Long-chain linear polyamines, their manufacturing process, and their uses

Abstract

The present invention relates to novel long-chain nitrogen-containing polymers, in particular polyamines (monomers containing amine groups) with more than four carbon atoms, and their manufacture by catalytic reduction (deoxygenation) of the corresponding polyamides. The present invention also relates to their manufacture process and their uses for CO2 capture, metallic salt extraction, water treatment, purification of contaminated media, manufacture of solid or semi-solid battery electrolytes, manufacture of flame retardants, as additives for motor oils, as building blocks for polymer synthesis, manufacture of plastics, manufacture of membranes and filters, and manufacture of antibacterial materials. Figure for the abstract: None

Description

Title of the invention: LONG-CHAIN ​​LINEAR POLYAMINES, PROCESS FOR THEIR MANUFACTURE, AND THEIR USES Technical field of the invention

[0001] The present invention relates to new nitrogen-containing polymers with a long carbon chain, in particular polyamines (monomers containing amine functions) with a number of carbon atoms greater than 4, and to their manufacturing process by catalytic reduction (deoxygenation) of the corresponding polyamides.

[0002] The present invention also relates to their manufacturing process as well as their uses for the capture of CO2, the extraction of metal salts, the treatment of water, the purification of contaminated environments, the manufacture of solid or semi-solid battery electrolytes, the manufacture of flame retardants, as additives for engine oils, as bricks for the synthesis of polymers, the manufacture of plastics, the manufacture of membranes and filters, the manufacture of anti-bacterial materials. Technical background

[0003] Naturally, polyamines with short carbon chains (between 2 and 4 carbon atoms) are biological regulators which play, among other things, an essential role in cell growth, the proper functioning of the central nervous system, and cell renewal, but their proliferation can induce the development of certain cancers. In addition to reacting like amines, polyamines have a chelating power much superior to the latter due to the synergistic effect of the amine groups.

[0004] Inspired by nature, scientists and industrialists have been interested for years in polyamines, the development of easier and less toxic synthetic routes, as well as their properties and possible uses. Today, polyamines are used in extraction processes, treatment and purification of contaminated media (e.g. heavy metals), in medical diagnosis and therapy. They also serve as additives for engine oils, hardeners in epoxy resins, crosslinking agents for coatings and as raw material for the synthesis of polyurethanes.

[0005] Currently, the technological barriers linked to their synthesis (multi-step methods, use of toxic and / or dangerous compounds) do not allow the synthesis of polyamines with long carbon chains (>4 carbon atoms).

[0006] The range of polyamines produced is reduced to oligoamines, polyamines containing a small number of amine groups. Oligoamines are, in general, molecules having degrees of polymerization that vary from two to a few tens and a maximum molar mass of 2000 g.mol *. However, compared to oligoamines, polyamines would have different intrinsic properties (lower viscosity and greater chelation), which would broaden their field of applications.

[0007] No current technology allows the synthesis of nitrogen-containing polymers with long carbon chains, in particular the synthesis of polyamines having a carbon chain of more than 4 carbon atoms and a molar mass greater than 3000 g.mol *. Existing synthesis routes lead to oligoamines, polyamines with a small number of amine groups, via multi-step processes and by using petro-sourced compounds, toxic and / or dangerous to handle (aziridines, acrylates, isocyanates, halides, acrylonitriles, ethylene diamine, nitriles, ammonia, etc.).

[0008] There is therefore a real need for new nitrogen-containing polymers with a long carbon chain, in particular polyamines (monomers containing amine functions) with a number of carbon atoms greater than 4 and a molar mass greater than 3000 g.mol *, and for a process allowing their synthesis from polyamides.

[0009] In particular, there is a real need for a process which allows the transformation of a polyamide, without cutting the polymer, to obtain the corresponding polyamine.

[0010] More particularly, there is a real need for a process for transforming a polyamide into the corresponding polyamine as described above, which is simple and which is carried out under mild temperature and pressure conditions using reagents which are less toxic and dangerous than those commonly used.

[0011] Furthermore, there is a real need to use a process as described above which makes it possible to treat polyamide waste by transforming it into polyamines (high added value products) unlike treatments such as mechanical recycling and / or chemical reprocessing methods which only make it possible to recover the carbonaceous material in the form of products without added value (polyamide free of any contaminants, or corresponding monomers or derivatives). Summary of the invention

[0012] The present invention aims precisely to meet these needs by providing polyamines of formulas (I), (II), (III) and (IV)

[0016]

[0017]

[0018]

[0019]

[0020]

[0014]

[0015] (IV) in which T and Z, identical or different, represent an alkyl group containing from 1 to 12 carbon atoms, an aryl group containing from 6 to 20 carbon atoms; R1 and R2, which may be identical or different, represent a hydrogen atom, an alkyl group comprising from 1 to 12 carbon atoms, an alkenyl group comprising from 2 to 12 carbon atoms, an alkynyl group comprising from 2 to 12 carbon atoms, an aryl group comprising from 6 to 20 carbon atoms, an alkoxy group in which the alkyl group comprises from 1 to 12 carbon atoms, an aryloxy group in which the aryl group comprises from 6 to 20 carbon atoms, a heteroaryl group comprising from 5 to 12 members, a 5 to 12 membered heterocycle, said alkyl, alkenyl, alkynyl, aryl, alkoxy, aryloxy, heteroaryl, heterocycle groups being optionally substituted, a group BR3R4 with R3 and R^ as defined below; R3 and R4, which may be identical or different, represent a hydrogen atom, an alkyl group containing 1 to 12 carbon atoms, an alkenyl group containing 2 to 12 carbon atoms, an alkynyl group containing 2 to 12 carbon atoms, a

[0021]

[0022]

[0023]

[0024] aryl group having from 6 to 20 carbon atoms, a heteroaryl group having from 5 to 12 members, a 5 to 12 membered heterocycle, an alkoxy group in which the alkyl group has from 1 to 12 carbon atoms, an aryloxy group in which the aryl group has from 6 to 20 carbon atoms, said alkyl, alkenyl, alkynyl, aryl, heteroaryl, heterocycle, alkoxy, aryloxy groups being optionally substituted; or R3 and R4 taken together with the boron atom to which they are bonded, form a heterocycle having from 5 to 12 members, a heteroaryl group having from 5 to 12 members, said heterocycle and heteroaryl groups being optionally substituted; X represents Cl, Br, I, HSO4, C1O4; characterized in that they have a molar mass greater than 3000 g.mol *, preferably greater than 4000 g.mol *. The invention also relates to a process for manufacturing polyamines of formulae (I), (II), (III) and (IV) characterized in that it comprises a step of bringing into contact a polyamide of formulae (V) and (VI)

[0025]

[0026]

[0027]

[0028] (V) IO Û —----n s-------------.ç—— | Ri | (VI) in which T, Z, R1 and R2 are as defined above, with a reducing agent of formula (VII)

[0029]

[0030] (VII) in which R3 and R4, identical or different, represent a hydrogen atom, a alkyl group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, an alkynyl group having 2 to 12 carbon atoms, an aryl group having 6 to 20 carbon atoms, a heteroaryl group having 5 to 12 members, a 5 to 12 membered heterocycle, an alkoxy group in which the alkyl group has 1 to 12 carbon atoms, an aryloxy group in which the aryl group has 6 to 20 carbon atoms, said alkyl, alkenyl, alkynyl, aryl, heteroaryl, heterocycle, alkoxy, aryloxy groups being optionally substituted; or - R3 and R4 taken together with the boron atom to which they are bonded, form a heterocycle comprising from 5 to 12 members, a heteroaryl group comprising from 5 to 12 members, said heterocycle and heteroaryl groups being optionally substituted;

[0031] in the presence of a metal catalyst chosen from - metal homoleptic complexes (((CH3)3Si)2N)n[M] with the bis(trimethylsilyl)amide ligand (((CH3)3Si)2N ) and [M] a rare earth chosen from lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, rhohnium, erbium, thulium, ytterbium, lutetium, scandium and yttrium - dual systems of type base / BEt3 in which the base is K0X° or NaOX' with X° and X' = H, OtBu, OMe, OAc, Ca(N(Si(CH3)3)2)2(THF)2 - lithium 2,6-di-tert-butylphenolate ([Li(OC6H3-2,6-tBu2) - a metal acetylacetonate of formula Ln4O(acac)i0 with Ln=La, Er, Eu, Gd, Y, - metallocene complexes of general formula M(C5H5)2, where M11 is a metallic element in the oxidation state +2 chosen from, (C5H5)2ZrH2, (C5H5)2 ZrHX” ​​(X” =C1, Br, I), - an alkali metal borohydride chosen from LiHBEt3, NaHBEt3, - zinc complexes chosen from Zn(O2CMe)2, Zn(O3SCF3)2, B(C6F5)3, - benzothiophene boronic acids chosen from

[0032] 2-Benzo[Z?]thiopheneboronic acid Z \ ,

[0033] 5-Bromobenzo[h]thiophene-2-boronic acid / , \ '7 - nickel dichloro(dimethoxyethane) or NiCl2(dme), - chlorobis(cyclooctene)iridium dimer or [Ir(COE)2Cl]2, - a cobalt-diphosphine complex, in particular cobalt acetylacetonate bis[(2-diphenylphosphino)phenyl] ether or Co(acac)2 / DPEphos, - molybdenum complexes chosen from Mo(CO)6, MoO2C12, MoO2C12(H2 O)2 - indium bromide or InBr2, - chloroplatinic acid hexahydrate or H2PtCl6-6H2O.

[0034] The present invention thus provides access to new polyamines of formulae (I), (II), (III) and (IV) from an innovative synthesis route which consists of reducing all the amide functions of a polyamide to amine functions.

[0035] Unlike current chemical processes for transforming polyamides which induce the cleavage of the carbon-nitrogen bonds of the polyamides and therefore a depolymerization towards the corresponding monomers or reduced derivatives, the process of the present invention allows the transformation of the polyamide, without cutting the polymer, to obtain the corresponding polyamine as shown in [Fig.l]. The polyamine obtained has a higher value than that of the starting material, it is therefore an upcycling.

[0036] The invention also relates to the use of polyamines of formulae (I), (II), (III) and (IV) for the capture of CO2, the extraction of metal salts, the treatment of water, the purification of contaminated environments, the manufacture of solid or semi-solid battery electrolytes, the manufacture of flame retardants, as additives for engine oils, as bricks for the synthesis of polymers, the manufacture of plastics, the manufacture of membranes and filters, the manufacture of anti-bacterial materials.

[0037] Another object of the invention is the use of a process according to the invention for the recovery and upcycling of polyamide / nylon waste into polyamines of formulae (I), (11), (111) and (IV). Brief description of the figures

[0038] Other characteristics and advantages of the invention will appear during the reading of the detailed description which follows for the understanding of which reference will be made to the appended drawings in which:

[0039] [Fig.l] is a schematic comparison of the products obtained from the reduction of polyamides by existing chemical processes with those obtained by the process of the invention (represented by the black arrow).

[0040] [Fig.2] and [Fig.3] represent respectively, the 'H NMR spectrum and the 13C NMR spectrum in D2O make it possible to confirm the structure of the polyamine in the form of ammonium salt prepared in example 1. The NMR spectra were carried out using a Bruker AVANCE Neo 400 MHz spectrometer. Detailed description of the invention

[0041] The present invention relates to polyamines (I), (II), (III) and (IV) H-, H- —|—N--(T)--Cf—H.--(Z)--C 4— ; Ri ï L- -J n

[0042] (I)

[0043]

[0044]

[0045] (IV)

[0046] in which

[0047] T and Z, identical or different, represent an alkyl group comprising from 1 to 12 carbon atoms, an aryl group comprising from 6 to 20 carbon atoms;

[0048] R1 and R2, identical or different, represent a hydrogen atom, an alkyl group comprising from 1 to 12 carbon atoms, an alkenyl group comprising 2 to 12 carbon atoms, an alkynyl group having 2 to 12 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkoxy group whose alkyl group has 1 to 12 carbon atoms, an aryloxy group whose aryl group has 6 to 20 carbon atoms, a heteroaryl group having 5 to 12 members, a 5 to 12 membered heterocycle, said alkyl, alkenyl, alkynyl, aryl, alkoxy, aryloxy, heteroaryl, heterocycle groups being optionally substituted, a group BR3R4with R3 and R^as defined below;

[0049] R3 and R4, which may be identical or different, represent a hydrogen atom, an alkyl group comprising 1 to 12 carbon atoms, an alkenyl group comprising 2 to 12 carbon atoms, an alkynyl group comprising 2 to 12 carbon atoms, an aryl group comprising 6 to 20 carbon atoms, a heteroaryl group comprising 5 to 12 members, a 5 to 12 membered heterocycle, an alkoxy group in which the alkyl group comprises 1 to 12 carbon atoms, an aryloxy group in which the aryl group comprises 6 to 20 carbon atoms, said alkyl, alkenyl, alkynyl, aryl, heteroaryl, heterocycle, alkoxy, aryloxy groups being optionally substituted; or

[0050] R3 and R4 taken together with the boron atom to which they are bonded, form a heterocycle comprising from 5 to 12 members, a heteroaryl group comprising from 5 to 12 members, said heterocycle and heteroaryl groups being optionally substituted;

[0051] X represents Cl, Br, I, HSO4, C1O4;

[0052] characterized in that they have a molar mass greater than 3000 g.mol *, preferably greater than 4000 g.mol *.

[0053] In the context of the present invention, the term "alkyl" is understood to mean, within the meaning of the present invention, a linear, branched or cyclic, saturated, optionally substituted carbon radical comprising 1 to 12 carbon atoms. In certain cases, the alkyl may comprise, for example, 4 to 12 carbon atoms, for example 6 to 12 carbon atoms. In other cases, the alkyl may comprise, for example, 1 to 11 carbon atoms, for example 1 to 8 carbon atoms, for example 1 to 6 carbon atoms. As saturated, linear or branched alkyl, mention may be made, for example, of the methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl, nonyl, decyl, undecyl, do-decanyl radicals and their branched isomers. As cyclic alkyl, we can cite the cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, bicylco[2,1,1]hexyl, bicyclo[2,2,1]heptyl radicals.

[0054] The alkyl groups may be optionally substituted by one or more hydroxyl groups; one or more alkoxy groups; one or more halogen atoms chosen from fluorine, chlorine, bromine or iodine atoms; one or more nitro groups (-NO2); one or more nitrile groups (-CN); one or more aryl groups, with the alkoxy and aryl groups as defined in the context of the present invention.

[0055] By "alkenyl" or "alkynyl" is meant a linear, branched or cyclic unsaturated carbon radical, optionally substituted, said unsaturated carbon radical comprising 2 to 12 carbon atoms comprising at least one double (alkenyl) or one triple bond (alkynyl). In this respect, mention may be made, for example, of the ethylenyl, propylenyl, butenyl, pentenyl, hexenyl, acetylenyl, propynyl, butynyl, pentynyl, hexynyl radicals and their branched isomers. As cyclic alkenyls, mention may be made, for example, of cyclopentenyl, cyclohexenyl. The alkenyl and alkynyl groups may comprise, for example, 2 to 8 carbon atoms.

[0056] The alkenyl and alkynyl groups may optionally be substituted by one or more hydroxyl groups; one or more alkoxy groups; one or more halogen atoms chosen from fluorine, chlorine, bromine or iodine atoms; one or more nitro groups (-NO2); one or more nitrile groups (-CN); one or more aryl groups, with the alkoxy and aryl groups as defined in the context of the present invention.

[0057] The term "aryl" denotes a cyclic aromatic substituent comprising from 6 to 20 carbon atoms. The aryl group may comprise, for example, 6 to 10 carbon atoms, for example 6 to 8 carbon atoms. The aryl group may comprise, for example, 6 carbon atoms. In the context of the invention, the aryl group may be mono- or polycyclic. By way of indication, mention may be made of the phenyl, benzyl, naphthyl, o-tolyl, m-tolyl, p-tolyl, mesityl, p-nitrophenyl, o-methoxyphenyl, m-methoxyphenyl and p-methoxyphenyl, o-methoxybenzyl, p-methoxybenzyl, m-methoxybenzyl, o-methylbenzyl, p-methylbenzyl and m-methylbenzyl groups.The aryl group may be optionally substituted by one or more hydroxyl groups, one or more alkoxy groups, several halogen atoms selected from fluorine, chlorine, bromine and iodine atoms, one or more nitro groups (-NO2), one or more nitrile groups (-CN), one or more alkyl groups, with the alkoxy groups, and alkyl as defined within the scope of the present invention.

[0058] The term "alkoxy" means an alkyl group, as defined above, linked through an oxygen atom (-O-alkyl).

[0059] The term "aryloxy" means an aryl group, as defined above, linked through an oxygen atom (-O-aryl).

[0060] By “halogen” atom is meant an atom chosen from fluorine, chlorine, bromine and iodine atoms. The “halide” anion denotes F, Cl, Br and I.

[0061] The term "heteroaryl" generally refers to a mono- or polycyclic aromatic substituent comprising from 5 to 12 members including at least 2 carbon atoms, and at least one boron atom and optionally another heteroatom chosen from nitrogen, boron, oxygen or sulfur. The heteroaryl group may include, for example, 5 to 7 members including at least 2 carbon atoms and one boron atom. For information, mention may be made of borabenzene groups (C5H5B), borole (C4H4BH), borepin (C6H6BH). The heteroaryl group may be optionally substituted by one or more hydroxyl groups, one or more alkoxy groups, one or more halogen atoms chosen from fluorine, chlorine, bromine and iodine atoms, one or more nitro groups (-NO2), one or more nitrile groups (-CN), one or more aryl groups, one or more alkyl groups, with the alkyl, alkoxy and aryl groups as defined in the context of the present invention. It is obvious that the term "heteroaryl" also encompasses mono- or polycyclic aromatic compounds comprising 5 to 12 members including at least 2 carbon atoms, and at least one heteroatom chosen from nitrogen, oxygen or sulfur, from which the aforementioned radicals / groups are derived.

[0062] The term "heterocycle or heterocyclic" within the meaning of the invention generally designates a mono- or polycyclic substituent, comprising from 5 to 12 members, saturated or unsaturated, containing from 1 to 4 heteroatoms including at least one boron atom and optionally another heteroatom chosen from nitrogen, oxygen, boron and sulfur. The heterocycle group may comprise, for example, 5 to 10 members and at least one boron atom, for example 5 to 9 members and at least one boron atom, for example 5 to 8 members and at least one boron atom. By way of indication, mention may be made of borolane, borinane, 9-borabicyclo[3.3.1]nonane (9-BBN), 1,3,2-benzodioxaborole (catecholborane or catBH), pinacolborane (pinBH).The heterocycle may be optionally substituted by one or more hydroxyl groups, one or more alkoxy groups, one or more aryl groups, one or more halogen atoms selected from fluorine, chlorine, bromine and iodine atoms, one or more nitro groups (-NO2), one or more nitrile groups (-CN), one or more alkyl groups, with the alkyl, alkoxy and aryl groups as defined in the context of the present invention. It is obvious that the term "heterocycle or heterocyclic" also encompasses mono- or polycyclic compounds, comprising from 5 to 12 members, saturated or unsaturated, containing from 1 to 4 heteroatoms selected independently of one another, from nitrogen, oxygen, boron and sulfur, from which the aforementioned radicals / groups are derived.

[0063] The term "polyamine" designates polymers in which the structural unit repeated in the chain contains the amine function in secondary or tertiary form or in the form of ammonium salts and having a molecular mass greater than 3000 g.mol *, and preferably greater than 4000 g.mol *.

[0064] The term "polyamide" designates polymers in which the structural unit repeated in the chain contains the amide function in secondary form (-CO-NH-) or in tertiary form (-CO-NR2- with R2 as defined in the context of the present invention).

[0065] According to a first embodiment of the invention, in the polyamines of formulas (I), (II), (III) and (IV),

[0066] T and Z, identical or different, represent an alkyl group comprising 1 to 12 carbon atoms, preferably 4 to 12 carbon atoms, more preferably 6 to 12 carbon atoms, an aryl group comprising 6 to 10 carbon atoms, preferably 6 to 8 carbon atoms, said alkyl and aryl groups being optionally substituted;

[0067] R 1 and R 2 , which may be identical or different, represent a group BR 3 R 4 with R 3 and R 4 as defined below, a hydrogen atom, an alkyl group comprising 1 to 12 carbon atoms, preferably 1 to 8 carbon atoms, more preferably 1 to 6 carbon atoms, an aryl group comprising 6 to 10 carbon atoms, preferably 6 to 8 carbon atoms, an alkenyl group comprising 2 to 12 carbon atoms, an alkynyl group comprising 2 to 12 carbon atoms, a heteroaryl group comprising 5 to 12 members, a 5 to 12 member heterocycle, an alkoxy group whose alkyl group comprises 1 to 12 carbon atoms, preferably 1 to 8 carbon atoms, more preferably 1 to 6 carbon atoms, an aryloxy group whose aryl group comprises 6 to 10 carbon atoms, preferably 6 to 8 carbon atoms, said alkyl, alkenyl, alkynyl, aryl, alkoxy, aryloxy, heteroaryl, heterocycle groups being optionally substituted;

[0068] R3 and R4, which may be identical or different, represent a hydrogen atom, an alkyl group comprising 1 to 12 carbon atoms, preferably 1 to 8 carbon atoms, more preferably 1 to 6 carbon atoms, an alkenyl group comprising 2 to 12 carbon atoms, an aryl group comprising 6 to 10 carbon atoms, an alkoxy group in which the alkyl group comprises 1 to 12 carbon atoms, preferably 1 to 8 carbon atoms, more preferably 1 to 6 carbon atoms, an aryloxy group in which the aryl group comprises 6 to 10 carbon atoms, preferably 6 to 8 carbon atoms, said alkyl, aryl, alkoxy or aryloxy groups being optionally substituted; or

[0069] R3 and R4 taken together with the boron atom to which they are bonded, form a heterocycle comprising from 5 to 12 members, a heteroaryl group comprising from 5 to 12 members, said heterocycle and heteroaryl groups being optionally substituted;

[0070] X represents Cl, Br, I, HSO4, C1O4.

[0071] Preferably, X is Cl.

[0072] In this embodiment, the molecular masses of the polyamines (I), (II), (III) and (IV) are greater than 3000 g.mol *, preferably greater than 4000 g.mol *.

[0073] According to a variant of this embodiment, T and Z, identical or different, represent an alkyl group comprising between 4 and 12 carbon atoms and preferably between 6 and 12.

[0074] According to another variant of this embodiment, R1 and R2, identical or different, represent a hydrogen atom, a BR3R4 group in which R3 and R4, taken together with the boron atom to which they are linked, form a 5-membered heterocycle, such as for example a catecholborane (CatBH), a pinacol group (2,3-dimethylbutane-2,3-diol).

[0075] According to a second embodiment of the invention, in the polyamines of formulas (I), (II), (III) and (IV),

[0076] R1 and R2, identical or different, represent a group BR3R4 with R3 and R4 as defined below, a hydrogen atom, an alkyl group comprising 1 to 12 carbon atoms, preferably 1 to 8 carbon atoms, more preferably 1 to 6 carbon atoms, an aryl group comprising 6 to 10 carbon atoms, preferably 6 to 8 carbon atoms, said alkyl and aryl radicals being optionally substituted;

[0077] T and Z, identical or different, represent an alkyl group comprising 1 to 12 carbon atoms, preferably 4 to 12 carbon atoms, more preferably 6 to 12 carbon atoms, an aryl group comprising 6 to 10 carbon atoms, preferably 6 to 8 carbon atoms, said alkyl and aryl groups being optionally substituted;

[0078] R3 and R4, which may be identical or different, represent a hydrogen atom, an alkyl group comprising 1 to 12 carbon atoms, preferably 1 to 8 carbon atoms, more preferably 1 to 6 carbon atoms, an aryl group comprising 6 to 10 carbon atoms, preferably 6 to 8 carbon atoms, an alkoxy group in which the alkyl group comprises 1 to 12 carbon atoms, preferably 1 to 8 carbon atoms, more preferably 1 to 6 carbon atoms, an aryloxy group in which the aryl group comprises 6 to 10 carbon atoms, preferably 6 to 8 carbon atoms, said alkyl, aryl, alkoxy or aryloxy groups being optionally substituted; or

[0079] R3 and R4 taken together with the boron atom to which they are bonded, form a heterocycle comprising from 5 to 10 members, a heteroaryl group comprising from 5 to 12 members, said heterocycle and heteroaryl groups being optionally substituted;

[0080] X represents Cl, Br, I, HSO4, C1O4.

[0081] Preferably, X is Cl.

[0082] According to a variant of this embodiment, T and Z, identical or different, represent an alkyl group comprising 11 carbon atoms.

[0083] According to another variant of this embodiment, T and Z, identical or different, represent an alkyl group comprising between 4 and 12 carbon atoms and preferably between 6 and 12.

[0084] According to yet another variant of this embodiment, R1 and R2, identical or different, represent a hydrogen atom, a BR3R4 group in which R3 and R4, taken together with the boron atom to which they are linked, form a 5-membered heterocycle, preferably a pinacol group (2,3-dimethyl butane-2,3-diol).

[0085] In this embodiment, the molar masses of the polyamines (I), (II), (III) and (IV) are greater than 3000 g.mol *, and preferably greater than 4000 g.mol *.

[0086] According to a third embodiment of the invention, in the polyamines of formulas (I), (II), (III) and (IV),

[0087] R1 and R2, identical or different, represent a group BR3R4 with R3 and R4 as defined below, a hydrogen atom, an alkyl group chosen from methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, and their branched isomers, or an aryl group chosen from phenyl, benzyl, naphthyl, said alkyl and aryl groups being optionally substituted;

[0088] T and Z, identical or different, represent an alkyl group chosen from methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, and their branched isomers, or an aryl group chosen from phenyl, benzyl, naphthyl, said alkyl and aryl groups being optionally substituted;

[0089] R3 and R4, which may be identical or different, represent a hydrogen atom, an alkyl group chosen from methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, and their branched isomers, an aryl group chosen from phenyl, benzyl, naphthyl, an alkoxy group chosen from methyloxy, ethyloxy, propyloxy, butyloxy, pentyloxy, hexyloxy, heptyloxy, and their branched isomers, or an aryloxy group chosen from phenyloxy, benzyloxy, naphthyloxy, said alkyl, aryl, alkoxy, aryloxy groups being optionally substituted;

[0090] X represents Cl, Br, I, HSO4, C1O4.

[0091] Preferably, X is Cl.

[0092] According to a variant of this embodiment, T and Z, identical or different, represent an alkyl group comprising between 4 and 12 carbon atoms and preferably between 6 and 12 carbon atoms.

[0093] In this embodiment, the molar masses of the polyamines (I), (II), (III) and (IV) are greater than 3000 g.mol *, preferably greater than 4000 g.mol *.

[0094] According to a fourth embodiment of the invention, in the polyamines of formulas (I), (II), (III) and (IV),

[0095] R1 and R2, identical or different, represent a group BR3R4 with R3 and R4 as defined below, a hydrogen atom, an alkyl group chosen from methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, and their branched isomers, or an aryl group chosen from phenyl, benzyl, naphthyl, said alkyl and aryl groups being optionally substituted;

[0096] T and Z, identical or different, represent an alkyl group chosen from methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, and their branched isomers, or an aryl group chosen from phenyl, benzyl, naphthyl, said alkyl and aryl groups being optionally substituted;

[0097] R3 and R4 taken together with the boron atom to which they are bonded, form a heterocycle comprising from 5 to 8 members, a heteroaryl group comprising from 5 to 12 members, said heterocycle and heteroaryl groups being optionally substituted;

[0098] X represents Cl, Br, I, HSO4, C1O4.

[0099] Preferably, X is Cl.

[0100] According to a variant of this embodiment, T and Z, identical or different, represent an alkyl group comprising between 4 and 12 carbon atoms and preferably between 6 and 12 carbon atoms.

[0101] According to another variant of this embodiment, R1 and R2, identical or different, represent a hydrogen atom, a BR3R4 group in which R3 and R4, taken together with the boron atom to which they are linked, form a 5-membered heterocycle, preferably a pinacol group (2,3-dimethyl butane-2,3-diol).

[0102] In this embodiment, the molar masses of the polyamines (I), (II), (III) and (IV) are greater than 3000 g.mol *, preferably greater than 4000 g.mol *.

[0103] New long carbon chain polyamines with a number of carbon atoms greater than 4 are manufactured from corresponding polyamides by a simple process.

[0104] This manufacturing process is based on the catalytic deoxygenation of the amide functions of the polyamide to generate the corresponding amine functions. This transformation is carried out using a catalyst / hydroborane system as a reducing agent, under mild pressure and temperature conditions. The corresponding polyamine is obtained in the case where all the amide functions of the polyamide have been reduced.

[0105] Thus, the invention also relates to a process for manufacturing polyamines of formulae (I), (II), (III) and (IV), characterized in that it comprises a step of bringing into contact a polyamide of formulae (V) and (VI) ™N----(T).------g---h ----C "H— .jn

[0106] (V)

[0107] (VI)

[0108] in which T, Z, Ri and R2 are as defined above,

[0109] with a reducing agent of formula (VII)

[0110] (VII) [YES] in which - R3 and R4, which may be identical or different, represent a hydrogen atom, an alkyl group containing 1 to 12 carbon atoms, an alkenyl group containing 2 to 12 carbon atoms, an alkynyl group containing 2 to 12 carbon atoms, an aryl group containing 6 to 20 carbon atoms, a heteroaryl group containing 5 to 12 members, a 5 to 12 membered heterocycle, an alkoxy group in which the alkyl group contains 1 to 12 carbon atoms, an aryloxy group in which the aryl group contains 6 to 20 carbon atoms, said alkyl, alkenyl, alkynyl, aryl, heteroaryl, heterocycle, alkoxy, aryloxy groups being optionally substituted; or - R3 and R4 taken together with the boron atom to which they are bonded, form a heterocycle comprising from 5 to 12 members, a heteroaryl group comprising from 5 to 12 members, said heterocycle and heteroaryl groups being optionally substituted;

[0112] in the presence of a metal catalyst chosen from - metal homoleptic complexes (((CH3)3Si)2N)n[M] with the bis(trimethylsilyl)amide ligand (((CH3)3Si)2N ) and [M] a rare earth chosen from lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, rhohnium, erbium, thulium, ytterbium, lutetium, scandium and yttrium - dual systems of type base / BEt3 in which the base is K0X° or NaOX' with X° and X' = H, OtBu, OMe, OAc, Ca(N(Si(CH3)3)2)2(THF)2 - lithium 2,6-di-tert-butylphenolate ([Li(OC6H3-2,6-tBu2) a metal acetylacetonate of formula Ln4O(acac)i0with Ln=La, Er, Eu, Gd, Y, metallocene complexes of general formula M(C5H5)2, where M11 is a metallic element in the oxidation state +2 chosen from, (C5H5)2ZrH2, (C5H5)2 ZrHX” ​​(X” =C1, Br, I ), an alkali metal borohydride selected from LiHBEt3, NaHBEt3, zinc complexes selected from Zn(O2CMe)2, Zn(O3SCF3)2, B(C6F5)3, benzothiophene boronic acids chosen from

[0113]

[0114] 2-Benzo[Z?]thiopheneboronic acid / 5-Bromobenzo[Z?]thiophene-2-boronic acid / Br nickel dichloro(dimethoxyethane) or NiCl2(dme), chlorobis(cyclooctene)iridium dimer or [Ir(COE)2Cl]2, a cobalt-diphosphine complex, in particular cobalt acetylacetonate bis[(2-diphenylphosphino)phenyl] ether or Co(acac)2 / DPEphos, molybdenum complexes selected from Mo(CO)6, MoO2C12, MoO2C12(H2 O)2 indium bromide or InBr2, chloroplatinic acid hexahydrate or H2PtCl6-6H2O.

[0115] All polyamides, regardless of the composition of the chain ends and their degree of polymerization, can be used in the process of the invention. This also includes all copolymers containing polyamide blocks, i.e. monomer blocks with amide functions (secondary or tertiary) as well as all plastic materials based on polyamides.

[0116] The polyamides of formula (V) and (VI) may be chosen from homopolymeric aliphatic polyamides, in particular PA 6, PA 12, PA 11, PA 4.6, PA 6.6, PA 6.9, PA 6.10, PA 6.12, PA 10.10, PA 10.12, or copolymers, in particular PA 6.6 / 6, PA 6 / 6, PA 6.10; semi-aromatic polyamides / polyphthalamides including polyhexamethylene isophthalamide (PA 6.1), polyhexamethylene terephthalamide (PA 6.T), polymetaxylylene adipamide (PA mXD.6); aromatic polyamides / aramids including polymetaphenylene isophthalamide (PA MPD.I), polymetaphenylene terephthalamide (PA PPD.T), poly-trimethylhexamethylene terephthalamide (PA 6 / 3-T).

[0117] The reducing agent may be a borane of formula (VII) "'B-----H

[0118] (VII)

[0119] in which R3 and R4, identical or different, represent a hydrogen atom, an alkyl group comprising 1 to 12 carbon atoms, an alkenyl group comprising 2 to 12 carbon atoms, an alkynyl group comprising 2 to 12 carbon atoms, an aryl group comprising from 6 to 20 carbon atoms, a heteroaryl group comprising from 5 to 12 members, a heterocycle comprising from 5 to 12 members, an alkoxy group whose alkyl group comprises 1 to 12 carbon atoms, an aryloxy group whose aryl group comprises from 6 to 20 carbon atoms, said alkyl, alkenyl, alkynyl, aryl, heteroaryl, heterocycle, alkoxy, aryloxy groups being optionally substituted.

[0120] According to a fifth embodiment of the invention, the polyamide of formula (V) and (VI) is PA 6, PA 11, PA 12, PA 4.6, PA 6.6, PA 6.10, PA 6.12.

[0121] The reducing agent is a borane of formula (VII) --H

[0122] (VII)

[0123] in which R3 and R4, taken together with the boron atom to which they are

[0124] linked, form a heteroaryl group comprising 5 to 12 members, a heterocycle comprising from 5 to 12 members, said heteroaryl and heterocycle being optionally substituted.

[0125] According to a sixth embodiment of the invention, the reducing agent is chosen from catecholborane (CatBH), pinacolborane (HBpin), HB(C6Hn)2, 9-BBN.

[0126] According to a seventh embodiment of the invention, the metal catalyst is chosen from (((CH3)3Si)2N)3La, KOtBu / BEt3, KOH / BEt3, Zn(O2CMe)2, Mo(CO)6, MoO2C12.

[0127] The catalyst may, if appropriate, be immobilized on a heterogeneous support, for example, in order to ensure easy separation of said catalyst and / or its recycling. Said heterogeneous supports may be chosen from supports based on silica gel, cationic polymers such as, for example, poly(ethyleneimine) (PEI), poly-L-(lysine) (PLL), polysaccharides, plastic polymers such as, for example, polystyrene; carbon supports chosen from carbon nanotubes; silicon carbide; alumina; and magnesium chloride.

[0128] The amount of catalyst can be between 0.1 mol% and 20 mol%, preferably between 0.05 and 15 mol%, more preferably between 1 and 10 mol%, relative to the polyamide of formula (V) and (VI).

[0129] The quantity of the reducing agent of formula (VII) can vary from 1 to 20 equivalents, preferably between 2 and 10 equivalents, relative to the polyamide of formula (V) and (VI).

[0130] The process can take place at atmospheric pressure under an inert atmosphere (nitrogen, argon for example).

[0131] It can also be carried out under a pressure of a gas or a mixture of inert gas(es) chosen from nitrogen and argon or the gas generated by the process, in particular dihydrogen. In this case, the pressure can be between 0.2 and 5 bar, for example between 1 and 2 bar.

[0132] The temperature at which the method of the invention is carried out may be between 100°C and 300°C, preferably between 150 and 250°C. In one embodiment of the invention, the temperature is 150°C.

[0133] The reaction time can vary from a few days to a few hours depending on the starting polyamide, the solvent, the nature and quantity of catalyst, the nature and quantity of the reducing agent, and the temperature. The optimal reaction time corresponds to the complete conversion of the starting polyamide. For example, the duration can be between 1 hour and 168 hours, preferably between 5 and 144 hours, more preferably between 15 and 120 hours.

[0134] The process of the invention, in particular the contacting of the polyamide of formula (V) and (VI) with the reducing agent of formula (VII) and the catalyst, can take place in the absence of solvent or in one or a mixture of at least two solvent(s). Thus, the solvent can be chosen from: - aromatic hydrocarbons selected from the group consisting of benzene, toluene, xylene (ortho, meta, para), ethylbenzene, cumene or isopropylbenzene, mesitylene or 1,3,5-trimethylbenzene; - ethers, linear or cyclic, chosen from the group consisting of diethyl ether, dibutyl ether, methyl tert-butyl ether, THF, 2-methyltetrahydrofuran, dioxane, diglyme, anisole.

[0135] In the absence of a solvent, the reducing agent, when liquid, can serve as both a reagent and a solvent.

[0136] The polyamines of formula (I), (II), (III) and (IV) are obtained after reduction by treatment with a strong acid chosen, for example, from HCl, HBr, HI, H2SO4, HClO4, or a strong base chosen, for example, from NaOH, KOH

[0137] The present invention opens access to new polyamines by a process of catalytic reduction of polyamides which is carried out under mild conditions of temperature and pressure using reagents which are less toxic and dangerous than those commonly used.

[0138] These new polyamine materials are generated from polyamide materials, polymers commonly called nylons. These nylons are used on a large scale in the field of fibers or engineering plastics for various application sectors (textiles, sports, automotive, construction, etc.). Despite the development of reuse routes to extend the life of products, the intensive use of these nylons inevitably leads to an accumulation of waste. Currently, the latter is mainly stored (landfilled or buried) or incinerated. Storage and incineration are not sustainable solutions in the long term. They lead to material waste, economic loss and generate numerous pollutions. During incineration, the reduction in mass and volume of waste burned at very high temperatures is accompanied by the production of gaseous effluents (N2O, CO, CO2, etc.) and liquids, toxic and / or having a strong greenhouse effect. The development of new mechanical and / or chemical treatment methods, more respectful of the environment, is therefore necessary to create a circular economy for this material and avoid pollution.

[0139] Mechanical recycling allows the processing of polyamides to form new ones, mostly reused for purposes other than their initial use. However, with each recycling cycle, the nylon is degraded. Its lifespan is therefore slightly extended but quickly ends with storage or incineration.

[0140] To circumvent these problems, chemical reprocessing methods are attractive and increasingly considered the most promising recovery routes. Compared to mechanical recycling, they theoretically offer sustainable use of the material over time. They are already being developed by a few industrial companies (ECONYL®, Aquafil) for the recycling of PA 6 and PA 6.6. On an academic or industrial scale, the rare chemical treatment routes for polyamides (CreaSolv® process, depolymerization by hydrolysis, alcoholysis, aminolysis or catalytic) only allow the recovery of carbonaceous material in the form of products without added value (polyamide free of any contaminants, monomers or corresponding derivatives). These methods require working under high pressures and / or high temperatures, and the use of expensive chemical compounds, sometimes in large quantities.To overcome these costs and make these techniques economically viable, it is necessary to recover this waste into high added value products that can be used in many industrial sectors.

[0141] The present invention therefore constitutes a double technological lever: an innovative way of treating polyamide waste (upcycling) and access to new polyamines with high recovery potential.

[0142] The invention also relates to the use of polyamines of formulas (I), (II), (III) and (IV) for CO2 capture, extraction of metal salts, water treatment, purification of contaminated environments, manufacture of solid or semi-solid battery electrolytes, manufacture of flame retardants, as additives for engine oils, as building blocks for polymer synthesis, manufacture of plastics, manufacture of membranes and filters, manufacture of anti-bacterial materials.

[0143] Another object of the invention is the use of a process according to the invention for the recovery and upcycling of polyamide / nylon waste into polyamines of formulae (I), (11), (111) and (IV). EXAMPLES Details of the procedure

[0144] General considerations:

[0145] The glassware is previously dried overnight at 80°C. The reagents are introduced at 20°C in an mBraunLabMasterDP glove box under an inert atmosphere (Ar). Since the catalyst and hydroborane are sensitive to water and air, it is necessary to operate under anhydrous and anaerobic conditions.

[0146] All reagents were purchased from a chemical supplier (Sigma-Aldrich), with a purity of 98% for the catalyst and 97% for the hydroborane. The products were degassed, stored in the glove box and used without further prior purification. NMR spectra were recorded on a Broker AVANCE Neo 400 MHz spectrometer at 20 °C. Chemical shift (δ) values ​​are referenced to the residual peaks of the solvent and reported in parts per million (ppm) relative to tetramethylsilane. Multiplicities are named singlet (s), doublet (d), triplet (t), quartet (q), multiplet or overlapped signals (m) and broad signal (br), the solvent is given in parentheses.

[0147] The numbers of moles and equivalents of polyamide correspond to those of the associated monomers. The quantities of catalyst and hydroborane to be introduced are calculated in relation to the number of amide functions to be deoxygenated. Example 1:

[0148] Procedure in an NMR tube:

[0149] In a J. Young NMR tube, the commercial PA 6 beads are introduced (34 mg, 0.30 mmol, 1 equiv.), La[N(SiMe3)2]3 (9.3 mg, 0.015 mmol, 5 mol%) and THF-d8 (0.3 mL, 3.70 mmol, 11 equiv.). Pinalcolborane (218 qL, 1.50 mmol, 5 equiv.) is then added to the reaction mixture. The tube is closed and then heated in a bath

[0150]

[0151]

[0152]

[0153] of oil at 150 °C for 24 h. After catalysis, the PA6 beads are no longer visible to the naked eye and a whitish opaque solution is obtained. The solvent and excess pinacolborane are then evaporated under vacuum until a whitish pasty solid is obtained. After adding THF, the reaction medium is filtered through basic alumina (activated, standard grade, Brockmann I, pore size 58 Å). The addition of 3 mL of a 1M HCl / MeOH solution allows the precipitation of the product in the form of ammonium salts. After centrifugation, the solid obtained is dried overnight on a ramp. A cottony white product is obtained with a total yield over the two stages of 70% (purity >90%). 'H and 13C NMR analyses in D2O confirm the structure of the product in the form of ammonium salt as shown in [Fig.2] and [Fig.3]. GPC (SEC) analysis confirms the polymeric structure of the product obtained: Mn=4309 g.mol1 (±3.073%), Mw=8932 g.mol1 (±0.785%) and Mw / Mn=2.073. j $ ® ? i 'H NMR (400 MHz, D2O) ô (ppm) = 3.00 (m, 4H, (C / / 2)a), 'N'" 'kH aeb M':f “HCl 1.66 (m, 4H, (C / / 2)b), 1.38 (m, 4H, (CH2)c). 13C{*H} NMR (400 MHz, D2O) ô (ppm) = 47.40 ((CH2)a), 25.34 ((CH2)b), 25.29 ((C H2)c). Example 2: Different systems tested on the PA 6: A. „ (N ©qui VJ U Sokant, A, time

[0154] [Tables 1] Entry Cat. (mol%; Red. (equiv.) Solvent Temperature (;,C) Time (h; Yield3 (%) 1 La[N(SiMe,h]3(ij HBpin {5} THF-ds 150 15 24 86 90 2 L3IN{SiMe:M(2) HBpin {5} THF-d 90 9 29 3 La[N(SiMe3)2h(5) HBpin (5) THF-ds 150 15 71 24 88 4 HBpin (5) THF-dg 150 15 24 47 75 5 LaRSiMe3)2]3{20) HBpin (54) 150-dg THF-dg 57 80 1 64 6 La[N(SiMe3)2]s(5) HBpin (5) THF-ds 200 5 83 15 77 7 La(N(SiMe3)2]3 (5) HBpin (5; Anisole 150 24 85 8 LaîN(SiMe3)2]s(5) HBpin 150 15 24 49 72 9 LafN(SiMe3)2]j(5) CatBH {5) THF-ds 150 24 54 W La{N(SiMe3),]3(5) 9BBN dimer (5) THF-dg {5} THF-ds 150 24 83 12 La[N(SiMe3),]3(5} HBpin <2,2} THF-dg 150 46 50 13 La(N(SiMe3}2]3(5) HBpin (10) THF-ds (20) THF-dg 150 46 67 15 Mo(CO)6 HBpin {5} THF-dg 150 48 27 16 Zn(QAc)2 HBpin (5) THF-ds 150 48 32 17 KO'Bu / BEtg (5} HBTHF-dg 18 KOH'BEL (5) HBpin (5) THF-ds 150 29 77 3 Yields calculated by NMR relative to the internal standard (mesityene). Example 3:

[0155] Deoxygenation of different polyamides:

[0156] [Tables2] Polyamide inlet Cat. (mol%) Red. (equiv.) Solvent Temperature {'C) Time (h) Yield3 (%) 1 PA 6 6 La[N(StMe 3)2]3 (5) HBpin (10) THF-d3 150 48 51 il PA 6.12 LaiN(SiMes)2]3(5) HBpin (10) THF-d8 150 24 92 3 PA 11 La^SiMes^Jj (5) HBpin (5) THF-ds 150 48 89 8 Yields calculated by 'H NMR compared to the internal standard (mesityene).

Claims

Claims

1.

1. Polyamines of formulas (I), (II), (III) and (IV) (II) (IV) in which T and Z, identical or different, represent an alkyl group containing from 1 to 12 carbon atoms, an aryl group containing from 6 to 20 carbon atoms; Ri and R2, identical or different, represent a hydrogen atom,

2. an alkyl group having from 1 to 12 carbon atoms, an alkenyl group having from 2 to 12 carbon atoms, an alkynyl group having from 2 to 12 carbon atoms, an aryl group having from 6 to 20 carbon atoms, an alkoxy group whose alkyl group has from 1 to 12 carbon atoms, an aryloxy group whose aryl group has from 6 to 20 carbon atoms, a heteroaryl group having from 5 to 12 members, a 5 to 12 membered heterocycle, said alkyl, alkenyl, alkynyl, aryl, alkoxy, aryloxy, heteroaryl, heterocycle groups being optionally substituted, a group BR3R4with R3 and R4as defined below; R3 and R4, which may be identical or different, represent a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, an alkynyl group having 2 to 12 carbon atoms, an aryl group having 6 to 20 carbon atoms, a heteroaryl group having 5 to 12 members, a 5 to 12 membered heterocycle, an alkoxy group whose alkyl group has 1 to 12 carbon atoms, an aryloxy group whose aryl group has 6 to 20 carbon atoms, said alkyl, alkenyl, alkynyl, aryl, heteroaryl, heterocycle, alkoxy, aryloxy groups being optionally substituted; or R3 and R4 taken together with the boron atom to which they are bonded, form a heterocycle having from 5 to 12 members, a heteroaryl group having from 5 to 12 members, said heterocycle and heteroaryl groups being optionally substituted; X represents Cl, Br, I, HSO4, C1O4; characterized in that they have a molar mass greater than 3000 g.mol *, preferably greater than 4000 g.mol *. Polyamines according to claim 1, characterized in that Ri and R2, identical or different, represent a group BR3R4 with R3 and R^ as defined below; T and Z, identical or different, represent an alkyl group containing 1 to 12 carbon atoms, an aryl group containing 6 to 10 carbon atoms, said alkyl and aryl groups being optionally substituted; R3 and R4, which may be identical or different, represent a hydrogen atom, an alkyl group containing 1 to 12 carbon atoms, an aryl group containing 6 to 10 carbon atoms, an alkoxy group whose alkyl group contains 1 to 12 carbon atoms, an aryloxy group the aryl group of which has 6 to 10 carbon atoms, said alkyl, aryl, alkoxy, aryloxy groups being optionally substituted; or R3 and R4 taken together with the boron atom to which they are bonded, form a heterocycle having 5 to 10 members, a heteroaryl group having 5 to 12 members, said heterocycle and heteroaryl groups being optionally substituted; X represents Cl, Br, I, HSO4, C1O4; and in that they have a molecular mass greater than 3000 g.mol *.

3. Polyamines according to one of claims 1 or 2, characterized in that, R1 and R2, identical or different, represent a group BR1R4 with R3 and R^ as defined below; T and Z, identical or different, represent an alkyl group chosen from methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, and their branched isomers, or an aryl group chosen from phenyl, benzyl, naphthyl, said alkyl and aryl groups being optionally substituted; R3 and R4, which may be identical or different, represent a hydrogen atom, an alkyl group chosen from methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, and their branched isomers, an aryl group chosen from phenyl, benzyl, naphthyl, an alkoxy group chosen from methyloxy, ethyloxy, propyloxy, butyloxy, pentyloxy, hexyloxy, heptyloxy, and their branched isomers, or an aryloxy group chosen from phenyloxy, benzyloxy, naphthyloxy, said alkyl, aryl, alkoxy, aryloxy groups being optionally substituted; X represents Cl, Br, I, HSO4, C1O4; and in that they have a molecular mass greater than 3000 g.mol *.

4. Polyamines according to one of claims 1 or 2, characterized in that, R1 and R2, identical or different, represent a group BR3R4 with R3 and R^ as defined below, a hydrogen atom, an alkyl group chosen from methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, and their branched isomers, or an aryl group chosen from phenyl, benzyl, naphthyl, said alkyl and aryl groups being optionally substituted; T and Z, identical or different, represent an alkyl group chosen from methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, and their

5. branched isomers, or an aryl group selected from phenyl, benzyl, naphthyl, said alkyl and aryl groups being optionally substituted; R3 and R4 taken together with the boron atom to which they are attached, form a heterocycle comprising from 5 to 8 members, a heteroaryl group comprising from 5 to 12 members, said heterocycle and heteroaryl groups being optionally substituted; X represents Cl, Br, I, HSO4, C1O4; and in that they have a molecular mass greater than 3000 g.mol *. Process for the manufacture of polyamines of formulae (I), (II), (III) and (IV) characterized in that it comprises a step of bringing into contact a polyamide of formulae (V) and (VI)

5. (V) (VI) in which T, Z, Ri and R2 are as defined in one of claims 1 to 4, with a reducing agent of formula (VII) "B.............H (VII) in which R3 and R4, identical or different, represent a hydrogen atom, an alkyl group containing 1 to 12 atoms of carbon, an alkenyl group having 2 to 12 carbon atoms, an alkynyl group having 2 to 12 carbon atoms, an aryl group having 6 to 20 carbon atoms, a heteroaryl group having 5 to 12 members, a 5 to 12 membered heterocycle, an alkoxy group in which the alkyl group has 1 to 12 carbon atoms, an aryloxy group in which the aryl group has 6 to 20 carbon atoms, said alkyl, alkenyl, alkynyl, aryl, heteroaryl, heterocycle, alkoxy, aryloxy groups being optionally substituted; or - R3 and R4 taken together with the boron atom to which they are bonded, form a heterocycle comprising from 5 to 12 members, a heteroaryl group comprising from 5 to 12 members, said heterocycle and heteroaryl groups being optionally substituted; in the presence of a metal catalyst chosen from - metal homoleptic complexes (((CH3)3Si)2N)n[M] with the bis(trimethylsilyl)amide ligand (((CH3)3Si)2N ) and [M] a rare earth chosen from lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, rhohnium, erbium, thulium, ytterbium, lutetium, scandium and yttrium - dual systems of type base / BEt3 in which the base is K0X° or NaOX' with X° and X' = H, OtBu, OMe, OAc, Ca(N(Si(CH3)3)2)2(THF)2 - lithium 2,6-di-tert-butylphenolate ([Li(OC6H3-2,6-tBu2) - a metal acetylacetonate of formula Ln4O(acac)i0with Ln=La, Er, Eu, Gd, Y, - metallocene complexes of general formula M(C5H5)2, where M11 is a metallic element in the oxidation state +2 chosen from, (C5H5)2ZrH2, (C5H5)2ZrHX” (X” = Cl, Br, I), - an alkali metal borohydride chosen from LiHBEt3, NaHBEt3, - zinc complexes chosen from Zn(O2CMe)2, Zn(O3SCF3) 2,

6.

7. B(C6F5)3, - benzothiophene boronic acids chosen from 2-Benzo[Z?]thiopheneboronic acid / ' \ , X “ / 5-Bromobenzo[h]thiophene-2-boronic acid / \ , 1 1 Xy— - nickel dichloro(dimethoxyethane) or NiCl2(dme), - chlorobis(cyclooctene)iridium dimer or [Ir(COE)2Cl]2, - a cobalt-diphosphine complex, in particular cobalt acetylacetonate bis[(2-diphenylphosphino)phenyl] ether or Co(acac)2 / DPEphos, - molybdenum complexes chosen from Mo(CO)6, MoO2C1 2, MoO2C12(H2O)2 - indium bromide or InBr2, - chloroplatinic acid hexahydrate or H2PtCl6-6H2O. Process according to claim 5, characterized in that the polyamides of formula (V) and (VI) are chosen from - aliphatic polyamide homopolymers, in particular PA 6, PA 12, PA 11, PA 4.6, PA 6.6, PA 6.9, PA 6.10, PA 6.12, PA 10.10, PA 10.12, or copolymers, in particular PA 6.6 / 6, PA 6 / 6, PA 6.10; - semi-aromatic polyamides / polyphthalamides, in particular polyhexamethylene isophthalamide (PA 6.1), polyhexamethylene terephthalamide (PA 6.T), polymetaxylylene adipamide (PA mXD.6); - aromatic polyamides / aramids, in particular polymetaphenylene isophthalamide (PA MPD.I), polymetaphenylene terephthalamide (PA PPD.T), polytrimethylhexamethylene terephthalamide (PA 6 / 3-T). Process according to one of claims 5 or 6, characterized in that the reducing agent of formula (VII) is chosen from catecholborane (CatBH), pinacolborane (HBpin), dicyclohexylborane (HB(C6Hn)2), 9-Borabicyclo[3.3.1]nonane (9-BBN).

8. Process according to any one of claims 5 to 7, characterized in that the quantity of catalyst is between 0.1 mol% and 20 mol%, relative to the polyamide of formula (V) and (VI).

9. Process according to any one of claims 5 to 8, characterized in that the quantity of the reducing agent of formula (VII) varies from 1 to 20 equivalents, relative to the polyamide of formula (V) and (VI).

10. Use of the polyamines of formulae (I), (II), (III) and (IV) according to any one of claims 1 to 4, for the capture of CO2, the extraction of metal salts, the treatment of water, the purification of contaminated media, the manufacture of solid or semi-solid battery electrolytes, the manufacture of flame retardants, as additives for engine oils, as bricks for the synthesis of polymers, the manufacture of plastics, the manufacture of membranes and filters, the manufacture of anti-bacterial materials.

11. Use of a process according to any one of claims 5 to 9, for the recovery and upcycling of polyamide / nylon waste into polyamines of formulae (I), (II), (III) and (IV) according to any one of claims 1 to 4.

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