride.

[0047] According to another embodiment, said fluorinated polymer Al is a copolymer of vinylidene fluoride with at least one comonomer compatible with vinylidene fluoride. The comonomers compatible with vinylidene fluoride may be halogenated (fluorinated, chlorinated or brominated) or non-halogenated. Examples of suitable fluorinated comonomers are: vinyl fluoride, tetrafluoroethylene, hexafluoropropylene, trifluoropropenes and in particular

[0048] 3.3.3-trifluoropropene, tetrafluoropropenes and in particular 2,3,3,3-tetrafluoropropene or

[0049] 1,3,3,3-tetrafluoropropene, hexafluoroisobutylene, perfluorobutylethylene, pentafluoropropenes and in particular 1,1,3,3,3-pentafluoropropene or 1, 2, 3,3,3-pentafluoropropene, perfluoroalkylvinylethers and in particular those of general formula Rf-O-CF-CF2, Rf being an alkyl group, preferably C1 to C4 (preferred examples being perfluoropropylvinylether and perfluoromethylvinylether). The fluorinated comonomer may comprise a chlorine or bromine atom. It may in particular be chosen from bromotrifluoroethylene, chlorofluoroethylene, chlorotrifluoroethylene and chlorotrifluoropropene. Chlorofluoroethylene may denote either 1-chloro-1-fluoroethylene or 1-chloro-2-fluoroethylene. The 1-chloro-1-fluoroethylene isomer is preferred. Chlorotrifluoropropene is preferably 1-chloro-3,3,3-trifluoropropene or 2-chloro-3,3,3-trifluoropropene.The VDF copolymer may also include non-halogenated monomers such as ethylene, and / or acrylic or methacrylic comonomers.

[0050] The fluorinated polymer Al preferably contains at least 50 mol% vinylidene fluoride, advantageously at least 60 mol% vinylidene fluoride, preferably at least 70 mol% vinylidene fluoride. The comonomer may be present in a content of 1 to 50%, advantageously 2 to 30% by weight relative to the weight of said fluorinated polymer Al.

[0051] According to a preferred embodiment, the fluoropolymer Al is a copolymer of vinylidene fluoride (VDF) and hexafluoropropylene (HFP) (P(VDF-HFP)), having a percentage by weight 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 Al. According to another embodiment, the fluoropolymer Al is a copolymer of vinylidene fluoride (VDF) and hexafluoropropylene (HFP) (P(VDF-HFP)), having a percentage by weight of hexafluoropropylene monomer units of 10 to 30%, advantageously of 10 to 25% by weight relative to the weight of said fluoropolymer Al.

[0052] According to another preferred embodiment, the fluoropolymer Al is a copolymer of vinylidene fluoride and tetrafluoroethylene (TFE).

[0053] According to another embodiment, the fluorinated polymer Al is a copolymer of vinylidene fluoride and chlorotrifluoroethylene (CTFE) containing at least 50 mol% vinylidene fluoride, advantageously at least 60 mol% vinylidene fluoride, preferably at least 70 mol% vinylidene fluoride.

[0054] According to another embodiment, the fluoropolymer Al is a VDF-TFE-HFP terpolymer. According to one embodiment, the fluoropolymer Al 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.

[0055] According to one embodiment, the fluorinated polymer Al 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 the VDF monomer, according to techniques well known to those skilled in the art.

[0056] According to one embodiment, the functional group carries a carboxylic acid function which is a (meth)acrylic acid type group chosen from acrylic acid, methacrylic acid, hydroxyethyl(meth)acrylate, hydroxypropyl(meth)acrylate and hydroxyethylhexyl(meth)acrylate. Thus, said fluoropolymer Al may comprise monomeric units derived from a monomer selected from the group consisting of acrylic acid, methacrylic acid, methyl acrylate, methyl methacrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate and hydroxyethylhexyl methacrylate.

[0057] According to one embodiment, the units carrying the carboxylic acid function further comprise a heteroatom chosen from oxygen, sulfur, nitrogen and phosphorus.

[0058] According to a preferred embodiment, said fluorinated polymer Al may be, for example, a copolymer of vinylidene fluoride and a monomer Ml' selected from the group consisting of acrylic acid, methacrylic acid, hydroxyethyl(meth)acrylate, hydroxypropyl(meth)acrylate, hydroxyethylhexyl(meth)acrylate and acryloyloxy propylsuccinate. Preferably, the content of monomer Ml' in said fluorinated polymer Al is from 0.01% to 5 mol%. In this embodiment, at least 40% of the units derived from the monomer Ml' are distributed between two vinylidene fluoride units.

[0059] The content of functional groups in said fluoropolymer Al is at least 0.01 mol%, preferably at least 0.1 mol%, and at most 15 mol%, preferably at most 10 mol%. The fluoropolymer Al preferably has a high molecular weight. By high molecular weight, as used herein, is meant a fluoropolymer Al having a melt viscosity greater than 100 Pa.s, preferably greater than 500 Pa.s, more preferably greater than 1000 Pa.s, according to the ASTM D-3835 method measured at 232°C and 100 sec-1.

[0060] According to one embodiment, said fluoropolymer Al carrying functional groups can crosslink either by self-condensation of its functional groups or by reaction with a catalyst and / or a crosslinking agent, such as melamine resins, epoxy resins and the like, as well as known low molecular weight crosslinking agents such as di- or higher polyisocyanates, polyaziridines, polycarbodiimides, polyoxazolines, dialdehydes such as glyoxal, acetoacetates, malonates, acetals, di- and trifunctional thiols and acrylates, cycloaliphatic epoxy molecules, organosilanes such as epoxysilanes and amino silanes, carbamates, diamines and triamines, inorganic chelating agents such as certain zinc and zirconium salts, titaniums, glycourils and other aminoplasts.In some cases, functional groups from other polymerization ingredients, such as surfactants, initiators, seed particles, may be involved in the crosslinking reaction. When two or more functional groups are involved in the crosslinking process, the complementary reactive group pairs are, for example, hydroxyl-isocyanate, acid-epoxy, amine-epoxy, hydroxyl-melamine, acetoacetate-acid. Acrylate and / or methacrylate monomers not containing functional groups capable of entering into crosslinking reactions after polymerization should preferably represent 70% or more by weight of the total monomer mixture, and more preferably should be greater than 90% by weight.According to one embodiment, the fluorinated polymer Al comprises a crosslinking agent selected from the group consisting of isocyanates, diamines, adipic acid, dihydrazides and combinations thereof.

[0061] According to another embodiment, said fluorinated polymer Al may be mixed with a hydrophilic polymer Al". Said polymer Al" comprises monomeric units derived from a monomer Ml" of formula R 1 R 2 C=C(R 3 )C(O)R in which the substituents R 1 , R 2 and R 3are independently of each other selected from the group consisting of H and C1-C5 alkyl; R is selected from the group consisting of -NHCfCHshd-hCfOjCHs or -OR' with R' selected from the group consisting of H and C1-C5 alkyl optionally substituted with one or more -OH groups or a five- or ten-membered heterocycle comprising at least one nitrogen atom in its ring chain. 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 C1-C5 alkyl groups.As mentioned above, the Ci-Cis alkyl is optionally substituted by said heterocycle. The latter may be linked to the alkyl chain by the nitrogen atom or any other atoms forming the heterocycle. Preferably the heterocycle is 2-pyrrolidone, delta-lactam, succinimide, 2-imidazolidinone, 4-imidazolidinone.

[0062] Preferably, said polymer Al" comprises monomeric units derived from a monomer Ml" of alkyl (meth)acrylate of formula R 1 R 2 C=C(R 3 )C(O)R in which the substituents R 1 , R 2 and R 3are independently of each other selected from the group consisting of H and C1-C5 alkyl; R is selected from the group consisting of -NHC(CH3)2CH2C(O)CH3 or -OR' with R' selected from the group consisting of C1-C5 alkyl optionally substituted by one or more -OH groups a five- or ten-membered heterocycle comprising at least one nitrogen atom in its ring chain. Preferably, the heterocycle is as defined above, in particular the heterocycle is 2-pyrrolidone, deltalactam, succinimide, 2-imidazolidinone, 4-imidazolidinone. The term "alkyl (meth)acrylate" encompasses alkyl acrylates and alkyl methacrylates.According to a preferred embodiment, the substituent R' is 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, hydroxybutyl, hydroxypropyl, ureido-substituted ethyl, hydroxyethyl, hydroxypropyl, hydroxybutyl.

[0063] In particular, said polymer PI" comprises monomeric units derived from a monomer Ml" of alkyl (meth)acrylate of formula R 1 R 2 C=C(R 3 )C(O)R in which the substituents R 1 and R 2 are H; R 3 is H or CH3; R is -OR' with R' selected from the group consisting of H, methyl, ethyl, propyl, n-butyl, isobutyl, t-butyl, hydroxy propyl, hydroxy butyl, 2-pyrrolidone, deltalactam, succinimide, 2-imidazolidinone, 4-imidazolidinone.

[0064] Thus, alkyl (meth)acrylate may be 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 acrylate, methyl acrylic acid, methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, t-butyl methacrylate, n-dodecyl methacrylate, methacrylate amyl, isoamyl methacrylate, hexyl methacrylate, 2-ethylhexyl methacrylate, lauryl methacrylate, n-octyl methacrylate, ureido methacrylate and mixtures thereof.Of these, alkyl acrylates with an alkyl group having 1 to 8 carbon atoms are preferred, and alkyl acrylates with an alkyl group having 1 to 5 carbon atoms are more preferable. These compounds may be used alone or as a mixture of two or more. Thus, said polymer PI" may be a homopolymer of a monomer Ml" as defined above or a copolymer derived from a mixture of one or more monomer Ml" as defined above.

[0065] The term "acrylate" herein includes both acrylates and methacrylates.

[0066] Said monomer Ml" can be copolymerized with an ethylenically unsaturated compound copolymerizable with alkyl acrylate and alkyl methacrylate such as:

[0067] - (A) an alkenyl compound containing a functional group, and

[0068] - (B) an alkenyl compound without a functional group.

[0069] The alkenyl compound (A) containing a functional group includes, for example, α,β-unsaturated carboxylic acids such as acrylic acid, methacrylic acid, fumaric acid, crotonic acid, itaconic acid and the like; vinyl ester compounds such as vinyl acetate, vinyl neodecanoate and the like; amide compounds such as acrylamide, methacrylamide, N-methylacrylamide, N-methylmethacrylamide, N-methylolacrylamide, N-methylolmethacrylamide, N-alkylacrylamide, N-alkylmethacrylamide, N,N-dialkylacrylamide, N,N-dialkylmethacrylamide, diacetone acrylamide and the like; acrylic acid esters such as 2-hydroxyethyl acrylate, N-dialkylaminoethyl acrylate, glycidyl acrylate, n-dodecyl acrylate, fluoroalkyl acrylate and the like;methacrylic acid esters such as dialkylaminoethyl methacrylate, fluoroalkyl methacrylate, 2-hydroxyethyl methacrylate, n-octyl methacrylate, t-butyl methacrylate, glycidyl methacrylate, ethylene glycol dimethacrylate and the like; maleic anhydride, and alkenyl glycidyl ether compounds such as allyl glycidyl ether and the like. Of these, acrylic acid, methacrylic acid, itaconic acid, fumaric acid, N-methylolacrylamide, N-methylolmethacrylamide, diacetone acrylamide, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate and allyl glycidyl ether are preferred. These compounds can be used alone or in mixtures of two or more.;

[0070] The functional group-free alkenyl compound (B) includes, for example, conjugated dienes such as 1,3-butadiene, isoprene and the like; divinyl hydrocarbon compounds such as divinyl benzene and the like; and alkenyl cyanides such as acrylonitrile, methacrylonitrile and the like. Among these, preferred are 1,3-butadiene, and acrylonitrile. These compounds may be used alone or as a mixture of two or more.

[0071] It is preferable that the functional alkenyl compound (A) is used in an amount of less than 50% by weight relative to the weight of the monomer mixture and that the functional group-free alkenyl compound (B) is used in an amount of less than 30% by weight relative to the weight of the monomer mixture.

[0072] In some embodiments, the Al, Al" polymers are bio-sourced compounds. The term "bio-sourced" means "derived from biomass". This makes it possible to improve the ecological footprint of the composition. The bio-sourced vinylidene fluoride may be characterized by a renewable carbon content, i.e. carbon of natural origin and originating from a biomaterial or biomass, of at least 1 atomic % as determined by the 14C content according to standard NF EN 16640. The term "renewable carbon" indicates that the carbon is of natural origin and originates from a biomaterial (or biomass), as indicated below.According to certain embodiments, the bio-carbon content of the VDF may be greater than 5%, preferably greater than 10%, preferably greater than 25%, preferably greater than or equal to 33%, preferably greater than 50%, preferably greater than or equal to 66%, preferably greater than 75%, preferably greater than 90%, preferably greater than 95%, preferably greater than 98%, preferably greater than 99%, advantageously equal to 100%.

[0073] The vinylidene fluoride homopolymers and copolymers used in the invention can be obtained by known polymerization methods such as emulsion or suspension polymerization. According to one embodiment, they are prepared by an emulsion polymerization process in the absence of a fluorinated surfactant.

[0074] The polymerization of vinylidene fluoride preferably results in a latex generally having a solids content of 10 to 60% by weight, preferably 10 to 50%, and having a weight average particle size of less than 1 micrometer, preferably less than 1000 nm, preferably less than 800 nm, and more preferably less than 600 nm. The weight average particle size is generally at least 20 nm, preferably at least 50 nm, and advantageously the average size is in the range of 100 to 400 nm. The polymer particles may form agglomerates having a weight average size of 1 to 30 micrometers, and preferably 2 to 20 micrometers. The agglomerates may break into discrete particles during formulation and application to a substrate.

[0075] When said fluorinated polymer Al is mixed with said polymer PI", the mass content of polymer Al is at least 50%, advantageously at least 60%, preferably at least 70%, more preferably at least 80%, in particular at least 90% based on the total weight of said polymers Al and PI" in said composition.

[0076] Polyamide A2

[0077] The term "polyamide" used in the present description covers both homopolyamides and copolyamides. Preferably, said polyamide A2 is an aliphatic semi-crystalline polyamide. Said polyamide A2 can be obtained from the polycondensation of at least one lactam, or from the polycondensation of at least one amino acid, or from the polycondensation of at least one diamine X with at least one dicarboxylic acid Y.

[0078] When said polyamide A2 is obtained from the polycondensation of at least one lactam, it can therefore comprise a single lactam or several lactams.

[0079] When said polyamide A2 is obtained from the polycondensation of at least one lactam, said at least one lactam is chosen from a C6 to C18 lactam, preferably a C8 to C12 lactam, more preferably a C10 to C12 lactam.

[0080] Advantageously, said polyamide A2 is obtained from the polycondensation of a single lactam and said lactam may be chosen in particular from caprolactam, lauryllactam and undecanolactam, advantageously lauryllactam.

[0081] When said polyamide A2 is obtained from the polycondensation of at least one amino acid, said at least one amino acid may be chosen from a C6 to C18 amino acid, preferably a C10 to C18 amino acid, more preferably a C10 to C12 amino acid.

[0082] A C6 to C12 amino acid includes 6-aminohexanoic acid, 9-aminononanoic acid, 10-aminodecanoic acid, 10-aminoundecanoic acid, 12-aminododecanoic acid, and 11-aminoundecanoic acid, as well as its derivatives, including N-heptyl-11-aminoundecanoic acid.

[0083] When said polyamide A2 is obtained from the polycondensation of at least one amino acid, it may comprise a single amino acid or several amino acids.

[0084] Advantageously, said polyamide A2 is obtained from the polycondensation of a single amino acid and said amino acid is chosen from 11-aminoundecanoic acid and 12-aminododecanoic acid, advantageously 11-aminoundecanoic acid.

[0085] When said polyamide A2 is obtained from the polycondensation of at least one diamine X with at least one diacid Y, then the diamine is C4-C36, preferably C6-C18, preferably C6-C12, more preferably C10-C12, with at least one diacid Y in C4-C36, preferably C6-C18, preferably C6-C12, more preferably C8-C12, and said at least one diamine X is an aliphatic diamine and said at least one diacid Y is an aliphatic diacid.

[0086] The diamine can be linear or branched. Advantageously, it is linear.

[0087] Said at least one C4-C36 diamine X may in particular be chosen from 1,4-butanediamine, 1,5-pentamethylenediamine, 1,6-hexamethylenediamine, 1,7-heptamethyldiamine, 1,8-octamethyldiamine, 1,9-nonamethyldiamine, 1,10-decamethyldiamine, 1,11-undecamethyldiamine, 1,12-dodecamethyldiamine, 1,13-tridecamethyldiamine, 1,14-tetradecamethyldiamine, 1,16-heXdecamethyldiamine and 1,18-octadecamethyldiamine, octadecenediamine, eicosanediamine, docosanediamine and diamines obtained from fatty acids.

[0088] Advantageously, said at least one diamine X is C6-C18 and chosen from 1,6-hexamethylenediamine, 1,7-heptamethylenediamine, 1,8-octamethylenediamine, 1,9-nonamethylenediamine, 1,10-decamethylenediamine, 1,11-undecamethylenediamine, 1,12-dodecamethylenediamine, 1,13-tridecamethylenediamine, 1,14-tetradecamethylenediamine, 1,16-hexadecamethylenediamine and 1,18-octadecamethylenediamine.

[0089] Advantageously, said at least one diamine X in C6 to C12, is in particular chosen from 1,6-hexamethylenediamine, 1,7-heptamethylenediamine, 1,8-octamethylenediamine, 1,9-nonamethylenediamine, 1,10-decamethylenediamine, 1,11-undecamethylenediamine, 1,12-dodecamethylenediamine.

[0090] Advantageously, the diamine X used is C10 to C12, in particular chosen from 1,10-decamethylenediamine, 1,11-undecamethylenediamine, 1,12-dodecamethylenediamine.

[0091] Said at least one dicarboxylic acid Y is C4 to C36 and may be chosen from succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, brassylic acid, tetradecanedioic acid, pentadecanedioic acid, hexadecanedioic acid, heptadecanedoic acid, octadecanedioic acid, and diacids obtained from fatty acids.

[0092] The diacid can be linear or branched. Advantageously, it is linear.

[0093] Advantageously, said at least one dicarboxylic acid Y is C6 to C18 and is chosen from adipic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, brassylic acid, tetradecanedioic acid, pentadecanedioic acid, hexadecanedioic acid, heptadecanedoic acid and octadecanedioic acid. Advantageously, said at least one dicarboxylic acid Y is C6 to C12 and is chosen from adipic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid and dodecanedioic acid.

[0094] Advantageously, the average number of carbon atoms relative to the nitrogen atom of the semi-crystalline aliphatic polyamide is greater than or equal to 6.

[0095] Advantageously, said at least one dicarboxylic acid Y is C8 to C12 and is chosen from suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid.

[0096] Advantageously, said at least one aliphatic semi-crystalline polyamide is obtained from the polycondensation of at least one C7 to C18 amino acid, preferably C7 to C12, more preferably C10 to C12, or at least one C7 to C18 lactam, preferably C7 to C12, more preferably C10 to C12.

[0097] More preferably, the average number of carbon atoms relative to the nitrogen atom of the semi-crystalline aliphatic polyamide is greater than or equal to 8.

[0098] In particular, the average number of carbon atoms relative to the nitrogen atom of the semi-crystalline aliphatic polyamide is between 8 and 14.

[0099] Advantageously, said polyamide A2 is chosen from PA510, PA512, PA514, PA610, PA612, PA1010, PA1012, PA1212, PAU and PA 12, in particular PA1010, PA1012, PA1212, PAU, PA 12. Even more advantageously, the average number of carbon atoms relative to the nitrogen atom of the semi-crystalline aliphatic polyamide is greater than or equal to 9.

[0100] In particular, the average number of carbon atoms relative to the nitrogen atom of the semi-crystalline aliphatic polyamide is between 9 and 14.

[0101] More preferably, the average number of carbon atoms relative to the nitrogen atom of the semi-crystalline aliphatic polyamide is greater than or equal to 10.

[0102] In particular, the average number of carbon atoms relative to the nitrogen atom of the semi-crystalline aliphatic polyamide is between 10 and 14.

[0103] Advantageously, said semi-crystalline aliphatic polyamide is chosen from PAU and PA12, in particular PAU.

[0104] In the case of a PA-XY type homopolyamide, the number of carbon atoms per nitrogen atom is the average of the X unit and the Y unit.

[0105] In the case of a copolyamide, the number of carbons per nitrogen atom is calculated according to the same principle. The calculation is carried out in molar proportion to the different amide units. When said polyamide A2 is obtained from the polycondensation of at least one diamine X with at least one dicarboxylic acid Y, it may comprise a single diamine or several diamines and a single dicarboxylic acid or several dicarboxylic acids.

[0106] In one embodiment, said polyamide A2 is obtained from the polycondensation of a single diamine X with a single dicarboxylic acid Y.

[0107] Advantageously, the aliphatic semi-crystalline polyamide is chosen from PA10, PAU, PA12, PA1010, PA1012, in particular PAU and PA12.

[0108] Advantageously, the semi-crystalline polyamide is partially or totally bio-resourced.

[0109] Polyamide-polyether block copolymers A3

[0110] Polyamide-polyether block copolymers are copolymers with amide units (Bal) and polyether units (Ba2), said amide unit (Bal) corresponding to an aliphatic repeating unit chosen from a unit obtained from at least one amino acid or a unit obtained from at least one lactam, or a unit obtained from polycondensation:

[0111] - at least one diamine, said diamine being preferably chosen from a linear or branched aliphatic diamine or a mixture thereof, and

[0112] - at least one dicarboxylic acid, said diacid being preferably chosen from: a linear or branched aliphatic diacid, or a mixture thereof, said diamine and said diacid comprising from 4 to 36 carbon atoms, advantageously from 6 to 18 carbon atoms; said polyether units (Ba2) being in particular derived from at least one polyalkylene ether polyol, in particular a polyalkylene ether diol,

[0113] A3 copolymers result in particular from the copolycondensation of polyamide sequences with reactive ends with polyether sequences with reactive ends, such as:

[0114] 1) Polyamide sequences with diamine chain ends with polyoxyalkylene sequences with dicarboxylic chain ends.

[0115] 2) Polyamide sequences with dicarboxylic chain ends with polyoxyalkylene sequences with diamine chain ends obtained by cyanoethylation and hydrogenation of aliphatic alpha-omega dihydroxylated polyoxyalkylene sequences called polyalkylene ether diols (polyetherdiols).

[0116] 3) Polyamide sequences with dicarboxylic chain ends with polyetherdiols, the products obtained being, in this particular case, polyetheresteramides. The copolymers of the invention are advantageously of this type. The polyamide sequences with dicarboxylic chain ends originate, for example, from the condensation of polyamide precursors in the presence of a chain-limiting dicarboxylic acid.

[0117] Polyamide sequences with diamine chain ends originate, for example, from the condensation of polyamide precursors in the presence of a chain-limiting diamine.

[0118] Polyamide block and polyether block copolymers can also include randomly distributed units. These polymers can be prepared by the simultaneous reaction of the polyether and the precursors of the polyamide blocks.

[0119] For example, polyetherdiol, polyamide precursors and a chain-limiting diacid can be reacted. The result is a polymer having essentially polyether blocks, polyamide blocks of very variable length, but also the various reactants having reacted randomly which are distributed randomly (statistically) along the polymer chain.

[0120] Polyetherdiamine, polyamide precursors and a chain-limiting diacid can also be reacted. The result is a polymer having essentially polyether blocks, polyamide blocks of very variable length, but also the various reactants having reacted randomly which are distributed randomly (statistically) along the polymer chain.

[0121] Amide unit (Bal): The amide unit (Bal) corresponds to an aliphatic repeating unit as defined above. Advantageously, the amide unit (Bal) is chosen from polyamide 11, polyamide 12, polyamide 610, polyamide 612, polyamide 1010, polyamide 1012, in particular polyamide 11. More advantageously, the amide unit (Bal) is chosen from polyamide 11 and polyamide 12.

[0122] Polyether motif (Ba2):

[0123] The polyether units are in particular derived from at least one polyalkylene ether polyol, in particular they are derived from at least one polyalkylene ether polyol, in other words, the polyether units are made up of at least one polyalkylene ether polyol. In this embodiment, the expression "at least one polyalkylene ether polyol" means that the polyether units are made up of alcohol chain ends and therefore cannot be a polyetherdiamine triblock type compound. Advantageously, the polyether units (Ba2) are chosen from polyethylene glycol (PEG), polypropylene glycol (PPG), polytrimethylene glycol (PO3G), polytetramethylene glycol (PTMG) and their mixtures or their copolymers, in particular PTMG. The number-average molecular mass (Mn) of the polyether blocks is advantageously between 200 and 4000 g / mol, preferably between 250 and 2500 g / mol, in particular between 300 and 1100 g / mol.

[0124] Copolymer A3 can be prepared by the following process:

[0125] - in a first step, the polyamide blocks (Bal) are prepared by polycondensation of the lactam(s), or of the amino acid(s), or of the diamine(s) and of the dicarboxylic acid(s); and where appropriate, of the comonomer(s) chosen from lactams and alpha-omega aminocarboxylic acids; in the presence of a chain limiter chosen from dicarboxylic acids; then

[0126] - in a second step, the polyamide blocks (Bal) obtained are reacted with polyether blocks (Ba2), in the presence of a catalyst.

[0127] The general method for the two-step preparation of the copolymers of the invention is known and is described, for example, in French patent FR 2 846 332 and in European patent EP 1 482 011. The block formation reaction (Bal) usually takes place between 180 and 300°C, preferably from 200 to 290°C, the pressure in the reactor is established between 5 and 30 bars, and is maintained for approximately 2 to 3 hours. The pressure is slowly reduced by bringing the reactor to atmospheric pressure, then the excess water is distilled, for example, for one or two hours. Once the polyamide with carboxylic acid ends has been prepared, the polyether and a catalyst are then added. The polyether can be added in one or more times, as can the catalyst. In an advantageous form, the polyether is added first, the reaction of the OH ends of the polyether and the COOH ends of the polyamide begins with the formation of ester bonds and the elimination of water.As much water as possible is removed from the reaction medium by distillation, then the catalyst is introduced to complete the bonding of the polyamide blocks and the polyether blocks. This second step is carried out with stirring, preferably under a vacuum of at least 15 mm Hg (2000 Pa) at a temperature such that the reactants and the copolymers obtained are in the molten state. For example, this temperature can be between 100 and 400°C and most often 200 and 300°C. The reaction is monitored by measuring the torque exerted by the molten polymer on the stirrer or by measuring the electrical power consumed by the stirrer. The end of the reaction is determined by the value of the target torque or power. It is also possible to add during the synthesis, at the most opportune moment, one or more molecules used as an antioxidant, for example Irganox® 1010 or Irganox® 245.

[0128] The process for preparing copolymer A3 can also be considered as adding all the monomers at the beginning, either in a single step, to carry out the polycondensation: of the lactam(s), or of the amino acid(s), or of the diamine(s) and of the dicarboxylic acid(s); and where appropriate, of the other polyamide comonomer(s);

[0129] - in the presence of a chain limiter chosen from dicarboxylic acids; - in the presence of (Ba2) blocks (polyether);

[0130] - in the presence of a catalyst for the reaction between the flexible blocks (Ba2) and the blocks (Bal).

[0131] Advantageously, said dicarboxylic acid is used as chain limiter, which is introduced in excess relative to the stoichiometry of the diamine(s).

[0132] Advantageously, the catalyst used is a derivative of a metal chosen from the group formed by titanium, zirconium and hafnium or a strong acid such as phosphoric acid, hypophosphorous acid or boric acid.

[0133] Polycondensation can be carried out at a temperature of 240 to 280°C.

[0134] Generally, the known copolymers with ether and amide units consist of linear and semi-crystalline aliphatic polyamide sequences. In one embodiment, the copolymer A3 has a flexural modulus of less than 200 MPa, in particular less than 100 MPa, as measured according to ISO 178:2010 at 23°C. In another embodiment, the copolymer A3 has a density greater than or equal to 1, as determined according to ISO 1183-3:1999.

[0135] Compound B

[0136] As mentioned above, said composition comprises a compound B.

[0137] According to a preferred embodiment, said compound B has an oxygen balance BO of less than 60, said oxygen balance being determined by the formula BO (%) = [1600*(d-2a-(b / 2)] / M in which a, b and d are respectively the number of carbon, hydrogen and oxygen atoms of compound B and M the molar mass of said compound B.

[0138] The oxygen balance, expressed as a mass percentage, represents the oxygen concentration contained in said compound B. It is defined as the level of oxygen available after oxidation of hydrogen, carbon and any metals present to produce water, carbon dioxide, and possibly metal oxides. If the oxygen balance value is positive, compound B is an oxidant, it is therefore rich in oxygen. Conversely, a negative oxygen balance indicates a low quantity of oxygen present. When there is enough oxygen to produce exclusively CO2 and H2O and metal oxides without excess, the oxygen balance is zero.

[0139] Advantageously, said oxygen balance of said compound B is less than 58%, preferably less than 56%, more preferably less than 54%, in particular less than 52%, more particularly less than 50%.

[0140] According to a preferred embodiment, said oxygen balance of said compound B is greater than -260%, advantageously greater than -225%, preferably greater than -200%, more preferably greater than -175%, in particular greater than -150%, more particularly greater than -125%, preferably greater than -100%.

[0141] Thus, said oxygen balance of said compound B may be less than 60%, advantageously less than 58%, preferably less than 56%, more preferably less than 54%, in particular less than 52%, more particularly less than 50%; and greater than -260%, advantageously greater than -225%, preferably greater than -200%, more preferably greater than -175%, in particular greater than -150%, more particularly greater than -125%, preferably greater than -100%.

[0142] According to a preferred embodiment, said compound B comprises at least one functional group selected from the group consisting of -NO2, NOs', -ON=O, -N=N-, -N =N + N -, NX3 with X being a halogen, -C=NO-, CIOs', CIO4', -O-O-, -O3- and -C CM with Mt a transition metal. Said transition metal may be a metal from columns 3 to 11 of the periodic table of elements. Preferably, said compound B comprises at least one functional group selected from the group consisting of -NO2, NOs', -ON=O, -N=N-, -N'=N + N-, CIOs', CIO4', -0-0- and -O3-.

[0143] According to a particularly preferred embodiment, said compound B has an oxygen balance of less than 60%, advantageously less than 58%, preferably less than 56%, more preferably less than 54%, in particular less than 52%, more particularly less than 50%; and this comprises at least one functional group selected from the group consisting of -NO2, NOs', -ON=O, -N=N-, -N =N + N -, NX3 with X being a halogen, -C=NO-, CIOs', CIO4', -O-O-, -O3- and -C CMÜ with Mt a transition metal. Preferably, said compound B has an oxygen balance of less than 60%, advantageously less than 58%, preferably less than 56%, more preferably less than 54%, in particular less than 52%, more particularly less than 50%; and it comprises at least one functional group selected from the group consisting of -NO2, NOs', -ON=O, -N=N-, -N'=N + N-, CIOs', CIO4', -0-0- and -O3-.

[0144] According to a more particularly preferred embodiment, said compound B has an oxygen balance of less than 60%, advantageously less than 58%, preferably less than 56%, more preferably less than 54%, in particular less than 52%, more particularly less than 50%; and greater than -260%, advantageously greater than -225%, preferably greater than -200%, more preferably greater than -175%, in particular greater than -150%, more particularly greater than -125%, preferably greater than -100%; and this comprises at least one functional group selected from the group consisting of -NO2, NO3', -ON=O, -N=N-, -N'=N + N -, NX3 with X being halogen, -C=NO-, CIO3', CIO4', -O-0-, -O3- and - CC Mt +with Mt a transition metal. Preferably, said compound B has an oxygen balance of less than 60%, advantageously less than 58%, preferably less than 56%, more preferably less than 54%, in particular less than 52%, more particularly less than 50%; and greater than -260%, advantageously greater than -225%, preferably greater than -200%, more preferably greater than -175%, in particular greater than -150%, more particularly greater than -125%, preferably greater than -100%; and this comprises at least one functional group selected from the group consisting of -NO2, NO3-, -ON=O, -N=N-, -N=N + N-, CIO3-, CIO4„ -OO- and -O3-.

[0145] As mentioned above, said compound B may preferably be a fertilizer, pesticide, oxidant or more generally an energetic compound. Thus, in a preferred embodiment, said compound B is selected from the group consisting of a salt of formula M + X _ wherein M is selected from the group consisting of Li, Na, K and NH4; and X is selected from the group consisting of a nitrate anion, a chlorate anion and a perchlorate anion. Said compound B may be ammonium nitrate, potassium nitrate, sodium nitrate, potassium chlorate, sodium chlorate, sodium perchlorate, potassium perchlorate, ammonium chlorate or ammonium perchlorate.

[0146] Use

[0147] As mentioned in the present application, said polymer A according to the present invention can be used in different fields.

[0148] According to a preferred embodiment, said polymer A is used as a stabilizer in an energy composition. Preferably, said polymer A is used as a stabilizer in a weedkiller, herbicide or fertilizer composition. In this case, said polymer A is as defined in the present invention, and preferably said polymer A is said fluorinated polymer A1 or a polyamide A2 or a polyamide-polyether block copolymer A3 or a mixture thereof.

[0149] According to another embodiment, the present invention relates to the use of a polymer A for the desensitization or sensitization of an energetic composition, said polymer A being as defined in the present invention and said energetic composition comprising a compound B having heat release properties or volume expansion properties; preferably said compound B is as defined in the present invention. Preferably, said polymer A1 is used for the desensitization of an energetic composition comprising a compound B having heat release properties or volume expansion properties; preferably said compound B is as defined in the present invention.Alternatively, said polyamide-polyether block copolymer A3 or said polyamide A2 is used for the sensitization of an energetic composition comprising a compound B having heat release properties or volume expansion properties; preferably said compound B is as defined in the present invention.

[0150] According to another embodiment, the present invention relates to a method for reducing or increasing the heat response liveliness of an energetic composition, said method comprising adding a polymer A as defined in the present invention to said energetic composition; the latter comprising a compound B having heat release properties or volume expansion properties; preferably said compound B is as defined in the present invention. Preferably, said method is a method for reducing the heat response liveliness of an energetic composition, said method comprising adding a polymer Al as defined in the present invention to said energetic composition; the latter comprising a compound B having heat release properties or volume expansion properties; preferably said compound B is as defined in the present invention.Alternatively, said method is a method for increasing the heat response liveliness of an energetic composition, said method comprising adding said polyamide-polyether block copolymer A3 or said polyamide A2 as defined in the present invention to said energetic composition; the latter comprising a compound B having heat release properties or volume expansion properties; preferably said compound B is as defined in the present invention.

[0151] Examples

[0152] DSC measurement

[0153] The prepared mixtures (approximately 5 mg) are introduced into 120 microliter pressure-resistant stainless steel test cells (at least 150 bars), and crimped using a crimping tool or a suitable press, with a suitable seal (silver, graphite or nickel) to ensure the device is watertight. The thermal stability of the mixtures was characterized by DSC using a DSC111 and Sensys calorimeter marketed by KEP-Setaram. The sample is subjected to a heating ramp between room temperature and 400°C at a rate of 5°C / min. The heat flux exchanges are then recorded as a function of temperature. The integration of the DSC signal provides access to the overall energy of the thermal phenomena. The level of the heat flux, and the shape of the peaks, makes it possible to evaluate the stabilizing or destabilizing nature of the compounds.

[0154] Different samples comprising a polymer and ammonium nitrate were subjected to differential scanning calorimetry. The samples tested were prepared by mixing 5% polymer to 95% by weight of ammonium nitrate. Examples 1 and 2 are carried out with fluoropolymers according to the present invention. In Example 1, the fluoropolymer used is a homopolymer of poly(vinylidene fluoride). In Example 2, the fluoropolymer used is a copolymer of vinylidene fluoride and hexafluoropropylene (between 20 and 25% by weight of hexafluoropropylene). Comparative Example 3 is carried out in the presence of polyvinyl butyral. The ammonium nitrate and the polyvinyl butyral were sieved to 400 microns. The reference example contains 100% ammonium nitrate. Example 4 contains a polyamide polyether block copolymer (PEBAX® ES 1745).

[0155] As can be seen in Figure 1, the profile of the peaks obtained is very different between the examples produced according to the present invention compared to the comparative example. The shape of the peaks is an indicator of the potential reaction rate of ammonium nitrate under the effect of heat. In the presence of the fluorinated polymers according to the present invention (Examples 1, 2 and 4), the ammonium nitrate is highly stabilized compared to a composition in which the ammonium nitrate is mixed with polyvinyl butyral (Example 3).

[0156] The evolution of pressure as a function of temperature was also evaluated for these compositions. In an open glass cell in a closed, pressure-resistant enclosure, the sample is subjected to a heating ramp of 2-4°C / min. The temperature in the sample and in the confinement enclosure, as well as the pressure in it, are measured over time. The results are shown in Figure 2. The profile obtained for Examples 1, 2 and 4 demonstrates that the fluorinated polymers Al and the polymers A3 make it possible to stabilize ammonium nitrate since the pressure increase is lower than for polyvinyl butyral (Example 3). At a given temperature, the pressure increase is lower for the polymers according to the present invention. Furthermore, as can be seen in Figure 2, the polymer according to Example 4 (polyamide-polyether block copolymer) has a greater capacity to generate a blast effect.This is useful in applications such as airbags, as a greater blast effect allows for faster inflation of the airbag.

Claims

Claims 1. Composition in powder form comprising a polymer A and a compound B comprising at least one functional group selected from the group consisting of -NO2, NO3-ON=O, -N=N-, -N =N + N -, NX3with X being a halogen, -C=NO-, CIO3CIO4-OO-, -O3- and -CC MÜ with Mt a transition metal; characterized in that: said polymer A is a fluorinated polymer Al, a polyamide A2 or a polyamide-polyether block copolymer A3 or a mixture thereof, and said compound B has an oxygen balance BO less than 60, said oxygen balance being determined by the formula BO (%) = [1600*(d-2a-(b / 2)] / M in which a, b and d are respectively the number of carbon, hydrogen and oxygen atoms of compound B and M the molar mass of said compound B.

2. Composition according to the preceding claim, characterized in that said polymer A is a polyamide A2 or a polyamide-polyether block copolymer A3 or a mixture thereof.

3. Composition according to any one of the preceding claims, characterized in that said compound B has a molar mass of less than 1000 g. mol 1 .

4. Composition according to any one of the preceding claims, characterized in that said compound B is selected from the group consisting of a salt of formula M + X _ wherein M is selected from the group consisting of Li, Na, K and NH4; and X is selected from the group consisting of a nitrate anion, a chlorate anion and a perchlorate anion.

5. Composition according to any one of the preceding claims, characterized in that it also comprises poly(vinyl butyrate).

6. Composition according to any one of the preceding claims 1, 3 to 5 characterized in that said polymer A is said fluorinated polymer Al comprises monomeric units derived from vinylidene fluoride and optionally monomeric units of a monomer selected from the group consisting of vinyl fluoride; trifluoroethylene (VF3); chlorotrifluoroethylene (CTFE); 1,2-difluoroethylene; Tl tetrafluoroethylene (TFE); hexafluoropropylene (HFP); perfluoro(alkyl vinyl) ethers such as perfluoro(methylvinyl) ether (PMVE), 5-perfluoro(ethyl vinyl) ether (PEVE) and perfluoro(propylvinyl) ether (PPVE); perfluoro(1,3-dioxole); perfluoro(2,2-dimethyl-1,3-dioxole) (PDD); the product of formula CF2=CFOCF2CF(CF3)OCF2CF2X in which X is SO2F, CO2H, CH2OH, CH2OCN or CH2OPO3H; the product of formula CF2=CFOCF2CF2SO2F; the product of formula F(CF2)nCH2OCF=CF2 in which n is 1, 2, 3, 4 or 5; the product of formula R 1CH2OCF=CF2 in which R 1 is hydrogen or F(CF2)m and m is 1, 2, 3 or 4; the product of formula R 2 OCF=CH2 in which R 2 is F(CF2)p and p is 1, 2, 3 or 4; perfluorobutyl ethylene (PFBE); 3,3,3-trifluoropropene and 2-trifluoromethyl-3,3,3-trifluoro-l-propene or a mixture thereof.

7. Composition according to the preceding claim, characterized in that said fluorinated polymer Al is selected from a homopolymer of vinylidene fluoride or a copolymer comprising monomeric units derived from vinylidene fluoride and monomeric units derived from a monomer selected from the group consisting of trifluoroethylene, chlorotrifluoroethylene, 1,2-difluoroethylene, tetrafluoroethylene, hexafluoropropylene or a mixture thereof.

8. Composition according to any one of the preceding claims 7 or 8, characterized in that said fluorinated polymer Al comprises at least 50 mol% of monomeric units derived from vinylidene fluoride.

9. Composition according to any one of the preceding claims 1 to 5, characterized in that said polymer A3 is a polyamide-polyether block copolymer is a copolymer with amide units (Bal) and polyether units (Ba2), said amide unit (Bal) corresponding to an aliphatic repeating unit chosen from a unit obtained from at least one amino acid or a unit obtained from at least one lactam, or a unit obtained from the polycondensation: - at least one diamine, said diamine being preferably chosen from a linear or branched aliphatic diamine or a mixture thereof, and - at least one dicarboxylic acid, said diacid being preferably chosen from: a linear or branched aliphatic diacid, or a mixture thereof, said diamine and said diacid comprising from 4 to 36 carbon atoms, advantageously from 6 to 18 carbon atoms carbon; said polyether units (Ba2) being in particular derived from at least one polyalkylene ether polyol, in particular a polyalkylene ether diol.

10. Composition according to any one of the preceding claims, characterized in that the mass content of polymer A in said composition is from 0.1 to 35%, preferably from 1 to 30%, in particular from 1 to 15% based on the total weight of the composition.

11. Composition according to any one of the preceding claims, characterized in that the mass content of said compound B in said composition is greater than 65% based on the total weight of the composition.

12. Composition according to any one of the preceding claims 1 to 5, 9 to 11 characterized in that the mass content of said compound B in said composition is greater than 65% based on the total weight of the composition; and said polymer A is a polyamide A2 or a polyamide-polyether block copolymer A3 or a mixture thereof.

13. Composition according to any one of the preceding claims 1, 3 to 8, 10, 11 characterized in that the mass content of said compound B in said composition is at least 80% based on the total weight of the composition; and said polymer A is a fluorinated polymer Al.

14. Composition according to any one of the preceding claims, characterized in that it consists of said polymer A and said compound B and optionally poly(vinyl butyrate).

15. Use of a polymer A as a stabilizer for an energy composition, in particular a weedkiller, herbicide or fertilizer composition, said polymer A being as defined in any one of the preceding claims 1, 2, 6 to 9 and preferably said composition comprises a compound B as defined according to any one of claims 1, 3 to 4.

16. Use of a polymer A for the desensitization or sensitization of an energetic composition, said polymer A being as defined in any one of the preceding claims 1, 2, 6 to 9 and said composition comprises a compound B having heat release properties or volume expansion properties; preferably said compound B is as defined according to any one of claims 1, 3 to 4.

17. Use according to claim 15 or 16 characterized in that the mass content of polymer A in said composition is from 0.1 to 35%, preferably from 1 to 30%, in particular from 1 to 15% based on the total weight of the composition; and preferably the mass content of said compound B in said composition is greater than 65% based on the total weight of the composition.

18. Use according to the preceding claim, characterized in that the mass content of said compound B in said composition is greater than 65% based on the total weight of the composition; and said polymer A is a polyamide A2 or a polyamide-polyether block copolymer A3 or a mixture thereof; or the mass content of said compound B in said composition is at least 80% based on the total weight of the composition; and said polymer A is a fluorinated polymer Al.

19. A method for reducing or increasing the heat response liveliness of an energetic composition, said method comprising adding a polymer A as defined in any one of the preceding claims 1, 2, 6 to 9 to said composition; the latter comprising a compound B having heat release properties or volume expansion properties; preferably said compound B is as defined in any one of claims 1, 3 to 4.

20. Method according to the preceding claim, characterized in that the mass content of polymer A in said composition is from 0.1 to 35%, preferably from 1 to 30%, in particular from 1 to 15% based on the total weight of the composition; and preferably the mass content of said compound B in said composition is greater than 65% based on the total weight of the composition.

21. Method according to the preceding claim, characterized in that the mass content of said compound B in said composition is greater than 65% based on the total weight of the composition; and said polymer A is a polyamide A2 or a polyamide-polyether block copolymer A3 or a mixture thereof; or the mass content of said compound B in said composition is at least 80% based on the total weight of the composition; and said polymer A is a fluorinated polymer Al.

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