MATERIAL FUNCTIONALIZED BY AN ALIPHATIC POLYAMINE

Abstract

The present invention relates to a material, in particular a fluorocarbon polymer, functionalized with an aliphatic polyamine selected from aliphatic diamines possessing two primary amines and aliphatic triamines possessing two or three primary amines, or with a phosphoramide, its preparation process, and its uses. The invention also relates to the use of a composition of an alkali metal and such an aliphatic polyamine for the preparation of a functionalized material, in particular a fluorocarbon polymer. (no figure)

Description

Description Title of the invention: MATERIAL FUNCTIONALIZED BY A ALIPHATIC POLYAMINE

[0001] — The present invention relates to a material, in particular a fluorescent polymer rocarbonated, functionalized with an aliphatic polyamine chosen from among the diamines aliphatic compounds possessing two primary amines and aliphatic triamines possessing two or three primary amines, or by a phosphoramide, its preparation process and its uses. The invention also relates to the use of a composition of a alkali metal and such an aliphatic polyamine for the preparation of a material, in in particular a functionalized fluorocarbon polymer.

[0002] — Fluoropolymers possess unique qualities that make them essential in numerous application sectors. They possess excellent anti- properties They are adhesive and significantly reduce friction and rubbing. They resist the corrosion as well as at extreme temperatures, do not conduct electricity and They do not absorb water.

[0003] — The anti-stick properties, resistance, chemical inertness, anti-adhesion, the du- The reliability and biocompatibility of fluoropolymers make this type of Plastic, an indispensable ally of the medical profession, is being exploited by the dis- industry With positive medical applications in numerous fields, these materials have been adopted in particularly in the manufacture of implants, vascular grafts, catheters, capillary tubes, but also packaging for medical and pharmaceutical products.

[0004] — However, these qualities, particularly this chemical inertness, can also prove to be disadvantages when it becomes necessary to make it functional, by example with molecules of interest, these fluoropolymers.

[0005] — Fluorocarbon polymers can, however, be sensitive to alkali metals. When in contact with an alkali metal, these polymers are susceptible to undergoing a trans- Irreversible formation with elimination of the corresponding fluoride. The dissolution of The presence of alkali metals in liquid ammonia is known from prior art, but requires a permanent condensation of the solvent at -40°C (ammonia boils at -33°C under 1 bar). For example, the reactivity of PTFE with sodium in liquid ammonia has This has already been applied in the past but requires secure infrastructure linked to the handling a highly irritating and potentially explosive liquefied gas.

[0006] A composition comprising an alkali metal and a A specific aliphatic polyamine that allows for the chemical modification of a material. in particular a chemically almost inert fluorocarbon polymer, and this in mild conditions, particularly at ambient temperature and standard pressure. This function- However, this process allows the intrinsic mechanical properties of the material to be preserved. This method of processing materials, particularly fluorocarbon polymers, is simple to implement because it involves few chemical compounds, no irritating, toxic, and / or explosive solvents, and is carried out under normal temperature and pressure conditions. This method is therefore economically and environmentally advantageous. Furthermore, this modification allows for the functionalization of the material, particularly a fluorocarbon polymer, under mild conditions, notably at ambient temperature and standard pressure. This functionalization has the advantage of allowing the material to retain its intrinsic mechanical properties. This functionalization is also facilitated by the presence of free and reactive amine groups on the surface of the modified material. Thus, according to a first aspect, the invention relates to a material selected from among fluorocarbon polymers, aromatic carbon materials and boron-based ceramic materials, including: all or part of the -F atoms for fluorocarbon polymers is substituted by; a portion of the carbon atoms for aromatic carbon materials carries; And a portion of the boron atoms for boron-based ceramic materials door; an aliphatic polyamine chosen from aliphatic diamines possessing two primary amines and aliphatic triamines possessing two or three primary amines, or by a phosphoramide. By "all or part of the -F atoms of fluorocarbon polymers is substituted by", we mean in particular that all or part of the -F atoms of fluorocarbon polymers are replaced by the aliphatic polyamine or the phosphoramide. Thus, in particular, all or part of the CF bonds of the fluorocarbon polymers are replaced by a covalent bond between said carbon atoms and the aliphatic polyamine or the phosphoramide. By "part of the carbon atoms for aromatic carbon materials" we mean in particular that part of the carbon atoms of the aromatic carbon material is substituted by (in the sense of forming a covalent bond with) the aliphatic polyamine or the phosphoramide. Similarly, by "a portion of the boron atoms in boron-based ceramic materials" we mean in particular that a portion of the boron atoms in the boron-based ceramic material carry (in the sense of forming a covalent bond with) the aliphatic polyamine or phosphoramide. According to a particular embodiment, the invention relates to a material selected from fluorocarbon polymers, aromatic carbon materials and boron-based ceramic materials, including: all or part of the -F atoms for fluorocarbon polymers is substituted by; a portion of the carbon atoms for aromatic carbon materials carries; And a portion of the boron atoms for boron-based ceramic materials door ; an aliphatic polyamine chosen from among the aliphatic diamines possessing two primary amines and the aliphatic triamines possessing two or three primary amines. More generally, the aliphatic polyamine is chosen from among those capable of dissolving and chelating an alkali metal as defined below. This dissolution and chelation of the alkali metal by said aliphatic polyamine generally allows the formation of solvated electrons, typically in the form of an intense blue solution. The material chosen from among fluorocarbon polymers, aromatic carbon materials and boron-based ceramic materials can for example be substituted by an aliphatic polyamine chosen from among polyamines bearing more than three primary amines and polyamines of the type H,N-(CH,-CH;-NH),-CH-CH;-NH;, with n ranging in particular from 2 to 10. According to a particular embodiment, the invention relates to a material as defined above, which is a fluorocarbon polymer, in which all or part of the -F atoms are substituted by an aliphatic polyamine chosen from aliphatic diamines having two primary amines and aliphatic triamines having two or three primary amines, or by a phosphoramide. The fluorocarbon polymer can notably be a perfluorocarbon polymer or a hydrofluorocarbon polymer. According to a particular embodiment, the invention relates to a material as defined above, which is an aromatic carbon material, a portion of whose carbon atoms for aromatic carbon materials bears an aliphatic polyamine chosen from aliphatic diamines possessing two primary amines and aliphatic triamines possessing two or three primary amines, or by a phosphoramide. The aromatic carbon material can include graphene, one or more carbon nanotubes, or fullerene. According to a particular embodiment, the invention relates to a material as defined above, which is a boron-based ceramic material, a portion of whose boron atoms for aromatic carbon materials carry an aliphatic polyamine selected from aliphatic diamines possessing two primary amines and aliphatic triamines possessing two or three primary amines, or by a phosphoramide. The boron-based ceramic material can notably be a boron nitride. According to a particular embodiment, the aliphatic polyamine has the following formula (A): HN-R (A), in which R is a linear or C,-C;3 branched alkyl, and: R is substituted by one or two groups —NH, or R is substituted by a —NH group, and one of the carbon atoms of R is replaced by a nitrogen atom. According to a particular embodiment, R is a linear or branched C,-C12 alkyl, substituted by one or two —NH groups, in particular one —NH group. According to a particular embodiment, R is a linear alkyl in CC,2, substituted by a —NH, group, in particular on the terminal carbon atom, the aliphatic polyamine of formula (A) being more particularly of the following formula (Aa): H; N- CH,-CH-NH,, or H,N-CH;-CH,-CH,-NH;, even more particularly H,N-CH,-CH --NH,. According to a particular embodiment, R is a linear or Cz-C,2 branched alkyl substituted by a —NH, group, one of the carbon atoms of R being further replaced by a nitrogen atom, the aliphatic polyamine of formula (A) being more particularly of the following formula (Aa): H,N-CH,-CH,-NH-CH,-CH,-NH. According to a particular embodiment, the aliphatic polyamine is chosen from ethylenediamine, 1,3-diaminopropane, and diethylenetriamine. According to a particular embodiment, the invention relates to a material selected from fluorocarbon polymers, aromatic carbon materials and boron-based ceramic materials, including: all or part of the -F atoms for fluorocarbon polymers is substituted by; a portion of the carbon atoms for aromatic carbon materials carries; And a portion of the boron atoms for boron-based ceramic materials door ; a phosphoramide. According to a particular embodiment, the phosphoramide is chosen from among the phos- phoramides of the following formula (B): X,X,P(=O)X. (B) in which: - X, and X, are chosen independently from the groups —NR,R, where R, and R, are chosen independently from H and linear or branched alkyls at C, to Cç, X, and X, being notably —NMe, ; - X, is chosen from the groups —NR,R,, where R, and R, are independently chosen from H and linear or branched alkyls at C, to C4, the groups —OH and -OR,, where R, is a linear or branched alkyl at C, to C4, X. being notably -NMe,. Thus, nitrogen or oxygen from groups X, X, and X, is linked to phosphorus. In particular, the phosphoramide is hexamethylphosphoramide (HMPA). Without limiting ourselves to any particular theory, phosphoramide is, for example, linked to the fluorocarbon polymer via a carbon (of the fluorocarbon polymer) – phosphorus (of the phosphoramide) bond. Thus, in particular, all or part of the CF bonds of the fluorocarbon polymer are replaced by a covalent bond between these carbon atoms and the phosphoramide, more specifically the phosphorus of the phosphoramide. Similarly, and without limiting ourselves to any particular theory, phosphoramide is, for example, linked to the aromatic carbon material via a carbon (of the aromatic carbon material) – phosphorus (of the phosphoramide) bond. Thus, in particular, some of the carbon atoms of the aromatic carbon material are substituted by (in the sense of forming a covalent bond with) the phosphoramide, more specifically through the formation of a covalent bond between these carbon atoms and the phosphorus of the phosphoramide. Modifying the material with a phosphoramide is likely to make the surface of that material cytotoxic when desired. According to a particular embodiment: The aliphatic polyamine is 1,3-diaminopropane, and the material is... PTFE: The aliphatic polyamine is ethylenediamine or diethylenetriamine, and the The material is ePTFE; The aliphatic polyamine is ethylenediamine or diethylenetriamine, and the material is an acidic perfluorosulfonic polymer, for example Nafion; The phosphoramide is hexamethylphosphoramide (HMPA), and the material is PTFE. According to a particular embodiment, the invention relates to a fluorocarbon polymer as defined above, in which a portion of the -F atoms is substituted by a group of formula (I): —NH-R (D, in which R is a linear or C,-C;3 branched alkyl, and: R is substituted by one or two groups —NH, or R is substituted by a -NH group, and one of the carbon atoms of R is replaced by a nitrogen atom. According to a particular embodiment, the invention relates to an aromatic carbon material as defined above, a portion of the carbon atoms bearing a group of formula (I): —NH-R (D, in which R is a linear or C,-C;3 branched alkyl, and: R is substituted by one or two groups —NH, or R is substituted by a -NH group, and one of the carbon atoms of R is replaced by a nitrogen atom. According to a particular embodiment, the invention relates to a boron-based ceramic material as defined above, in which a portion of the boron atoms bear a group of formula (I): —NH-R (D, in which R is a linear or Cz-C2 branched alkyl, and: R is substituted by one or two groups —NH, or R is substituted by a -NH group, and one of the carbon atoms of R is replaced by a nitrogen atom. According to a particular embodiment, the invention relates to a fluorocarbon polymer as defined above, in which a portion of the -F atoms is substituted by a group of formula (II): -P(=O)X,X. (ID, in which: X, is chosen from the groups —-NR,R,, where R, and R, are independently chosen from H and linear or C-branched alkyls, to Ce, X, being in particular —NMe; ; X, is chosen from the groups —-NR,R,, where R, and R, are independently chosen from H and linear or branched alkyls at C, to C5, the groups —OH and -OR, where R is a linear or C-branched alkyl, to Ce, X. being in particular —-NMe, According to a particular embodiment, the invention relates to an aromatic carbon material as defined above, a portion of the carbon atoms bearing a group of formula (II): -P(=O)X,X. (ID, in which: X is chosen from the groups —NR,R, where R, and R, are independently chosen from H and linear or C-branched alkyls, to Ce, X, being in particular —NMe, ; X is chosen from the groups —NR,R,, where R, and R, are independently chosen from H and linear or branched alkyls at C, to C, the groups —OH and -OR, where R is a linear or C-branched alkyl, to Ce, X. being in particular —-NMe,. The substitution by said group of formula (I) on the material chosen from among fluorocarbon polymers, aromatic carbon materials and boron-based ceramic materials, can be characterized by one of the techniques well known to those skilled in the art, for example by attenuated total reflectance infrared (ATR-IR) spectroscopy, X-ray photoelectron spectroscopy (or X-ray photoelectron spectrometry, XPS), or Raman spectroscopy. According to a particular embodiment, R is a linear or branched C,-C12 alkyl, substituted by one or two —NH groups, in particular one —NH group. According to a particular embodiment, R is a linear alkyl in CC,2, substituted by a —NH, group, in particular on the terminal carbon atom, the group of formula (I) being more particularly of the following formula (Ia): -NH-CH,-CHz-NH, or —NH-CH--CH,-CH,-NH, even more particularly —-NH-CH,-CH,-NH.. According to a particular embodiment, R is a linear or Cz-Cy2 branched alkyl, substituted by a —NH group, one of the carbon atoms of R being further replaced by a nitrogen atom, the group of formula (I) being more particularly of the following formula (Ia): -NH-CH,-CH,-NH-CH,-CH,-NH,. According to a particular embodiment, the material is chosen from polytetrafluoroethylene (PTFE), perfluorosulfonic acid polymer (PFSA), for example Nafion, poly(vinyl fluoride) (PVF), poly(vinylidene fluoride) (PVDF), polychlorotrifluoroethylene (PCTFE), perfluoroalkoxy (PFA), fluorinated ethylene propylene (FEP), ethylene tetrafluoroethylene (ETFE), polyethylenechlorotrifluoroethylene (ECTFE), perfluoropolyether (PFPE), perfluoropolyoxetane, and fluoroelastomers, said material being in particular a polytetrafluoroethylene (PTFE), more particularly an expanded polytetrafluoroethylene (ePTFE), or a perfluorosulfonic acid. According to another aspect, the invention also relates to the use of a composition consisting of or comprising an alkali metal and an aliphatic polyamine selected from aliphatic diamines having two primary amines and aliphatic triamines having two or three primary amines, or by a phosphoramide, for the preparation of a material as defined above, in particular a fluorocarbon polymer. All the embodiments defined previously also apply here, alone or in combination. According to another aspect, the invention also relates to the use of a composition consisting of or comprising an alkali metal and an aliphatic polyamine selected from aliphatic diamines having two primary amines and aliphatic triamines having two or three primary amines, or by a phosphoramide, for the pickling of a material selected from fluorocarbon polymers, aromatic carbon materials and boron-based ceramic materials, in particular a fluorocarbon polymer, in particular a fluorocarbon polymer. All the embodiments defined previously also apply here, alone or in combination. According to another aspect, the invention also relates to the use of a composition consisting of or comprising an alkali metal and an aliphatic polyamine selected from aliphatic diamines having two primary amines and aliphatic triamines having two or three primary amines, or by a phosphoramide, for the reprocessing of a material selected from fluorocarbon polymers, aromatic carbon materials and boron-based ceramic materials, in particular a fluorocarbon polymer. All the embodiments defined previously also apply here, alone or in combination. According to another aspect, the invention also relates to the use of a composition consisting of or comprising an alkali metal and an aliphatic polyamine selected from aliphatic diamines having two primary amines and aliphatic triamines having two or three primary amines, or by a phosphoramide, for the functionalization of a material selected from fluorocarbon polymers, aromatic carbon materials and boron-based ceramic materials, in particular a fluorocarbon polymer, in particular an antibacterial or biocompatibilizing functionalization. All the embodiments defined previously also apply here, alone or in combination. According to another aspect, the invention also relates to a method for preparing a modified material, in particular as defined above, which includes a step (i) of contacting a material selected from fluorocarbon polymers, aromatic carbon materials and boron-based ceramic materials, in particular a fluorocarbon polymer, with a composition consisting of or comprising an alkali metal and an aliphatic polyamine selected from aliphatic diamines having two primary amines and aliphatic triamines having two or three primary amines, or with a phosphoramide, to obtain said material, in particular said polymer of which a part of the -F atoms is substituted by said aliphatic polyamine or said phosphoramide. The material thus obtained is also known as modified material. All the embodiments defined previously also apply here, alone or in combination. According to a particular embodiment, the alkali metal is lithium or sodium. According to a particular embodiment, step (i) is carried out at a temperature between the melting point and the boiling point of the aliphatic polyamine. According to a particular embodiment, step (i) is carried out at a temperature of 10°C to 80°C, in particular at a temperature of 15 to 25°C, in particular about 20°C. According to a particular embodiment, step (i) is carried out under an inert atmosphere, in particular under argon. The mass concentration of alkali metal in aliphatic polyamine is, for example, approximately 5 g / L. The initial material mass ratio / aliphatic polyamine is, for example, approximately 0.129. According to a particular embodiment, the alkali metal / aliphatic polyamine molar ratio is from 0.1 to 0.9, in particular from 0.2 to 0.8, or from 0.3 to 0.7, or from 0.4 to 0.6, this ratio being in particular about 0.5. According to a particular embodiment, step (1) is followed by a step (ii) of rinsing the material obtained at the end of step (i) with a solvent consisting of or comprising an alcohol, in particular ethanol, this step (ii) being optionally followed by a step (ii') of rinsing with a solvent consisting of or comprising water. According to another aspect, the invention also relates to a product that can be obtained by a process comprising a step (i) of bringing into contact a material selected from fluorocarbon polymers, aromatic carbon materials and boron-based ceramic materials, in particular a fluorocarbon polymer, with a composition consisting of or comprising an alkali metal and an aliphatic polyamine selected from aliphatic diamines having two primary amines and aliphatic triamines having two or three primary amines, or by a phosphoramide, to obtain said modified material. All the embodiments defined previously also apply here, alone or in combination. According to another aspect, the invention also relates to a material selected from fluorocarbon polymers, aromatic carbon materials, and boron-based ceramic materials, including: all or part of the -F atoms for fluorocarbon polymers is substituted by; a portion of the carbon atoms for aromatic carbon materials carries; And a portion of the boron atoms for boron-based ceramic materials door ; an aliphatic polyamine selected from aliphatic diamines having two primary amines and aliphatic triamines having two or three primary amines, or by a phosphoramide, all or part of these aliphatic polyamines being further linked, in particular by crosslinking, to a compound of interest independently selected from polysaccharides, in particular polysaccharides consisting of or comprising at least one osamine motif, in particular chitosans or chitins, polymers consisting of or comprising at least one motif comprising a primary or secondary amine, or a lactam, in particular polyethyleneimines (PEI), in particular linear, branched or dendrimeric polyethyleneimines, polyvinylpyrrolidones (PVP), and antibacterial compounds. As an illustration, antibacterial compounds may be chosen from among antibacterial compounds of less than 500 Da, for example tetrahydrocarbazoles, in particular 1-amino substituted tetrahydrocarbazoles (such as those described by Reithuber et al., PNAS November 23, 2021 118 (47) e2108244118), and antibacterial peptides, such as those described by Zhang et al. (Military Med Res 8, 48 (2021)). All the embodiments defined previously also apply here, alone or in combination. According to a particular embodiment, all or part of these aliphatic polyamines are linked to the compound of interest by one or more non-covalent interactions, including weak interactions. According to a particular embodiment, all or part of these aliphatic polyamines are linked to the compound of interest by a covalent bond, in particular via a linking group. According to a particular embodiment, the material is a fluorocarbon polymer in which a portion of the -F atoms is substituted by a group of formula (I): —NH-R -Z (D, in which R is a linear or C>-C,3 branched diyl alkane, and: R is substituted by one or two groups —NH, or R is substituted by a —NHz group, and one of the carbon atoms of R is replaced by a nitrogen atom, Z is carried by a nitrogen atom as defined above and is chosen from among the polysaccharides, in particular polysaccharides made up of or including at least one osamin motif, notably chitosans or chitins, polymers made up of or comprising at least one motif comprising a primary or secondary amine, or a lactam, in particular polyethyleneimines (PET), particularly linear polyethyleneimines, branched or dendrimeric polyvinylpyrrolidones (PVP), and compounds antibacterials, Z being optionally linked to R via a group of liaison. According to a particular embodiment, the material is an aromatic carbon material in which a portion of the carbon atoms bears a group of formula (I): —NH-R -Z (D, in which R is a linear or C,-C,> branched diyl alkane, and: R is substituted by one or two groups —NH, or R is substituted by a -NH group, and one of the carbon atoms of R is replaced by a nitrogen atom, Z is carried by a nitrogen atom as defined above and is chosen from among the polysaccharides, in particular polysaccharides made up of or including at least one osamin motif, notably chitosans or chitins, polymers made up of or comprising at least one motif comprising a primary or secondary amine, or a lactam, in particular polyethyleneimines (PET), particularly linear polyethyleneimines, branched or dendrimeric polyvinylpyrrolidones (PVP), and compounds antibacterials, Z being optionally linked to R via a group of liaison. According to a particular embodiment, the material is a boron-based ceramic material in which a portion of the boron atoms bear a group of formula (I): —NH-R -Z (D), in which R is a linear or C-branched diyl alkane, and: R is substituted by one or two groups —NH, or R is substituted by a —NH₂ group, and one of the carbon atoms of R is replaced by a nitrogen atom, Z is carried by a nitrogen atom as defined above and is chosen from among the polysaccharides, in particular polysaccharides made up of or including at least one osamin motif, notably chitosans or chitins, polymers made up of or comprising at least one motif comprising a primary or secondary amine, or a lactam, in particular polyethyleneimines (PET), particularly linear polyethyleneimines, branched or dendrimeric polyvinylpyrrolidones (PVP), and compounds antibacterials, Z being optionally linked to R via a group of liaison. The term "linking group" refers specifically to any group that allows the R group to be linked to the Z residue. This may be a group consisting of or comprising a chain, in particular a C,-Czy alkyl group or a PEG chain, said chain optionally bearing at its ends groups that allow the R group and the Z residue, respectively. These groups may be chosen from esters, ethers, ketones, amines, imines, amides, triazines, etc. According to another aspect, the invention relates to the use of a modified material as defined above, for the preparation of a functionalized material as defined above. All the embodiments defined previously also apply here, alone or in combination. According to another aspect, the invention relates to a process for preparing a functionalized material, in particular as defined above, comprising the following steps: a step (i) of bringing into contact a material chosen from among the polymers fluorocarbons, aromatic carbon materials and ce- materials Boron-based ramics, with a composition consisting of or comprising an alkali metal and an aliphatic polyamine chosen from the ali- diamines phatic compounds possessing two primary amines and aliphatic triamines possessing two or three primary amines, or by a phosphoramide, for to obtain a modified material; Optionally, a step (ii) of rinsing the modified material obtained at the result of step (i) by a solvent consisting of or comprising an alcohol, including ethanol, this step (ii) being optionally followed by a step (ii”) of rinsing with a solvent consisting of or comprising water; a step (iii) of bringing the modified material obtained at the end of step (i), (ii) or (ii”) with a compound selected from the polysaccharides, in in particular polysaccharides made up of or comprising at least one motif osamine, particularly chitosans or chitins, are polymers made up of of or comprising at least one motif comprising a primary amine or se- secondary, or a lactam, in particular polyethyleneimines (PET), including linear, branched or dendrimeric polyethyleneimines, polyvinylpyrrolidones (PVP), and antibacterial compounds, optionally in the presence of a bifunctional compound capable of forming a group of connection. In another aspect, the invention relates to a method for preparing a material as defined above, which is a fluorocarbon polymer, comprising the Next steps: a step (i) of contacting a fluorocarbon polymer with a com- position consisting of or comprising an alkali metal and a polyamine ali- phatic compound chosen from among the aliphatic diamines possessing two amines primary and aliphatic triamines possessing two or three amines primary, or by a phosphoramide, to obtain said polymer of which a part of the -F atoms is substituted by said aliphatic polyamine or said phosphoramide; Optionally, a step (ii) of rinsing the polymer obtained at the end of step (i) with a solvent consisting of or comprising an alcohol, in particular ethanol, this step (ii) being optionally followed by a step (ii') of rinsing with a solvent consisting of or comprising water; a step (iii) of bringing the polymer obtained at the end of step (1) into contact, (ii) or (ii') with a compound selected from polysaccharides, in particular polysaccharides consisting of or comprising at least one osamin motif, including chitosans or chitins, polymers made of or comprising at least one motif including a primary or secondary amine, or a lactam, in particular polyethyleneimines (PEIs), especially po- linear, branched or dendrimeric lyethyleneimines, polyvinylpyr- rolidones (PVP), and antibacterial compounds, optionally in the presence of a bifunctional compound capable of forming a bonding group, by for example, glutaraldehyde. According to another aspect, the invention relates to a process for preparing a material as defined above, which is an aromatic carbonaceous material, comprising the following steps: a step (i) of contacting an aromatic carbon material with a composition consisting of or comprising an alkali metal and a polyamine aliphatic chosen from among the aliphatic diamines possessing two amines primary and aliphatic triamines possessing two or three amines primary, or by a phosphoramide, to obtain said material of which a part of the atoms -C is covalently bonded to said polyamine ali- phatic; Optionally, a step (ii) of rinsing the material obtained at the end of step (i) with a solvent consisting of or comprising an alcohol, in particular ethanol, this step (ii) being optionally followed by a step (ii') of rinsing with a solvent consisting of or comprising water; a step (iii) of bringing the material obtained at the end of step (1) into contact, (ii) or (il') with a compound selected from polysaccharides, in particular polysaccharides consisting of or comprising at least one osamin motif, including chitosans or chitins, polymers made of or comprising at least one motif including a primary or secondary amine, or a lactam, in particular polyethyleneimines (PEIs), especially po- linear, branched or dendrimeric lyethyleneimines, polyvinylpyr- rolidones (PVP), and antibacterial compounds, optionally in the presence of a bifunctional compound capable of forming a bonding group. In another aspect, the invention relates to a process for preparing a material as defined above, which is a boron-based ceramic material, comprising the following steps: a step (i) of contacting a boron-based ceramic material with a composition consisting of or comprising an alkali metal and a aliphatic polyamine chosen from aliphatic diamines possessing two primary amines and aliphatic triamines possessing two or three amines primary, or by a phosphoramide, to obtain said material of which a part of the atoms -B is covalently bonded to said polyamine ali- phatic; Optionally, a step (ii) of rinsing the material obtained at the end of step (i) with a solvent consisting of or comprising an alcohol, in particular ethanol, this step (ii) being optionally followed by a step (ii') of rinsing with a solvent consisting of or comprising water; a step (iii) of bringing the material obtained at the end of step (i) into contact, (ii) or (il') with a compound selected from polysaccharides, in particular polysaccharides consisting of or comprising at least one osamin motif, including chitosans or chitins, polymers made of or comprising at least one motif including a primary or secondary amine, or a lactam, in particular polyethyleneimines (PET), especially po- linear, branched or dendrimeric lyethyleneimines, polyvinylpyr- rolidones (PVP), and antibacterial compounds, optionally in the presence of a bifunctional compound capable of forming a bonding group. All embodiments defined previously also apply here, alone or in combination. When step (i) involves a phosphoramide, the compound selected from polysaccharides, in particular polysaccharides consisting of or comprising at least one osamine motif, including chitosans or chitins, polymers consisting of or comprising at least one motif comprising a primary or secondary amine, or a lactam, in particular polyethyleneimines (PEDs), including linear, branched or dendrimeric polyethyleneimines, polyvinylpyrrolidones (PVPs), and Antibacterial compounds, in particular, are halogenated, for example chlorinated. This could notably be a halogenated chitosan. FIGURES Figure [Fig.1] shows the IR-ATR spectra on diamond crystal before (A) and after functionalization (B) of PTFE, by 1,3-diaminopropane, in the presence of lithium, according to example 1. Figure 2 relates to the Raman spectrum after functionalization of carbon nanotubes with ethylenediamine in the presence of lithium, as shown in Example 4. EXAMPLES Example 1: Modification of PTFE and ePTFE according to the invention The following steps were carried out in a glove box under an argon atmosphere: - 10 square samples of ePTFE of 1x1cm were introduced into a 40mL bottle containing 10mL (9.00 g) of ethylenediamine and 0.05g of lithium (mass ratio Li / EDA= 0.0056, mass ratio ePTFE / EDA=0.129); - The mixture thus obtained was stirred with a glass-covered magnetic stir bar, using a magnetic stirrer for 17 to 18 hours; - The ePTFE samples thus obtained were collected with a glass spatula in a crystallizer, then removed from the glove box. The following steps were then carried out directly under a fume hood: - the samples were placed in an excess of pure ethanol and treated with ultrasound for 10 minutes; - the ethanol was removed and then the operation was repeated twice with ultrapure water (Millipore); - the modified ePTFE samples were placed to dry in a petri dish under a fume hood at room temperature. Samples of ePTFE modified with diethylenetriamine were obtained in a similar manner. In addition, modified PTFE samples, particularly using 1,3-diaminopropane or hexamethylphosphoramide, were obtained in a similar manner. The ePTFE and modified PTFE samples thus obtained were analyzed by IR-ATR spectroscopy, using different crystals / prisms, including the diamond one which allows probing, over a small thickness, the first functionalization layers. For example, [Fig.1] shows the IR-ATR spectra on diamond crystal before and after functionalization with 1,3-diaminopropane according to the PTFE invention. IR characterization shows that the samples have indeed been chemically modified, as evidenced in particular by the presence of characteristic bands. IR bands such as -CH2, -NH, and -NH2 appear on the spectra of modified polymers. This indicates an irreversible modification of these polymer materials and the formation of covalent bonds between the polymer carbon and the amine of the polyamine or HMPA. The products of the invention were also demonstrated by XPS spectroscopy Example 2: Functionalization of ePTFE according to the invention Chitosan was grafted onto ePTFE, as follows: - Solubilization of chitosan: in a 30mL flask, 0.200g of chitosan and 0.094mL of 106M acetic acid were added, then the flask was filled with water up to the calibration mark and left to be shaken for 10min; - The reaction mixture was then filtered; - the 10 modified ePTFE samples as obtained from the example | were added, followed by 0.30mL of 25% glutaraldehyde solution. - After stirring for 2 hours, the medium was discarded and the samples rinsed in an excess of ultrapure water (Millipore), 3 times 10 minutes under stirring. PVP (in this case without the glutaraldehyde treatment step) and PEI were also successfully grafted, with a protocol similar to the one above. IR characterization before and after functionalization according to the invention shows that in all cases, the samples were successfully functionalized. The functionalized samples of the invention were also highlighted by XPS spectroscopy. Example 3: Modification of Nafion according to the invention Modified Nafion samples, for example with ethylenediamine or diethylenetriamine, were successfully obtained, similarly to those in example l Example 4: Other modifications according to the invention Samples of boron nitride (single-walled BN) and single-walled carbon nanotubes (SWCNT) were also modified according to the invention, and characterized by IR-ATR and XPS analyses. Single-walled carbon nanotubes (Sigma-Aldrich) have notably been treated according to the invention with ethylenediamine in the presence of lithium, according to a procedure similar to that presented in Example 1. The modified carbon nanotubes were analyzed by Raman spectroscopy ([Fig. 2]). The peaks of the D, G, and RBM bands are irreversibly modified, highlighting that the carbon nanotubes of the invention are functionalized by ethylenediamine.

Claims

Demands

1. Material selected from fluorocarbon polymers, materials aromatic carbon compounds and boron-based ceramic materials, including: all or part of the atoms -F for fluoro- polymers carbon is substituted by; a portion of the carbon atoms for carbonaceous materials aro- door systems; and a portion of the boron atoms for ceramic materials to base of boron door; an aliphatic polyamine chosen from among the aliphatic diamines possessing two primary amines and aliphatic triamines possessing two or three primary amines, or a phosphoramide.

2. Material according to claim 1, which is a fluorocarbon polymer of which a portion of the -F atoms is substituted by a group of formula {D: —NH-R (D, in which R is a linear or C>-C branched alkyl,,, and: R is substituted by one or two groups —NH, or R is substituted by a —NH group, and one of the atoms of carbon in R is replaced by a nitrogen atom.

3. Material according to any one of claims 1 to 2, which is chosen from polytetrafluoroethylene (PTFE), a perfluoro- polymer sulfonic acid (PFSA), poly(vinyl fluoride) (PVF), poly(fluoride vinylidene) (PVDF), polychlorotrifluoroethylene (PCTFE), perfluoro- roalkoxy (PFA), fluorinated ethylene propylene (FEP), tetrafluoroethylene roethylene (ETFE), polyethylenechlorotrifluoroethylene (ECTFE), per- fluoropolyether (PFPE), perfluoropolyoxether, and fluoroelastomers, said material being in particular a polytetrafluoroethylene (PTFE), more specifically expanded polytetrafluoroethylene (ePTFE), or a perfluorosulfonic acid.

4. Use of a composition made of or comprising a metal alkaline and an aliphatic polyamine chosen from the ali- diamines phatic compounds possessing two primary amines and aliphatic triamines possessing two or three primary amines, or a phosphoramide, for the preparation of a material as defined in any of the claims instructions 1 to 3.

5. A method for preparing a material as defined in a any of the claims | to 3, which includes a step (i) of contacting a material chosen from among the fluoro- polymers carbonaceous materials, aromatic carbonaceous materials and ce- boron-based ramics, in particular those made from a fluorocarbon polymer with a composition consisting of or comprising an alkali metal and an aliphatic polyamine chosen from among the aliphatic diamines possessing two primary amines and aliphatic triamines possessing two or three primary amines, or a phosphoramide, to obtain said material, in particular said polymer of which a part of the -F atoms is substituted by said aliphatic polyamine or said phosphoramide.

6. A process according to claim 5, wherein the alkali metal is from lithium or sodium.

7. A method according to any one of claims 5 to 6, wherein step (i) is carried out at a temperature between 10°C and 80°C, by- particularly at a temperature between 15 and 25°C, especially around 20°C.

8. A method according to any one of claims 5 to 7, wherein the The molar ratio of alkali metal to aliphatic polyamine is between 0.1 at 0.9, in particular from 0.2 to 0.8, or from 0.3 to 0.7, or from 0.4 to 0.6, this the ratio being in particular around 0.

5.

9. Material according to claim 1 selected from fluoro- polymers carbonaceous materials, aromatic carbonaceous materials and ce- Boron-based ramics, including: all or part of the atoms -F for fluoro- polymers carbon is substituted by ; a portion of the carbon atoms for carbonaceous materials aro- door systems; and a portion of the boron atoms for ceramic materials to base of boron door; an aliphatic polyamine chosen from among the aliphatic diamines possessing two primary amines and aliphatic triamines possessing two or three primary amines, or a phosphoramide, all or part of these aliphatic polyamines being further bound, particularly by crosslinking, to a compound of independent interest chosen from among the polysaccharides, in particular the polysaccharides consisting of or comprising at least one osamine motif, in particular the chitosans or chitins, polymers made up of or comprising at less a motif comprising a primary or secondary amine, or a lactam, in particular polyethyleneimines (PEI), especially po- linear, branched or dendrimeric lyethyleneimines, polyvinyl- pyrrolidones (PVP), and antibacterial compounds.

10. | A method according to claim 5 for preparing a material such as defined in claim 9, which is a fluorocarbon polymer, including the following steps: a step (i) of bringing a fluorocarbon polymer into contact with a composition made up of or comprising a metal alkaline and an aliphatic polyamine chosen from the aliphatic diamines possessing two primary amines and the aliphatic triamines possessing two or three amines primary, or a phosphoramide, to obtain said polymer of which a portion of the -F atoms is substituted by said aliphatic polyamine; Optionally, a step (ii) of rinsing the polymer obtained at the end of step (i) by a solvent consisting of or including an alcohol, in particular ethanol, this step (ii) optionally followed by a step (ii) of rinsing by a solvent consisting of or containing water; a step (iii) of bringing the polymer obtained at the end of step (i), (ii) or (il) with a compound chosen from the po- lysaccharides, in particular polysaccharides made up of or comprising at least one osamine motif, in particular the chitosans or chitins, polymers made of or comprising at least one motif comprising an amine primary or secondary, or a lactam, in particular poly- ethyleneimines (PEI), in particular polyethyleneimines linear, branched or dendrimeric, polyvinylpyr- rolidones (PVP), and antibacterial compounds, optional- metrically in the presence of a bifunctional compound likely to form a liaison group; or of a material as defined in claim 9, which is an aromatic carbon material, comprising the following steps: a step (i) of bringing a carbonaceous material into contact aromatic with a composition consisting of or comprising an alkali metal and an aliphatic polyamine chosen from the aliphatic diamines possessing two primary amines and the aliphatic triamines possessing two or three amines primary, or a phosphoramide, to obtain said material of which a portion of the -C atoms are covalently bonded to said aliphatic polyamine; Optionally, a step (ii) of rinsing the material obtained at the end of step (i) by a solvent consisting of or including an alcohol, in particular ethanol, this step (ii) optionally followed by a rinsing step (ii”) by a solvent consisting of or containing water; a step (iii) of bringing the material obtained at the end of step (i), (il) or (il') with a compound chosen from the po- lysaccharides, in particular polysaccharides made up of or comprising at least one osamine motif, in particular the chitosans or chitins, polymers made of or comprising at least one motif comprising an amine primary or secondary, or a lactam, in particular poly- ethylencimines (PEIs), in particular polyethyleneencimines linear, branched or dendrimeric, polyvinylpyr- rolidones (PVP), and antibacterial compounds, optional- metrically in the presence of a bifunctional compound likely to form a liaison group; or of a material as defined in claim 9, which is a boron-based ceramic material, comprising the following steps: a step (i) of bringing a ceramic material into contact with boron base with a composition consisting of or comprising an alkali metal and an aliphatic polyamine chosen from among the aliphatic diamines possessing two amines primary and aliphatic triamines possessing two or three primary amines, or a phosphoramide, to obtain said material in which a portion of the -B atoms is covalently linked to said aliphatic polyamine; optionally, a step (ii) of rinsing the material obtained at the end of step (i) with a solvent consisting of or comprising an alcohol, in particular ethanol, this step (ii) being optionally followed by a step (ii”) of rinsing with a solvent consisting of or comprising water; a step (iii) of bringing the material obtained at the end of step (i), (ii) or (il”) into contact with a compound selected from polysaccharides, in particular polysaccharides consisting of or comprising at least one osamine motif, in particular chitosans or chitins, polymers consisting of or comprising at least one motif comprising a primary or secondary amine, or a lactam, in particular polyethyleneimines (PEDs), in particular linear, branched or dendrimeric polyethyleneimines, polyvinylpyrrolidones (PVPs), and antibacterial compounds, optionally in the presence of a bifunctional compound capable of forming a linking group.