Stabilized composition based on fertilizer or pesticide or oxidant

Abstract

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

Description

TECHNICAL FIELD

[0001] The present invention relates to compositions containing a compound having exothermic or volume expansion properties under long-term or inappropriate storage conditions. In particular, the present invention relates to compositions containing energetic compounds or oxidizing agents, such as fertilizers, herbicides or weed killers. BACKGROUND

[0002] Ammonium nitrate-based fertilizers are commonly used in the agricultural field. Although ammonium nitrate is generally a stable compound, the risk of explosion cannot be ruled out; in particular under certain storage conditions. Indeed, ammonium nitrate is classified as an oxidizing agent. In the event of contamination with combustible or incompatible substances, in the event of heating, in particular under confinement, the gases produced by combustion being kept confined, or in the event of very heavy impact by an object or a shock wave, an explosion is possible.

[0003] In the past, the instability of ammonium nitrate under certain conditions has led to industrial accidents, causing very serious effects of explosion, such as in Toulouse or recently in Beirut. Solutions have been developed to stabilize ammonium nitrate-based compositions. For example, from the document US 9,630,886, a fertilizing composition is known comprising ammonium nitrate and an effective amount of a stabilizer material to obtain a specific impulse of no more than 13.5 kPa ms / kg when measured according to the Blast Effects Propagation Test; wherein the stabilizer material comprises hydrocalumite, hydroxyapatite, hydrotalcite and / or apatite, wherein the stabilizer material is at least 12.5% by weight of the total fertilizing composition, wherein the stabilizer material is no more than 35% by weight of the total fertilizing composition.

[0004] EP 1 292 537 also discloses a process for producing heat and mechanically stable granular ammonium nitrate, characterized in that a cross-linked 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 cross-linked metal silicate is treated with ammonia to form an ammonium nitrate slurry and to neutralize the solution, and the ammonium nitrate slurry is then dried and granulated.

[0005] From EP 1 981 830, a fertilizer is also known comprising ammonium nitrate in the form of a double salt and at least one stabilizer, wherein the at least one stabilizer is selected from the group consisting of MgS04, CaC03, MgC03, dolomite, Mg(N03)2, and combinations of two or more thereof, or silicon oxide, thiourea, ammonium tartrate, ammonium oxalate, ammonium sulfate, and combinations thereof.

[0006] ​It is also known that ammonium nitrate tends to agglomerate or form lumps under the action of humidity during storage, which leads to the risk of degranulation and caking of the fertilizer, which tends to destabilize the composition. A method for preventing the agglomeration of fertilizers by adding a solution comprising a polymer such as polyvinyl butyral is known, for example, from US 3,660,070. However, it has been observed that polymers such as polyvinyl butyral exhibit an inappropriate behavior under heating conditions, taking into account the risk of explosion of ammonium nitrate.

[0007] There remains a need to provide stable fertilizing, weeding or weed-killing compositions which make it possible to limit the risk of explosion of compounds such as ammonium nitrate, while preventing the formation of lumps during the storage of said compounds. SUMMARY

[0008] According to a first aspect, the present application provides a composition in powder form comprising a polymer A and a compound B, said compound B comprising at least one functional group chosen from the following: -N02, N03 - -ON=0, -N=N-, -N - =N + N - -, NX3, with X being a halogen, -C=N-O-, CIO3 - , CIO4 - , -0-0-, -03-, and -C=C - Mt + , with Mt being a transition metal, characterized in that:

[0009] - said polymer A is a fluoropolymer A1, a polyamide A2 or a polyamide-polyether block copolymer A3 or a mixture thereof, and

[0010] - said compound B has an oxygen balance OB of less than 60, said oxygen balance being determined by the formula OB (%) = [1600 (d - 2a - (b / 2)] / M, with a, b and d being the number of atoms of carbon, hydrogen and oxygen in the compound B, respectively, and M being the molar mass of said compound B.

[0011] The use of one of the polymers A defined in the present application can have various effects on the behavior of said compound B as defined above, in particular when the latter is subjected to rapid heating. The choice of the polymer A in the composition makes it possible to act specifically on the behavior of said compound B according to the targeted application, for example when the composition is intended to be used in a fertilizing, weeding, energetic or weed-killing formulation.

[0012] 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 makes it possible to prevent the release of HF when the reaction takes place during the release of heat or deflagration.

[0013] According to a preferred embodiment, the molar mass of the compound B is less than 1000 g.mol -1 .

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

[0015] According to a preferred embodiment, the composition further comprises poly(vinyl butyral).

[0016] According to a preferred embodiment, the polymer A is the fluoropolymer A1 comprising monomer units derived from vinylidene fluoride and optionally monomer units of a monomer selected from vinyl fluoride; trifluoroethylene (VF3); chlorotrifluoroethylene (CTFE); 1,2-difluoroethylene; tetrafluoroethylene (TFE); hexafluoropropylene (HFP); perfluoro(alkyl vinyl) ethers such as perfluoro(methyl vinyl) ether (PMVE), 5 perfluoro(ethyl vinyl) ether (PEVE) and perfluoro(propyl vinyl) ether (PPVE); perfluoro(1,3-dioxole); perfluoro(2,2-dimethyl-1,3-dioxole) (PDD); products of the formula CF2=CFOCF2CF(CF3)OCF2CF2X, wherein X is SO2F, CO2H, CH2OH, CH2OCN or CH2OPO3H; products of the formula CF2=CFOCF2CF2SO2F; products of the formula F(CF2)nCH2OCF=CF2, wherein n is 1, 2, 3, 4 or 5; products of the formula R 1 CH2OCF=CF2, wherein R 1 is hydrogen or F(CF2)m, and m is 1, 2, 3 or 4; products of the formula R 2 OCF=CH2, wherein 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-1-propene, or mixtures thereof.

[0017] According to a preferred embodiment, the fluoropolymer A1 is selected from a vinylidene fluoride homopolymer or a copolymer comprising monomer units derived from vinylidene fluoride and monomer units derived from a monomer selected from trifluoroethylene, chlorotrifluoroethylene, 1,2-difluoroethylene, tetrafluoroethylene, hexafluoropropylene or mixtures thereof.

[0018] According to a preferred embodiment, the fluoropolymer A1 comprises at least 50 mol% of monomer units derived from vinylidene fluoride.

[0019] According to a preferred embodiment, the polymer A3 is a polyamide-polyether block copolymer which is a copolymer having amide units (Ba1 ) corresponding to aliphatic repeating units selected from units obtained from at least one amino acid, units obtained from at least one lactam, or units obtained from polycondensation of:

[0020] - at least one diamine, the diamine being preferably selected from linear or branched aliphatic diamines or mixtures thereof, and

[0021] - at least one dicarboxylic acid, the diacid being preferentially selected from linear or branched aliphatic diacids, or mixtures thereof, the diamine and the diacid comprising from 4 to 36 carbon atoms, advantageously from 6 to 18 carbon atoms; the 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 the 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 the compound B in the composition is greater than 65%, based on the total weight of the composition.

[0024] According to a preferred embodiment, the mass content of the compound B in the composition is greater than 65%, based on the total weight of the composition; and the 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 the compound B in the composition is at least 80%, based on the total weight of the composition; and the polymer A is a fluoropolymer A1.

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

[0027] According to another aspect, the present application relates to the use of a polymer A as defined in the present application as a stabilizer for an energetic composition, in particular a weeding, weed-killing or fertilizing composition; preferably, the polymer A is the fluoropolymer A1 and the composition preferably comprises a compound B as defined in the present application.

[0028] According to another aspect, the present application relates to the use of a polymer A, as defined in the present application, for desensitizing or sensitizing an energetic composition, said composition comprising a compound B having exothermic or volume expansion properties; said compound B being preferably as defined in the present application.

[0029] According to a preferred embodiment, the mass content of the polymer A in the composition is between 0.1 and 35 %, preferably between 1 and 30 %, in particular between 1 and 15 %, relative to the total weight of the composition; and the mass content of the compound B in the composition is preferably greater than 65 %, based on the total weight of the composition.

[0030] According to a preferred embodiment, the mass content of the compound B in the composition is greater than 65 %, based on the total weight of the composition; and the polymer A is a polyamide A2 or a polyamide-polyether block copolymer A3, or a mixture thereof, or the mass content of the compound B in the composition is at least 80 %, based on the total weight of the composition; and the polymer A is a fluoropolymer A1.

[0031] According to a preferred embodiment, the mass content of the polymer A in the composition is between 0.1 and 35 %, preferably between 1 and 30 %, in particular between 1 and 15 %, relative to the total weight of the composition; and the mass content of the compound B in the composition is preferably greater than 65 %, based on the total weight of the composition.

[0032] According to a preferred embodiment, the mass content of the compound B in the composition is greater than 65 %, based on the total weight of the composition; and the polymer A is a polyamide A2 or a polyamide-polyether block copolymer A3, or a mixture thereof, or the mass content of the compound B in the composition is at least 80 %, based on the total weight of the composition; and the polymer A is a fluoropolymer A1. BRIEF DESCRIPTION OF DRAWINGS

[0033] Figure 1 are graphs showing the differential scanning calorimetry of different comparative compositions or of a composition according to a particular embodiment of the present application.

[0034] Figure 2It is a graph showing the change of pressure with temperature for different comparative compositions or compositions according to a specific embodiment of the invention. Detailed Implementation

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

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

[0037] Preferably, the mass content of compound B in the composition is from 25% to 99.9% of the total weight of the composition. According to a preferred embodiment, the mass content of compound B in the composition is from 30% to 99.5% of the total weight of the composition, advantageously from 35% to 99%, preferably from 40% to 99%, more preferably from 50% to 95%. Preferably, based on the total weight of the composition, the mass content of compound B in the composition is greater than 65%, advantageously greater than 66%, preferably greater than 67%, more preferably greater than 68%, particularly greater than 69%, and even more particularly greater than 70%. Based on the total weight of the composition, the mass content of compound B in the composition is greater than 71%, advantageously 72%, preferably greater than 73%, more preferably greater than 74%, particularly greater than 75%, even more particularly greater than 76%, advantageously greater than 77%, preferably advantageously greater than 78%, preferably advantageously greater than 79%, more preferably advantageously greater than 80%, particularly advantageously greater than 81%, and even more particularly advantageously greater than 82%. Preferably, based on the total weight of the composition, the mass content of compound B in the composition may be greater than 83%, advantageously 84%, preferably greater than 85%, more preferably greater than 86%, particularly greater than 87%, even more particularly greater than 88%, advantageously greater than 89%, and preferably advantageously greater than 90%.

[0038] When the composition contains polyamide A2 or polyamide-polyether block copolymer A3 or a mixture thereof as polymer A, the mass content of compound B in the composition is greater than 65% based on the total weight of the composition. Advantageously, when the composition contains polyamide A2 or polyamide-polyether block copolymer A3 or a mixture thereof as polymer A, the mass content of compound B in the composition is greater than 70% based on the total weight of the composition. Preferably, when the composition contains polyamide A2 or polyamide-polyether block copolymer A3 or a mixture thereof as polymer A, the mass content of compound B in the composition is greater than 75% based on the total weight of the composition. More preferably, when the composition contains polyamide A2 or polyamide-polyether block copolymer A3 or a mixture thereof as polymer A, the mass content of compound B in the composition is greater than 80% based on the total weight of the composition. In particular, when the composition contains polyamide A2 or polyamide-polyether block copolymer A3 or a mixture thereof as polymer A, the mass content of compound B in the composition is greater than 85% based on the total weight of the composition. More specifically, when the composition comprises polyamide A2 or polyamide-polyether block copolymer A3 or a mixture thereof as polymer A, the mass content of compound B in the composition is greater than 90% based on the total weight of the composition. According to a preferred embodiment, when the composition consists of polymer A1 and compound B, and optionally poly(vinyl butyral), the mass content of compound B is one of the aforementioned mass contents, and the polymer A and optionally poly(vinyl butyral) form the remainder, i.e., less than 35% by weight, less than 30% by weight, less than 25% by weight, less than 20% by weight, or less than 15% by weight based on the total weight of the composition.

[0039] When polymer A is a fluoropolymer A1, the mass content of compound B in the composition is at least 70% of the total weight of the composition. Advantageously, when polymer A is a fluoropolymer A1, the mass content of compound B in the composition is at least 75% of the total weight of the composition. Preferably, when polymer A is a fluoropolymer A1, the mass content of compound B in the composition is at least 80% of the total weight of the composition. Specifically, when polymer A is a fluoropolymer A1, the mass content of compound B in the composition is at least 85% of the total weight of the composition. According to a preferred embodiment, when the composition consists of polymer A1 and compound B, and optionally poly(vinyl butyral), the mass content of compound B is one of the above-mentioned mass contents, and polymer A and optionally poly(vinyl butyral) form the remainder, i.e., less than 30% by weight, less than 25% by weight, less than 20% by weight, or less than 15% by weight based on the total weight of the composition.

[0040] The composition can be prepared by adding various ingredients in powder form in desired proportions. Alternatively, one or all of the ingredients can be in solution, and after mixing them, a drying step is performed to obtain the composition in powder form.

[0041] Depending on the nature of compound B present in the composition, the composition may be a weeding, fertilizing, or septic composition, or more generally, an energy-containing composition. An "energy-containing composition" refers to a composition in which compound B is an energy-containing substance, typically in the form of a solid crystalline powder, and may exhibit exothermic or thermally expanding properties depending on the conditions the compound is subjected to. Such energy-loaded substances are particularly found in compositions that can be used in fertilizers, fertilizing agents, herbicides, demolition, welding, or, for example, gas-generating or pyrotechnic substances.

[0042] In addition, the composition may contain other components, such as anti-caking agents, defoamers, hydrophobic agents, or corrosion inhibitors. According to one specific embodiment, the composition particularly comprises polyvinyl butyral, polyvinyl acetate, polybutadiene, polyurethane, thermoplastic elastomers, or polysulfides, or mixtures thereof.

[0043] Polymer A

[0044] As described above, the composition comprises polymer A. The latter may be a fluoropolymer A1, a polyamide A2, or a polyamide-polyether block copolymer A3, or a mixture thereof.

[0045] Fluoropolymer A1

[0046] According to a preferred embodiment, the fluoropolymer A1 comprises monomer units derived from monomers including: vinylidene fluoride, vinyl fluoride; trifluoroethylene (VF3); 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-m-dioxacyclopentene); perfluoro(2,2-dimethyl-1,3-m-dioxacyclopentene) (PDD); products of the formula CF2=CFOCF2CF(CF3)OCF2CF2X, where X is SO2F, CO2H, CH2OH, CH2OCN or CH2OPO3H; products of the formula CF2=CFOCF2CF2SO2F; products of the formula F(CF2)nCH2OCF=CF2, where n is 1, 2, 3, 4 or 5; products of the formula R 1 The product of CH2OCF=CF2, where R 1 It is hydrogen or F(CF2)m, and m is 1, 2, 3 or 4; Formula R2 Products with OCF=CH2, where R 2 It is F(CF2)p and p is 1, 2, 3 or 4; perfluorobutylethylene (PFBE); 3,3,3-trifluoropropylene and 2-trifluoromethyl-3,3,3-trifluoro-1-propylene, or mixtures thereof.

[0047] According to one embodiment, the fluoropolymer A1 is a homopolymer of vinylidene fluoride.

[0048] According to another embodiment, the fluoropolymer A1 is a copolymer of vinylidene fluoride and at least one comonomer compatible with vinylidene fluoride. The comonomer compatible with vinylidene fluoride may be halogenated (fluorinated, chlorinated, or brominated) or non-halogenated. Examples of suitable fluorinated comonomers are: vinyl fluoride, tetrafluoroethylene, hexafluoropropylene, trifluoropropylene, especially 3,3,3-trifluoropropylene, tetrafluoropropylene and especially 2,3,3,3-tetrafluoropropylene or 1,3,3,3-tetrafluoropropylene, hexafluoroisobutylene, perfluorobutylethylene, pentafluoropropylene, especially 1,1,3,3,3-pentafluoropropylene or 1,2,3,3,3-pentafluoropropylene, perfluoroalkyl vinyl ethers, especially those of the general formula Rf-O-CF-CF2, where Rf is an alkyl group, preferably C1 to C4 alkyl (preferred examples are perfluoropropyl vinyl ether and perfluoromethyl vinyl ether). The fluorinated comonomer may include chlorine or bromine atoms. It may be specifically selected from bromotrifluoroethylene, chlorofluoroethylene, chlorotrifluoroethylene, and chlorotrifluoropropylene. Chlorofluoroethylene may represent 1-chloro-1-fluoroethylene or 1-chloro-2-fluoroethylene. 1-chloro-1-fluoroethylene isomers are preferred. Chlorotrifluoropropylene is preferably 1-chloro-3,3,3-trifluoropropylene or 2-chloro-3,3,3-trifluoropropylene. The VDF copolymer may also contain non-halogenated monomers, such as ethylene and / or acrylic or methacrylic acid comonomers.

[0049] The fluoropolymer A1 preferably contains at least 50 mol% vinylidene fluoride, advantageously at least 60 mol% vinylidene fluoride, and more preferably at least 70 mol% vinylidene fluoride. The content of the comonomer may be 1 to 50% by weight of the fluoropolymer A1, advantageously 2 to 30%.

[0050] According to a preferred embodiment, the fluoropolymer A1 is a copolymer of vinylidene fluoride (VDF) and hexafluoropropylene (HFP) (P(VDF-HFP)), wherein the weight percentage of the hexafluoropropylene monomer unit is 2 to 30% of the weight of the fluoropolymer A1, advantageously 2 to 25%, preferably 2 to 20%, and most preferably 4 to 15%. According to another embodiment, the fluoropolymer A1 is a copolymer of vinylidene fluoride (VDF) and hexafluoropropylene (HFP) (P(VDF-HFP)), wherein the weight percentage of the hexafluoropropylene monomer unit is 10 to 30% of the weight of the fluoropolymer A1, advantageously 10 to 25%.

[0051] According to another preferred embodiment, the fluoropolymer A1 is a copolymer of vinylidene fluoride and tetrafluoroethylene (TFE).

[0052] According to another embodiment, the fluoropolymer A1 is a copolymer of vinylidene fluoride and chlorotrifluoroethylene (CTFE) containing at least 50 mol% vinylidene fluoride, advantageously at least 60 mol% vinylidene fluoride, and preferably at least 70 mol% vinylidene fluoride.

[0053] According to another embodiment, the fluoropolymer A1 is a VDF-TFE-HFP terpolymer. According to another embodiment, the fluoropolymer A1 is a VDF-TrFE-TFE terpolymer (TrFE being trifluoroethylene). In these terpolymers, the mass content of VDF is at least 10%, and the comonomers are present in variable proportions.

[0054] According to one embodiment, the fluoropolymer A1 comprises a monomer unit having at least one of the following functional groups: carboxylic acid, carboxylic anhydride, carboxylic ester, epoxy group (such as glycidyl group), amide, hydroxyl group, carbonyl group, mercapto group, sulfide, oxazoline, phenolic group, ester, ether, siloxane, sulfonic acid group, sulfate group, phosphoric acid group, or phosphonic acid group. This functional group is introduced by a chemical reaction, which may be a grafting or copolymerization of a vinylidene fluoride (VDF) monomer with a monomer having at least one of the said functional groups and a vinyl functional group capable of copolymerizing with the VDF monomer, performed according to techniques well known to those skilled in the art.

[0055] According to one embodiment, the functional group has a carboxylic acid functional group, which is a (meth)acrylic acid type group selected from acrylic acid, methacrylic acid, hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, and hydroxyethylhexyl (meth)acrylate. Therefore, the fluoropolymer A1 may comprise monomer units derived from monomers selected from acrylic acid, methacrylic acid, methyl acrylate, methyl methacrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, and hydroxyethylhexyl methacrylate.

[0056] According to one embodiment, the unit with the carboxylic acid functional group further includes heteroatoms selected from oxygen, sulfur, nitrogen, and phosphorus.

[0057] According to a preferred embodiment, the fluoropolymer A1 may be, for example, a copolymer of vinylidene fluoride and monomer M1', wherein monomer M1' is selected from acrylic acid, methacrylic acid, hydroxyethyl methacrylate, hydroxypropyl methacrylate, hydroxyethylhexyl methacrylate, and acryloyloxypropyl succinate. Preferably, the content of monomer M1' in the fluoropolymer A1 is from 0.01 mol% to 5 mol%. In this embodiment, at least 40% of the units derived from monomer M1' are distributed between two vinylidene fluoride units.

[0058] The content of functional groups in the fluoropolymer A1 is at least 0.01 mol%, preferably at least 0.1 mol%, and at most 15 mol%, preferably at most 10 mol%.

[0059] Fluoropolymer A1 preferably has a high molecular weight. As used herein, "high molecular weight" means having a molecular weight that meets the requirements of ASTM D-3835 method at 232°C and 100 seconds. -1 Fluoropolymer A1 with a melt viscosity greater than 100 Pa·s, preferably greater than 500 Pa·s, and more preferably greater than 1000 Pa·s as measured below.

[0060] According to one embodiment, the fluoropolymer A1 with functional groups can be crosslinked via the self-condensation of its functional groups or by reaction with a catalyst and / or crosslinking agent, such as melamine resins, epoxy resins, etc., and known low molecular weight crosslinking agents, such as di- or higher polyisocyanates, polyaziridinium, polycarbodiimide, polyoxazoline, dialdehydes such as glyoxal, acetoacetate, malonic acid esters, acetals, thiols and acrylates (which are di- and trifunctional), alicyclic epoxy molecules, organosilanes such as epoxysilanes and aminosilanes, urethanes, diamines and triamines, inorganic chelating agents such as certain zinc salts and zirconium salts, titanium, glycourea and other amino plastics. In some cases, functional groups derived from other polymerizing components such as surfactants, initiators or seed particles may participate in the crosslinking reaction. When two or more functional groups participate in the crosslinking process, the complementary reactive group pairs are, for example, hydroxy-isocyanate, acid-epoxy, amine-epoxy, hydroxy-melamine, and acetoacetate-acid. The acrylate and / or methacrylate monomers, which do not contain functional groups capable of participating in the crosslinking reaction after polymerization, should preferably account for 70% by weight or more, more preferably greater than 90% by weight of the total monomer mixture. According to one embodiment, the fluoropolymer A1 comprises a crosslinking agent selected from isocyanates, diamines, adipic acid, dihydrazides, and combinations thereof.

[0061] According to another embodiment, the fluoropolymer A1 can be mixed with a hydrophilic polymer A1''. The polymer A1'' comprises a compound derived from the formula R... 1 R 2 C=C(R 3 The monomeric unit M1'' of C(O)R, wherein the substituent R 1 R 2 and R 3 Independently selected from H and C1-C5 alkyl groups; R selected from -NHC(CH3)2CH2C(O)CH3 or –OR', wherein R' is selected from H and optionally substituted C1-C 18 Alkyl group: a five- or ten-membered heterocycle containing at least one nitrogen atom in its ring chain or a –OH group. The heterocycle may be saturated, unsaturated, or aromatic. The heterocycle may be monocyclic or bicyclic. The heterocycle may be pyrrole, pyrrolidine, pyridine, piperidine, pyrimidine, pyrazine, 1,4-dihydropyridine, indole, hydroxyindole, indigo, quinoline, isoquinoline, quinazoline, imidazoline, pyrazolidine, 2-pyrrolidone, δ-lactam, succinimide, 2-imidazolidinone, or 4-imidazolidinone ring. The heterocycle may be substituted with one or more C1-C5 alkyl groups. As described above, C1-C 18 The alkyl group is optionally replaced by the heterocycle. The latter can be bonded to the alkyl chain via a nitrogen atom or any other atom that forms the heterocycle. Preferably, the heterocycle is a 2-pyrrolidone, a δ-lactam, a succinimide, a 2-imidazolidineone, or a 4-imidazolidineone.

[0062] Preferably, the polymer A1'' comprises a derivative of formula R 1 R 2 C=C(R 3 The monomer unit of (meth)acrylate alkyl ester monomer M1'' of C(O)R, wherein the substituent R 1 R 2 and R 3 Independently selected from H and C1-C5 alkyl groups; R selected from -NHC(CH3)2CH2C(O)CH3 or -OR', wherein R' is selected from C1-C groups optionally substituted with the following... 18 Alkyl: a five- or ten-membered heterocycle containing one or more -OH groups or at least one nitrogen atom in its ring chain. Preferably, the heterocycle is as defined above; in particular, the heterocycle is 2-pyrrolidone, δ-lactam, succinimide, 2-imidazolium ketone, or 4-imidazolium ketone. The term "(meth)acrylate alkyl ester" includes alkyl acrylate and alkyl methacrylate. According to a preferred embodiment, the substituent R' is selected from H, methyl, ethyl, propyl, n-butyl, isobutyl, tert-butyl, n-dodecyl, pentyl, isopentyl, hexyl, 2-ethylhexyl, lauryl, n-octyl, hydroxybutyl, hydroxypropyl, and ethyl, which are substituted with ureido, hydroxyethyl, hydroxypropyl, or hydroxybutyl.

[0063] Specifically, the polymer P1'' contains a derivative of formula R 1 R 2 C=C(R 3 The monomer unit of (meth)acrylate alkyl ester monomer M1'' of C(O)R, wherein the substituent R 1 and R 2 It is H; R 3 It is H or CH3; R is -OR', where R' is selected from H, methyl, ethyl, propyl, n-butyl, isobutyl, tert-butyl, hydroxypropyl, hydroxybutyl, 2-pyrrolidone, δ-lactam, succinimide, 2-imidazolidineone or 4-imidazolidineone.

[0064] Therefore, (meth)acrylate alkyl esters can be methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, n-dodecyl acrylate, pentyl acrylate, isoamyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, diacetone acrylamide, lauryl acrylate, n-octyl acrylate, hydroxypropyl methacrylate, hydroxybutyl acrylate, methacrylic acid, methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, tert-butyl methacrylate, n-dodecyl methacrylate, pentyl methacrylate, isoamyl methacrylate, hexyl methacrylate, 2-ethylhexyl methacrylate, lauryl methacrylate, n-octyl methacrylate, urea methacrylate, and mixtures thereof. Preferably, alkyl acrylates have 1 to 8 carbon atoms, more preferably alkyl acrylates have 1 to 5 carbon atoms. These compounds can be used alone or as mixtures of two or more. Therefore, the polymer P1'' can be a homopolymer of monomer M1'' as defined above or a copolymer derived from a mixture of one or more monomers M1'' as defined above.

[0065] The term "acrylate" here encompasses both acrylates and methacrylates.

[0066] The monomer M1'' can be copolymerized with an olefinically unsaturated compound, which can be copolymerized with alkyl acrylates and alkyl methacrylates, for example:

[0067] -(A) Alkenyl compounds containing functional groups, and

[0068] -(B) Alkenyl compounds that do not have functional groups.

[0069] Alkenyl compounds (A) containing functional groups include, for example, α,β-unsaturated carboxylic acids such as acrylic acid, methacrylic acid, fumaric acid, crotonic acid, itaconic acid, etc.; vinyl ester compounds such as vinyl acetate, vinyl neodecanoate, etc.; acrylamide, methacrylamide, N-methacrylamide, N-methylmethacrylamide, N-hydroxymethylacrylamide, N-alkylacrylamide, N-alkylmethylacrylamide, N,N-dialkylacrylamide, N,N-dialkylmethylacrylamide, etc. Amide compounds such as acetone acrylamide; acrylates, such as 2-hydroxyethyl acrylate, N-dialkylaminoethyl acrylate, glycidyl acrylate, n-dodecyl acrylate, fluoroalkyl acrylate, etc.; and methacrylates, such as dialkylaminoethyl methacrylate, fluoroalkyl methacrylate, 2-hydroxyethyl methacrylate, n-octyl methacrylate, tert-butyl methacrylate, glycidyl methacrylate, ethylene glycol dimethacrylate, etc.; maleic anhydride and alkenyl glycidyl ether compounds such as allyl glycidyl ether, etc. Among these, acrylic acid, methacrylic acid, itaconic acid, fumaric acid, N-hydroxymethylacrylamide, N-hydroxymethylmethacrylamide, diacetone acrylamide, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, and allyl glycidyl ether are preferred. These compounds can be used alone or as a mixture of two or more.

[0070] Alkenyl compounds (B) that do not contain functional groups include, for example, conjugated dienes such as 1,3-butadiene, isoprene, etc.; divinyl hydrocarbon compounds such as divinylbenzene, etc.; and alkenyl cyanides such as acrylonitrile, methacrylonitrile, etc. Among these, 1,3-butadiene and acrylonitrile are preferred compounds. These compounds can be used alone or as a mixture of two or more.

[0071] Preferably, the proportion of the functional alkenyl compound (A) used is less than 50% by weight relative to the weight of the monomer mixture, and the proportion of the alkenyl compound (B) without functional groups used is less than 30% by weight relative to the weight of the monomer mixture.

[0072] According to certain embodiments, polymers A1 and A1'' are bio-based compounds. The term "bio-based" means "produced from biomass." This allows for an improvement in the composition's ecological footprint. Bio-based vinylidene fluoride is characterized by a content of at least 1 atomic percent of renewable carbon (i.e., carbon derived from biological material or biomass and of natural origin) as determined by the content of 14C according to standard NFEN 16640. The term "renewable carbon" indicates that the carbon is of natural origin and derived from biological material (or derived from biomass), as shown below. According to certain embodiments, the bio-carbon content of 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 copolymers and homopolymers of vinylidene fluoride used in this invention can be obtained by known polymerization methods (such as emulsion or suspension polymerization). According to one embodiment, they are prepared by emulsion polymerization in the absence of fluorinated surfactants.

[0074] The polymerization of vinylidene fluoride preferably produces a latex, which typically has a weight solids content of 10 to 60%, preferably 10 to 50%, and a weight-average particle size of less than 1 micrometer, preferably less than 1000 nanometers, more preferably less than 800 nanometers, and even more preferably less than 600 nanometers. The weight-average particle size is typically 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 can form aggregates with a weight-average size of 1 to 30 micrometers, preferably 2 to 20 micrometers. During formulation and application to a substrate, the aggregates can be broken down into discrete particles.

[0075] When the fluoropolymer A1 is mixed with the polymer P1'', the weight content of polymer A1 is at least 50%, advantageously at least 60%, preferably at least 70%, more preferably at least 80%, and particularly at least 90%, based on the total weight of polymers A1 and P1'' in the composition.

[0076] Polyamide A2

[0077] The term "polyamide" as used in this specification encompasses both homopolymers and copolymers. Preferably, the polyamide A2 is a semi-crystalline aliphatic polyamide. The polyamide A2 may be obtained by the polycondensation of at least one lactam, or by the polycondensation of at least one amino acid, or by the polycondensation of at least one diamine X with at least one dicarboxylic acid Y.

[0078] When the polyamide A2 is obtained by polycondensation of at least one lactam, it may contain a single lactam or several lactams.

[0079] When the polyamide A2 is obtained by polycondensation of at least one lactam, the at least one lactam is selected from C6 to C6. 18 lactams, preferably C8 to C9 12 lactam, more preferably C 10 To C 12 Lactam.

[0080] Advantageously, the polyamide A2 is obtained by the condensation polymerization of a single lactam, and the lactam may be particularly selected from autolactam, lauryllactam and undecyllactam, with lauryllactam being advantageous.

[0081] When the polyamide A2 is obtained by polycondensation of at least one amino acid, the at least one amino acid may be selected from C6 to C6. 18 Amino acids, preferably C 10 To C 18 Amino acids, preferably C 10 To C 12 Amino acids.

[0082] C6 to C 12 Amino acids, particularly 6-aminohexanoic acid, 9-aminononanoic acid, 10-aminodecanoic acid, 10-aminoundecanoic acid, 12-aminododecanoic acid and 11-aminoundecanoic acid and their derivatives, especially N-heptyl-11-aminoundecanoic acid.

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

[0084] Advantageously, the polyamide A2 is obtained by the condensation polymerization of a single amino acid, and the amino acid is selected from 11-aminoundecanoic acid and 12-aminododecanoic acid, advantageously 11-aminoundecanoic acid.

[0085] When the polyamide A2 is obtained by polycondensation of at least one diamine X and at least one diacid Y, the diamine is C4-C. 36 C6-C is preferred. 18 C6-C is preferred. 12 C, more preferably 10 -C 12 At least one diacid Y is C4-C 36 C6-C is preferred. 18 C6-C is preferred. 12 More preferably C8-C 12 Furthermore, the at least one diamine X is an aliphatic diamine and the at least one diacid Y is an aliphatic diacid.

[0086] Diamines can be linear or branched. Advantageously, they are linear.

[0087] The at least one C4-C 36 Diamine X may be specifically selected from 1,4-butanediamine, 1,5-pentamethylenediamine, 1,6-hexamethylenediamine, 1,7-heptamethylenediamine, 1,8-octamethylenediamine, 1,9-nonamethylenediamine, 1,10-decamethylenediamine, 1,11-undecamethylenediamine, 1,12-dodecanediamine, 1,13-tetridemethylenediamine, 1,14-tetradecanemethylenediamine, 1,16-hexadecanemethylenediamine, and 1,18-octadecanemethylenediamine, octadecenediamine, eicosanediamine, docosanediamine, and diamines obtained from fatty acids.

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

[0089] Advantageously, the at least one C6 to C 12 Diamine X is specifically selected from 1,6-hexamethylenediamine, 1,7-heptamethylenediamine, 1,8-octamethylenediamine, 1,9-nonamethylenediamine, 1,10-decamethylenediamine, 1,11-undecamethylenediamine, and 1,12-dodecanediamine.

[0090] Advantageously, the diamine X used is C 10 To C 12 Diamines, particularly those selected from 1,10-decamethylenediamine, 1,11-undecamethylenediamine, and 1,12-dodecimethylenediamine.

[0091] The at least one dicarboxylic acid Y is C4-C 36 Dicarboxylic acids, and may be selected from succinic acid, glutaric acid, adipic acid, octanoic acid, azelaic acid, sebacic acid, undecanoic acid, dodecanoic acid, tridecanoic acid, tetradecanoic acid, pentadecanoic acid, hexadecanoic acid, heptadecanoic acid, octadecanoic acid, and diacids obtained from fatty acids.

[0092] Dicarboxylic acids can be linear or branched. Advantageously, they are linear.

[0093] Advantageously, the at least one dicarboxylic acid Y is C6-C. 18 Dicarboxylic acids, including octanoic acid, azelaic acid, sebacic acid, undecanoic acid, dodecanoic acid, tridecanoic acid, tetradecanoic acid, pentadecanoic acid, hexadecanoic acid, heptadecanic acid, and octadecanoic acid.

[0094] Advantageously, the at least one dicarboxylic acid Y is C6-C. 12 Dicarboxylic acids, including succinic acid, octanoic acid, azelaic acid, sebacic acid, undecanoic acid, and dodecanoic acid.

[0095] Advantageously, the semi-crystalline aliphatic polyamide has an average number of carbon atoms relative to nitrogen atoms greater than or equal to 6.

[0096] Advantageously, the at least one dicarboxylic acid Y is C8-C. 12 Dicarboxylic acids selected from octanoic acid, azelaic acid, sebacic acid, undecanoic acid, and dodecanoic acid.

[0097] Advantageously, the at least one semi-crystalline aliphatic polyamide is composed of at least one C7 to C8 group. 18 Amino acids (preferably C7 to C4) 12 C is preferred 10 To C 12 or at least one C7 to C 18 lactams (preferably C7 to C1) 12 C is preferred 10 To C 12 ) is obtained through condensation polymerization.

[0098] More advantageously, the semi-crystalline aliphatic polyamide has an average number of carbon atoms relative to nitrogen atoms greater than or equal to 8.

[0099] Specifically, the semi-crystalline aliphatic polyamides have an average carbon number of 8 to 14 relative to nitrogen atoms.

[0100] Advantageously, the polyamide A2 is selected from PA510, PA512, PA514, PA610, PA612, PA1010, PA1012, PA1212, PA11 and PA12, especially PA1010, PA1012, PA1212, PA11 and PA12.

[0101] Even more advantageously, the semi-crystalline aliphatic polyamide has an average number of carbon atoms relative to nitrogen atoms greater than or equal to 9.

[0102] Specifically, the semi-crystalline aliphatic polyamides have an average carbon number of 9 to 14 relative to nitrogen atoms.

[0103] More advantageously, the semi-crystalline aliphatic polyamide has an average number of carbon atoms relative to nitrogen atoms greater than or equal to 10.

[0104] Specifically, the semi-crystalline aliphatic polyamides have an average number of carbon atoms relative to nitrogen atoms of 10 to 14.

[0105] Advantageously, the semi-crystalline polyamide is selected from PA11 and PA12, more particularly PA11.

[0106] In the case of PA-XY type homopolymers, the number of carbon atoms per nitrogen atom is the average of that of unit X and unit Y.

[0107] In the case of copolyamides, the number of carbon atoms per nitrogen atom is calculated using the same principle. For different amide units, the calculation is performed in molar proportions.

[0108] When the polyamide A2 is obtained by polycondensation of at least one diamine X and at least one dicarboxylic acid Y, it may therefore contain a single diamine or several diamines and a single dicarboxylic acid or several dicarboxylic acids.

[0109] In one embodiment, the polyamide A2 is obtained by the polycondensation of a single diamine X and a single dicarboxylic acid Y.

[0110] Advantageously, the semi-crystalline aliphatic polyamide is selected from PA10, PA11, PA12, PA1010 and PA1012, especially PA11 and PA12.

[0111] Advantageously, semi-crystalline polyamides are partially or fully bio-based.

[0112] Polyamide-polyether block copolymer A3

[0113] The polyamide-polyether block copolymer is a copolymer containing amide units (Ba1) and polyether units (Ba2), wherein the amide units (Ba1) correspond to aliphatic repeating units selected from units obtained from at least one amino acid, units obtained from at least one lactam, or units obtained by polycondensation of the following:

[0114] - At least one diamine, preferably selected from straight-chain or branched aliphatic diamines or mixtures thereof, and

[0115] - At least one dicarboxylic acid, preferably selected from:

[0116] Straight-chain or branched aliphatic diacids or mixtures thereof,

[0117] The diamine and the diacid contain 4 to 36 carbon atoms, advantageously 6 to 18 carbon atoms;

[0118] The polyether unit (Ba2) is specifically derived from at least one polyalkylene ether polyol, particularly polyalkylene ether diol.

[0119] Copolymer A3 is specifically derived from the cocondensation of polyamide blocks with reactive ends and polyether blocks with reactive ends, for example:

[0120] 1) Polyamide blocks with diamine chain ends and polyoxyethylene blocks with dicarboxylic acid chain ends.

[0121] 2) Polyamide blocks with dicarboxylic acid chain ends and polyoxyethylene blocks with diamine chain ends are obtained by cyanoethylation and hydrogenation of aliphatic α,ω-dihydroxylated polyoxyethylene blocks called polyalkylene ether glycols (polyether glycols).

[0122] 3) Polyamide blocks with dicarboxylic acid chain ends and polyether glycols, in this particular case, yield a polyether ester amide. The copolymers of the present invention are advantageously of this type.

[0123] Polyamide blocks with dicarboxylic acid chain ends originate from, for example, the condensation of a polyamide precursor in the presence of a chain-restricted dicarboxylic acid.

[0124] Polyamide blocks with diamine chain ends originate from, for example, the condensation of a polyamide precursor in the presence of a chain-restricted diamine.

[0125] Copolymers containing polyamide and polyether blocks may also contain randomly distributed units. These polymers can be prepared by the simultaneous reaction of polyether and polyamide block precursors.

[0126] For example, polyether glycols, polyamide precursors, and chain-restricted diacids can be reacted. The resulting polymers essentially have polyether and polyamide blocks of highly variable length, but also have different reactants that react randomly, distributed (statistically) along the polymer chain.

[0127] It can also react polyether diamines, polyamide precursors, and chain-restricted diacids. The resulting polymers are essentially polyether and polyamide blocks of highly variable length, but also contain different reactants that react randomly, which are distributed randomly (statistically) along the polymer chain.

[0128] Amide unit (Ba1): The amide unit (Ba1) corresponds to the aliphatic repeating unit as defined above. Advantageously, the amide unit (Ba1) is selected from polyamide 11, polyamide 12, polyamide 610, polyamide 612, polyamide 1010, polyamide 1012, and especially polyamide 11. More advantageously, the amide unit (Ba1) is selected from polyamide 11 and polyamide 12.

[0129] Polyether unit (Ba2):

[0130] The polyether units are specifically 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 consist of at least one polyalkylene ether polyol. In this embodiment, the term "at least one polyalkylene ether polyol" means that the polyether unit is composed of alcohol chain ends, and therefore cannot be a polyether diamine triblock type compound. Advantageously, the polyether unit (Ba2) is selected from polyethylene glycol (PEG), polypropylene glycol (PPG), polytrimethylene glycol (PO3G), polytetramethylene glycol (PTMG) and mixtures thereof or copolymers thereof, especially PTMG. The number average molecular weight (Mn) of the polyether block is advantageously from 200 to 4000 g / mol, preferably from 250 to 2500 g / mol, and particularly from 300 to 1100 g / mol.

[0131] Copolymer A3 can be prepared by the following method, according to which:

[0132] - In the first step, polyamide blocks (Ba1) are prepared by polycondensation in the presence of a chain restrictor selected from dicarboxylic acids:

[0133] One or more lactams, or

[0134] One or more amino acids, or

[0135] One or more diamines and one or more dicarboxylic acids; and, where appropriate, one or more comonomers selected from lactams and α,ω-aminocarboxylic acids; then

[0136] - In the second step, the obtained polyamide block (Ba1) is reacted with the polyether block (Ba2) in the presence of a catalyst.

[0137] A two-step general method for preparing the copolymers of the present invention is known and described, for example, in French Patent FR 2 846332 and European Patent EP 1 482 011. The reaction for forming the blocks (Ba1) is typically carried out between 180°C and 300°C, preferably between 200°C and 290°C, and the pressure in the reactor is established between 5 bar and 30 bar and maintained for about 2 to 3 hours. The pressure is slowly reduced while the reactor is restored to atmospheric pressure, and then excess water is distilled off, for example, over one or two hours. Once the polyamide with carboxylic acid end groups is prepared, the polyether and catalyst are then added. The polyether can be added once or in multiple steps, as can the catalyst. In an advantageous form, the polyether is added first; the reaction between the OH end groups of the polyether and the COOH end groups 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, and then the catalyst is introduced to complete the connection of the polyamide and polyether blocks. This second step is carried out under stirring, preferably under a vacuum of at least 15 mmHg (2000 Pa), at a temperature that allows the reactants and the resulting copolymer to be in molten form. For example, this temperature can be between 100 and 400°C, more typically between 200 and 300°C. The reaction is monitored by measuring the torque applied to the stirrer by the molten polymer or by measuring the electrical power consumed by the stirrer. The termination of the reaction is determined by the target torque or power value. One or more molecules acting as antioxidants, such as Irganox® 1010 or Irganox® 245, may also be added during the synthesis process at what is considered the most suitable time.

[0138] Another approach to preparing copolymer A3 could be considered, such that all monomers are added at the outset (i.e., in a single step) to allow for the following polycondensation:

[0139] - One or more lactams, or

[0140] - One or more amino acids, or

[0141] One or more diamines and one or more dicarboxylic acids; and, where appropriate, one or more other polyamide comonomers;

[0142] - In the presence of a chain restrictor selected from dicarboxylic acids;

[0143] -In the presence of the (Ba2)(polyether) block;

[0144] - In the presence of a catalyst for the reaction between the flexible (Ba2) block and the (Ba1) block.

[0145] Advantageously, the dicarboxylic acid is used as a chain limiting agent and is introduced in excess relative to the stoichiometric amount of the diamine.

[0146] Advantageously, derivatives of metals selected from titanium, zirconium, and hafnium, or strong acids such as phosphoric acid, hypophosphoric acid, or boric acid are used as catalysts.

[0147] Polycondensation can be carried out at temperatures between 240 and 280°C.

[0148] Generally, known copolymers containing ether and amide units consist of semi-crystalline, linear aliphatic polyamide blocks. In one embodiment, copolymer A3 has a flexural modulus of less than 200 MPa, particularly less than 100 MPa, as measured at 23°C according to standard ISO 178:2010. In another embodiment, copolymer A3 has a density greater than or equal to 1, as measured according to ISO 1183-3:1999.

[0149] Compound B

[0150] As described above, the composition comprises compound B.

[0151] According to a preferred embodiment, compound B has an oxygen balance OB of less than 60, the oxygen balance being given by the formula OB(%) =

[1600] . The value is determined by (d-2a-(b / 2)] / M, where a, b, and d are the number of carbon, hydrogen, and oxygen atoms in compound B, respectively, and M is the molar mass of compound B.

[0152] The oxygen balance, expressed as a mass percentage, represents the concentration of oxygen contained in compound B. It is defined as the amount of oxygen available after the oxidation of hydrogen, carbon, and metals (which may be present to produce water, carbon dioxide, and optional metal oxides). If the oxygen balance is positive, compound B is an oxidizing agent and is therefore rich in oxygen. Conversely, a negative oxygen balance indicates the presence of a small amount of oxygen. The oxygen balance is zero when there is sufficient oxygen specifically for the production of CO2 and H2O, as well as metal oxides, without excess.

[0153] Advantageously, the oxygen balance of compound B is less than 58%, preferably less than 56%, more preferably less than 54%, particularly less than 52%, and even more particularly less than 50%.

[0154] According to a preferred embodiment, the oxygen balance of compound B is greater than -260%, advantageously greater than -225%, preferably greater than -200%, more preferably greater than -175%, particularly greater than -150%, even more particularly greater than -125%, and advantageously greater than -100%.

[0155] Therefore, the oxygen balance of compound B can be less than 60%, advantageously less than 58%, preferably less than 56%, more preferably less than 54%, particularly less than 52%, and even more particularly less than 50%; and greater than -260%, advantageously greater than -225%, preferably greater than -200%, more preferably greater than -175%, particularly greater than -150%, even more particularly greater than -125%, and advantageously greater than -100%.

[0156] According to a preferred embodiment, compound B contains at least one functional group selected from the following: -NO2, NO3. - -ON=O, -N=N-, -N - =N + N - -,NX3, where X is a halogen, -C=NO-,ClO3 - ClO4 - -OO-, -O3- and -C≡C - Mt + Mt is a transition metal. The transition metal can be a metal from column 3 to column 11 of the periodic table. Preferably, compound B contains at least one element selected from -NO2 and NO3. - -ON=O, -N=N-, -N - =N + N - -, ClO3 - ClO4 - Functional groups of -OO- and -O3-.

[0157] According to a particularly preferred embodiment, the oxygen balance of compound B is less than 60%, advantageously less than 58%, preferably less than 56%, more preferably less than 54%, particularly less than 52%, and even more particularly less than 50%; and the compound contains at least one functional group selected from the group consisting of -NO2, NO3. - -ON=O, -N=N-, -N - =N + N - -,NX3, where X is a halogen, -C=NO-,ClO3 - ClO4 - -OO-, -O3- and -C≡C - Mt + Mt is a transition metal. Preferably, the oxygen balance of compound B is less than 60%, advantageously less than 58%, preferably less than 56%, more preferably less than 54%, particularly less than 52%, and even more particularly less than 50%; and the compound contains at least one component selected from -NO2, NO3. - -ON=O, -N=N-, -N -=N + N - -, ClO3 - ClO4 - Functional groups of -OO- and -O3-.

[0158] According to a more particularly preferred embodiment, the oxygen balance of compound B is less than 60%, advantageously less than 58%, preferably less than 56%, more preferably less than 54%, particularly less than 52%, and even more particularly less than 50%; and greater than -260%, advantageously greater than -225%, preferably greater than -200%, more preferably greater than -175%, particularly greater than -150%, even more particularly greater than -125%, and advantageously greater than -100%; and the compound contains at least one functional group selected from the group consisting of -NO2, NO3. - -ON=O, -N=N-, -N - =N + N - -,NX3, where X is a halogen, -C=NO-,ClO3 - ClO4 - -OO-, -O3- and -C≡C - Mt + Mt is a transition metal. Preferably, the oxygen balance of compound B is less than 60%, advantageously less than 58%, preferably less than 56%, more preferably less than 54%, particularly less than 52%, and even more particularly less than 50%; and greater than -260%, advantageously greater than -225%, preferably greater than -200%, more preferably greater than -175%, particularly greater than -150%, even more particularly greater than -125%, advantageously greater than -100%; and the compound contains at least one component selected from -NO2, NO3. - -ON=O, -N=N-, -N - =N + N - -, ClO3 - ClO4 - Functional groups of -OO- and -O3-.

[0159] As described above, compound B is preferably a fertilizer, insecticide, or oxidizing compound, or more generally an energy-containing compound. Therefore, in a preferred embodiment, compound B is selected from formula M. + X - The salt, wherein M is selected from Li, Na, K and NH4; and X is selected from nitrate anion, chlorate anion and perchlorate anion. Compound B may be ammonium nitrate, potassium nitrate, potassium chlorate, sodium chlorate, sodium perchlorate, potassium perchlorate, ammonium chlorate or ammonium perchlorate.

[0160] use

[0161] As described in this application, the polymer A according to the present invention can be used in various fields.

[0162] According to a preferred embodiment, polymer A is used as a stabilizer in an energy-containing composition. Preferably, polymer A is used as a stabilizer in a weeding, scavenging, or fertilizing composition. In this case, polymer A is as defined in this invention, and polymer A is preferably the fluoropolymer A1, polyamide A2, or polyamide-polyether block copolymer A3, or a mixture thereof.

[0163] According to another embodiment, the present invention relates to the use of polymer A for desensitizing or sensitizing an energy-containing composition, said polymer A as defined herein, and said energy-containing composition comprising compound B having exothermic or volume expansion properties; said compound B preferably as defined herein. Preferably, polymer A1 is used to desensitize an energy-containing composition comprising compound B having exothermic or volume expansion properties; said compound B preferably as defined herein. Alternatively, the polyamide-polyether block copolymer A3 or the polyamide A2 is used to sensitize an energy-containing composition comprising compound B having exothermic or volume expansion properties; said compound B preferably as defined herein.

[0164] According to another embodiment, the present invention relates to a method for reducing or increasing the thermal response of an energy-containing composition, the method comprising adding a polymer A as defined in the present invention to the composition, the composition comprising a compound B having exothermic or volume expansion properties; the compound B is preferably as defined in the present invention. Preferably, the method is for reducing the thermal response of an energy-containing composition, the method comprising adding a polymer A1 as defined in the present invention to the composition, the composition comprising a compound B having exothermic or volume expansion properties; the compound B is preferably as defined in the present invention. Alternatively, the method is for increasing the thermal response of an energy-containing composition, the method comprising adding the polyamide-polyether block copolymer A3 or the polyamide A2 as defined in the present invention to the energy-containing composition, the composition comprising a compound B having exothermic or volume expansion properties; the compound B is preferably as defined in the present invention.

[0165] Example

[0166] DSC measurement

[0167] The prepared mixture (approximately 5 mg) was introduced into a 120 μL stainless steel test cell with a pressure resistance of at least 150 bar, and the cell was closed using a suitable press or crimping tool with a suitable seal (silver, graphite, or nickel) to ensure the apparatus was airtight. The thermal stability of the mixture was characterized using DSC with a DSC111 Sensys calorimeter sold by KEP-Setaram. The sample was subjected to a heating ramp between ambient temperature and 400°C at a rate of 5°C / min. Therefore, the heat flux exchange was recorded as a function of temperature. Integrating the DSC signal allowed the total energy of the thermal phenomena to be obtained. The level of the heat flux and the shape of the peaks allowed for the assessment of the stable or unstable properties of the compound.

[0168] Different samples containing polymer and ammonium nitrate were subjected to differential scanning calorimetry. Test samples were prepared by mixing 5% polymer with every 95% by weight of ammonium nitrate. Examples 1 and 2 were performed using fluoropolymers according to the invention. In Example 1, the fluoropolymer used was a poly(vinylidene fluoride) homopolymer. In Example 2, the fluoropolymer used was a copolymer of vinylidene fluoride and hexafluoropropylene (hexafluoropropylene was between 20% and 25% by weight). Comparative Example 3 was performed in the presence of polyvinyl butyral. Ammonium nitrate and polyvinyl butyral were sieved to 400 micrometers. The reference example contained 100% ammonium nitrate. Example 4 contained a polyamide-polyether block copolymer (PEBAX®ES 1745).

[0169] from Figure 1 As can be seen, the peak profiles obtained in the examples according to the present invention are very different from those in the comparative examples. The shape of the peaks indicates the potential reaction rate of ammonium nitrate under thermal action. Compared with the composition in which ammonium nitrate is mixed with polyvinyl butyral (Example 3), ammonium nitrate is greatly stabilized in the presence of the fluoropolymer according to the present invention (Examples 1, 2 and 4).

[0170] The pressure changes of these compositions over time were also evaluated. The samples were subjected to a heating ramp of 2–4°C / min in an open glass unit within a closed pressure chamber. The temperature of the samples and the chamber, as well as the pressure within the chamber, were measured over time. The results are presented in… Figure 2 The curves obtained in Examples 1, 2, and 4 show that fluoropolymers A1 and A3 stabilize ammonium nitrate because the pressure increase is less than that of polyvinyl butyral (Example 3). For a given temperature, the pressure increase of the polymers according to the invention is smaller. Furthermore, from... Figure 2 As can be seen, the polymer (polyamide-polyether block copolymer) according to Example 4 has a greater ability to generate a blowing effect. This is advantageous in applications such as airbags, because the greater blowing effect allows the airbag to inflate more quickly.

Claims

1. A composition in powder form comprising a polymer A and a compound B, said compound B comprising at least one functional group selected from the group consisting of: -NO2, NO3 - -ON=O, -N=N-, -N - =N + N - -, NX3 wherein X is halogen, -C=N-O-, CIO3 - , CIO4 - , -O-O-, -O3- and -C≡C - Mt + wherein Mt is a transition metal, characterized in that: - said polymer A is a fluoropolymer A1, a polyamide A2 or a polyamide-polyether block copolymer A3 or a mixture thereof, and - said compound B has an oxygen balance OB of less than 60, said oxygen balance being determined by the formula OB (%) = [1600 (d - 2a - (b / 2)) / M, wherein a, b and d are the number of atoms of carbon, hydrogen and oxygen in compound B, respectively, and M is 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. The composition according to any one of the preceding claims, characterized in that, The compound B has a molar mass of less than 1000 g.mol -1 -1.

4. The composition according to any one of the preceding claims, characterized in that, The 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. The composition according to any one of the preceding claims, characterized in that, said composition further comprises a poly(vinyl butyral).

6. The composition according to any of the preceding claims 1 and 3 to 5, characterized in that, The polymer A is the fluorine-containing polymer A1 comprising monomeric units derived from vinylidene fluoride and optionally monomeric units of a monomer selected from the group consisting of fluoroethylene; trifluoroethylene (VF3); chlorotrifluoroethylene (CTFE); 1,2-difluoroethylene; tetrafluoroethylene (TFE); hexafluoropropylene (HFP); perfluoro(alkyl vinyl) ethers such as perfluoro(methyl vinyl) ether (PMVE), 5 perfluoro(ethyl vinyl) ether (PEVE) and perfluoro(propyl vinyl) ether (PPVE); perfluoro(1,3-dioxolane); perfluoro(2,2-dimethyl-1,3-dioxolane) (PDD); products of the formula CF2=CFOCF2CF(CF3)OCF2CF2X, wherein X is SO2F, CO2H, CH2OH, CH2OCN or CH2OPO3H; products of the formula CF2=CFOCF2CF2SO2F; products of the formula F(CF2)nCH2OCF=CF2, wherein n is 1, 2, 3, 4 or 5; products of the formula R 1 CH2OCF=CF2, wherein R 1 is hydrogen or F(CF2)m, and m is 1, 2, 3 or 4; products of the formula R 2 OCF=CH2, wherein 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-1 -propene, or mixtures thereof.

7. Composition according to the preceding claim, characterized in that, said fluoropolymer A1 is selected from a vinylidene fluoride homopolymer or a copolymer comprising monomer units derived from vinylidene fluoride and monomer units derived from a monomer selected from the group consisting of trifluoroethylene, chlorotrifluoroethylene, 1,2-difluoroethylene, tetrafluoroethylene, hexafluoropropylene, or a mixture thereof.

8. The composition according to any of the preceding claims 7 and 8, characterized in that, said fluoropolymer A1 comprises at least 50 mol% of monomer units derived from vinylidene fluoride.

9. The composition according to any of the preceding claims 1 - 5, characterized in that, said polymer A3 is a polyamide-polyether block copolymer which is a copolymer having amide units (Ba1 ) and polyether units (Ba2), said amide units (Ba1 ) corresponding to aliphatic repeating units selected from units obtained from at least one amino acid, units obtained from at least one lactam, or units obtained from polycondensation of: - at least one diamine, said diamine being preferably selected from linear or branched aliphatic diamines or a mixture thereof, and - at least one dicarboxylic acid, said diacid being preferably selected from linear or branched aliphatic diacids, 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) are 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 the polymer A in the 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. The composition according to any one of the preceding claims, characterized in that, The mass content of the compound B in the composition is greater than 65% based on the total weight of the composition.

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

13. The composition according to any of the preceding claims 1, 3 to 8, 10 and 11, characterized in that, The mass content of the compound B in the composition is at least 80% based on the total weight of the composition; and the polymer A is a fluoropolymer A1.

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

15. Use of a polymer A as defined in any one of the preceding claims 1, 2 and 6 to 9 as a stabilizer for an energetic composition, in particular a herbicidal, weeding or fertilizing composition, said composition preferably comprising a compound B as defined in any one of claims 1, 3 and 4.

16. Use of a polymer A as defined in any one of the preceding claims 1, 2 and 6 to 9 for desensitizing or sensitizing an energetic composition, said composition comprising a compound B having exothermic or volumetric expansion properties; said compound B being preferably as defined in any one of claims 1, 3 and 4.

17. Use according to claim 15 or 16, characterized in that, The mass content of the polymer A in the 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 the mass content of the compound B in the composition is preferably 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 the compound B in the composition is greater than 65 %, based on the total weight of the composition; and the polymer A is a polyamide A2 or a polyamide-polyether block copolymer A3, or a mixture thereof; or the mass content of the compound B in the composition is at least 80 %, based on the total weight of the composition; and the polymer A is a fluoropolymer A1.

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

20. The method according to the preceding claim, characterized in that, The mass content of the polymer A in the 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 the mass content of the compound B in the composition is preferably greater than 65 %, based on the total weight of the composition.

21. The method according to the preceding claim, characterized in that, The mass content of the compound B in the composition is greater than 65 %, based on the total weight of the composition; and the polymer A is a polyamide A2 or a polyamide-polyether block copolymer A3, or a mixture thereof; or the mass content of the compound B in the composition is at least 80 %, based on the total weight of the composition; and the polymer A is a fluoropolymer A1.

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