Use of a polymer derived from muconic or sorbic acid in a method for treating non-keratinized materials, polymer, composition, method and products for breaking down such a polymer

Abstract

The present invention relates to novel homopolymers or copolymers derived from muconic or sorbic acid, to the method for preparing same, to a non-cosmetic composition comprising at least one homopolymer or copolymer derived from muconic or sorbic acid, and to a method for treating a non-keratinized material with at least one homopolymer or copolymer derived from muconic or sorbic acid, or with a composition comprising at least one such polymer. The invention further relates to a method for breaking down such polymers, as well as to diacid derivatives that can be obtained by such a method.

Description

[0001] USE OF A POLYMER DERIVED FROM MUCONIC OR SORBIC ACID IN A PROCESS FOR TREATMENT OF NON-KERATINIZED MATERIALS, POLYMER, COMPOSITION, PROCESS AND DEGRADATION PRODUCTS OF SUCH A POLYMER

[0002] TECHNICAL FIELD

[0003] The present invention relates to novel homopolymers or copolymers derived from muconic or sorbic acid, their preparation process, a composition comprising at least one such polymer derived from muconic and / or sorbic acid, and a process for treating a non-keratinized material comprising applying such a polymer or such a composition to at least a portion of said non-keratinized material. The invention further relates to a process for degrading such polymers, as well as diacid compounds that can be obtained by such a degradation process.

[0004] TECHNOLOGICAL BACKGROUND

[0005] Polyacrylates are polymers formed from acrylic monomers. These plastics are known for their transparency, fracture resistance, hydrogel formulation, adhesiveness, and elasticity. They are used in a wide range of applications, from paints to cosmetic formulations and baby diapers.

[0006] However, there are few bio-based acrylate monomers, and very few processes for degrading polyacrylates after use.

[0007] Nowadays, environmental concerns make it essential to promote the use of bio-based and / or degradable materials after use.

[0008] It would therefore be desirable to have polymers that could represent bio-based and / or biodegradable alternatives to polyacrylates. Preferably, the synthesis processes for these polymers should allow for a wide variety of polymers in terms of length and structure.

[0009] Muconate esters are derived from muconic acid (MA), also called 2,4-hexadienedioic acid, which is both a conjugated diene and a dicarboxylic acid.

[0010] Several synthetic routes, including bio-based ones, have been developed from muconic acid since 1980 (see, for example, "Biotechnological Production of Muconic Acid: Current Status and Future Prospects," Biotechnol. Adv. 2014, 32(3), 615-622 and "Muconic Acid Isomers as Platform Chemicals and Monomers in the Biobased Economy," Green Chem. 2020, 22(5), 1517-1541), and numerous sources for muconic acid production are currently being considered. These include biotechnologies involving the fermentation of lignin or glucose derivatives. One of the advantages of muconic or sorbic acid polymers obtained by step-growth polymerization is the presence of unsaturations (C=C double bonds) in the backbone, allowing for post-polymerization modifications, particularly to adjust their properties.

[0011] Matsumoto et al. developed a 1,4-topochemical polymerization route of dialkyl muconates by photoirradiation of the monomers in their crystalline state, forming stereoregular polymer chains (X Stereospecific Polymerisation of Diethyl (Z,Z)-Hexa-2,4-Dienedioate in the Crystalline State. J. Chem. Soc. Chem. Commun. 1994, No. 11, 1389).

[0012] More recently, Junkers et al. reported the solution radical polymerization of dialkyl muconates, forming high molecular weight polymers (> 100,000 g mol'). 1 ). (Muconic Acid Esters as Bio-Based Acrylate Mimics. Polym. Chem. 2019, 10 (40), 5555-5563).

[0013] Monomers can also be polymerized in a controlled manner by the reversible addition fragmentation radical transfer (RAFT) polymerization process. However, to achieve high monomer conversion, radical polymerization reactions are very slow and time-consuming, for example, between 24 and 48 hours at 120°C.

[0014] Alkyl sorbates exhibit structural similarities to alkyl muconates as polar conjugated dienes.

[0015] Four major synthetic routes of alkyl polysorbates are known: a) living anionic polymerization (LAP), (Microstructure of Poly(Methyl Sorbate). Eur. Polym. J. 1985, 21 (1), 71-74); b) coordinated anionic polymerization, (Highly Threo Diastereoselective Anionic Polymerization of (E,E)-Methyl Sorbate Catalyzed by a Bulky Organoaluminum Lewis Acid. Macromolecules 2001, 34 (19), 6548-6550); c) Lewis Pair Catalyzed Regioselective Polymerization of (E,E)-Alkyl Sorbates for the Synthesis of (AB)n Sequenced Polymers. Angew. Chem. Int. Ed. 2021, 60 (45), 24306-24311); and d) group transfer polymerization (GTP), (Organocatalyzed Group Transfer Polymerization of Alkyl Sorbate: Polymer Synthesis, Postpolymerization Modification, and Thermal Properties. Macromolecules 2021, 54 (19), 9039-9052).

[0016] This latest group transfer polymerization method contrasts with many "controlled / live" polymerization methods, as GTP polymerization can be carried out at room temperature and does not require the use of sulfur-containing control agents, metal catalysts, or halogenated initiators. This is particularly important for specific applications where the presence of contaminants can be detrimental and necessitate additional purification steps.

[0017] To our knowledge, only one report briefly describes the GTP synthesis of trans,trans-diethyl muconate. However, the polymerization carried out in THF was not controlled, resulting in a low molecular weight, high-dispersity polymer. (Group Transfer Polymerization with Polyunsaturated Esters and Silyl Polyenolates. J. Am. Chem. Soc. 1988, 110 (17), 5841-5853)

[0018] In this context, the inventors of the present invention have developed a group transfer polymerization (GTP) synthesis process for polymers applicable to both muconic acid and sorbic acid polymers. The process thus enables the versatile, controlled, and predictable production of polymers that can be used in applications similar to those targeted by polyacrylates. Polymerization takes place within minutes. The resulting polymers can be bio-based, modified post-polymerization, and degraded post-use, notably by ozonolysis.

[0019] Due to their unique structure, polymers derived from muconic and / or sorbic acid possess properties similar to those of polyacrylates and polar dienes. The resulting polymers can be advantageously used in compositions to impart specific properties to the composition and / or the substrate to which it is applied (or coated).

[0020] SUMMARY OF THE INVENTION

[0021] Thus, a first object of the invention is a process for treating a non-keratinized material, comprising applying to at least a part of the non-keratinized material at least one polymer comprising several repeating units selected from the following units (A), as well as their optical and geometric isomers, their acid or base salts, organic or mineral, and their solvates such as hydrates, or a composition comprising at least one such polymer: unit (A), units (A) in which:

[0022] Ri represents an (Ci-C4)alkyl group such as methyl, or a -C(O)-OR'4 group;

[0023] R2 and R3, whether identical or different, represent a hydrogen atom or a hydroxy group;

[0024] R2 and R3 together form a connection, or

[0025] R2 and R3 together form a saturated or unsaturated heterocycle, preferably saturated, comprising at least one oxygen atom, and comprising 3 to 6 links;

[0026] R4 and R4', whether identical or different, represent i) a hydrogen atom, ii) a cationic counter ion M +, or iii) a hydrocarbon group, saturated or unsaturated, linear, branched or cyclic, aromatic or non-aromatic, comprising from 1 to 140 carbon atoms, said hydrocarbon group being further: optionally substituted by one or more (di)(Ci-C4)(alkyl)amino groups; and / or optionally interrupted by one or more a') heteroatoms such as O, S, N(R a ), and Si(Rb)(Rc), b') S(O)r with r being 1, 2 or 3, carbonyl, or c') the associations of a') with b');

[0027] Ra, Rb, Rc, identical or different, representing a hydrogen atom or a (C i-C4)alkyl group, it being understood that:

[0028] - when R2 (and / or R3) represents a hydroxyl radical and R4 (and / or R'4) represents a hydrogen atom or a cationic counterion M + , then R2 and the group -C(O)-OR4 (and / or R3 and the group -C(O)-OR'4) can together form a heterocycle with 5 or 6 members; and

[0029] - when R4 and / or R4' represents a cationic counter ion M + , then the oxygen atom of the group -OR4 and / or R4' is in anionic form -O' , and the Ri of the different units (A), the R2 of the different units (A), the R3 of the different units (A), the R.4 of the different units (A), and the RA of the different units (A), can be identical or different.

[0030] In some embodiments, the at least one polymer is a homopolymer, a copolymer, and / or a mixture of at least one homopolymer and at least one copolymer. In some embodiments, the polymer comprises:

[0031] (i) several units chosen from among the units (A) as defined above, and

[0032] (ii) one or more unit(s) chosen independently from units (Al) to (A15), their optical isomers, geometric isomers, their acid or base salts, organic or mineral, their solvates such as hydrates and mixtures thereof:

[0033] Table 1

[0034]

[0035] in which RI, R2, R3 and R4 are such as defined for Ri, R2, R3 and R4 respectively for units (A),

[0036] X represents an oxygen atom, sulfur atom or an amino group N(Ra) with Ra representing a hydrogen atom or a (Cl-C4)alkyl group;

[0037] RET, whether identical or different, represents a group resulting from the crosslinking of one or more reactive group(s) of at least one unit (A) with one or more crosslinking agents; and

[0038] I represents the point of attachment of the group to the rest of the molecule; it being understood that the Ri, R2, R3, R4, R'4 of the different units (A) and RI, R2, R3 and R4 of the units (Al) to (A15) can be identical or different.

[0039] In some embodiments, the units (A) are such that Ri represents a (Ci-C4)alkyl group such as methyl.

[0040] In some embodiments, the units (A) are such that Ri represents a -C(O)- OR'4 group with the R'4, identical or different, representing i) a hydrogen atom, ii) a cationic counterion M + , preferably an alkali or alkaline earth metal cation, or an ammonium cation, or iii) a hydrocarbon chain, saturated or unsaturated, linear or branched, non-cyclic or saturated or unsaturated cyclic, aromatic or non-aromatic, comprising from 1 to 30 carbon atoms; preferably comprising from 2 to 20 carbon atoms, preferably said hydrocarbon chain being saturated cyclic linear or branched, or cyclic; said hydrocarbon chain further being: optionally substituted by one or more (di)(Ci-C4)(alkyl)amino groups; and / or optionally interrupted by one or more a') heteroatoms such as O, S, N(R a ), and Si(Rb)(Rc), b') S(O) rwith r being 1, 2 or 3, carbonyl, or c') associations of a') with b') such as the groups -C(O)-O-, -OC(O)-, amide -C(O)- N(R a )- or -N(R a )-C(O)-, urethane -N(R a )-C(O)-O- or -OC(O)- N(R a )-, urea - N(R a )-(CO)- N(Rb)-, carbonate -OC(O)-O-, -[O-Si(Rb)(Rc)] P - or -[(CR a 2) q -O] P - , q being an integer between 1 and 4; with p between 1 and 200, in which R' represents a hydrogen atom, a (Ci-C4)alkyl group or S(O) r with r equal to 1, 2 or 3, R a , Rb and R c , identical or different, represent a hydrogen atom or an (Ci-C4)alkyl group, particularly R a represents a hydrogen atom, Rb and R c , being as defined previously, preferably represent a (Ci-C4)alkyl group such as methyl.

[0041] In some embodiments, the units (A) are such that R2 and R3, identical or different, represent a hydrogen atom or a hydroxy group, it being understood that R2 and R3 cannot simultaneously represent a hydrogen atom, preferably R2 and R3 represent a hydroxy group; preferably the units (A) are units (B): units (B) in which Ri and R4 are as defined above, particularly units (B) are such that R4 represents a hydrogen atom or a cationic counterion M +, preferably an alkali or alkaline earth metal cation, or ammonium, a primary, secondary or tertiary (Ci-Cs)alkylamine which may comprise one or more nitrogen and / or oxygen atoms and may comprise several alcohol functions, it being understood that at least one of the nitrogen atoms is protonated so as to form an ammonium and that each of the amines is protonated, said units (B) being able to be in the form of cyclized units (Bl), particularly in acidic media:

[0042] (B) (Bl) and when Ri represents a -C(O)-OR'4 group, in particular carboxy, or carboxylate -C(O)OM, then the units (B) are units (B'), said units (B') being able to cyclize, in particular in acidic medium, to lead to bicyclic units (B'1):

[0043] In some embodiments, the units (A) are such that R2 and R3 together form a link; more particularly, the units (A) are units (C): units (C), units (C) in which Ri and R4 are as defined above; particularly units (C) such that Ri represents a -C(O)-OR'4 group, in particular a carboxy or carboxylate group -C(O)O'M + , M + being a cationic counter-ion as defined above.

[0044] In some embodiments, the units (A) are such that R2 and R3 together form a saturated or unsaturated heterocycle, preferably saturated, comprising at least one oxygen atom, and comprising 3 to 6 links, preferably 3 links, such as epoxy; in particular, the units (A) are units (D): units (D) in which Ri and R4 are as defined above; in particular Ri represents a group -C(O)-OR'4, notably carboxy or carboxylate -C(O)OM, M + being a cationic counter-ion as defined above.

[0045] In some embodiments, the units (A), and optionally the units (Al) to (Al 5), further comprise one or more units resulting from the polymerization of one or more additional monomer(s) chosen from

[0046] (Ci-C4)(alkyl)acrylate of (Ci-C22)(cyclo)alkyl, preferably (meth)acrylate of (C5-C22)(cyclo)alkyl, and / or

[0047] 11) (Ci-C4)(alkyl)acrylamide of (Ci-C22)(cyclo)alkyl, preferably (meth)acrylamide of (Cs-C22)(cyclo)alkyl.

[0048] In some embodiments, units (A), and optionally units (Al) to (Al 5), further comprise one or more units resulting from the polymerization of one or more additional monomer(s) selected from the monomers of formula (II): H2C=C(R6)-C(O)-E-Rs, in which E represents an oxygen atom or N(R), preferably E represents an oxygen atom, with R representing a hydrogen atom or a (C1-C4)alkyl group such as methyl, and R.6 represents a hydrogen atom, a (C1-C4)alkyl group such as methyl, and Rs represents:

[0049] - a (Ci-C22)alkyl group, preferably (Ci-C2o)alkyl, more preferably (Ci-Cio)alkyl, linear or branched, optionally interrupted by one or more oxygen atoms, preferably R5 represents a methyl, ethyl, n-propyl, i-propyl, n-butyl, s-butyl, t-butyl, n-hexyl, n-heptyl, 2-ethylhexyl, n-octyl, i-octyl, n-decyl, methoxyethyl, ethoxyethyl, methoxypropyl, isodecyl, lauryl, stearyl, hexadecyl, more preferably methyl, or

[0050] - a (Cs-C22)cycloalkyl group, preferably (Cs-C2o)cycloalkyl, in particular cyclohexyl, norbomyl or isobomyl, preferably isobomyl, or

[0051] - an aryl or aryl(Ci-C4)alkyl group such as benzyl; the additional monomer(s) being more preferentially chosen from among the monomers of formula (II'): H2C=C(R6)-C(O)-O-Rs , with R5 representing a linear or branched (Ci-C6)alkyl group such as methyl and Re representing a hydrogen atom or a (Ci-C4)alkyl group such as methyl.

[0052] In some embodiments, at least one copolymer further comprises units of formula (III): formula (III), in which Re is as defined above and A represents a hydroxy, amino, or OM group + with M + representing a cationic counterion.

[0053] In certain embodiments, the polymer further comprises one or more units (Al) to (A15) as defined above or in claim 3, where RET represents a group resulting from the crosslinking of at least one hydroxyl group and / or a -C(O)-OR'4 group and / or -C(O)-OR4 of a unit (A) with at least one crosslinking agent selected from:

[0054] - organic compounds comprising at least 2 heterocyclic groups comprising 3 to 10 links, preferably 3 links, and 1 to 3 heteroatoms such as O, S, N, and / or 1 to 3 carbonyl groups, preferably epoxide and / or aziridine heterocyclic groups;

[0055] - organic compounds comprising at least one electron-donating group such as a primary or secondary amine group, preferably at least two electron-donating groups such as hydroxyl or thiol; and

[0056] - (in)organic compounds comprising at least one phosphorus group -OP(O)(OH)2, -OP(O)(O'M +)2, -P(O)(OH)2 OR -P(O)(O'M + )2 with M + as defined above.

[0057] In some embodiments, the non-keratinized material is a metallic substrate or a non-metallic substrate, such as a substrate selected from the group consisting of wood, paper, mineral materials, non-keratinized organic materials, cellulosic materials, textile materials, inorganic materials, plastic materials and internal organs and / or mucous membranes of animals or humans.

[0058] In some embodiments, the composition comprising at least one polymer is chosen from the group consisting of superabsorbents, complexing agents, binders, electrolytes, thickeners, electrode separators, adhesives, paints, varnishes, detergents and oils.

[0059] Another object of the invention is a polymer comprising several repeating units selected from the units (A) as defined above, chosen from:

[0060] 1) statistical, sequenced or gradient copolymers, comprising several identical repeating units selected from units (A) as defined above, and at least one from: one or more units selected from units (Al) to (A15) as defined above, and / or one or more units resulting from the polymerization of one or more additional monomers as defined above;

[0061] 2) statistical, sequenced or gradient copolymers comprising at least two different repeating units chosen from units (A) as defined above, possibly one or more units chosen from units (Al) to (Al 5) as defined above, and possibly one or more units resulting from the polymerization of one or more additional monomers as defined above; 3) homopolymers comprising units (A) as defined above in which Ri represents a -C(O)-OR'4 group, R2 and R3 together form a bond and R4 and R'4, preferably identical, each represent a linear or branched (Cs-Csj)alkyl group other than i-propyl, n-butyl, and 2-ethylhexyl, such as t-butyl or n-octyl; or a (C3-Cio)cycloalkyl group other than cyclohexyl such as isobotyl, said homopolymers being further different from cis-cis-di-n-octylmuconate;

[0062] 4) homopolymers comprising units (A) as defined above in which Ri represents a -C(O)-OR'4 group, and R2 and R3 together form a saturated or unsaturated heterocycle, preferably saturated, comprising at least one oxygen atom, and comprising 3 to 6 links, preferably 3 links, such as epoxy and R4 and R'4, preferably identical, are as defined above;

[0063] 5) homopolymers comprising units (A) in which R2 and R3, identical or different, represent a hydrogen atom or a hydroxy group, it being understood that R2 and R3 cannot simultaneously represent a hydrogen atom, preferably R2 and R3 represent a hydroxy group.

[0064] Another object of the invention is a method for preparing a polymer comprising several repeating units selected from the units (A) as defined above, in particular a polymer according to the invention or a polymer applied by a method according to the invention, comprising the following steps i) to iii): i) the polymerization of a diene of formula (IC), of one of its geometric isomers or of a mixture of such dienes to obtain a polymer of formula (C): , preferably in the presence of at least one catalyst and / or initiator, in a solvent, preferably an organic solvent, in particular an aprotic solvent, at a temperature less than or equal to 120°C, in which Ri and R4 are as defined above; ii) the epoxidation of the polymer of formula (C) to form the polymer of formula (D): , preferably in the presence of at least one oxidizing agent selected from the group consisting of dioxygen, peroxides such as hydrogen peroxide H2O2, peracids, preferably aromatic, in particular (halo)perbenzoic acids, such as m-chloroperbenzoic acid and / or at least one organic, organometallic or enzymatic catalyst, such as titanium derivatives, manganese derivatives, aluminium derivatives, lipases that epoxidize unsaturates, peroxygenases, non-heme monooxygenases, halogenoperoxidases such as chloroperoxy dase and cytochrome P450 monooxygenases; and iii) hydrolysis of the polymer of formula (D) to form one or more diol polymers of formula (B): in which Ri and R4 are as defined above, preferably in water or in a mixture of water and at least one organic solvent.

[0065] Another object of the invention is a polymer obtained by a preparation process according to the invention.

[0066] Another object of the invention is a process for degrading a polymer comprising several repeating units selected from the units (A) as defined above by oxidative degradation, preferably by contact with an alkali metal permanganate, such as potassium permanganate, or by ozonolysis, in particular by ozonolysis.

[0067] Another object of the invention is a compound of formula (Dl) as defined below

[0068] Dl in which Ri and R4 are as defined above, or Ri and / or R4 represents a motif , with X and RET as defined above, this motif being linked to the rest of the (Dl) molecule via X.

[0069] FIGURES

[0070] Figure 1 is a graph of the evolution of conductivity over time in the example relating to the complexation of metals with polymers according to the invention. DETAILED DESCRIPTION

[0071] A first object of the invention is a process for treating a non-keratinized material, comprising applying to at least a portion of the non-keratinized material a polymer comprising several repeating units selected from the units (A) as defined above, as well as their optical and geometric isomers, their acid or base salts, organic or mineral, and their solvates such as hydrates, or a composition comprising such a polymer. Definitions

[0072] In the present invention, the terms have the following definitions, unless otherwise specified. "Non-keratinized material" means any material to which a composition can be applied, and which is not composed of all or part of living human tissue containing keratin. Keratinized materials, which are therefore distinct from non-keratinized materials, include skin, nails, hair, and scalp.

[0073] The term “crosslinking agent”, “crosslinking agent” or “crosslinking agent” refers to a chemical compound capable of creating a three-dimensional network by (photo)chemical, thermal, catalytic, and / or enzymatic reaction with the repeating units of the polymer.

[0074] A "polyol" designates an organic hydrocarbon compound comprising 2 to 100 carbon atoms, preferably 2 to 40 carbon atoms, saturated or unsaturated cyclic, or even aromatic or acylic, saturated or unsaturated, containing at least two hydroxyl groups (-OH), preferably 2 to 6 hydroxyl groups, said compound possibly comprising one or more heteroatoms selected from O, S, N, said heteroatom(s) possibly being intercalated in the chain and / or in the ring(s) (in particular, an ether function); particularly, polyols include diols (2 hydroxyl groups), triols (3 hydroxyl groups), tetraols (4 hydroxyl groups), pentols (5 hydroxyl groups), and hexols (6 hydroxyl groups);

[0075] By "(Cx-Cy)alkyl", we mean a monovalent acyclique hydrocarbon chain, saturated, linear or branched, comprising x to y carbon atoms. Thus, (Ci-C11)alkyl refers to an alkyl group comprising 1 to 6 carbon atoms, such as a methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, t-butyl, pentyl, or hexyl group. (Ci-C4)alkyl refers to an alkyl group comprising 1 to 4 carbon atoms, such as a methyl, ethyl, n-propyl, n-butyl, isobutyl, or tert-butyl group. (Cs-C22)alkyl refers to a saturated hydrocarbon group at C8-C22, particularly at C10-C20, preferably at C12-C18, more preferably at C12-C16, linear or branched, preferably linear, such as lauryl (C12), myristyle (C14), hexadecyl (ClO), or stearyl. (Cis), arachidyl (C20), behenyl (C22); more particularly (Cs-Ci s) alkyl is a linear or branched, preferably linear, C's-C'is saturated hydrocarbon group.

[0076] A "(meth)acrylate" refers to an acrylate or a methacrylate.

[0077] An "alkylene radical" is a divalent saturated hydrocarbon group in Ci-Cs, linear or branched, especially in Ci-Co, preferably in C1-C4 such as methylene, ethylene, or propylene.

[0078] A hydrocarbon chain is "unsaturated" when it contains one or more conjugated or non-conjugated double bonds and / or one or more triple bonds, preferably one or more conjugated or non-conjugated double bonds.

[0079] A hydrocarbon chain is "saturated" when it contains no unsaturation.

[0080] A hydrocarbon chain can be linear or branched, and may include a cyclic group that interrupts said hydrocarbon chain. A "cycloalkyl" radical is a saturated cyclic hydrocarbon group comprising 1 to 3 rings, preferably 2 rings, and comprising 3 to 12 carbon atoms, preferably between 5 and 10 carbon atoms, such as cyclopentyl, cyclohexyl, cycloheptyl, norbomyl, or isobomyl, the cycloalkyl radical being able to be substituted by one or more (Ci-C4)alkyl groups such as methyl, preferably the cycloalkyl radical is an isobomyl group.

[0081] A "cyclic" radical is a cyclic hydrocarbon group, saturated or unsaturated, aromatic or non-aromatic, comprising 1 to 3 rings, preferably 1 ring, and comprising 3 to 10 carbon atoms, such as cyclohexyl or phenyl.

[0082] An "aryl" radical is an unsaturated aromatic cyclic radical, comprising from 6 to 12 carbon atoms, mono- or polycyclic, fused or unfused, and in which at least one ring is aromatic; preferably the aryl radical is a phenyl, biphenyl, naphthyl, or indenyl group, preferably phenyl, and preferably the aryl group comprises one ring of 6 carbon atoms, such as phenyl. The aryl radical may be substituted by at least one substituent attached to a carbon atom, chosen from:

[0083] - C1-C4 alkyl;

[0084] - halogen;

[0085] - hydroxyl;

[0086] - alkoxy in C1-C2;

[0087] - (poly)-hydroxyalkoxy at C2-C4;

[0088] - amino;

[0089] - amino substituted by one or two alkyl radicals, identical or different, in C1-C4,

[0090] - acylamino (-NR-C(O)-R') in which R and R', identical or different, each independently represent a hydrogen atom or an alkyl radical in C1-C4;

[0091] - carbamoyl ((R)2N-C(O)-) in which the R radicals, identical or not, represent a hydrogen atom or an alkyl radical in C1-C4;

[0092] - alkylsulfonylamino (R'-S(O)2-N(R)-) in which R and R', identical or different, each independently represent a hydrogen atom or an alkyl radical in C1-C4;

[0093] - aminosulfonyl ((R)2N-S(O)2-) in which the R radicals, identical or not, represent a hydrogen atom or an alkyl radical in C1-C4;

[0094] - carboxylic in acidic or salified form (preferably with an alkali metal or an ammonium, substituted or unsubstituted);

[0095] - cyano;

[0096] - nitro or nitroso;

[0097] - polyhaloalkyl, preferably trifluoromethyl;

[0098] - alkylcarbonylamino (RC(O)-N(R')-) in which the radical R' is a hydrogen atom or a C1-C4 alkyl radical possibly bearing at least one hydroxyl group and the radical R is a C1-C2 alkyl or amino radical possibly substituted by one or two identical or different C1-C4 alkyl groups;

[0099] - alkylcarbonyloxy (RC(O)-O-) in which the radical R is a C1-C4 alkyl radical or an amino group optionally substituted by one or two identical or different C1-C4 alkyl groups; - alkoxy carbonyl (RGC(O)-) in which the radical R is a C1-C4 alkoxy radical, G is an oxygen atom, or an amino group optionally substituted by a C1-C4 alkyl group.

[0100] A cyclic radical, or a non-aromatic part of an aryl radical, can also be substituted^) by one or more oxo groups.

[0101] By "inorganic polymer" we mean a polymer whose skeleton does not contain carbon atoms.

[0102] By "hybrid polymer" or "organo-mineral polymer" we mean a polymer comprising carbon atoms and heteroatoms, notably oxygen and / or silicon such as silane; polymers comprising organic and inorganic components are called hybrid polymers.

[0103] The term "homopolymer" refers to a polymer resulting from the polymerization of identical monomers. The term "copolymer" refers to a polymer resulting from the polymerization of different monomers, in particular at least two different monomers. Preferably, the copolymer of the invention is derived from two or three different monomers, more preferably from two different monomers.

[0104] By "statistical copolymer" we mean a polymer resulting from the polymerization of several different monomers, generating chains with random sequences of the different monomers. For example, a statistical copolymer of monomers A and B could have the following sequences: -ABBAABABAA-;

[0105] By "gradient copolymers" we mean copolymers exhibiting a change in the ratio of the different monomers along the chain; the distribution of the comonomers in the polymer chains depends on the evolution of the relative concentrations of the comonomers during synthesis. The gradient copolymers according to the invention preferably comprise at least two different monomers whose concentration along the polymer chain changes gradually, systematically, and predictably;

[0106] The term "sequenced copolymer" refers to a polymer comprising at least two distinct successive sequences, i.e., sequences of different chemical natures. Each sequence, or block, of the sequenced copolymer according to the invention is derived from one or more different types of monomer. This means that each sequence can be composed of a homopolymer or a copolymer; this copolymer constituting the sequence can, in turn, be random, alternating, or gradient; the distribution of monomers within each sequence can therefore be random or controlled depending on the nature and / or reactivity of the monomers and / or the preparation process used. The sequenced copolymer according to the invention thus comprises at least two sequences, advantageously two sequences (diblock), three sequences (triblock), or five sequences (pentablock).

[0107] A polymer is said to be "ethylenic" if it is derived from the polymerization of at least ethylenic monomers.

[0108] By "ethylenic monomer" we mean an organic compound having one or more >C=C< type unsaturations, conjugated or not, capable of polymerizing; preferably where the monomer(s) is / are chosen from the monomer(s) of the following formula (V): H2C=C(R)-C(O)-O-R'” formula (V) in which R represents a hydrogen atom or (Ci-C4)al-kyle group such as methyl, and R'” represents a (Ci-C22)(cyclo)alkyl group, preferably (Cs-C2o)al-kyle, in particular (C2n)alkyl with n an integer equal to 5, 6, 7, 8, 9, or 10, preferably R'” represents isodecyl, lauryl, stearyl, hexadecyl, more preferably stearyl, or else R'” represents a (Cs-Cio)cycloalkyl group such as norbomyl or isobomyl, preferably isobornyl.

[0109] By "non-crosslinked polymer" is meant a homopolymer or a copolymer, said polymers comprising several repeating units selected from units (A) together with their optical, geometric isomers, their acid or base salts, organic or mineral, and their solvates such as hydrates; and not comprising any unit selected from units (Al), (A2), (A3), (A4), (A5), (A6), (A7), (A8), (A9), (A10), (All), (A12), (A13), (A14) and (A15) as defined above or mixtures thereof, together with their optical, geometric isomers, their acid or base salts, organic or mineral, and their solvates such as hydrates;

[0110] By "crosslinked polymer" is meant a homopolymer or copolymer, said polymers comprising several repeating units selected from units (A) together with their optical, geometric isomers, their acid or base salts, organic or mineral, and their solvates such as hydrates and at least one unit selected from units (Al), (A2), (A3), (A4), (A5), (A6), (A7), (A8), (A9), (A10), (All), (A12), (A13), (A14) and / or (A15) as defined above or mixtures thereof, together with their optical, geometric isomers, their acid or base salts, organic or mineral, and their solvates such as hydrates;

[0111] By "Ri, R2, R3, R4, R'4 of the different units (A), (Al), (A2), (A3), (A4), (A5), (A6), (A7), (A8), (A9), (A10), (All), (A12), (A13), (A14) and / or (A15) may be identical or different" we mean that:

[0112] - the Ri radicals of different units (A) may be identical or different from each other and identical or different from the RI radicals of possible units (Al), (A2), (A4), (A5), (A8), (A9), and / or (Ail), which may also be identical or different from each other,

[0113] - the R2 radicals of different units (A) may be identical or different from each other and identical or different from the R2 radicals of possible units (A2), (A3), (A4), (A6), (All), (A12), and / or (Al 3), which may also be identical or different from each other,

[0114] - the R3 radicals of different units (A) may be identical or different from each other and identical or different from the R3 radicals of possible units (Al), (A3), (A4), (A6), (A7), (A8), and / or (Al 5) which may also be identical or different from each other and

[0115] - the radicals R4 and / or R'4 of different units (A) can be identical or different from each other and identical or different from the radicals R4 of possible units (Al), (A2), (A3), (A5), (A7), (A12), and / or (A14) which can also be identical or different from each other.

[0116] The term "fats" refers to an organic compound that is immiscible in water at ordinary room temperature (25°C) and atmospheric pressure (760 mm Hg) (solubility less than 5%, preferably 1%, and even more preferably 0.1%). They preferably have in their structure at least one hydrocarbon chain with at least six carbon atoms or a chain of at least two siloxane groups. Furthermore, fats are generally soluble in organic solvents under the same temperature and pressure conditions, such as ethanol, ether, petrolatum, or decamethyl cyclopentasiloxane. These fats are neither polyoxyethylenated nor polyglycerolated. They differ from fatty acids because saline fatty acids constitute soaps, which are generally soluble in aqueous media.

[0117] By "liquid" fat, we mean in particular a fat that is liquid at 25°C and 1 atmosphere, preferably said fat has a viscosity less than or equal to 7000 centipoise at 20°C;

[0118] By "hydrocarbon" fat is meant a fat which comprises at least 50% by weight, in particular from 50 to 100% by weight, for example from 60 to 99% by weight, or from 65 to 95% by weight, or even from 70 to 90% by weight, relative to the total weight of said fat, of carbonaceous compound, having an overall solubility parameter according to the HANSEN solubility space less than or equal to 20 (MP a) 1 / 2, or of a mixture of such compounds;

[0119] - The overall solubility parameter d according to the HANSEN solubility space is defined in the article "Solubility parameter values" by Grulke, in the book "Polymer Handbook" 3rd edition, Chapter VII, pages 519-559 by the relation d = ( dD2 + dP2 + dH2)l / 2 in which: - dD characterizes the LONDON composition forces arising from the formation of induced dipoles during molecular collisions, - dP characterizes the DEBYE interaction forces between permanent dipoles,

[0120] - dH characterizes the specific interaction forces (hydrogen bond type, acid / base, donor / acceptor, etc.); The definition of solvents in the three-dimensional solubility space according to HANSEN is described in HANSEN's article: "The three dimensional solubility parameters" J. Paint Technol. 39, 105 (1967);

[0121] By "oil" we mean a liquid fat at room temperature (25 °C) and atmospheric pressure;

[0122] The term "hydrocarbon oil" refers to an oil composed primarily of, or even made up of, carbon and hydrogen atoms, and possibly oxygen and nitrogen atoms, but containing no silicon or fluorine atoms. It may contain hydroxyl, ester, ether, carboxylic acid, amine, and / or amide groups.

[0123] By "dyes" we mean oxidation dyes, and direct dyes used to color a substrate, a material and / or a fiber.

[0124] An "anhydrous" dispersion or composition means a composition containing less than 2% by weight of water, or even less than 0.5% of water, and in particular free of water; where applicable, such small quantities of water may be introduced by ingredients of the composition which may contain residual amounts.

[0125] The expression "at least one" is equivalent to "one or more".

[0126] The boundaries of a range of values ​​are included in that range, particularly in the expressions "between" and "ranging from . . . to . . .".

[0127] The expression "inclusively", especially for a range of concentrations, means that the bounds of the range are part of the defined interval.

[0128] V Polymer comprising (A) units

[0129] The at least one polymer applied according to the invention comprises several repeating units (A) as defined above.

[0130] In units (A), preferably, R2 and R3 are not simultaneously a hydrogen atom.

[0131] In units (A), preferably, when R2 and R3 together form a heterocycle, the heterocycle is a 3-membered ring such as an epoxy.

[0132] In units (A), preferably M+ is an alkali or alkaline earth metal cation, or an ammonium cation.

[0133] In units (A), when R4 and / or R4' represent a hydrocarbon group, it preferably comprises 2 to 20 carbon atoms.

[0134] In units (A), when R4 and / or Rf represent a hydrocarbon group, it is preferably saturated linear or branched acyclique, or cyclic.

[0135] In units (A), when the hydrocarbon group is interrupted by an association of a') with b'), it is preferably a group such as -C(O)-O-, -OC(O)-, amide -C(O)- N(Ra)-, -N(Ra)- C(O)-, urethane -N(Ra)-C(O)-O- or -OC(O)- N(Ra)-, urea - N(Ra)-(CO)-N(Rb)-, carbonate -O- C(O)-O-, -[O-Si(Rb)(Rc)]p- or -[(CRa2)qO]p- with q an integer between 1 and 4 and p between 1 and 200.

[0136] In units (A), preferably Ra represents a hydrogen atom and Rb and Rc preferably represent a (Ci-C4)alkyl group such as methyl.

[0137] In one embodiment, at least one polymer is a homopolymer. In another embodiment, at least one polymer is a copolymer. In another embodiment, at least one polymer is a mixture of at least one homopolymer and at least one copolymer.

[0138] In some embodiments, the polymer comprises, in addition to units (A), one or more units independently selected from units (Al) to (Al 5).

[0139] In formulas (Al) to (Al 5), RET is preferably obtained by crosslinking one or more reactive groups selected from a hydroxyl group and / or a -C(O)-OR'4 group and / or -C(O)-OR4 group. In formulas (Al) to (A15), the crosslinking agent is preferably selected from crosslinking agents bl) to b8) as defined below in the section on crosslinking agents.

[0140] In formulas (Al) to (A15), where R2 (and / or R3) represents a hydroxyl radical and R4 (and / or R'4) represents a hydrogen atom or a cationic counterion M + , then R2 and the group - C(O)-OR4 (and / or R3 and the group -C(O)-OR'4) can together form a heterocycle with 5 or 6 links.

[0141] Furthermore, when the radical R4 and / or R4' represents a cationic counter ion, then the oxygen atom of the group -OR4 and / or R4' is in its anionic form -O'.

[0142] Finally, the radicals Ri, R2, R3, R4, R'4, RI, R2, R3 and R4 of the different units (A), (Al), (A2), (A3), (A4), (A5), (A6), (A7), (A8), (A9), (A10), (All), (A12), (A13), (A14) and / or (A15) can be identical or different.

[0143] In general, in the present invention, the mention of a polymer also includes its optical isomers, geometric isomers, its acid or base salts, organic or mineral, and its solvates such as its hydrates, even if this is not explicitly mentioned.

[0144] Similarly, the mention of a given formula unit also includes its optical and geometric isomers, its acid or base salts (organic or mineral), and its solvates such as its hydrates, even if not explicitly stated. Process for treating non-keratinized material

[0145] The process for treating a non-keratinized material includes a step of applying to the non-keratinized material at least one polymer comprising several repeating units of formula (A) and / or a composition comprising such a polymer.

[0146] In some embodiments, the at least one polymer is a mixture of polymers comprising several repeating units of formula (A). The non-keratinized material may be any substrate not comprising keratinized materials, in particular human materials, and which can benefit from the application of the at least one polymer and / or a composition comprising it.

[0147] In some embodiments, the non-keratinized material is selected from the group consisting of metallic and non-metallic substrates. The non-metallic substrate may, in particular, be selected from the group consisting of wood, paper, mineral materials, non-keratinized organic materials, cellulosic materials, textile materials, especially cotton-based materials, inorganic materials such as glass, and plastic materials. In some embodiments, the non-keratinized material is selected from the group consisting of glass, cardboard, and paper, preferably glass or cardboard.

[0148] Non-keratinized material can be porous or non-porous.

[0149] In other embodiments, the non-keratinized material is all or part of an internal organ and / or veterinary or human mucous membrane.

[0150] The polymers according to the invention can be applied to a support to give it absorption properties, or even super-absorption properties.

[0151] The polymers according to the invention are super-absorbents effective for absorbing aqueous substances, but also for absorbing oily and / or organic substances.

[0152] The polymers according to the invention are particularly advantageous as superabsorbents because their degradability is particularly easy to control. Indeed, the inventors have demonstrated that the polymers used according to the invention are stable during use. For example, they are not hydrolyzable in the presence of moisture. On the other hand, they are easily degradable by simple processing, with a low environmental impact. Thus, it is possible to easily degrade the polymers, for example by thermal means and / or by ozonolysis, at the desired time, for example, when their use is complete. The degradation conditions are particularly simple and involve inexpensive processes. Furthermore, degradation by ozonolysis allows for a simple and efficient separation of the compounds absorbed by the polymer from the polymer degradation residues themselves.

[0153] Thus, non-keratinized materials and / or substrates may include all or part of the finished products selected from the group consisting of:

[0154] - personal hygiene items (diapers, feminine hygiene products, incontinence products...), dressings, bandages, dental products;

[0155] - films or nets for agriculture, including mulch films;

[0156] - plates or barriers to absorb accidental spills, such as pollution control barriers;

[0157] - products in contact with food, such as food packaging;

[0158] - single-use plastic items, particularly in the medical field; and

[0159] - electrical cables and components.

[0160] The polymers according to the invention can be applied to a substrate to impart complexing properties. For example, the polymers according to the invention could be used to complex toxic elements such as uranium, and / or metals, particularly precious metals. The polymers according to the invention can also advantageously replace difficult-to-recycle organic polymers used in any application. Examples include polymers used in or as components of electricity storage systems such as batteries.

[0161] Thus, the polymers according to the invention can be used to coat and / or manufacture components such as battery binders, solid electrolytes, thickeners, electrode separators, electrodes, and / or battery packaging, particularly for lithium batteries. The use of the polymers according to the invention facilitates the extraction and purification of battery metals. Specifically, if the polymers according to the invention are degraded by ozonolysis, acid molecules are simultaneously generated and the metals are oxidized, thereby facilitating their extraction. In other embodiments, the non-keratinized materials and / or substrates can be mucous membranes and / or human or animal organs, which do not contain keratin.Indeed, the polymers used according to the invention, which contain a large number of unsaturations, can be used to carry, vectorize, and / or deliver pharmaceutical actives, particularly in the presence of reactive oxygen species (ROS). Specifically, the polymers according to the invention, which contain double bonds, are degradable in the presence of oxidizing derivatives, thus enabling the release of pharmaceutical actives in the presence of reactive oxygen species. Furthermore, micelles formed by the polymers according to the invention can demonstrate greater stability than those formed by lipids, thereby preventing the unintended release of the pharmaceutical active.

[0162] The application to the substrate can be carried out using any suitable technique known in the art. Examples include, but are not limited to, application with a brush or roller, application by pouring, application by immersion, application by injection, and / or application by spraying. In one embodiment, the application is carried out by spin coating.

[0163] The application can result in a film-like coating on the substrate. However, the application within the meaning of the present invention is in no way limited to the form of such a coating. The application consists of bringing the substrate into contact with a polymer or a composition comprising the polymer. At least a portion of the polymer or composition remains in contact with the substrate after the application step itself.

[0164] In some embodiments, at least one polymer is non-crosslinked during the application step, i.e., it does not include (Al) to (A15) units. In other embodiments, at least one polymer is at least partially crosslinked during the application step, i.e., it includes at least one unit selected from the (Al) to (A15) units.

[0165] In some embodiments, the application step is an application step of a composition comprising at least one polymer.

[0166] In some embodiments, the application step of at least one polymer, preferably non-crosslinked, and / or of the composition comprising such a polymer, preferably non-crosslinked, is carried out in combination with a step of applying at least one crosslinking agent to the non-keratinized material. The combination may be simultaneous or sequential; that is, the at least one crosslinking agent is applied to the non-keratinized material either before, at the same time as, or after the application of the at least one polymer or the composition comprising it to the substrate. The process makes it possible to coat the substrate with a polymer having desirable properties, which may be bio-based, and which can be degraded post-use by typically quite simple techniques.

[0167] Another object of the invention is a coating obtained by a process according to the invention.

[0168] Another object of the invention is a treated (or coated) substrate obtained by a process according to the invention.

[0169] According to one embodiment, the process uses one or more homopolymer(s) comprising several repeating units chosen from the units (A) as defined above, it being understood that said process does not use a copolymer comprising several repeating units (A).

[0170] According to one embodiment, the process uses one or more copolymer(s) comprising several repeating units chosen from the units (A) as defined above, it being understood that said use does not use homopolymer comprising several repeating units (A).

[0171] According to one embodiment, the process uses one or more homopolymer(s) comprising several repeating units chosen from the units (A) as defined above and one or more copolymer(s) comprising several repeating units chosen from the units (A) as defined above.

[0172] According to one embodiment, the units (A) are such that Ri represents a (Ci-C4)alkyl group such as methyl.

[0173] According to one embodiment, the copolymer(s) are obtained from the polymerization of several units (A) with i) one or more monomer(s) selected from (Ci-Cis)(alkyl)acrylate of (Ci-C22)(cyclo)alkyl, preferably (meth)acrylate of (Cs-C22)(cyclo)alkyl, and / or ii) with one or more monomer(s) selected from (Ci-Cis)(alkyl)acrylamide of (Ci-C22)(cyclo)alkyl, preferably (meth)acrylamide of (Cs-C22)(cyclo)alkyl.

[0174] Preferably, the monomer(s) is / are chosen from the monomers of the following formula (II): H2C=C(R6)-C(O)-E-Rs formula (II) in which E represents an oxygen atom or an N(R) group, preferably E represents an oxygen atom, with R representing a hydrogen atom or a (Ci-C4)alkyl group such as methyl, and Re represents a hydrogen atom, a (Ci-C4)alkyl group such as methyl, or represents an Rs group with Rs representing: a (Cs-C22)alkyl group, preferably (Cs-C2o)alkyl, in particular (C2r)alkyl with r an integer equal to 5, 6, 7, 8, 9, or 10, preferably Rs represents isodecyl, lauryl, stearyl, hexadecyl, more preferably stearyl, or a group (Cs-C22)cycloalkyl, preferably (Cs-C2o)cycloalkyl, in particular norbomyl or isobomyl, preferably isobomyl.

[0175] Preferably, Re represents a hydrogen atom or a (Ci-C4)alkyl group such as methyl. Preferably, the monomer(s) (II) is / are chosen from isodecyl, lauryl, stearyl, hexadecyl, behenyl (meth)acrylates, more particularly stearyl (meth)acrylate, even more preferably stearyl methacrylate.

[0176] Examples of preferred Rs groups are methyl, ethyl, n-propyl, i-propyl, n-butyl, s-butyl, t-butyl, n-hexyl, n-heptyl, 2-ethylhexyl, n-octyl, i-octyl, n-dodecyl or lauryl, i-decyl, isoboromyl, cyclohexyl, benzyl, stearyl, methoxyethyl, ethoxyethyl and methoxypropyl groups and more preferentially, ethyl, i-propyl, t-butyl, n-octyl and isoboronyl groups.

[0177] In particular, after polymerization of the copolymer(s) as defined above with the monomer units i) (Ci-Cis)(alkyl)acrylate of (Cs-C22)(cyclo)alkyl, and / or ii) (Ci-Cis)(al-kyl)acrylamide of (Cs-C22)(cyclo)alkyl, the copolymers can be hydrolyzed, leading to a copolymer comprising polymeric units of the following formula (III): formula (III) in which Re is as defined previously in formula (II), and A represents a hydroxy, amino, or OM group + with M + as defined below.

[0178] According to another embodiment, the process and composition of the invention employ one or more homopolymer(s) and / or copolymer(s) comprising several repeating units selected from the units (A) in which R2 and R3 represent a hydroxy group.

[0179] More specifically, units (A) are units (B): formula (B) in which Ri and R4 are as defined previously.

[0180] According to one embodiment, the units (B) are such that R4 represents a hydrogen atom or an M + as defined previously. The units (B) can then be found in the form of cyclized units (Bl), particularly in acidic media:

[0181] According to one embodiment, the units (B) are such that Ri represents a -C(O)-OR'4 group, in particular carboxy, or carboxylate -C(O)OM, then the units (B) are units (B'):

[0182] These polymeric units (B') can cyclize, particularly in acidic media, to lead to bicyclic units (B'1): According to another embodiment, the process and composition of the invention employ one or more homopolymer(s) and / or copolymer(s) comprising several repeating units chosen from the units (A) in which R2 and R3 together form a bond.

[0183] More specifically, units (A) are units (C): formula (C) in which Ri and R4 are as defined previously.

[0184] According to one embodiment, the units (C) are such that Ri represents a -C(O)-OR'4 group, in particular carboxy, or carboxylate -C(O)OM, then the units (C) are units (C'): Formula (C') with R4 and R' 4, identical or different, preferably identical, are as defined previously.

[0185] According to another embodiment, the process and composition of the invention employ one or more homopolymer(s) and / or copolymer(s) comprising several repeating units chosen from the units (A) in which R2 and R3 together form a saturated or unsaturated heterocycle, preferably saturated, comprising at least one oxygen atom, and comprising 3 to 6 links, preferably with 3 links such as epoxy.

[0186] More specifically, units (A) are units (D); formula (D) in which Ri and R4 are as defined previously.

[0187] According to one embodiment, the units (D) are such that Ri represents a -C(O)-OR'4 group, in particular carboxy, or -C(O)OM, then the units (D) are units (D'):

[0188] Formula (D') with R4 and R'4, identical or different, preferably identical, are as defined previously.

[0189] According to one embodiment, the process and composition of the invention employ one or more homopolymer(s) and / or copolymer(s) comprising several repeating units selected from units (A) to (D) as defined above in which Ri represents a -C(O)-OR'4 group.

[0190] According to one embodiment, R4 and / or R4' represents i) a hydrogen atom.

[0191] According to one embodiment, R4 and / or R4' represents ii) a cationic counter ion M +, preferably an alkali or alkaline earth metal cation, or ammonium, a primary, secondary, or tertiary (Ci-Cs)alkylamine that may contain one or more nitrogen and / or oxygen atoms and may therefore contain, for example, several alcohol functional groups, it being understood that at least one of the nitrogen atoms is protonated by a hydrogen atom to form an ammonium group. Examples include 2-amino-2-methyl-2-propanol, triethanolamine, dimethylamino-2-propanol, lysine, and 3-(dimethylamino)propylamine, it being understood that each of these amines is protonated. Preferably, M + is chosen from alkali metals such as Na + , Li + K + alkaline earths such as Ca 2+ , and Zn metal 2+ , or the following protonated amines: protonated 2-amino-2-methyl-2-propanol, or protonated triethanolamine.

[0192] According to one embodiment, R4 and / or R4' represents iii) a hydrocarbon chain, saturated or unsaturated, linear or branched, non-cyclic, or saturated or unsaturated cyclic, aromatic or non-aromatic, comprising from 2 to 20 carbon atoms, preferably said hydrocarbon chain being saturated linear or branched cyclic, or cyclic. More preferably, R4 and / or Rti represents a (Ci-Cis)alkyl group, preferably a (Ci-Ci2)alkyl group, linear or branched, in particular selected from methyl, ethyl, n-propyl, i-propyl, n-butyl, sec-butyl, t-butyl, n-hexyl, n-heptyl, 2-ethylhexyl, n-octyl, i-octyl, methoxyethyl, methoxypropyl, i-decyl, n-dodecyl or lauryl, and stearyl.

[0193] According to one embodiment, R4 and / or Rf represents a hydrocarbon chain, saturated or unsaturated, aromatic or non-aromatic, comprising from 2 to 20 carbon atoms, preferably is / are chosen from among saturated cyclic groups (Cs-Ci2)cycloalkyls such as cyclo-hexyl or isobotyl, unsaturated aromatic cyclics such as (C6-Ci2)aryl or (Ce-Ci2)aryl(Ci-C4)alkyl such as benzyl.

[0194] Examples of preferred R4 and / or R'4 groups are methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, t-butyl, hexyl, heptyl, 2-ethylhexyl, octyl, lauryl, isooctyl, isodecyl, isobomyl, cyclohexyl, benzyl, stearyl, methoxyethyl, ethoxyethyl and methoxypropyl groups and more preferably R4 and / or R4' represents an ethyl, i-propyl, t-butyl, n-octyl, or isobomyl group.

[0195] According to one embodiment, the process and / or composition of the invention employs one or more homopolymer(s) and / or copolymer(s) comprising several repeating units selected from units (A) to (D') as defined above, wherein R4 and R4', identical or different, represent iii) a hydrocarbon chain, saturated or unsaturated, linear or branched, non-cyclic, or saturated or unsaturated cyclic, aromatic or non-aromatic, comprising from 1 to 30 carbon atoms; preferably comprising from 2 to 20 carbon atoms, preferably said hydrocarbon chain being saturated, acyclic, linear or branched, or cyclic, said hydrocarbon chain being further substituted by one or more (di)(C1-C4)(alkyl)amino groups; and / or interrupted by one or more (a') heteroatoms selected from O, N(R a ), and Si(Rb)(Rc), b') carbonyls, c') or associations of a') with b') such as -C(O)-O-, -OC(O)-, amide -C(O)- N(R a)-, -N(R a )- C(O)-, urethane -N(R a )-C(O)-O- or -OC(O)- N(R a )-, urea - N(R a )-(CO)- N(Rb)-, carbonate -O- C(O)-O-, -[O-Si(Rb)(Rc)] P - or -[(CRa2)pO] q - with p an integer greater than or equal to 1, preferably between 1 and 200, and q represents an integer between 1 and 4; with n between 1 and 200, in which R a represents a hydrogen atom, Rb and Rc being as defined above, and preferably represent a (Ci-C4)alkyl group such as methyl. Another object of the invention is the use of at least one polymer comprising several repeating units of formula (A) or of a composition comprising it as described above for treating and / or coating a non-keratinized material.

[0196] Another object of the invention is the use of at least one polymer comprising several repeating units of formula (A) or of a composition comprising it to manufacture an object not having a cosmetic application. Crosslinking The Inventors have demonstrated that, for certain uses, it is advantageous for polymers comprising several repeating units of formula (A) to be in crosslinked form.

[0197] It is known to use crosslinked polymers of (meth)acrylic, maleic, or fumaric acid and sorbic or muconic acid of specific molecular weights as detergents and water absorbers in drilling fluids or in layers (see, for example, JP2002012628). These polymers are crosslinked through unsaturations (double bonds) originating from sorbic or muconic acid.

[0198] In the present invention, the crosslinking of polymers preferably occurs at motifs other than the double bonds originating from sorbic or muconic acid. Thus, crosslinked polymers possessing a significant number of double bonds can subsequently be easily degraded by ozonolysis, which is not the case for polymers that no longer possess double bonds following their crosslinking.

[0199] By “crosslinker” we mean more particularly a chemical compound capable of linking by at least two atoms by (photo)chemical, thermal, catalytic, and / or enzymatic reaction with units (A) to (D') as defined above, RET, identical or different, representing a group resulting from the crosslinking of at least one reactive group of at least one unit (A) preferably of at least one hydroxy group and / or at least one -C(O)-OR'4 group and / or -C(O)-OR4 of one unit (A) with at least one crosslinker in particular chosen from crosslinkers b-1) to b-8), preferably chosen from (S'), (E), (F), (G), (H), (I), (J), (K), (L), (M), (N), (O) and (P) as defined below, more preferably chosen from (S'), (E), (F), (K), and (O).

[0200] In one embodiment, at least one crosslinking agent is chosen from compounds b-1) to b-8) as defined below, and any one of their mixtures.

[0201] According to one embodiment, "crosslinking agent" means a compound capable of creating at least two covalent bonds with at least two reactive functions of at least one unit (A), said reactive functions being preferably chosen from among the hydroxy groups and / or the -C(O)-OR'4 and / or -C(O)-OR4 groups of at least one unit (A).

[0202] In particular, the crosslinking agents have the formula (S'):

[0203] Formula (S') in which:

[0204] Core represents a polymeric or non-polymer multivalent radical, in particular Core represents: either i) a multivalent, acyclic, saturated or unsaturated, linear or branched hydrocarbon group, or a saturated or unsaturated cyclic hydrocarbon group, aromatic or non-aromatic, comprising from 2 to 40 carbon atoms, in particular from 3 to 36 carbon atoms, said hydrocarbon group being able to a) be interrupted by one or more heteroatoms or groups selected from the atoms of oxygen, sulfur, nitrogen, silicon or -[O-Si(Rb)(R c )] P - with Rb, R care such as defined previously, p between 1 and 200, carbonyl -C(O)-, or their associations such as ester -C(O)-O-, -OC(O)-, amide -C(O)-N(R')-, -N(R')-C(O)-, urethane -N(R')-C(O)-O- or -OC(O)-N(R')-, urea -N(R')-(CO)- N(R')-, or carbonate -OC(O)-O-, in which R' represents a hydrogen atom, an alkyl group having from 1 to 4 carbon atoms; or ii) an organic polymer, preferably selected from an ethylenic homopolymer and an ethylenic copolymer; or iii) an inorganic polymer; or iv) a hybrid polymer; provided that the core in its polymer form ii), iii), or iv) may be dendrimeric, or hyperbranched; and n, o, and p, identical or different, each represent an integer preferably between 0 and 10, more preferably between 0 and 5, provided that the sum of o+n+p is greater than or equal to 2, preferably between 2 and 10.

[0205] In another embodiment, a "crosslinking agent" is defined as a compound capable of forming at least one covalent bond with at least one reactive functional group Fl of at least one unit (A) and at least one reactive functional group F2 other than Fl, capable of reacting with at least one constituent of the composition to form a network. For example, Fl could be an amino group and F2 an alkoxysilane group such as ethoxysilane. In a particular embodiment, the crosslinking agent(s) is / are chosen from:

[0206] 1) organic compounds comprising at least 2 heterocyclic groups comprising 3 to 10 links (preferably 3 links), and 1 to 3 heteroatoms such as O, S, N, and / or 1 to 3 carbonyls, preferably epoxide or aziridine;

[0207] 2) organic compounds comprising at least one electron-donating group such as a primary amine or secondary amine such as amino, hydroxy, or thiol, preferably at least two electron-donating groups such as hydroxy, amino, or thiol; and

[0208] 3) (In)organic compounds comprising at least one phosphorus group -OP(O)(OH)2, -OP(O)(O'M + )2, -P(O)(OH)2 OR -P(O)(O'M + )2 with M + as defined previously.

[0209] The homopolymer(s) and / or copolymer(s) comprising several repeating units selected from units (A) to (D') as defined above is / are particularly crosslinked by reaction with one or more compounds containing at least two epoxide functions (epoxide crosslinker), or at least one amine function (amine crosslinker) and another reactive function, or at least two acid functions, or at least one acid function and at least one amine function, or at least two thiol functions, or at least two aziridine functions, or at least two alcohol functions, or an (in)organic compound comprising at least one phosphorus group -OP(O)(OH)2, -OP(O)(O'M + )2, -P(O)(OH)2 OR -P(O)(O'M + )2 with M + as defined previously.

[0210] The homopolymer(s) and / or copolymer(s) comprising several repeating units selected from units (A) to (D') as defined above is / are particularly crosslinked by the reaction of one or more compounds selected from b-1), b-2), b-3), b-4), b-5), b-6), b-7), and b-8) and their mixtures. b-1) Crosslinking agent comprising at least 2 epoxide functions:

[0211] According to one embodiment of the invention, the crosslinking agent(s) is / are chosen from those of family 1) as defined above, and more particularly from the epoxy crosslinking agents of formula (E) below:

[0212] Formula (E) in which: n represents an integer greater than or equal to 2, preferably between 2 and 10, more preferably between 3 and 5;

[0213] The core is as defined previously in formula (S').

[0214] Preferably, the crosslinkers of formula (E) are such that Core represents a linear or branched, saturated, polyvalent (particularly divalent or trivalent) acylic hydrocarbon group comprising from 2 to 20 carbon atoms, better from 3 to 10 carbon atoms, optionally interrupted by one or more heteroatoms such as oxygen, and n is such as defined above, preferably equal to 2 or 3.

[0215] These may be polyglycidyl ethers of alkane polyols or polyglycidyl ethers of poly(alkylene glycol) such as, but not limited to, ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, 1,3-butanediol diglycidyl ether, 1,4-butanediol diglycidyl ether, neopentyl glycol diglycidyl ether, glycerol diglycidyl ether, glycerol trigly cidy 1 ether, trimethylolpropane diglycidyl ether, trimethylolethane trigly cidy ether, triethylolpropane diglycidyl ether, triethylolethane trigly cidy ether, glycerol propoxylate trigly cidy ether, pentaerythritol tetragly cidy ether, castor oil polyglycidyl ether, sorbitol polyglycidyl ether, polyglycerol polyglycidyl ether, bisepoxides of alkanes or aralkanes such as 1,2,3,4-diepoxybutane, 1,2,4,5-diepoxypentane, 1,2,5,6-diepoxyhexane, 1,2,7,8-diepoxyoctane, 1,4- and 1,3-divinylbenzene diepoxides, bisphenol A diglycidyl ether,bisphenol F diglycidyl ether, resorcinol diglycidyl ether and mixtures of these polyepoxides.

[0216] Preferred are ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, 1,3-butanediol diglycidyl ether, 1,4-butanediol diglycidyl ether, neopentyl glycol diglycidyl ether, glycerol diglycidyl ether, glycerol triglycidyl ether, trimethylolpropane diglycidyl ether, trimethylolethane triglycidyl ether, triethylolpropane diglycidyl ether, triethylolethane triglycidyl ether, glycerol propoxylate triglycidyl ether, pentaerythritol tetragly cidyl ether, and more specifically ethylene glycol diglycidyl ether (EGDE) and trimethylol propane triglycidyl ether (TPTE). b-2) Crosslinking agent containing at least 1 amine group:

[0217] Crosslinking agents containing at least one amine function have at least two reactive groups, including at least one amine function.

[0218] In one embodiment, the crosslinkers b-2) comprise at least two amine groups, preferably only amine groups, as reactive functions. In another embodiment, the crosslinkers b-2) comprise one amine group and at least one other reactive function other than an amine group.

[0219] According to one embodiment of the invention, the crosslinking agent(s) is / are chosen from those of family 2) as defined above, and more particularly from the amine crosslinking agents of formula (F) below

[0220] Formula (F) in which n, and Core are such as defined previously for (E) and R represents a hydrogen atom or a (Ci-Ce)alkyl group, linear or branched, possibly substituted by one or more aryl groups such as phenyl.

[0221] According to one embodiment, the amine crosslinking agent(s) used in the invention are chosen from among amine compounds having one or more primary and / or secondary amine groups. It can therefore be chosen from among monoamine, diamine, triamine, or multiamine compounds.

[0222] According to one embodiment, the amine crosslinker(s) may comprise from 2 to 40 carbon atoms, in particular 3 to 36 carbon atoms, or even 4 to 24 carbon atoms.

[0223] According to another embodiment, the amine crosslinker(s) are polymeric having a weight average molecular weight ranging from 500 to 1,000,000, preferably ranging from 500 to 500,000, and preferably ranging from 500 to 100,000 g / mol.

[0224] Among the amine crosslinking agents, we can mention n-butylamine, tert-butylamine, isobutylamine, propylamine, n-hexylamine, glycine, ethanolamine, 3-aminopropanol, dopamine, 7-amino-4-methylcoumarin, 1,4-bis(3-aminopropyl)piperazine, 3-aminopropyltriethoxysilane (APTES), 3-aminophenylboronic acid, N-methyl-1,3-diaminopropane, N-propyl 1,3-diaminopropane, N-isopropyl 1,3-diaminopropane, N-cyclohexyl 1,3-diaminopropane, 2-(3-aminopropylamino)ethanol, 3-(2-aminoethyl)aminopropylamine, bis(3-aminopropyl)amine, and methyl bis(3-aminopropyl)amine. N-(3-aminopropyl)-1,4-diaminobutane, N,N-dimethyldipropylene triamine, 1,2-bis(3-aminopropylamino)ethane, N,N'-bis(3-aminopropyl)-1,3-propanediamine, ethylenediamine, 1,3-propylenediamine, 1,4-butylenediamine, 1,6-hexamethylenediamine, amino acids such as lysine, glutamine, cysteine, glutamic acid, serine, cystamine,xylene diamine, tris(2-aminoethyl)amine, spermidine. Preferably, the amino crosslinking agent(s) is / are chosen from n-butylamine, 3-aminopropanol, dopamine, 7-amino-4-methylcoumarin, 1,4-bis(3-aminopropyl)piperazine, 3-aminopropyltriethoxysilane (APTES), N-methyl-1,3-diaminopropane, N-propyl 1,3-diaminopropane, N-isopropyl 1,3-diaminopropane, N-cyclohexyl 1,3-diaminopropane, 2-(3-aminopropylamino)ethanol, 3-(2-aminoethyl)aminopropylamine, bis(3-aminopropyl)amine, methyl bis(3-aminopropyl)amine, N-(3-aminopropyl)-1,4-diaminobutane, N,N-dimethyldipropylene triamine, the 1,2-bis(3-aminopropylamino)ethane, N,N'-bis(3-aminopropyl)-1,3-propanediamine, ethylenediamine, 1,6-hexamethylenediamine, lysine, glutamic acid, serine, cysteine, glutamine.

[0225] According to a particular embodiment of the invention, the amino crosslinking agent(s) is / are chosen from poly((C2-Cs)alkylene imines), and in particular polyethyleneimines and polypropyleneimines, notably poly(ethylene imine) (for example that sold under reference 46,852-3 by Aldrich Chemical); poly(allylamine) (for example that sold under reference 47,913-6 by Aldrich Chemical); polyvinylamines and their copolymers, in particular with vinylamides; one can notably mention vinylamine / vinylformamide copolymers such as those marketed under the name LUPAMIN® 9030 by BASF; polyamino acids having NH2 groups such as polylysine, for example that sold by JNC Corporation (formerly Chisso); Amino dextran, such as that sold by CarboMer Inc; acrylamidopropyl lamin-based copolymers.

[0226] According to one embodiment, the amino crosslinker(s) is / are chosen from among organic amine polysaccharide polymers such as chitosans.

[0227] According to a particular embodiment of the invention, the amine crosslinking agent(s) is / are chosen from inorganic or hybrid polymers, preferably hybrid, in particular chosen from polydimethylsiloxanes comprising primary amine groups at the end of the chain and / or on side chains, for example terminal or lateral aminopropyl groups, such as those of formula (G), (H), (I) or (J): H2N-ALK-Si(Re)(Rf)-O[Si(R'e)(R'f)O-]u-Si(Re)(Rf)-ALK'-NH2 (G)

[0228] Re-Sl(Re)(Rf)-O[Sl(R'e)(R'f)O-]v-[Sl(R'e)(ALK-NH2)-O] w -Sl(Re)(Rf)2 (H)

[0229] H2N-ALK-Si(Re)(Rf)-O[Si(R'e)(R'f)O-]x-Si(Re)(Rf)-ALK'-H (I)

[0230] Rg-Si(Re)(Rf)-O[Si(R'e)(R'f)O-] y-[Si(R'e)(ALK”-NH-ALK”'-NH2)-O]z-Si(Re)(Rf)-R'g (J) In formulas (G), (H), (I) or (J):

[0231] ALK and ALK', identical or different, preferably identical, represent a linear or branched (Ci-Ce)alkylene group, preferably (Ci-C4)alkylene such as propylene;

[0232] ALK” represents a linear or branched (Ci-C6)alkylene group, preferably (Ci-C4)alkylene such as propylene,

[0233] ALK'” represents a linear or branched (Ci-C6)alkylene group, preferably (Ci-C4)alkylene such as ethylene;

[0234] Re, Rf, R' e and R'f, identical or different, preferably identical, represent a (Ci-C4)alkyl group such as methyl;

[0235] R'e, R g and R' g, identical and different, represent a hydroxy group, (Ci-C4)alkyl; u represents an integer greater than or equal to 2, preferably u represents an integer such that the average molecular weight by weight of silicone is between approximately 500 and 55,000; v and w represent an integer and are such that the average molecular weight by weight of silicone is between approximately 50 and 3,000; y and z represent an integer and are such that the average molecular weight by weight of silicone is between approximately 5,000 and 500,000.

[0236] Examples of amino-based silicone (G) include those sold under the names "DMS-A11", "DMS-A12", "DMS-A15", "DMS-A21", "DMS-A31", "DMS-A32", and "DMSA35" by GELEST. Examples of silicone (H) include those sold under the names "AMS-132", "AMS-152", "AMS-162", "AMS-163", "AMS-191", and "AMS-1203" by GELEST. Examples of silicone (I) include those sold under the names "MCR-A11" and "MCR-A12" by GELEST. According to one embodiment, the amine crosslinker(s) is / are chosen from among the amine polyethers known in particular under the reference JEFFAMINE from the company HUNTSMAN; and in particular: polyethylene glycols and / or polypropylene glycols with amine function at the end of the chain (monamine or diamine) such as those sold under the names JEFFANINE M-600, M-1000, M-2005, M-2070, D-230, D-400, D-2000, D-4000, ED600, ED-9000, ED-2003.

[0237] According to one embodiment, the amine crosslinker(s) is / are chosen from polytetrahydrofurans (or polytetramethylene glycols) with amine function at the end of the chain (monoamine or diamine), polybutadienes with amine function at the end of the chain (monoamine or diamine).

[0238] According to another embodiment, the amine crosslinker(s) is / are chosen from among dendrimers and hyperbranched polymers with primary or secondary amine function (PAMAM), and poly(meth)acrylates or poly(meth)acrylamides bearing primary or secondary lateral amine functions such as poly(3-aminopropyl)methacrylamide, poly(2-aminoethyl) methacrylate.

[0239] Preferably, the amine crosslinker(s) is / are chosen from among amine polymers, such as polyethylene imine, poly lysine, chitosans, polyethylene oxide and / or propylene oxide with terminal amine groups.

[0240] According to another embodiment, the amino crosslinking agent(s) is / are selected from non-polymer amine compounds such as ethylenediamine, 1,6-hexamethylenediamine, lysine, glutamic acid, glutamine, cysteine, amino polyethers, and 3-aminopropyltriethoxysilane (APTES). b-3) Crosslinking agent containing at least two carboxy(late) functions:

[0241] According to another embodiment, the crosslinker(s) of the invention is / are chosen from organic crosslinkers comprising at least 2 carboxy groups, also called polycarboxylated crosslinkers, and more particularly from the polycarboxylated crosslinkers of formula (K) below, as well as their organic or mineral base salts:

[0242] Formula (K) in which n, and Core are such as defined previously for (E).

[0243] Among the polycarboxylated crosslinking agents of the invention, the following may be mentioned, alone or in mixtures: decanedioic acid, dodecanedioic acid, cyclopropanedicarboxylic acid, cyclohexanedicarboxylic acid, cyclobutanedicarboxylic acid, naphthalene-1,4-dicarboxylic acid, naphthalene-2,3-dicarboxylic acid, naphthalene-2,6-dicarboxylic acid, suberic acid, oxalic acid, malonic acid, succinic acid, phthalic acid, terephthalic acid, isophthalic acid, pimelic acid, sebacic acid, azelaic acid, homophthalic acid, adipic acid, fumaric acid, maleic acid, itaconic acid, cyclohexanetricarboxylic acid, and... trimellitic, 1,2,3-benzenetricarboxylic acid, 1,3,5-benzenetricarboxylic acid;citric acid, butanetetracarboxylic acid, pyromellitic acid, tartaric acid, furan dicarboxylic acid, muconic acid (cis-cis or cis-trans, or trans-trans), sorbic acid (cis-cis or cis-trans, or trans-trans) b-4) Crosslinker containing at least 2 aziridine functions:;

[0244] According to another embodiment, the crosslinker(s) of the invention is / are chosen from organic crosslinkers comprising at least 2 aziridine groups optionally substituted by one or more (Ci-C4)alkyl groups such as methyls, and more particularly from polyaziridine crosslinkers of formulas (L) or (M) below:

[0245] Formulas (L) and (M) in which n, and Core are such as defined previously for (E). Among the polyaziridine crosslinkers of the invention, one may mention the polyaziridinyl derivatives of alkane polyols such as, for example, Pentaerythritol tetrakis(beta-aziridino)propionate, pentaerythritol-tris-3-(N-aziridinyl)propionate, trimethylolpropane-tris-3-(N-aziridinyl)propionate, pentaerythritol-bis-3-(N-aziridinyl)propionate and trimethylolpropane-bis-3-(N-aziridinyl)propionate.

[0246] Other examples include polyaziridinyl derivatives of propionic esters of erythritol, pentaerythritol, trimethylolethane, and trimethylolpropane, which can be prepared by adding aziridine to the corresponding acrylate ester of a polyol. Examples include polyaziridinyl crosslinkers sold by Poly Aziridine Global such as PZP-1000, PZE 1000, PZBI-25, PZ-33 (pentaerythritol-tris-3-(l-aziridinyl)propionate), and PZ-28 (trimethylolpropane tris(2-methyl-l-aziridinyl)propionate). Mixtures of the aziridins listed above can also be used.

[0247] According to another embodiment, the crosslinking agent(s) of the invention is / are selected from organic crosslinking agents comprising at least two aziridine groups, optionally substituted by one or more (Ci-C4)alkyl groups such as methyl, and more particularly from polyaziridine crosslinking agents of formulas (L) or (M) above. b-5) Mixed crosslinking agents containing at least two functional groups, including at least one aziridine and at least one

[0248] According to another embodiment, the crosslinker(s) of the invention is / are chosen from among the organic crosslinkers comprising at least 1 aziridine group optionally substituted by one or more (Ci-C4)alkyl groups such as methyl, and at least one epoxide group, and more particularly from among the mixed crosslinkers of formula (N) below:

[0249] Formula (N) in which n represents an integer greater than or equal to 1, preferably between 1 and 10, o, and p, identical or different, represent an integer between 0 and 10, more preferably between 0 and 5, it being understood that the sum of o+p is an integer greater than or equal to 1 and preferably the sum n+o+p is an integer between 2 and 10;

[0250] The core is as defined previously for (S'). b-6) Crosslinking agent containing at least 2 hydroxyl groups

[0251] According to another embodiment, the crosslinking agent(s) of the invention is / are chosen from organic crosslinking agents comprising at least 2 hydroxyl groups; and more particularly from polyhydroxylated crosslinking agents chosen from those of the following formula (O):

[0252] Formula (O) in which n, and Core are such as defined previously for (E).

[0253] The polyhydroxylated crosslinking agents of the invention are more particularly selected from glycerol, ethylene glycol, triethylene glycol, trimethylolpropane, pentaerythritol (tetramethylolmethane), erythritol, diglycerol, xylitol, triglycerol, sorbitol, mannitol or dipentaerythritol, isosorbide, hexamethylene glycol, hexylene glycol, hexanediol, neopentyl glycol, 1,2-propanediol; 1,3-propanediol; 1,2-butanediol, 1,3-butanediol, 2,3-butanediol,

[0254] 1.4-butanediol; 2,4-butanediol, 3,4-butanediol; 1,4-Pentanediol; 1,5-pentanediol,

[0255] 2.2.4-Trimethyl-1,3-pentanediol, 1,6-hexanediol, 1,2-octanediol, 1,8-octanediol, 1,10-decanediol, 2,2-dimethyl-1,3-propanediol, 3-methyl-1,5-propanediol, hexylene glycol, F-isoprene glycol, 1,12-octadecanediol, 1,10-decanediol, 1,16-hexadecanediol, 1,12-dodecanediol, pripol 2033, or oligomers comprising 2 alcohol functions such as polypropanediol, polyethylene glycol, polytetramethylene glycol with Mw ranging from 100 to 10000 g / mol and mixtures thereof. b-7) Crosslinking agent containing at least 2 thiol functions. According to another embodiment, the crosslinking agent(s) of the invention is / are chosen from organic crosslinking agents comprising at least 2 thiol groups; and more particularly from polythiol crosslinking agents chosen from those of the following formula (P):

[0256] (P)

[0257] Formula (P) in which n, and Core are such as defined previously for (E).

[0258] The polythiol crosslinkers of the invention are more particularly selected from pentaerythritol tetra(3-mercaptopropionate) and trimethylolpropane tris(3-mercaptopropionate). b-8) (In)organic phosphorus crosslinker

[0259] According to another embodiment, the crosslinker(s) of the invention is / are chosen from among phosphorus-containing (in)organic crosslinkers, such as alkali or alkaline earth metal tri(Ci-C6)alkylphosphates such as alkali or alkaline earth metal trimethaphosphates (of sodium) and other phosphorus esters.

[0260] In formulas (Al) to (A15), the crosslinking agent is preferably chosen from (S'), (E), (F), (G), (H), (I), (J), (K), (L), (M), (N), (O) and (P) as defined above, more preferably chosen from (S'), (E), (F), (K), and (O). Composition

[0261] Another object of the invention is a composition comprising at least one polymer comprising several repeating units of formula (A), and optionally one or more units selected from units (Al) to (A15). The composition is intended to be applied to a non-keratinized material; it is therefore a non-cosmetic composition.

[0262] In some embodiments, the composition according to the invention comprises at least one polymer comprising several repeating units of formula (A), optionally one or more units selected from units (Al) to (A15), and optionally one or more units resulting from the polymerization of one or more additional monomer(s) selected from i) (Ci-C4)(al-kyl acrylate of (Ci-C22)(cyclo)alkyl preferably (meth)acrylate of (Cs-C22)(cyclo)alkyl, and / or ii) (Ci-C4)(alkyl)acrylamide of (Ci-C22)(cyclo)alkyl preferably (meth)acrylamide of (Cs-C22)(cyclo)alkyl.

[0263] The composition according to the invention preferably comprises at least one polymer comprising several repeating units of formula (A) and a solvent. The solvent may be either an aqueous solvent, an organic solvent, and / or a mixture of such solvents.

[0264] In some embodiments, the composition includes at least one crosslinking agent.

[0265] In some embodiments, the composition does not include a crosslinking agent and / or the polymer does not include a unit selected from units (Al) to (Al 5), nor a unit resulting from the polymerization of one or more additional monomer(s) as defined above, and in units (A) R.2 and R.3 form a bond together. In such embodiments, the composition preferably includes an additive, in particular at least one compound selected from fats, preferably liquid at 25 °C and atmospheric pressure, colorants, pigments, and mixtures thereof.

[0266] In some embodiments, the composition includes at least one fat, in particular an oil, and the at least one polymer is in this case such that R2 and R3 preferably form a bond together.

[0267] In some embodiments, the composition includes at least water, and at least one polymer is in this case such that R2 and R3 preferably form a bond together.

[0268] In some embodiments, the composition includes at least one alcohol, and the at least one polymer is in this case such that R2 and R3 preferably form a bond together.

[0269] The composition according to the invention may include any other additional component and / or additive suitable for the intended use of the composition. Examples of such additional components and / or additives include fats, colorants, pigments, thickeners, and rheology modifiers.

[0270] In some embodiments, the composition is chosen from the group consisting of superabsorbents, complexing agents, binders, electrolytes, thickeners, electrode separators, adhesives, paints, varnishes, detergents and oils.

[0271] The composition according to the invention can be liquid or fluid, but it can also be a viscous composition, in the form of a gel, or even a solid.

[0272] The homopolymer(s) and / or copolymer(s) comprising units (A) as defined above preferably represent between 0.1% and 50% by weight, in particular between 1% and 30% by weight, better between 3% and 20% by weight, and even better between 5% and 10% of the total weight of the composition.

[0273] The composition according to the invention can lead, after application to a substrate, to film-forming, shiny and grease-resistant deposits at room temperature (25°C).

[0274] The composition according to the invention remains stable even for several months at 20°C.

[0275] According to one embodiment, the composition of the invention comprises one or more homopolymer(s) comprising several repeating units selected from the units (A) as defined above, it being understood that said composition does not comprise a copolymer comprising several repeating units (A).

[0276] According to one embodiment, the composition comprises one or more copolymer(s) comprising several repeating units selected from the units (A) as defined above, it being understood that said composition does not comprise a homopolymer comprising several repeating units (A).

[0277] According to one embodiment, the composition comprises one or more homopolymer(s) comprising several repeating units selected from the units (A) as defined above, and one or more copolymer(s) comprising several repeating units (A) as defined above.

[0278] According to one embodiment, the composition comprises a polymer selected from polymers 1) to 5) described below.

[0279] Polymers comprising units (A) as defined above, and in particular polymers 1), 2), 3), 4), and 5) and their mixtures, are easy to incorporate into compositions, are easy to manufacture even industrially, and remain stable over time, even in solution. Indeed, the use, processing, and / or application of the composition incorporating the polymer(s) comprising units (A) as defined above, and in particular polymers 1), 2), 3), 4), and 5) and their mixtures, makes it possible to obtain polymeric material deposits on the substrate that are highly resistant to external aggressions.

[0280] According to one embodiment, the composition of the invention employs one or more homopolymer(s) and / or copolymer(s) comprising several repeating units chosen from the units (A) in which Ri represents a (Ci-C4)alkyl group such as methyl.

[0281] According to one embodiment, the composition of the invention incorporates one or more homopolymer(s) and / or copolymer(s) comprising several repeating units selected from the units (A) in which Ri represents a -C(O)-OR'4 group

[0282] According to one embodiment, the process and / or composition of the invention employs one or more copolymer(s) comprising several repeating units chosen from the units (A) and one or more units resulting from the polymerization of one or more additional monomer(s) as defined above.

[0283] Preferably, the additional monomer(s) iii) is / are chosen from the monomers of the following formula (II): H2C=C(Re)-C(O)-E-R5 formula (II) in which E represents an oxygen atom or N(R), preferably E represents an oxygen atom, with R representing a hydrogen atom or (Ci-C4)alkyl group such as methyl, and Re represents a hydrogen atom, a (Ci-C4)alkyl group such as methyl and Rs represents:

[0284] - a (Ci-C22)alkyl group, preferably (Ci-C2o)alkyl, more preferably (Ci-Cio)alkyl, linear or branched, optionally interrupted by one or more oxygen atoms, preferably Rs represents methyl, ethyl, n-propyl, i-propyl, n-butyl, s-butyl, t-butyl, n-hexyl, n-heptyl, 2-ethylhexyl, n-octyl, i-octyl, n-decyl, stearyl, methoxyethyl, ethoxyethyl and methoxypropyl, isodecyl, lauryl, hexadecyl, more preferably methyl,

[0285] - a (Cs-C22)cycloalkyl group, preferably (Cs-C2o)cycloalkyl, in particular cyclohexyl, norbomyl or isobomyl, preferably isobomyl, or

[0286] - an aryl or aryl(Ci-C4)alkyl group such as benzyl.

[0287] More preferably, the additional monomer(s) iii) is / are chosen from among the monomers of formula (II') following: H2C=C(Re)-C(O)-O-R5 (IF) with Rs representing a linear or branched (Ci-Ce)alkyl group such as methyl and Re representing a hydrogen atom, a (Ci-C4)alkyl group such as methyl.

[0288] Preferably, Re represents a hydrogen atom or a (Ci-C4)alkyl group such as methyl. Examples of preferred Rs groups are methyl, ethyl, n-propyl, i-propyl, n-butyl, s-butyl, t-butyl, n-hexyl, n-heptyl, 2-ethylhexyl, isobotyl, cyclohexyl, and more preferably, methyl, ethyl, i-propyl, t-butyl, isobotyl, and even better, methyl.

[0289] Particularly after obtaining the copolymers X as defined above, the latter are hydrolyzed leading to copolymers comprising polymeric units of the following formula (III): formula (III) in which Re is as defined previously in formula (II) or (II'), and A represents a hydroxy, amino, or OM group + with M + as defined previously in formula (A).

[0290] According to another particular embodiment of the invention, the process and / or the composition of the invention employs one or more homopolymer(s) and / or copolymer(s) comprising several repeating units chosen from the units (A) in which R2 and R3 represent a hydroxy group.

[0291] More specifically, according to this embodiment, all or part of the polymeric units (A) are polymeric units (B): formula (B) in which Ri and R4 are as defined previously in formula (A); particularly the polymer units (B) are such that R4 represents a hydrogen atom or an M + representing a cationic counterion, preferably an alkali or alkaline earth metal cation, or ammonium, a primary, secondary, or tertiary (Ci-Cs)alkylamine that may comprise one or more nitrogen and / or oxygen atoms (such as 2-amino-2-methyl-2-propanol, triethanolamine, 2-dimethylamino-2-propanol, lysine, or 3-(dimethylamino)propylamine) and may comprise several alcohol functional groups, it being understood that at least one of the nitrogen atoms is protonated by a hydrogen atom to form an ammonium group, it being understood that each of these amines is protonated. Said units (B) may then be found in the form of a cyclized polymeric unit (Bl), particularly in acidic media.

[0292] According to one embodiment, the polymeric units (B) for which R4 represents a hydrogen atom or an M + as defined previously, can be found in the form of a cyclized polymeric unit (Bl), particularly in acidic media: According to one embodiment, units (B) such that Ri represents a -C(O)-OR'4 group, in particular carboxy, or carboxylate -C(O)OM, are represented by the formula (B'):

[0293] These units (B') can cyclize, particularly in acidic media, to lead to bicyclic units (B'1):

[0294] According to another embodiment, the process and / or the composition of the invention employs at least one polymer comprising several repeating units chosen from the units (A) in which R2 and R3 together form a bond.

[0295] More specifically, the polymer units (A) in which R2 and R3 together form a bond are polymer units (C);

[0296] According to one embodiment, units (C) such that Ri represents a -C(O)-OR'4 group, in particular carboxy, or carboxylate -C(O)OM, are represented by the formula (C'):

[0297] According to another embodiment, the process and / or the composition of the invention implements at least one polymer comprising several repeating units chosen from the units (A) in which R2 and R3 together form a saturated or unsaturated heterocycle, preferably saturated, comprising at least one oxygen atom, and comprising 3 to 6 links, preferably 3 links such as epoxy.

[0298] More specifically, units (A) for which R2 and R3 together form a saturated or unsaturated heterocycle, preferably saturated, comprising at least one oxygen atom, and comprising 3 to 6 links, preferably with 3 links such as epoxy, are polymeric units (D);

[0299] According to one embodiment, the units (D) for which Ri represents a -C(O)-OR'4 group, in particular carboxy, or -C(O)OM are the polymeric units (D'):

[0300] According to another embodiment, the process and / or the composition of the invention implements at least one polymer comprising several repeating units chosen from the units (A) in which R4 and / or Rti represent a hydrogen atom.

[0301] According to another embodiment, the process and / or the composition of the invention employs at least one polymer comprising several repeating units selected from the units (A) in which R4 and / or R4' represent a cationic counter ion M + Preferably an alkali metal, alkaline earth, or ammonium cation, a primary, secondary, or tertiary (Ci-Cs)alkylamine that may contain one or more nitrogen and / or oxygen atoms and may therefore contain, for example, several alcohol functional groups, it being understood that at least one of the nitrogen atoms is protonated by a hydrogen atom to form an ammonium group. Examples include 2-amino-2-methyl-2-propanol, triethanolamine, dimethylamino-2-propanol, lysine, and 3-(dimethylamino)propylamine, it being understood that each of these amines is protonated.

[0302] Preferably, M + is chosen from alkali metals such as Na + , Li + K+ , alkaline earth metals such as Ca 2+ and the metal Zn 2+ , or the following protonated amines: protonated 2-amino-2-methyl-2-propanol, or protonated triethanolamine.

[0303] According to another embodiment, the process and / or the composition of the invention implements at least one polymer comprising several repeating units selected from the units (A) in which R4 and / or R4' represent a hydrocarbon group, saturated or unsaturated, linear or branched, non-cyclic, or saturated or unsaturated cyclic, aromatic or non-aromatic, comprising from 1 to 30 carbon atoms, preferably from 2 to 20 carbon atoms, preferably said hydrocarbon group is saturated acyclic linear or branched, or cyclic. According to a preferred embodiment, R4 and / or R4' represent(s) a (Ci-Cis)alkyl group, preferably a (Ci-Ci2)alkyl group, linear or branched, optionally interrupted by one or more heteroatoms such as oxygen, in particular selected from methyl, ethyl, n-propyl, i-propyl, n-butyl, sec-butyl, t-butyl, n-hexyl, n-heptyl, 2-ethylhexyl, n-octyl, i-octyl and more preferably selected from t-butyl and n-octyl.

[0304] According to another embodiment R4 and / or R4' represent a saturated or unsaturated cyclic hydrocarbon group, aromatic or non-aromatic, comprising from 2 to 20 carbon atoms, preferably are chosen from saturated cyclic groups (Cs-Ci2)cycloalkyls such as cyclo-hexyl or isobotyl, unsaturated aromatic cyclics such as (C6-Ci2)aryl or (C6-Ci2)aryl(Ci-C4)alkyl such as benzyl.

[0305] Examples of preferred R4 and / or R'4 groups are ethyl, propyl, isopropyl, n-butyl, sec-butyl, t-butyl, 2-ethylhexyl, n-octyl, isooctyl, isobomyl, cyclohexyl, benzyl, and more preferably R4 and / or Rf represent an ethyl, i-propyl, t-butyl, n-octyl, or isobomyl group.

[0306] According to one embodiment, the process and / or the composition of the invention employs at least one polymer comprising several repeating units selected from units (A) to (D') as defined above, wherein R4 and R4', identical or different, represent a hydrocarbon group, saturated or unsaturated, linear or branched, non-cyclic, or saturated or unsaturated cyclic, aromatic or non-aromatic, comprising from 1 to 30 carbon atoms; preferably comprising from 2 to 20 carbon atoms, preferably said hydrocarbon group being saturated acyclic linear or branched, or cyclic, said hydrocarbon group being further substituted by one or more (di)(Ci-C4)(alkyl)amino groups; and / or interrupted by (a') one or more heteroatoms selected from O, N(R a ), and Si(Rb)(R c ), b') S(O) r with r = 1, 2 or 3 or carbonyl, c') or associations of a') with b') such as -C(O)-O-, -OC(O)-, amide -C(O)- N(R a)-, -N(Ra)-C(O)-, urethane -N(R a )-C(O)-O- or -OC(O)- N(R a )-, urea - N(Ra)-(CO)- N(Rb)-, carbonate -OC(O)-O-, -[O-Si(Rb)(R c )]p- or -[(CRa2)pO] q - with p an integer greater than or equal to 1, preferably between 1 and 200, and q represents an integer between 1 and 4; in which R a represents a hydrogen atom, Rb and R c , being as defined previously and preferably representing a (Ci-C4)alkyl group such as methyl. Polymer

[0307] Another object of the present invention is a polymer comprising several repeating units of formula (A) as defined above.

[0308] In one embodiment, the polymer comprising one or more repeating units of formula (A) as described above is chosen from the group consisting of:

[0309] 1) statistical, sequenced or gradient copolymer(s) comprising i) several identical repeating units selected from units (A) and their optical, geometric isomers, their acid or base salts, organic or mineral, and their solvates such as hydrates and ii) at least one unit selected from units (Al) to (Al 5) as defined above or mixtures thereof, and / or iii) one or more units resulting from the polymerization of one or more additional monomer(s) selected from iii1) (Ci-C4)(alkyl)acrylate of (Ci-C22)(cyclo)alkyl preferably (meth)acrylate of (Cs-C22)(cyclo)alkyl, and / or iii2) (Ci-C4)(alkyl)acrylamide of (Ci-C22)(cyclo)al- kyle preferably (meth)acrylamide of (Cs-C22)(cyclo)alkyl;

[0310] 2) the statistical, sequenced or gradient copolymer(s) comprising i) at least two different repeating units selected from units (A) and possibly ii) at least one unit selected from units (Al) to (Al 5) defined previously or mixtures thereof, and possibly iii) one or more units resulting from the polymerization of one or more additional monomer(s) selected from iii1) (Ci-C4)(alkyl)acrylate of (Ci-C22)(cyclo)alkyl, and / or iii2) (Ci-C4)(alkyl)acrylamide of (Ci-C22)(cyclo)alkyl as defined previously;

[0311] 3) homopolymers comprising units (A) for which Ri represents a -C(O)- group OR'4, R2 and R3 together form a bond and R4 and R'4 represent a linear or branched (Cs-Csjalkyl) group other than i-propyl, n-butyl, and 2-ethylhexyl, as defined above;

[0312] 4) homopolymers comprising units (A) for which Ri represents a -C(O)- OR'4 group, and R2 and R3 together form a saturated or unsaturated heterocycle, comprising at least one oxygen atom, and comprising 3 to 6 members, as defined above; and

[0313] 5) homopolymers comprising units (A) in which R2 and R3, identical or different, represent a hydrogen atom or a hydroxy group, it being understood that R2 and R3 cannot simultaneously represent a hydrogen atom, as defined above.

[0314] According to one embodiment, the polymer of the invention is a copolymer 1) comprising units (A) or (C) as defined above and below, wherein Ri represents a (Ci-C4)alkyl group such as methyl, or a -C(O)-OR'4 group, R2 and R3 together form a bond, and R4 and Rf are as defined above. More preferably, the copolymers 1) are statistical and comprise units (A) in which Ri represents a -C(O)-OR'4 group, R2 and R3 together form a bond, and R4 and R'4 are preferably identical, as defined above, preferably represent iii) as defined above.

[0315] An object of the invention is a statistical copolymer 2) comprising units (A) or (C') as defined above and below for which Ri represents a -C(O)-OR'4 group, R2 and R3 together form a bond and R4 and R'4 preferably identical, are different from a hydrogen atom, preferably represent iii) as defined above.

[0316] An object of the invention is a homopolymer 3) comprising units (A) or (C') as defined above and below, for which Ri represents a -C(O)-OR'4 group, and R2 and Ra together form a bond and R4 and R'4 preferably identical, represent a linear or branched (C3-Csjalkyl) group other than i-propyl, n-butyl, and 2-ethylhexyl such as t-butyl or n-octyl; or a (C3-Cio)cycloalkyl group other than cyclohexyl such as isobotyl.

[0317] An object of the invention is a homopolymer 4) or a copolymer 1) or 2) comprising units (A), or (D') as defined above and below, for which Ri represents a -C(O)-OR'4 group, R2 and R3 together form a saturated or unsaturated heterocycle, preferably saturated, comprising at least one oxygen atom, and comprising 3 to 6 links, preferably 3 links such that epoxy and R4 and R'4 preferably identical are as defined above.

[0318] An object of the invention is a homopolymer 5) or copolymer 1) or 2) comprising units (A), (B), (Bl), (B') and (B' 1) as defined below for which R2 and R3, identical or different, represent a hydrogen atom or a hydroxy group, it being understood that preferably R2 and R3 cannot simultaneously represent a hydrogen atom, preferably R2 and R3 represent a hydroxy group.

[0319] An object of the invention is a homopolymer or copolymer comprising several repeating units chosen from units (A) to (D') as defined above and below, crosslinked by b) one or more crosslinking agent(s) (E), (F), (K), and (O), such as defined below, in particular of formula (E).

[0320] According to a particular embodiment of the invention, the homopolymer(s) comprise several repeating units distributed statistically among the units (A) which are chosen from those of formula (E') as well as their geometric isomers Z / E and solvates such as hydrates:

[0321] Formula (E') in which

[0322] Rio representing a hydrogen atom, a cationic counterion, a (Ci-Cio)alkyl group, linear or branched, such as ethyl,

[0323] R represents a hydrogen atom, a cationic counterion, a linear or branched (Ci-Cio)alkyl group other than n-butyl and 2-ethylhexyl such as n-octyl, -butyl, i-propyl, or a cycloalkyl group such as isobotyl, and n is an integer greater than or equal to 1, preferably between 10000 and 5, more preferably between 1000 and 5, and even more preferably between 300 and 5. More particularly, the homopolymer(s) is / are chosen from Al-1 to Al-4, as well as their Z / E geometric isomers and solvates such as hydrates:

[0324] Table 2

[0325] The Al-1 to Al-4 homopolymers are such that n is an integer greater than or equal to 1, preferably between 10000 and 5, more preferably between 1000 and 5 and even more preferably between 300 and 5.

[0326] According to a particular embodiment of the invention, the copolymer(s) a2) comprises several repeating units distributed statistically among the units (A) which is / are chosen from those of formula (F) as well as their geometric isomers Z / E and solvates such as hydrates:

[0327] Formula (F) in which

[0328] Rio representing a hydrogen atom, a cationic counterion, a (Ci-Cio)alkyl group, linear or branched, such as ethyl,

[0329] Ru representing a hydrogen atom, a cationic counter ion, a linear or branched (Ci-Cio)alkyl group, such as n-octyl or t-butyl,

[0330] R12 different from Ru, representing a hydrogen atom, a cationic counter ion, a (C i- Cio)alkyl group, linear or branched, such as ethyl, or t-butyl and u and v represent the molar percentage of each statistically distributed repeating unit;

[0331] The final degree of polymerization of the polymer is preferably between 10000 and 5, more preferably between 1000 and 5 and even more preferably between 300 and 5.

[0332] Preferably, the copolymer(s) comprise several repeating units chosen from units (A) selected from:

[0333] Table 3

[0334] More specifically, the copolymer(s) is / are chosen from A2-1 to A2-4 as well as their geometric isomers Z / E and solvates such as hydrates:

[0335] Table 4

[0336] According to one embodiment of the invention, the copolymer(s) comprise several repeating units distributed in a sequential manner, chosen from the units (A) which are chosen from those of formula (G) as well as their geometric isomers Z / E and solvates such as hydrates:

[0337] Formula (G) in which

[0338] Rio representing a hydrogen atom, a cationic counterion, a (Ci-Cio)alkyl group, linear or branched, such as ethyl

[0339] Ru representing a hydrogen atom, a cationic counterion, a linear or branched (Ci-Cio)alkyl group, such as n-octyl, and

[0340] R12 different from Ru, representing a hydrogen atom, a cationic counter ion, a (C i- Cio)alkyl group, linear or branched, such as ethyl or t-butyl, and w and x being the molar percentage of each repeating unit distributed sequentially; preferably the final degree of polymerization of the polymer (G) is between 10000 and 5, more preferably between 1000 and 5 and even more preferably between 300 and 5.

[0341] Preferably, the copolymers are of the diblock type with formula G in which:

[0342] Table 5

[0343] More specifically, the copolymer(s) are of the diblock type chosen from A2-4 to A2-6 as well as their geometric isomers Z / E and solvates such as hydrates:

[0344] Table 6

[0345] According to one embodiment, the copolymers are of the triblock type and preferably comprise several repeating units selected from units (A) chosen from those of formula (H) as well as their geometric isomers Z / E and solvates such as hydrates: formula (H) in which Rio, Ru and R12 are as defined previously, R13 represents a Ru group; in particular Rio and Ru identical and preferably represent an ethyl, R12 represents an octyl, and R13 represents a hydrogen atom, a cationic counterion, a (C 1- Cio)alkyl group, linear or branched-such as ethyl.

[0346] Preferably, the final degree of polymerization of the polymer (H) is between 10000 and 5, more preferably between 1000 and 5 and even more preferably between 300 and 5.

[0347] Preferably, the copolymers are of formula (H) in which:

[0348] Table 7

[0349] More specifically, the copolymer(s) are of the triblock type chosen from A2-7, along with their geometric isomers Z / E and solvates such as hydrates:

[0350] According to one embodiment, the copolymer(s) comprise several repeating units distributed in a sequential manner, chosen from the units (A) which is / are chosen from those of formula (J) as well as their geometric isomers Z / E and solvates such as hydrates:

[0351] Formula (J) in which

[0352] Rio representing a (Ci-Cio)alkyl group, linear or branched, such as ethyl;

[0353] Ru representing a (Ci-Cio)alkyl group, linear or branched, such as ethyl; R12 representing a (Ci-Cio)alkyl group, linear or branched, such as ethyl, and w and x being the molar percentage of each repeating unit distributed in a sequenced manner.

[0354] Preferably, the final degree of polymerization of the polymer (J) is between 10000 and 5, more preferably between 1000 and 5 and even more preferably between 300 and 5.

[0355] More specifically, the copolymer(s) are of the diblock type chosen from A2-8 and A2-9 as well as their geometric isomers Z / E and solvates such as hydrates:

[0356] Table 10

[0357] According to one embodiment, the copolymer(s) comprise several repeating units distributed in a sequential manner, chosen from units (A) which is / are chosen from those of formula (K) as well as their geometric isomers Z / E and solvates such as hydrates:

[0358] Formula (K) in which

[0359] Rio represents a (Ci-Cio)alkyl group, linear or branched, such as methyl.

[0360] R' 10 representing a hydrogen atom or a linear or branched (Ci-C4)alkyl group, such as methyl

[0361] Ru representing a (Ci-Cio)alkyl group, linear or branched, such as methyl or butyl

[0362] R12 represents a linear or branched (Ci-Cio)alkyl group, such as ethyl, and w and x are the molar percentage of each repeating unit distributed in a sequenced manner.

[0363] Preferably the final degree of polymerization of the polymer (J) is between 10000 and 5, more preferably between 1000 and 5 and even more preferably between 300 and 5.

[0364] The polymer according to the invention may be at least partially crosslinked or uncrosslinked. In the case where the polymer according to the invention is at least partially crosslinked, the crosslinking agent is preferably as defined above.

[0365] The polymer according to the invention is preferably semi-crystalline or amorphous.

[0366] The crystallinity of a polymer is the degree of structural order within the solid polymer. Unlike inorganic crystals, which exhibit a highly ordered and repeating structure over long distances, in one embodiment, the polymer(s) according to the invention preferably take the form of semi-crystalline materials, composed of crystalline (ordered) and amorphous (disordered) regions. In the "crystalline" regions, the polymer chains are aligned in a highly ordered and compact manner, forming regular and repeating structures (such as lamellae or spherulites). These regions have a distinct melting point (Tm). In contrast, in the "amorphous" regions, the polymer chains are randomly and disorderedly entangled, without a repeating structure over long distances. These regions are generally more flexible and have a lower density than the crystalline regions.Semi-crystalline polymers are characterized by a glass transition temperature (Tg), below which the material becomes rigid and brittle, and above which it becomes more flexible and rubbery.

[0367] More preferably, the polymer(s) of the invention are amorphous, that is to say non-crystalline, they do not include crystalline regions.

[0368] In some embodiments, the polymer(s) according to the invention have a crystallinity level of less than 50%, preferably less than or equal to 40%, preferably less than or equal to 30%, preferably less than or equal to 20%, preferably less than or equal to 10%, preferably less than or equal to 5%. In some embodiments, the polymer(s) according to the invention are semi-crystalline or amorphous, preferably amorphous or non-crystalline.

[0369] The degree of crystallinity of the polymer(s) can be measured by any suitable technique known in the art. In particular, it can be measured by thermal analysis, for example by differential scanning calorimetry (DSC), specifically by measuring the ratio between the enthalpies of melting at the melting point of said polymer and of a fully crystalline polymer.

[0370] According to a preferred embodiment, the polymer(s) according to the invention are statistical copolymers (2) comprising at least two different repeating units selected from the units (A), optionally one or more units selected from the units (Al) to (Al 5), and optionally one or more units resulting from the polymerization of one or more additional monomers having a degree of crystallinity less than 50%, preferably less than or equal to 40%, preferably less than or equal to 30%, preferably less than or equal to 20%, preferably less than or equal to 10%, preferably less than or equal to 5%. In some embodiments, the polymer(s) according to the invention are such semi-crystalline or amorphous statistical copolymers, preferably amorphous or non-crystalline.

[0371] According to another preferred embodiment, the polymer(s) according to the invention are homopolymers comprising units (A) and having a degree of crystallinity less than 50%, preferably less than or equal to 40%, preferably less than or equal to 30%, preferably less than or equal to 20%, preferably less than or equal to 10%, preferably less than or equal to 5%, even better less than 2%. In some embodiments, the polymer(s) according to the invention are such semi-crystalline or amorphous homopolymers, preferably amorphous or non-crystalline.

[0372] The polymer according to the invention possesses interesting properties and can advantageously be used to replace currently used polymers, such as polyacrylates. It exhibits certain properties similar to those of polyacrylates, and is also bio-based and / or can be degraded by typically simple post-use methods.

[0373] A person skilled in the art is able to determine the appropriate conditions for degrading the polymer, based in particular on its chemical structure.

[0374] The polymers according to the invention have the advantage of being easily degradable, either by simple thermal degradation, or by any other suitable degradation technique, such as ozonolysis in particular when the polymer includes double bonds.

[0375] In certain embodiments, particularly when the polymers according to the invention include hydroxyl and / or epoxide groups, the polymers could also be biodegradable, i.e., they could be degraded by living organisms.

[0376] The degradation of polymers according to or used according to the invention preferably produces monomers and / or oligomers, particularly low molecular weight oligomers. Method for preparing a polymer

[0377] Another object of the invention is a process for preparing a polymer comprising several repeating units of formula (A) as defined above. In some embodiments, it is a process for preparing a polymer according to the invention. The process according to the invention is a process for synthesizing polymers comprising several repeating units of formula (A) by GTP.

[0378] The invention thus relates to a process for preparing polymers 1), 2), 3), 4), and 5) as defined above. The preparation process comprises at least step i) and optionally at least one of steps ii) and iii) as defined in Scheme 1 below:

[0379] The polymer(s) comprising several repeating units chosen from the units (A) of the invention can be prepared according to route i) from the polycondensation of diene (I-C) and its geometric isomers Z / Z, Z / E, E / Z or E / E, preferably in the presence of catalysts) and / or initiator(s) (radical initiators), in a particularly organic solvent, preferably aprotic, more preferably polar aprotic, at a temperature less than or equal to 120 °C, to lead to the polymer(s) (C) which can be of configuration Z or E according to the following scheme 2.

[0380] Scheme 2 in which the compound (IC) and the polymer (C) contain RI and R4 radicals which are as defined previously.

[0381] Preferably, polymerization (or polycondensation) by route i) is carried out by group transfer (GTP) according to a repetition of "Mukaiyama / Michael" reactions. It is preferably "initiated" by one or more initiators as defined below, in particular by one or more silylated acetal ketene (ACS) type compounds of general structure (a), which add to unsaturated monomers of the "Michael acceptor" type, preferably in the presence of one or more Lewis acid or base type catalyst(s), and preferably using an aprotic solvent (see e.g. OW Webster, WR Hertler, DY Sogah, WB Farnham and TV Rajan-Babu, J. Am. Chem. Soc., 1983, 105, 5706-5708).The preferred Initiator / Catalyst / Monomer / Solvent mixture allows for anionic polymerization carried out either under so-called "living" and "controlled" conditions and allows for obtaining statistical homopolymers and copolymers, block, star, hyperbranched or dendrimeric, of well-defined structure, controlled molar masses and low dispersity via in particular the initial Monomer / initiator ratio, particularly the Monomer / initiator ratio is between 10000 and 5, more preferably between 1000 and 5 and even more preferably between 300 and 5.

[0382] Preferably the molar ratio Initiator / Catalyst is between 10000 and 1, more preferably between 1000 and 10 and even more preferably between 100 and 10.

[0383] According to a preferred embodiment of the invention, the polymerization process does not use malodorous organometallic or sulfur catalysts used in certain controlled radical polymerization techniques such as ATRP or RAFT.

[0384] According to one embodiment, anionic polymerization uses one or more lithia initiator(s), this technique can be carried out at room temperature (25 °C + / - 3 °C) or above and therefore does not require working at very low temperature, which is a major advantage from an industrial point of view.

[0385] According to one embodiment of the invention, the process uses one or more catalysts selected from Lewis acids and bases and catalytic bases, in particular selected from i) carbenes; ii) phosphazenes and Verkade bases; iii) nitrogen bases; iv) phosphines; v) Lewis acids derived from boron or sulfur; and vi) quaternary ammoniums.

[0386] According to one embodiment of the invention, the process uses one or more catalysts selected from Lewis bases and catalytic bases, preferably strong organic bases or organocatalysts, in particular selected from i) N-heterocyclic carbenes (NHCs), especially imidazolium derivatives (such as IPr, IMes) and Arduengo carbenes; ii) phosphazenes such as 1-tert-butyl-4,4,4-tris(dimethylamino)-2,2-bis[tris(dimethylamino)phosphoranyl-denamino]-2 5,4 5-catenadi(phosphazene) (t-Bu-P4 or P4-t-Bu), 1-tert-butyl-2,2,4,4,4-pentakis(dimethylamino)-2 5,4 5 5-catenadi(phosphazene) (t-Bu-P2 or P2-t-Bu); Proazaphos-phatranes (or Verkade bases) or bases which are structurally polycyclic compounds containing nitrogen and phosphorus, often with a cage structure, the central phosphorus being hypervalent such as 2,8,9-triisobutyl-2,5,8,9-tetraaza-l-phosphabicyclo[3.3.3) undecane; iii) Amidines and guanidines such as DBU (1,8-Diazabicyclo[5.4.0]undec-7-ene), TBD (1,5,7-Triazabicyclo[4.4.0]dec-5-ene) or MTBD (7-methyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene), and iv) Sterically hindered amino bases or phosphines such as Triazabicyclodecene (TBD), tetramethylpyridine (TMP), Quinuclidine, tri(Cl-C6)alkylphosphine, diarylphosphine, triarylphosphine, dicycloalkylphosphine, tricycloalkylphosphine and v) halogenated Lewis acid derived from boron and sulfur.

[0387] According to a preferred embodiment, the process uses one or more catalyst(s) chosen from Lewis acids and bases, and particularly chosen from:

[0388] - N-heterocyclic carbenes such as 1,3-diisopropyl-4,5-dimethylimidazol-2-ylidene, 1,3-diisopropylimidazol-2-ylidene or 1,3-di-tert-butylimidazol-2-ylidene;

[0389] - phosphazenes such as l-tert-butyl-4,4,4-tris(dimethylamino)-2,2-bis[tris(dimethylamino)-phosphoranylidenamino]-2A5,4A5-catenadi(phosphazene) (t-Bu-P4 or P4-t-

[0390] Bu), 1-tert-butyl-2,2,4,4,4-pentakis(dimethylamino)-2A5,4A5-catenadi(phosphazene) (t-Bu-P2 or P2-t-Bu); - nitrogenous bases such as 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU), 2,8,9-trimethyl-2,5,8,9-tetraaza-l-phosphabicyclo[3.3.3]undecane (TMP) and 2,8,9-triisobutyl-2,5,8,9-tetraaza-l-phosphabicyclo[3.3.3]undecane (TiBP); and

[0391] - phosphines such as tri-(Cl-C6)alkylphosphine, triarylphosphine, or tricycloalkylphosphine in particular tri-n-butylphosphine (Bu3P), tricyclohexylphosphine (Cy3P), triphenylphosphine (Ph3P), and tris(2,4,6-trimethoxyphenyl)phosphine (TTMPP);

[0392] - Lewis acids derived from boron and sulfur such as tris-(pentafluorophenyl)borane, triethylsilyl trifluoromethane sulfonate, or a combination of these two catalysts, N-(triethylsilyl)-bis-(trifluoromethane sulfonyl)imide, triphenylmethyl tetrakis(pentafluorophenyl)borate (TTPB), trifluoromethane sulfonimide, 2,3,4,5,6-pentafluorophenyl-1,1-bis(trifluoromethanesulfonyl)methane; and

[0393] - quaternary ammoniums in particular tetra(Cl-C6)alkylammonium halides such as tetran-butyl ammonium fluoride, tetran-butyl ammonium 3-chlorobenzoate cyanide, tetran-butyl ammonium benzoate, tetran-butyl ammonium bisbenzoate, tetran-butyl ammonium 3-chlorobenzoate, tetran-butyl ammonium bis 3-chlorobenzoate.

[0394] Preferably, the catalyst(s) used according to the invention are chosen from strong organic bases or organic catalysts, in particular phosphazenes, such as 1-tert-butyl-4,4,4-tris(dimethylamino)-2,2-bis[tris(dimethylamino)phosphoranylidenamino]-2

[0395] A 5.4 A 5-catenadi(phosphazene) (t-Bu-P4 or P4-t-Bu or Phosphazene-P4 base) or 1-tert-butyl-2,2,4,4,4-pentakis(dimethylamino)-2 A 5.4 A 5-catenadi(phosphazene) (t-Bu-P2 or P2-t-Bu or Phosphazene-P2 base), in particular t-Bu-P2.

[0396] It is preferable to use phosphazenes such as 4 A 5 - catenadi(phosphazene) or t-Bu-P4, also known as P4-t-Bu, with the following formula: t-Bu-P4 or l-tert-butyl-2,2,4,4,4-pentakis(dimethylamino)-2A5,4A5-catenadi(phosphazene) of formula t Bu-P2. According to a particular embodiment of the invention, the process uses one or more initiators which are silylated acetal ketene (ACS) type derivatives of general structure (a) as well as its geometric isomers E / Z: Formula (a) in which:

[0397] PI and P4, whether identical or different, represent an (Ci-C4)alkyl group such as methyl or ethyl; and

[0398] P2 and P3, identical or different, represent a hydrogen atom, a (Ci-Ci2)alkyl group such as methyl, or a (C2-Ci2)alkenyl group such as vinyl -CH=CH2, preferably P2 and P3 are different, more preferably P2 is a hydrogen atom and P3 represents a (C2-Ci2)alkenyl group such as vinyl -CH=CH2;

[0399] The preferred ACS (a) used in the process of the invention are represented below by (ACS1)

[0400] (ACS2) RN = 73311-50-9

[0401] According to another embodiment, the initiators are of the following formula (b), as well as its geometric isomers Z / E:

[0402]

[0403] Formula (b) in which:

[0404] PI, P3, P4 and n are as defined previously and

[0405] Core represents a hydrocarbon group, acyclic saturated or unsaturated, linear or branched, or cyclic saturated or unsaturated, aromatic or non-aromatic, comprising from 2 to 40 carbon atoms, particularly 3 to 36 carbon atoms, said hydrocarbon group being able to a) be interrupted by one or more heteroatoms or groups selected from the atoms of oxygen, sulfur, nitrogen, silicon or -[O-Si(Rb)(Rc)]p- with Rb, Rc are as defined above, p between 1 and 200, carbonyl -C(O)-, or their associations such as ester -C(O)-O-, -OC(O)-, amide -C(O)-N(R')-, -N(R')-C(O)-, urethane -N(R')-C(O)-O- or -OC(O)-N(R')-, urea -N(R')- (CO)-N(R')-, or carbonate -OC(O)-O-, in which R' represents a hydrogen atom, an alkyl group having from 1 to 4 carbon atoms.Preferably n is 2 and / or Core represents a hydrocarbon group, acyclic saturated or unsaturated, linear or branched, or cyclic saturated or unsaturated, comprising from 2 to 10 carbon atoms, particularly 3 to 8 carbon atoms. More particularly, the initiators of formula (b) are chosen from those of formula (bl) to (b4) as well as their geometric isomers Z / E.

[0406] Table 11

[0407] According to one embodiment of the process of the invention, the first step i) is carried out in one or more aprotic solvent(s), in particular if the polymerization (or polycondensation) of route i) is carried out by group transfer (GTP) as defined above, the solvent(s) is / are chosen from: polar aprotic solvents, in particular halo(Cl-C6)alkanes such as dichloromethane, heterocycles such as tetrahydrofuran (THF) or THF substituted with a C1-C6 alkyl group such as methyl-THF, (C1-C4)alkylnitriles such as acetonitrile, C1-C12 alkanool and C1-C12 coxylic acid esters such as ethyl acetate, butyl acetate, isopropyl myristate, isononyl isononate, and aprotic nonpolar solvents including aromatics such as toluene, xylene, anisole, and linear or branched C8 to C20 alkanes such as isododecane, or paream.

[0408] More preferably the solvent(s) used in route i) is chosen from among the esters mentioned above, cyclic nonpolar aprotic solvents, preferably aromatic, such as toluene, or non-cyclic such as isododecane or parleam and cyclic polar aprotic solvents such as tetrahydrofuran or THF substituted by a C1-C4 alkyl such as methyl-THF or acyclic such as (di)glyme.

[0409] In particular, polymerization is carried out at a temperature between -80 °C and + 100 °C, preferably from 0 °C to 100 °C and more preferably from 0 °C to 50 °C.

[0410] To complete the polymerization, one or more nucleophilic compounds or polar protic solvents such as water, saturated or unsaturated cyclic or non-cyclic carboxylic acids, preferably aromatic, or alcohols and polyols, particularly (C1-C6) alkanols, can be used. Methanol, ethanol, or benzoic acid are preferred.

[0411] Other electrophilic mono- or multi-functional termination agents that induce the formation of one or more chemical functions at the end of the chain can be used, including aldehydes, halogenated compounds (fluorinated, chlorinated, brominated, iodinated) cyclic or non-cyclic, saturated or unsaturated, aromatic or non-aromatic.

[0412] Initiators, catalysts, solvents, and temperature ranges are described, for example, for GTP-type polymerization in the following references: F. Bandermann et al. Macromolecules, 1989, 190, 9, 2183-219; T. Kakuchi et al. Polymer Chemistry 2013, 4, 4278-4291, and US patent application US 20230174071. According to a particular embodiment of the invention, the copolymer(s) comprising several different repeating units chosen from the units (A) as defined above are of the diblock type. Preferably the diblock-type copolymer(s) a2 is / are prepared by polymerization using a first monomer and one or more monofunctional initiator(s), in particular of formula (a), then once this monomer is "consumed", a second monomer different from the first is added.

[0413] According to one embodiment, the copolymer(s) comprising several repeating units chosen from the units (A) as defined above is / are of triblock or multiblock type, the starters of Formula (a) or (b) can be used and the different monomers of interest added sequentially.

[0414] Preferably in the process of the invention the molar ratio Initiator / catalyst between 10000 and 1, more preferably between 1000 and 10 and even more preferably between 100 and 10.

[0415] The said polymer(s) (C) can then be partially or totally epoxidized according to route ii), in a particularly organic solvent, preferably aprotic, at a temperature less than or equal to 120 °C, to give rise to the epoxidized polymer(s) (D) according to the following scheme (3):

[0416] Scheme 3 in which polymers (C) and (D) contain radicals Ri and R4 which are as defined previously.

[0417] Epoxidation pathways on unsaturated organic compounds are known to those skilled in the art and can be carried out using oxidizing agent(s) and / or catalyst(s) (see, for example: Mohammed, ML; Saha, B. Recent Advances in Greener and Energy Efficient Alkene Epoxidation Processes. Energies 2022, 75, 2858. Babot ED, Aranda C, Kiebist J, Scheibner K, Ullrich R, Ho- frichter M, Martinez AT, Gutiérrez A. Enzymatic Epoxidation of Long-Chain Terminal Alkenes by Fungal Peroxygenases. Antioxidants (Basel). 2022 Mar 8;11(3):522. doi: 10.3390 / antioxl 1030522).

[0418] Among the oxidizing agent(s) of particular interest for carrying out epoxidation, we can mention dioxygen O2, peroxides such as H2O2, peracids, especially aromatic ones such as (halo)perbenzoic acids such as m-chloroperbenzoic acid, organic, organometallic or enzymatic catalysts such as derivatives of Titanium, Manganese, Aluminium.

[0419] Among the relevant enzymes for carrying out the epoxidation of unsaturates, we can mention lipases, which transform acids into peracids that epoxidize unsaturates, but also peroxygenases, nonheme monooxygenases, halogen peroxidases such as chloroperoxidase, and cytochrome P450 monooxygenases. The aforementioned polymer(s) (D) can be hydrolyzed via pathway iii) to obtain one or more diol polymer(s) (B) according to the following scheme 4:

[0420] Scheme 4 in which the polymers (B) contain radicals Ri and R4 which are as defined previously, it being understood that (B) can be in cyclic (Bi) and bicy clique (B'i) form if Ri represents a -C(O)-OR'4 group.

[0421] The methods of epoxide hydrolysis are known to those skilled in the art (for example, for a description of the conditions for epoxide hydrolysis, see the publications: S. Bonollo; D. Lanari and L. Vaccaro: Ring Opening of Epoxides in Water Eur. J. Org. Chem. 2011, 2587-2598 Bucko, M.; Kaniakovâ, K.; Hronskâ, H.; Gemeiner, P.; Rosenberg, M. Epoxide Hydrolases: Multipotential Biocatalysts. Int. J. Mol. Sci. 2023, 24, 7334.)

[0422] According to one embodiment, the epoxidation step is carried out in water or in a mixture of (a)polar (a)protic organic solvent(s) and water, the hydrolysis of the epoxide according to route iii) can be carried out concomitantly with route ii) to generate the corresponding vicinal diol of the polymer diol(s) (B).

[0423] According to one embodiment, hydrolysis is carried out in a second step according to route iii) subsequent to route ii) using an alkaline, neutral or acidic medium, preferably an acidic or basic medium, using different types of catalysts such as organic bases (amines such as triethylamine, phosphines such as tributylphosphines, heteronitrogenous bases such as 1,4-diazabicyclo[2.2.2]octane (DABCO)), inorganic bases including alkali or alkaline earth metal hydroxides such as NaOH, or KOH, organometallic catalysts derived from Titanium, Aluminum, Zirconium, Bismuth, Scandium, Erbium, Cobalt, P-cyclodextrin, enzymes such as Epoxide Hydrolases).

[0424] According to another variant of the process of the invention, the polymer(s) (C) can be (di)hydroxylated via route iv) to obtain one or more mono- or dihydroxylated polymer(s), preferably dihydroxylated (B) according to the following scheme 5: iv)

[0425] M — ► (B)

[0426] Scheme 5 in which the polymers (C) are as defined previously, and (B) are mono- or dihydroxylated, preferably dihydroxylated as defined previously.

[0427] According to one embodiment of the process of the invention, step iv) (di)hydroxylation on the unsaturation is carried out directly on the unsaturations of the polymer (C). The methods of (di)hydroxylation are known to those skilled in the art (see for example T. Achard and S. Bellemin-Laponnaz: Recent advances on catalytic osmium free olefin syn-dihydroxylation 2021, 6, 877-896, C. Santi, R. Di Lorenzo, C. Tidei, L. Bagnoli, T. Wirth Stereoselective Selenium catalyzed dihydroxylation and hydroxymethoxylation of alkenes Tetrahedron 2012, 68, 10530-10535. J. Chen, W. Song, YM Lee, W. Nam, B. Wang: Biologically inspired nonheme iron complex catalyzed cis dihydroxylation of alkenes modeling Rieske dioxygenases Coordination Chemistry reviews 2023, 477, 214945).

[0428] According to one embodiment of the process of the invention, step iv) employs one or more oxidizing agents of the periodate type, such as alkali or alkaline earth metal periodates of the sodium periodate type, oxone, peroxides, selenium derivatives, but also metal catalysts such as OsCl, RuCl, other ruthenium complexes such as the RuCh / NalCl association, manganese derivatives such as KMnCl or other manganese complexes, iron, palladium, and silver complexes. These organometallic catalysts are used with various types of oxidants, such as H2O2, O2, or other peroxides. Enzymes such as Rieske dexogenases can also be used.

[0429] At each of the steps of the process according to the invention, the total or partial hydrolysis of the ester group(s) -C(O)-OR4, -C(O)-OR'4, can be carried out using strong base(s), or strong organic or inorganic acid(s) to lead to -C(O)-O-M+ groups with M+ as defined above.

[0430] The hydrolysis of ester groups within homopolymers and copolymers can be partial or complete depending on the synthesis conditions, generating a copolymer containing repeating units of formula (A) in which -C(O)-OR4, -C(O)-OR'4, correspond to ester groups, statistically distributed with repeating units of formula (A) in which -C(O)-OR4, -C(O)-OR'4, correspond to carboxy or carboxylate groups -C(O)-OM + with M + as defined previously.

[0431] The crosslinked polymers of the invention (i.e. comprising at least one unit selected from the units (Al), (A2), (A3), (A4), (A5), (A6), (A7), (A8), (A9), (A10), (All), (A12), (A13), (A14) and (A15) defined above) are obtained by reacting at least one polymer and / or as defined above with at least one crosslinker as defined above.

[0432] Copolymers can be statistical polymers, sequenced in particular in blocks or gradients.

[0433] Another object of the invention is a polymer that can be obtained, in particular obtained, by a preparation process according to the invention. Degradation process

[0434] The polymers used in a process according to the invention are particularly interesting in that they can be easily degraded, for example at the end of their use.

[0435] Thus, another object of the present invention is a process for degrading a polymer comprising several repeating units chosen from the units (A) as defined above, as well as their optical, geometric isomers, their acid or base salts, organic or mineral, and their solvates such as hydrates.

[0436] The degradation process according to the invention can be implemented by any suitable technique, and advantageously allows obtaining monomers, oligomers and / or derivatives thereof.

[0437] In one embodiment, the degradation process is carried out by oxidative degradation, for example by contact with an alkali metal permanganate, such as potassium permanganate, or by ozonolysis, preferably by ozonolysis.

[0438] “Ozonolysis” refers to the reaction of a polymer comprising several repeating units chosen from the units (A) with an ozone molecule.

[0439] Preferably, the polymer comprising several repeating units selected from the units (A) degraded by a degradation process according to the invention comprises at least one double bond. Preferably, each of the units (A) of the polymer comprises a double bond. Even more preferably, the polymer comprising several repeating units selected from the units (A) is such that R.2 and R3 form a bond. In particular, the polymer comprising several repeating units selected from the units (A) has the formula (C) as defined above.

[0440] In one embodiment, the polymer comprising several repeating units selected from units (A) further comprises at least one unit selected from units (A1) to (A15), in particular at least one unit (A3), (A4), or (A6). In particular, units (A3), (A4), and / or (A6) are such that R2 and R3 together form a bond.

[0441] In one embodiment, the degradation, preferably ozonolysis, is carried out by contacting the polymer with ozone in a solvent that is preferably organic, more preferably a polar solvent. In one embodiment, the solvent comprises or is composed of a polar protic solvent, such as a C1-C4 alkanol, in particular methanol. The contact is preferably carried out at a temperature between 0°C and the reflux of the solvent, preferably less than or equal to 120°C, in particular between 5°C and 60°C. In one embodiment, the temperature is 50°C ± 5°C.

[0442] In one embodiment, the degradation process includes a subsequent step of subjecting the reaction mixture obtained in the first oxidative degradation step, or a portion thereof, to a second oxidation. This is particularly useful when the reaction mixture obtained in the first oxidative degradation step contains oligomers in addition to the polymer degradation products as described in the following paragraph.

[0443] The second oxidation can be carried out under any suitable conditions. In one embodiment, it is carried out in an acidic medium, particularly in the presence of at least one inorganic acid. Preferably, the second oxidation is carried out in the presence of an oxidizing agent, in particular hydrogen peroxide, and an inorganic acid, in particular sulfuric acid.

[0444] The implementation of the second oxidation can, among other things, improve the yield of the degradation process into degradation products, particularly into degradation products of formula (Dl).

[0445] Degradation products

[0446] The polymer degradation process comprising several repeating units selected from the units (A) according to the invention leads to the production of degradation products. A "degradation product" is defined as a compound that can be obtained by the degradation of such a polymer. In one embodiment, the degradation products are compounds of formula (Dl):

[0447] Dl in which Ri and R4 are as defined above, or Ri and / or R4 represents a motif

[0448] ..RE T

[0449] A, with X and RET as defined above, this motif being linked to the rest of the (Dl) molecule via X.

[0450] Thus, another object of the invention is a compound of formula (Dl).

[0451] In one embodiment, Ri represents a -C(O)-OR'4 group, with R'4 as defined above. In such an embodiment, R4 and R'4 are preferably identical. In particular, R4 and R'4 represent a hydrocarbon group, saturated or unsaturated, linear or branched, or cyclic, aromatic or non-aromatic, comprising from 2 to 20 carbon atoms. Preferably, the hydrocarbon group is saturated, linear or branched, or cyclic.

[0452] In one embodiment, the compounds of formula (Dl) are different from the following compounds: a) 1,4-dimethyl 2,2,3,3-butanetetracarboxylate, b) 1,2-diethyl 1,1,2,2 ethanetetracarboxylate, c) 1,4-di-2-propen-l-yl 2,2,3,3-butanetetracarboxylate, d) 1,2 bis(2,2-dimethylpropyl) 1,2-diphenyl ester, and e) 1,1,2,2 ethanetetracarboxylic acid 1,2-diphenyl ester.

[0453] The degradation products, in particular the compounds of formula (Dl), can be obtained by any technique known in the art. In some embodiments, they are obtained by the degradation of a polymer comprising several repeating units selected from the units (A). In other embodiments, they are obtained by synthesis from suitable reagents.

[0454] Degradation products, particularly degradation products of formula (Dl), are analogs of extracting compounds, especially metal extracting compounds. Thus, these compounds can advantageously be used in applications requiring metal complexation, such as battery recycling, particularly lithium battery recycling. The invention will be better understood upon reading the following examples, which are given by way of illustration and not limitation of the invention. EXAMPLES

[0455] Abbreviations:

[0456] DEM corresponds to trans, trans diethylmuconate or E,E-diethylmuconate, c,t DEM corresponds to cis, trans diethylmuconate or Z,E-diethylmuconate; c,c DEM corresponds to cis,cis diethylmuconate or Z,Z-diethylmuconate; DMM corresponds to trans, trans dimethylmuconate or E,E-dimethylmuconate DIM corresponds to trans, trans diisopropylmuconate or E,E-diisopropylmuconate DOM corresponds to trans, trans dioctylmuconate or E,E-dioctylmuconate

[0457] DtBuM corresponds to trans,trans ditert-butylmuconate or E,E-ditert-butylmuconate. D corresponds to the polydispersity obtained by size exclusion chromatography (SEC).

[0458] P2-tBu corresponds to l-tert-butyl-2,2,4,4,4-pentakis(dimethylamino)-2 5 ,4 TO 5 -catenadi(phos-phazene) or phosphazene-P2 base. P2-tBu and P4-TBu or phosphazene-P4 base correspond to the following formulas:

[0459] Phosphazene "P2 base"

[0460] Rheology measurement protocol:

[0461] The rheometer used was the Anton Paar MCR 302 rheometer. The cone / sandblasted plane geometry 25 mm / 2° (gap 104 pm) was used at an analysis temperature of 25°C.

[0462] The shear stress scan analysis is performed as follows:

[0463] Waiting time of 2 minutes

[0464] Shear stress sweep from 0.1 Pa to 1000 Pa, f = 1 Hz (no steady-state mode). This analysis allows the determination of the viscoelastic modulus (G*) and the loss factor (6) of the linear viscoelastic domain (LVED).

[0465] All reagent percentages described in the examples are weight percentages. Example 1: Synthesis of ACS 2 initiator:

[0466] The 3-step synthesis is adapted from the reference Hertler, WR; Reddy, GS; Sogah, DY Anion-Catalyzed Reactions of Silyl Ester Poly enolates with Electrophiles. J. Org. Chem. 1988, 53 (15), 3532 - 3539.

[0467] Scheme in which: rt to 75 °C means that the reaction is at room temperature (20-30 °C) then heated to 75 °C, 0 °C (or -84 °C) to rt or means that the reaction is at 0°C (or -84 °C) then is left to heat to room temperature (20-30 °C).

[0468] But-2-enoyl chloride SI:

[0469] In a 100 mL round-bottom flask equipped with a magnetic stirrer, 10 g (116 mmol, 1 eq.) of crotonic acid is added, and an inert gas (Ar) vacuum is applied. 20.7 g (12.6 mL, 174 mmol, 1.5 eq.) of thionyl chloride is then added dropwise, along with a few drops of DMF. The mixture is then heated to 75 °C and stirred for 1 h. The orange solution is allowed to cool to room temperature and then evaporated under vacuum. But2-enoyl chloride (Si) is then used directly for the second synthesis step.

[0470] Synthesis of Ethyl but-2-enoate (S2):

[0471] In a round-bottom flask under an inert atmosphere and fitted with a magnetic stir bar, 10.2 mL of dry ethanol (8 g, 174 mmol, 1.5 eq.), 80 mL of dry pentane, and 16.2 mL of triethylamine (11.74 g, 116 mmol, 1 eq.) are added. This mixture is placed in an ice bath at 0 °C. The previously prepared but-2-enoyl(SI) chloride (116 mmol, 1 eq.) is then added dropwise. The reaction mixture is allowed to cool to room temperature, and a white precipitate forms. The mixture is stirred for 3 h before the addition of 10 mL of a saturated NaHCl solution, followed by 50 mL of deionized water. The reaction mixture is then transferred to a separatory funnel. The organic phase is extracted from the aqueous phase by washing with 3 times 30 ml of diethyl ether. The organic phases are then combined and washed with a saturated NaCl solution.The resulting organic phase is then dried over magnesium sulfate before the volatile solvents are removed using a rotary evaporator. The product is purified by distillation and stored on a dried 4 Å molecular sieve. The structure is confirmed by spectroscopic method with a yield greater than 40%.

[0472] Synthesis of 1-Ethoxy-l-(Trimethylsiloxy)-L3-butadiene (ACS2):

[0473] In a 100 mL Schlenk flask under an inert atmosphere (Ar), 16.5 mL of a 1.5 M lithium diisopropyl amine (LD A) solution are added in solution to a ternary solvent mixture of THF / heptane / ethylbenzene (24.08 mmol, 1.4 eq.) and 20 mL of anhydrous THF. The mixture is cooled to a temperature below -80 °C. Then, 2 g (2 mL, 17.2 mmol, 1 eq.) of ethyl but-2E-enoate (S2) are slowly added. After 30 minutes, 3.5 mL (27.5 mmol, 1.6 eq.) of chlorotrimethyl silane are added. The reaction mixture is allowed to return to room temperature, and a white precipitate forms. After 20 minutes, the reaction mixture is filtered under an inert atmosphere. The filtrate is then evaporated under vacuum, hexane is added, and the resulting mixture is filtered again. The filtrate is evaporated under vacuum, and the product is purified by cryodistillation under vacuum. The final product is analyzed by spectroscopic methods (67% cis and 33% trans). Yield greater than 60%.

[0474] For diethyl muconate (DEM), diisopropyl muconate (DIM), and dioctyl muconate (DOM), the following general protocol was used. The corresponding alcohols were used as solvents to form the different diesters: respectively, ethanol, isopropanol, and 1-octanol.

[0475] Chlorotrimethylsilane (18.3 mL, 144 mmol, 4 eq) is added to a solution of trans,trans-muconic acid (5.12 g, 36 mmol, 1 zq) in the corresponding alcohol (150 mL excess) in a 250 mL two-necked flask. The reaction mixture is then heated to 80 °C for ethanol, 90 °C for isopropanol, or 100 °C for 1-octanol for 3 h. The reaction is monitored by spectroscopy or spectrometry. Once the reaction is complete, the reaction mixture is allowed to cool to room temperature.

[0476] The same purification method is used for all three diesters: once the reaction mixture has returned to room temperature, a saturated solution of NaHCl (70 mL) is added and the mixture is stirred for 10 minutes. The mixture is then transferred to a separatory funnel, to which 70 mL of diethyl ether is added. The organic phase is subsequently washed with a saturated solution of NaCl (70 mL), dried over magnesium sulfate, and then filtered before being evaporated under reduced pressure. The resulting solid is then recrystallized in methanol before being dried by azeotropic evaporation with toluene in a Schlenk flask. The muconic acid diesters are then stored under an inert atmosphere (Ar). Yield greater than 90%.

[0477] The synthesis of trans,trans-dimethylmuconate (DMM) differs slightly in the synthesis and purification process:

[0478] Chlorotrimethylsilane (18.3 mL, 144 mmol, 4 eq) was added to a solution of trans,trans-muconic acid (5.12 g, 36 mmol, 1 eq) in methanol (150 mL) in a 250 mL two-necked flask. The reaction mixture was then heated to 65 °C for 5 h. The reaction was monitored by spectroscopy or spectrometry. When the reaction mixture had cooled to room temperature, a saturated solution of NaHCl (70 mL) was added, and the mixture was stirred for 10 minutes. The mixture was then transferred to a separatory funnel to which 70 mL of dichloromethane was added. The organic phase was then washed with a saturated solution of NaCl (70 mL), dried over magnesium sulfate, and filtered before being evaporated under reduced pressure. The resulting solid was then recrystallized in THF before being dried by azeotropic evaporation with THF in a Schlenk. Yield greater than 95%.

[0479] For di-tButyl Muconate (DtBuM), the synthesis is different:

[0480] Diagram in which: rt to 75 °C means that the reaction is at room temperature (20-30 °C) then heated to 75 °C, 0 °C to rt means that the reaction is at 0°C then is left to heat to room temperature (20-30 °C).

[0481] Synthesis of 2,4-hexanedienedioyl (S3) chloride:

[0482] In a 100 mL round-bottom flask, 4 g (28 mmol, 1 eq.) of trans,trans-muconic acid are introduced under argon before 6 mL (9.84 g, 83 mmol, 3 eq.) of thionyl chloride is added dropwise. After the thionyl chloride has been completely added, 3 drops of DMF are added. The reaction mixture is then heated to 75 °C until the gas evolution ceases. The pale orange solution is allowed to cool to room temperature, and the excess thionyl chloride is evaporated under vacuum. The resulting 2,4-hexadienedioyl (S3) chloride is used directly in the next step of the reaction.

[0483] In a 250 mL round-bottom flask equipped with a magnetic stirrer, 4.16 g (5.34 mL, 56 mmol, 2 eq) of t-butyl alcohol and 30 mL of dry THF are introduced. The mixture is cooled in an ice bath, and then 22.4 mL of a 2.5 M n-butyl lithium solution in hexane is slowly added (56 mmol, 2 eq). Once the addition is complete, the ice bath is removed to allow the reaction mixture to return to room temperature. After 1 h at this temperature, the mixture is again cooled in an ice bath, and then 2,4-hexadienedioyl chloride (S3, 5.04 g, 28 mmol, 1 eq), previously dissolved in 25 mL of dry THF, is added to the lithium t-butylate. A brown color appears during the addition. The reaction mixture is left under stirring for 1 hour at room temperature, then the reaction is stopped by adding 20 ml of deionized water.

[0484] The reaction mixture is then transferred to a separatory funnel to which 70 mL of diethyl ether is added. The organic phase is set aside, and the aqueous phase is extracted twice with 30 mL of diethyl ether. The organic phases are combined and washed with 70 mL of a saturated NaCl solution. The resulting organic phase is dried over magnesium sulfate, filtered, and dried with a rotary evaporator. The resulting brown solid is recrystallized 10 times in acetone and once in toluene. The di-butylmuconate crystals thus obtained are introduced into a Schlenk apparatus with 5 mL of toluene, followed by toluene azeotropic distillations to obtain a water-free monomer. Yield >65%.

[0485] Synthesis of cis,cis diethylmuconate and cis,trans diethylmuconate:

[0486] E,Z-DEM ZZ-DEM

[0487] Chlorotrimethylsilane (18.3 mL, 144 mmol, 4 eq) was added to a solution of cis,cismuconic acid (5.12 g, 36 mmol, 1 eq) in ethanol (150 mL) in a 250 mL two-necked flask. The reaction mixture was then heated at 80 °C for 3 h. The reaction was monitored by spectroscopy or spectrometry. Once the reaction was complete, the reaction mixture was allowed to cool to room temperature.

[0488] When the reaction mixture had cooled to room temperature, a saturated solution of NaHCCh (70 mL) was added, and the mixture was stirred for 10 minutes. The mixture was then transferred to a separatory funnel to which 70 mL of diethyl ether was added. The organic phase was washed with a saturated solution of NaCl (70 mL), dried over magnesium sulfate, and filtered before being evaporated under reduced pressure. The resulting solid was then purified by silica column chromatography (cyclohexane / dichloromethane 50 / 50v eluent) to separate the cis, trans, and cis,cis isomers. After separation, the cis,trans diethylmuconate (c,t DEM), in liquid form, was added to calcium hydride, cryodistilled, and then stored under argon. The cis, cis DiethylMuconate (c,c DEM), in solid form, was dried 3 times by azeotropic evaporation in a schlenk with toluene and then stored under Argon.The overall yield thus obtained is greater than 90% with more than 30% cis, trans isomer and more than 60% cis, cis isomer.

[0489] Example 3: Synthesis of homopolymers of ethyl polymuconates (PDEM), isopropyl polymuconates (PDIM), n-octyl polymuconates (PDOM) and t-butyl polymuconates (PDtBuM)

[0490] All polymerizations were carried out under anhydrous conditions. Monomers and solvents were dried, distilled, or recrystallized to eliminate impurities and traces of water. The polymer structure was confirmed by NMR. X H and 13 C and the mass distribution of the polymers is analyzed by size exclusion chromatography (SEC) in THF (PMMA calibration).

[0491] Polymerization using ACSL as an initiator:

[0492] In a typical procedure, polymerizations are carried out in a schlenk in a glove box at room temperature. For example, for a polyDiethylMuconate with a theoretical degree of polymerization (DPn) of 100, a mixture is prepared in the following molar proportions: [DEM]o / [ACSl]o / [t-Bu-P4]0= 100 / 1 / 0.01.

[0493] Thus, 100 µl of an ACS1 solution is introduced into toluene (100 mmol.L 1 , 10 pmol), 100 μl of P4-t-Bu in solution in toluene (1 mmol.L' 1 , 0.1 pmol) and 3 ml of dry toluene in a 10 ml Schlenk. The mixture is stirred for 1 minute, then 1 ml of Diethyl Muconate (DEM, 1 mol.L) is added. 1 in toluene, 1 mmol). After stirring for 6 minutes, the reaction mixture is quenched by adding a few drops of benzoic acid in a 100 mmol solution. 1in toluene. The progress of the reaction is monitored by 1H NMR and confirms that DEM consumption is complete. The volatile solvents are evaporated, and then the polymer is resolubilized in toluene before being precipitated in n-pentane, filtered, and then dried under vacuum. The polymerization yield is >99%.

[0494] The DEM homopolymer thus obtained is such that Mn: 64,800 g / mol, polydispersity index D: 1.80.

[0495] Polymerization using ACS2 as a initiator in toluene:

[0496] The same procedure is used to polymerize each of the monomers. Polymerizations are carried out under an inert atmosphere and at room temperature (25 °C). For example, for PDEM1, 2 ml of an ACS2 solution in toluene (100 mmol L 1 , 200 pmol), 2ml of P4-t-Bu in solution in toluene (1 mmol L' 1, 2 pmol) and 10 ml of dry toluene are added to a Schlenk. This mixture is stirred, then 10 ml of diethyl muconate (DEM) diluted in toluene (1 mol L' 1 10 mmol) are added. The reaction is then stopped after 1 to 20 minutes by adding a few drops of methanol. Spectroscopic or spectrometric analysis confirms the complete conversion of the monomers.

[0497] The solvents are then evaporated, and the polymer is re-soluble in toluene before being precipitated in n-pentane for PDEM, PDIM, and PDtBuM, or in methanol in the case of PDOM. The yields obtained are > 95%.

[0498] Table 12

[0499] You: Toluene, Vol = volume

[0500] Polymerization using ACS2 as a initiator in THF:

[0501] The polymerizations were carried out under an inert atmosphere and at room temperature (25 °C).

[0502] For example, for PDEM4, 100 µl of an ACS2 solution in THF (100 mmol L 1 , lOpmol), 100 μl of P4-t-Bu in solution in THF (1 mmol L' 1 0.1 pmol) and 2 ml of dry THF were added to a Schlenk. This mixture was stirred, then 1 ml of diethyl muconate diluted in THF (1 mol L' 1 1 mmol) were added. After 5 minutes, the reaction was stopped by adding a few drops of methanol. 1H NMR analysis confirmed the complete conversion of the monomers. A similar process is used for the polymerization of DtBuM in THF (to give PDtBuM2).

[0503] Table 13

[0504] Polymerization using FACS2 as an initiator in THF and P2-tBu as a catalyst: Polymerizations were carried out under an inert atmosphere and at room temperature (25 °C). For example, for PDEM9, 100 µl of an ACS2 solution in THF (100 mmol L 1, lOpmol), 100 μl of P2-t-Bu in solution in THF (10 mmol L' 1 , 1 pmol) and 3 ml of dry THF were added to a Schlenk. This mixture was stirred and then 1 ml of trans,trans-diethyl muconate diluted in THF (1 mol L 1 1 mmol) were added. After 5 minutes, the reaction was stopped by adding a few drops of methanol. 1H NMR analysis confirmed the complete conversion of the monomers. A similar procedure was used for the polymerization of the different monomers listed below in THF.

[0505] Table 14

[0506] Polymerization of DEM using ACS2 as an initiator in Me-THF and P2-tBu as a catalyst (PDEM10):

[0507] In a typical procedure, 100 µl of an ACS2 solution is introduced into the Me-THF (100 mmol.L 1 , 10 pmol), 100 μl of P2-t-Bu in solution in Me-THF (10 mmol.L' 1, 1 pmol) and 3 ml of dry Me-THF in a 10 ml Schlenk. The medium is stirred for 1 minute, then 1 ml of DiethylMuconate (DEM, 1 mol.L) is added. 1 in Me-THF, 1 mmol). After 5 minutes, the reaction is stopped by adding a few drops of methanol. 1H NMR analysis confirms the complete conversion of the monomer. Mn (g.mol' 1 ) = 30400, £>=1.13

[0508] Bulk polymerization of DEM using FACS2 as an initiator and PHBu as a catalyst (PDEM11):

[0509] 500pl of a solution of ACS2 in THF (100 mmol.L' 1 , 50 pmol), 50 μl of PH-Bu in solution in THF (10 mmol.L' 10.5 pmol) are introduced into a 10 mL Schlenk flask and shaken under an inert atmosphere. 1 g of trans,trans-diethylmuconate (DEM) is first melted by heating to 65°C and then added to the initiator and catalyst mixture prepared above. After 5 minutes, the reaction is stopped by adding a few drops of methanol. 1H NMR analysis confirms the complete conversion of the monomer. Mn (g.mol) 1 ) = 38400, £>=1.51

[0510] Bulk polymerization of DOM using FACS2 as an initiator and P4-tBu as a catalyst (PDOM5):

[0511] 300 ml of an ACS2 solution in THF (100 mmol / L) 1 , 30 pmol), 30 μl of P4-t-Bu in solution in THF (10 mmol.L' 10.3 pmol) are introduced into a 10 mL Schlenk flask and shaken under an inert atmosphere. 1.1 g of trans,trans diOctylmuconate (DOM) is first melted by heating to 65°C and then added to the initiator and catalyst mixture prepared above. After 5 minutes, the reaction is stopped by adding a few drops of methanol. 1H NMR analysis confirms the complete conversion of the monomer. Mn (g.mol) 1 ) = 84800, £>=1.55 Example 4: Statistical copolymer synthesis solution (100 eq) RT, 1 min

[0512] 3) MeOH

[0513] Diagram in which RT means that the reaction is at room temperature (20-30 °C). The same procedure is used as for the preceding homopolymers starting from ACS2. Polymerization yields are greater than 95%. PDEM structures n-stat- PDOMm represent statistical copolymers whose theoretical DPn is n for DEM and m for DOM. Since monomer consumption is quantitative, this also represents the molar composition of the polymers. Table 15

[0514] Example 5: Synthesis of block copolymers Diagram in which rt means that the reaction is at room temperature (20-30 °C).

[0515] 5-1) Synthesis of PDEM5o-b-PDOM5o diblock in toluene using P4-t-Bu as a catalyst

[0516] For the first step the ratio respected is [DEM]o / [ACS2]o / [P4-t-Bu]o=5O / l / O,Ol.

[0517] In a 10 ml Schlenk, 100 µl of ACS2 in toluene solution (100 mmol L) are introduced. 1 ; 10 pmol), 100 μl of P4-t-Bu in solution in toluene (1 mmol L' 1 ; 0.1 pmol) and 3 ml of toluene. The mixture is stirred for 1 minute, then 0.5 ml of DEM diluted in toluene (1 mol L'1 0.5 mmol) is then added. This mixture is added for 1 minute: the progress of the reaction is evaluated by spectroscopy or spectrometry. 0.5 ml of DOM diluted in toluene (1 mol L' 1 0.5 mmol) is then added. The reaction mixture is stirred, and then polymerization is stopped by adding methanol. The structure of the resulting polymer is confirmed by spectroscopy or spectrometry and CES (serum extrusion chromatography) in THF (PMMA standard). Table 16

[0518] 5-1-2) Synthesis of PDEMso-b-PDOMso diblock in THF using P2-tBu as catalyst (PDEMso-b-PDOMso (2))

[0519] In a 10 ml Schlenk, 100 µl of ACS2 in solution in THF (100 mmol L' 1; 10 pmol) and 100 µl of P2-t-Bu in solution in THF (10 mmol L' 1) are introduced. 1; 1 pmol) and 3 ml of dry THF. The medium is stirred with a magnetic stir bar for 1 minute, then 0.5 ml of a trans,trans diethylmuconate (DEM) solution at 1 mol / L 1 in the THF, 0.5 mmol) are added. After stirring for 1 min, a sample is taken which demonstrates complete consumption of the monomer by 1H NMR and the following mass distribution by CES Mn = 1100 g.mol' 1 , D= 1.19. To the PDEM reaction mixture thus obtained, 0.5 ml of a dioctylmuconate (DOM) solution at 1 mol / L is added. 1 in THF, 0.5 mmol). The medium is stirred for an additional 5 minutes, then the reaction is stopped by adding a few drops of methanol. 1H NMR analysis confirms the complete consumption of DOM, and CES analysis demonstrates the formation of a PDEM-b-PDOM diblock polymer with a Mn of 43,300 g / mol. 1 and £>= 1.16.

[0520] 5-2) Synthesis of PDOMso-b-PDtBuMso diblocks

[0521] The dibloc polymer was synthesized using the same process as for PDEMso-b-PDOMso, but polymerizing the DOM to obtain the 1 er block then adding the DtBuM for the 2 ème block.

[0522] Table 17

[0523] 5-3) Synthesis of PDtBuMso- b-PDEMso diblock

[0524] The dibloc polymer was synthesized using the same process as for PDEMso-b-PDOMso, but polymerizing DtBuM to obtain the 1 er block and by adding the DEM to obtain the 2 eme block.

[0525] Table 18

[0526] 5-4) Synthesis of a polyEthylSorbate-β-PolyDiEthylMuconate diblock: PESso-β-PDEMso

[0527] The diblock polymer was synthesized using the same process as for PDEMso-b-PDOMso, but polymerizing ethylsorbate to obtain the first block with a ratio [ES]₀ / [ACS2]₀ / [P4-ABU]₀ = 50 / 1 / 0.01. DEM is introduced for the second eme block using the same concentrations and volumes of monomers in toluene as in the l ere stage.

[0528] Table 19

[0529] 5-5) Synthesis of triblock PDEMso-b-PDOMso-b-PDEMso:

[0530] The triblock polymer was synthesized using the same process as for the PDEMso-b-PDOM50 diblock but using a different ratio: [DEM]o / [ACS2]o / [P4-t-Bu]o=5O / l / O,Ol for the first step.

[0531] After the polymerization of the 2 eme block of DOM, we add 50 equivalents of DEM using the same concentrations and the same volumes of monomers in toluene.

[0532] Table 20

[0533] 5-6) Synthesis of PMMA25-b-PDEM5o diblock:

[0534] Diagram in which RT means that the reaction is at room temperature (20-30 °C).

[0535] In a typical procedure, 100 µl of an ACSL solution (100 mmol.L 1 in toluene, 10 pmol), 100 μl of P4-t-Bu in solution (1 mmol.L' 1 in toluene, 0.1 pmol) and 3ml of dry toluene are introduced into a 10 ml Schlenk.

[0536] The mixture is stirred for 1 minute, then 0.25 ml of methyl methacrylate (MMA) (1 mol.L) is added. 1 in toluene; 0.25 mmol) is added. After stirring for 1 h at room temperature, 0.5 ml of diethylmuconate (DEM, 1 mol.L) 1 in toluene; 0.5 mmol) are added. The reaction mixture is stirred for 1 minute and then the reaction is stopped by adding a few drops of methanol.

[0537] PMMA25: Mn: 4,600 g / mol, £>: 1.14 PMMA25-6-PDEM50: Mn: 87600 g / mol, £>: 1.88

[0538] 5-7) Synthesis of PBAso-b-PDEMso diblock

[0539] In a typical procedure, 100 µl of an ACSL solution (100 mmol.L 1 in toluene, 10 pmol), 100 μl of P4-t-Bu in solution (1 mmol.L' 1 in toluene, 0.1 pmol) and 3 ml of dry toluene were introduced into a 10 ml Schlenk flask. The medium was stirred for 1 minute, then 0.25 ml of butyl acrylate (BA) (1 mol / L) 1 in toluene; 0.25 mmol) was added. After stirring for 1 h at room temperature, 0.5 ml of diethyl muconate (DEM, 1 mol.L) 1 in toluene; 0.5 mmol) were added. The reaction mixture was stirred for 1 minute and then the reaction was stopped by adding a few drops of methanol.

[0540] PBAso: Mn: 9200 g / mol, £>: 1.85

[0541] PBA50-6-PDEM50: Mn: 26600 g / mol, £>: 3.06.

[0542] 5.8) Synthesis of Pentabloc (PDOM-co-PDtBuM)-b-(PDOM-co-PDtBuM)-b-(PDOM-co-PDt-BuM)-b-(PDOM-co-PDtBuM)-b-(PDOM-co-PDtBuM) or (PDOM-co-PDtBuM)s:

[0543] In a 25 ml Schlenk, 100 µl of ACS2 in toluene solution (100 mmol L) were introduced. 1 ; 10 pmol), 200 μl of P4-t-Bu in solution in toluene (1 mmol L' 1 ; 0.2 pmol) and 3 ml of toluene. The mixture was stirred for 1 minute, then a 2.5 ml solution of a mixture of DOM and DtBuM monomers in toluene (DOM: 0.2 mol L' 1 0.5 mmol; DtBuM 0.2 mol L' 1 0.5 mmol) was then added. This mixture was stirred for 3 minutes, after which 200 µl of PH-Bu in toluene solution (1 mmol L) were added. 1 ; 0.2 pmol) followed by a new 2.5 ml solution of a mixture of DOM monomers and DtBuM in toluene (DOM: 0.2 mol L' 1 0.5 mmol; DtBuM 0.2 mol L' 1(0.5 mmol). The medium is stirred for 3 min before the next block is added. The additions of PH-Bu and monomer solutions are repeated 3 more times for a total of 5 blocks. 3 minutes after the addition of the last block, polymerization is stopped by adding two drops of methanol. The structure of the resulting polymer is confirmed by 1H NMR and by CES in THF (PMMA standard). The molar mass results are compiled in Table 21 below.

[0544] Table 21

[0545] 5.9) Synthesis of PDONfos-b-PDEMso diblocks in isododecane or in an isododecane / toluene mixture

[0546] In a 10 ml Schlenk, 100 µl of ACS2 in solution in isododecane (100 mmol L) were introduced. 1 ; 10 pmol), 100 μl of PH-Bu in solution in isododecane (1 mmol L' 1; 0.1 pmol) and 2 ml of isododecane. The mixture was stirred for 1 minute, then a solution of 1 ml of DOM monomer in isododecane (DOM: 0.25 mol L' 1 0.25 mmol) was then added. This mixture was stirred for 1 minute: the progress of the reaction was monitored by 1H NMR. A 4 mL solution of DEM monomer in isododecane (DEM: 0.125 mol L' 1 0.5 mmol) is then added and the mixture is stirred for 3 min. A cloudiness develops during the minute following the addition of the second block (PDEM). Three minutes after the addition of the second block, polymerization is stopped by adding two drops of methanol. The structure of the polymer thus obtained is confirmed by 1H NMR and CES in THF (PMMA standard).

[0547] A similar reaction is carried out in an isododecane / toluene mixture (90 / 10 v / v). The molar masses obtained are compiled in Table 22 below:

[0548] Table 22

[0549] Example 6: Polymerization of DEM using ACS2 as an initiator and TBAF as a catalyst:

[0550] The polymerizations were carried out under an inert atmosphere and at room temperature (25 °C). In a 10 ml Schlenk flask, 100 µl of ACS2 in solution in THF (100 mmol L'; 10 pmol) and 50 µl of TBAF (tetra-n-butylammonium fluoride) in solution in THF (10 mmol L') were introduced. 1 ; 0.5 pmol) and 2 mL of THF. The mixture was stirred for 1 minute, then 1 mL of DEM dissolved in THF (1 mol L' 1 1 mmol) was then added. This mixture was stirred for 5 minutes: the progress of the reaction was assessed by spectroscopy or spectrometry, and then the polymerization was stopped by adding methanol. The structure of the polymer thus obtained was confirmed by spectroscopy or spectrometry and CES (size exclusion chromatography) in THF (PMMA standard).

[0551] The solvents were then evaporated, and the polymer was resolubilized in THF before being precipitated in n-pentane for PDEM. The yields obtained are > 95%. The characteristics of the polymers obtained are summarized in Table 23.

[0552] Table 23

[0553] Example 7: Epoxidation of polymuconates

[0554] The following experimental protocol is applicable to all unsaturated polymers described in the invention. 127 mg of PDtBuMl (repeating motif M = 254 g.mol) are introduced. 10.5 mmol (1 eq.), 5 mL of chloroform, and 478 mg of m-chloroperbenzoic acid (2 mmol, 4 eq.) were placed in a 25 mL Schlenk flask. The mixture was then heated at 60 °C for 12 h. The reaction was monitored by spectrometry or spectroscopy. When the reaction was complete, 2 mL of a saturated sodium thiosulfate solution were added to the reaction mixture, which was then stirred for 10 minutes. The organic phase was washed with a saturated sodium bicarbonate solution, followed by a saturated sodium chloride solution, before being dried over magnesium sulfate. The solvent was evaporated under vacuum to obtain a pale yellow polymer with a yield greater than 80% (EPPDtBuMl).

[0555] Example 7b: Epoxidation of diethyl polymuconates

[0556] The following experimental protocol is applicable to all unsaturated polymers described in the invention. 127 mg of PDEMôb (repeating motif M = 254 g.mol⁻¹) are introduced. 10.5 mmol (1 eq.), 5 mL of chloroform, and 478 mg of m-chloroperbenzoic acid (2 mmol (4 eq.)) were added to a 25 mL Schlenk. The mixture was then heated at 60 °C for 12 h. The reaction was monitored by spectrometry or spectroscopy. When the reaction was complete, 2 mL of a saturated sodium thiosulfate solution were added to the reaction mixture, which was then stirred for 10 minutes. The organic phase was washed with a saturated sodium bicarbonate solution, followed by a saturated sodium chloride solution, before being dried over magnesium sulfate. The solvent was evaporated under vacuum to obtain a pale yellow polymer with a yield greater than 80% (EPPDEM1). A 10% partial epoxidation was carried out using 0.1 eq. of mCPBA, leading to a 10% epoxidized polymer named EPPDEM2.

[0557] Example 7c: Epoxidation of dioctyl polymuconates

[0558] PDOM4b EPPDOM1

[0559] The following experimental protocol is applicable to all unsaturated polymers described in the invention. 366 mg of PDOM4b (repeating motif M = 366 g.mol⁻¹) are introduced. 1 1 mmol, 1 eq.), 5 mL of chloroform and 346 mg of m-chloroperbenzoic acid (2 mmol, 2 eq.) in a 25 mL Schlenk. The mixture is then heated at 60 °C for 6 h. The reaction is monitored by spectrometry or spectroscopy. When the reaction is complete, 3 mL of a saturated sodium thiosulfate solution are added to the reaction mixture, which is then stirred for 10 minutes. The organic phase is washed with a saturated sodium bicarbonate solution, then a saturated sodium chloride solution, before being dried over magnesium sulfate. The solvent is evaporated under vacuum to obtain a pale yellow polymer with a yield greater than 80% (EPPDOM1). 10% of dioctvle

[0560] PDOM4b EPPD0M2

[0561] The following experimental protocol is applicable to all unsaturated polymers described in the invention. 3.66 g of PDOM4b (repeating motif mass = 366 g.mol) are introduced. 1 10 mmol (1 eq.), 17 mL of chloroform, and 173 mg of m-chloroperbenzoic acid (1 mmol, 0.1 eq.) were placed in a 100 mL Schlenk. The mixture was then heated at 60 °C for 6 h. The reaction was monitored by spectrometry or spectroscopy. When the reaction was complete, 20 mL of a saturated sodium thiosulfate solution were added to the reaction mixture, which was then stirred for 10 minutes. The organic phase was washed with a saturated sodium bicarbonate solution, followed by a saturated sodium chloride solution, before being dried over magnesium sulfate. The solvent was evaporated under vacuum to obtain a pale yellow polymer with a yield greater than 80% (EPPDOM2). sodium

[0562] 8-1) By alkaline hydrolysis from PDEM:

[0563] In a typical process, 1.60 g of PDEM (number of units in mol = 8.07 mmol, M) is added to a flask equipped with a condenser. n (motif) = 198.22 g / mol, 1 eq.) diluted in 20 mL of ethanol. 16 mL of a 2 mol / L aqueous NaOH solution (32.28 mmol, 4 eq.) are then added to the mixture. The mixture is refluxed for 1 h. An orange precipitate forms. The mixture is then concentrated under vacuum and diluted with 100 mL of distilled water. The poly(sodium muconate) (PMuNa) solution is dialyzed (membrane, pore size: 3.5 kDa) for one day. The solution is collected and evaporated under vacuum. The resulting polymer is a translucent orange solid. Mass yield: 85.6%

[0564] PDEM 1, PDEM2, PDEM3 are thus hydrolyzed to give respectively PMCOO1, PMCOO2 and PMCOO3 of increasing molecular weight.

[0565] 8-2) By selective acid hydrolysis of a PDQM50-stat-PDtBuM50:

[0566] 200 mg of PDOM50-stat-PDtBuM50 (MDtBuM unit = 254 g mol) were introduced. 1 0.5 mmol (1 eq.) in a 25 mL Schlenk flask, then 2 mL of acetic acid and 0.5 mL of trifluoroacetic acid are added. The mixture is stirred at room temperature: the disappearance of the characteristic peak of the tBu group is monitored by spectroscopy or spectrometry. After 6 h, the reaction is complete and yields a statistical polymer containing DOM units and MCOOH muconic acid units: PDOM50-stat-PMCOOH50. Example 9: Dihydroxylation and hydrolysis of polymuconates

[0567] In a protocol applicable to all epoxidized polymers described in the invention, 135 mg of EPPDtBuMl (Repeating Pattern = 270 g.mol⁻¹, 0.5 mmol, 1 eq.), 4 mL of formic acid, and 1 mL of trifluoroacetic acid (TFA) were introduced into a 10 mL test tube. The mixture was then stirred at room temperature for 4 h. The reaction was monitored by spectrometry or spectroscopy. When the reaction was complete, the excess acid was evaporated under high vacuum. 10 mL of an aqueous sodium hydroxide solution (10 mL, 0.1 M, 1 Mol) was added to the mixture. The solvent was evaporated under vacuum to obtain a yellow / orange polymer with a yield greater than 80% (PMNadiOH).

[0568] Example 10: Crosslinking Protocol

[0569] In a typical procedure for the chemical crosslinking of 10% of PMCOO acidic repeating units in water, 50 mg of PMCOO (number of mol units = 0.269 mmol, 186 g / mol per repeating unit, 1 eq.) are diluted in 1 mL of distilled water in a flask containing a magnetic stirrer. The mixture is homogenized for 5 minutes. 269 pL of a 0.1 mol / L (26.9 pmol, 0.1 eq.) ethylene glycol diglycidyl ether (EGDE) solution in THF is added to the mixture. The medium is then placed in an oven at 150 °C for 1 h. The crosslinked polymer is an opaque orange solid. The resulting residue is then mixed with 5 mL of distilled water to form a gel.

[0570] This cross-linked polymer gel is analyzed using rheology.

[0571] The following gels were made from the polymers PMCOO1, PMCOO2 and PMCOO3 using different proportions of difunctional (such as EGDE) or trifunctional (such as trimethylol propane triglycidyl ether (TPTE) crosslinkers:

[0572] Table 24

[0573] (a) The percentage indicated corresponds to the molar percentage of epoxide functions relative to muconic acid motifs in the starting polymer

[0574] Table 25 (a) The percentage indicated corresponds to the molar percentage of epoxide functions relative to muconic acid motifs in the starting polymer

[0575] Table 26

[0576] (a) The percentage indicated corresponds to the molar percentage of epoxide functions relative to muconic acid motifs in the starting polymer

[0577] Other types of crosslinking agents were used: hexamethylenediamine (HMD), triethylene glycol (TEG), sorbitol (S), and citric acid (AC) according to the protocol described above (Table 27).

[0578] (a) The percentage indicated corresponds to the molar percentage of reactive functions relative to the muconic acid motifs in the starting polymer.

[0579] Example 11: Protocol for the ozonolysis degradation of PDEM and the production of dicarboxylic acid-diester

[0580] A 250 mL flask containing a magnetic stir bar was loaded with a 50 mL solution of PDEM5 in methanol (20 gL' 1 , 1 g). The mixture was cooled in an ice bath to limit solvent evaporation. A glass pipette, connected to an ozone generator (Model: C-L010-DT), was used to inject gas at a rate of 5 L / min. 1 (Theoretical ozone concentration: 2 mg / L)1The medium was left under ozonolysis for 1 hour. The solvent was then evaporated at low temperature (< 30°C) in a rotary evaporator. The resulting product (a colorless oil) was then dispersed in 50 mL of demineralized water. 10 mL of 30% (w / w) aqueous H₂O₂ solution and 0.5 mL of 98% H₂SO₄ were added to the medium. The reaction was maintained under reflux (100°C) for 30 minutes. The medium was then extracted in a separatory funnel with 3 x 5 mL of diethyl ether. The organic phase was then neutralized and extracted with 10 mL of saturated sodium bicarbonate solution and subsequently extracted twice with 15 mL of demineralized water. The recovered basic aqueous phase was neutralized by adding IM hydrochloric acid dropwise until a solution with a pH below 4 was obtained. This acidic aqueous solution was extracted with 3x15mL of diethyl ether to extract the product of interest.The solvent was evaporated using a rotary evaporator, and the resulting product (a clear oil) was purified on a silica column with an eluent composed of a dichloromethane / acetic acid mixture (95 / 5 v / v). The structure of the recovered product was confirmed by ¹H NMR and ¹H NMR. 13 C.

[0581] Example 12: Thermal depolymerization protocol for PDEM:

[0582] In a 10 mL Schlenk flask containing a magnetic stir bar, 200 mg of PDEM4 and 1.5 mL of diphenyl ether were loaded. The mixture was stirred, and a stream of argon was introduced into the medium using a glass pipette for 10 minutes to remove oxygen. The medium was then heated to 230°C for 20 minutes. It was subsequently cooled to room temperature, and the diphenyl ether was removed on a silica column with a dichloromethane eluent. The pure monomer was recovered in greater than 60% yield. The nature of the recovered DEM monomer was confirmed by ¹H NMR and 13 C.

[0583] Example 13: Thermal depolymerization protocol of PDOM 1: Oct COOn-Oct COOn-Oct

[0584] A 10 mL Schlenk flask containing a magnetic stir bar was loaded with 107 mg of PDOM1 and 1 mL of diphenyl ether. The mixture was stirred, and an argon flow was introduced into the medium using a glass pipette for 10 min to remove oxygen. The medium was then heated to 230°C for 20 min. It was subsequently cooled to room temperature, and the diphenyl ether was removed on a silica column with a dichloromethane / cyclohexane eluent (80 / 20 v / v). The pure monomer was recovered with a yield greater than 70%. The nature of the recovered DOM monomer was confirmed by ¹H NMR and 13 C.

[0585] Example 14: Polymer deposition on different substrates

[0586] A thin polymer layer (PDEM / PDOM / epoxy-coated PDOM / crosslinked PDOM) was deposited by spin coating on various surfaces (cardboard, glass). A solution containing 50 mg of polymer and 1 mL of chloroform was prepared. 250 µL of this solution was dispensed with a syringe onto the chosen substrate, and then the spin coater was run at 1500 rpm for 1 minute. The epoxy-coated PDOM (EPPDOM2) is 10% epoxy-coated, and the crosslinked epoxy-coated PDOM (EPPDOM2) is 10% crosslinked with 1,10-diaminodecane relative to repeating units of unsaturated and epoxy-coated DOM.

[0587] The contact angle of a water droplet was measured for each of the polymers on each of the substrates.

[0588] Table 28 summarizes the measurements obtained for the contact angle for each polymer and each substrate, nd = not determined

[0589] Table 28

[0590] Coating the (rather hydrophilic) glass substrate with various polymers has increased its hydrophobicity. The degree of hydrophobicity can be easily adjusted by modifying the structure of the polymer used (number of carbon atoms, presence of oxygen atoms, cross-linking).

[0591] Similarly, coating the cardboard substrate with different polymers allowed for modulation of the support's hydrophobicity. The value of 112° obtained for the uncoated cardboard is probably related to the presence of an initial coating on the cardboard before its spin coating treatment. This initial coating, which is not according to the invention, is probably removed by the solvent during the spin coating process.

[0592] Example 15: Degradability by ozonolysis and substrate regeneration

[0593] A solution of EPPDOM2 and 10% 1,10-diaminodecane in THF was prepared. 0.25 mL of this solution was applied to a glass plate, which was then spun (1500 rpm for 1 minute). The glass plate was then placed in an oven at 110 °C for 1 hour to crosslink the polymer. After removal from the oven, the plate was immersed in chloroform for 30 minutes. After 30 minutes, the plate was removed from the chloroform and remained intact, with the crosslinked polymer still attached. The plate was then re-immersed in chloroform, and ozone was introduced into the flask for 5 minutes. At the end of the 5 minutes, the original glass plate (i.e., without polymer coating) was recovered.

[0594] The degradability of the coating according to the invention by ozonolysis has been demonstrated by this example.

[0595] Example 16: Adhesiveness test of polymers according to the invention on a substrate

[0596] The adhesion (Tack) test consists of measuring the force required to separate two pistons between which an adhesive is placed in order to evaluate its stickiness.

[0597] The possible behaviors are as follows:

[0598] - Adhesive: The polymer remains on the top or bottom geometry

[0599] - Cohesive: the polymer adheres to the top and bottom geometries, filaments are formed, when the filaments break, they spread out over the two geometries.

[0600] - Mixed: The polymer adhesion is such that filaments appear, but when they break, the polymer remains on one of the two geometries.

[0601] The behaviors obtained for the polymers according to the invention are listed in Table 29.

[0602] Table 29

[0603] Thus, the process according to the invention makes it possible to obtain a wide range of polymers whose adhesiveness can be easily modulated or controlled by selecting in particular the structure of the monomer, the epoxidation rate, the degree and nature of the crosslinking.

[0604] In the case of the tested polymers, epoxidation, even partial, imparts cohesive characteristics to the polymer. The 10% epoxidized PDEM (EPPDEM2) exhibits a better cohesive response, resulting in a longer-lasting force and more numerous, longer-lasting filaments.

[0605] The polymers crosslinked by a diamine are epoxy PDEM (EPPDEM2) and epoxy PDOM (EPPDOM2), which are 100% crosslinked relative to epoxides by a diamine (1,10 diaminodecane).

[0606] Tetrathiol-crosslinked polymers include PDEM and PDOM, which are crosslinked at 10% relative to the alkenes by a tetrathiol (pentaerythritol tetrakis (3-mercaptopropionate)) via UV thiol-ene. The crosslinking procedure is described in Example 17 below. Example 17: Gel Formation

[0607] 17.1. With thiol-ene crosslinked PDEM

[0608] Thiol-ene crosslinked PDEM was obtained as follows:

[0609] In a 10 mL amber bottle, 0.5 g of PDEMôb (2.5 mmol, 1 eq), 15 mg of diphenyl (2,4,6-trimethylbenzoyl) phosphine oxide (43 pmol, 3 wt.%), 31 mg of pentaerythritol tetrakis (3-mercaptopropionate) (61 mmol, 10 wt.), and 630 pL of acetonitrile (0.5 g, 50 wt.) were mixed with a spatula. The mixture was then applied to a glass slide using a spatula and spread evenly. The slide was then placed in a UV chamber and exposed for 5 min at 405 nm (70% intensity). The polymer exiting the UV chamber was crosslinked and remained colorless.

[0610] The same protocol was repeated for different quantities of thiols relative to the alkene motifs. Gelation was achieved as follows:

[0611] In a 3 mL vial, 33.1 mg of thiol-ene crosslinked PDEMôb (PDEMte) and 2.5 mL of THF were mixed. The solvent swelled during mixing, and the polymer was immersed in the closed vial for 3 days. The wet mass was determined by weighing the swollen polymer after filtering it of its solvent. The polymer was then placed in an oven at 110°C to evaporate the solvent, and the dry mass (final mass) was then recorded. The gel percentages and corresponding gel fractions were determined using the following equations:

[0612] Frost rate = ms mid ml * 100 and 100

[0613] With mi: initial mass ms: wet mass mf: final mass.

[0614] Table 30 groups together the different gel rates and gel fractions obtained with different % of thiols relative to the alkene motifs.

[0615] Table 30

[0616] The polymers according to the invention therefore have interesting gelling properties, which can be modulated in particular by the degree of crosslinking. Thus, with a 10% thiol content relative to the alkene motifs, the gel content obtained is on the order of 1900%, with gel fractions of around 80%.

[0617] 17.2. With the epoxy PDOM of (EPPDOM2) crosslinked by a diamine

[0618] Gelation was achieved as follows for 10% diamine crosslinking with respect to the alkene motif:

[0619] In a 3 mL bottle, 0.6 g of EPPDOM2 (1.6 mmol, 1 eq.), 17 mg of 1,10-diaminodecane, and 2 mL of tetrahydrofuran (THF) were introduced. Upon mixing the polymer and the diamine, the solution turned yellow. The mixture was heated to 110°C for 5 minutes. The bottle was then placed in a heating chamber to evaporate the THF and recover an orange-brown solid.

[0620] The solid was then mixed with 2 mL of toluene or isododecane using a spatula, and swelling of the polymer with the solvent was observed.

[0621] Gels were obtained with both a 1% mass polymer content in toluene and a 10% mass polymer content in isododecane. Therefore, gelling properties are achieved even with a low polymer content.

[0622] 17.3. Formation of aqueous gels

[0623] The gelation was achieved as follows:

[0624] In a 10 mL bottle, 300 mg of sodium polymuconate (obtained by the reaction between polymuconic acid and sodium hydroxide), 7 mg of ethylene glycol diglycidyl ether (EGDE), and 2 mL of water are mixed. The bottle is placed in an oven at 110°C for 1 hour. Upon removal from the oven, a 5% (w / w) aqueous gel was obtained by mixing the 300 mg of crosslinked polymer with 5.7 g of water.

[0625] Example 18: Metal Complexation

[0626] The mixture of 300 mg sodium polymuconate, 7 mg EGDE, and 2 mL of water obtained in the previous example was deposited onto a paper filter and then incubated at 100°C for one hour to crosslink the polymer onto the paper. After incubation, the filter with the crosslinked polymer was immersed in an ultrapure water solution using a conductivity probe. The water was changed repeatedly until a constant conductivity equal to that of the ultrapure water (10 pS / cm) was obtained. A few drops of a 1 M iron chloride solution were added to achieve a conductivity of 712 pS / cm. The crosslinked polymer was then immersed in the solution, and its conductivity was recorded.

[0627] Figure 1 is a graph showing the evolution of conductivity as a function of time.

[0628] The decrease in conductivity, from 712 pS / cm to a plateau of 655 pS / cm after approximately 2 minutes, demonstrates effective metal complexation.

Claims

Demands 1. A process for treating a non-keratinized material, comprising applying to at least a part of the non-keratinized material at least one polymer comprising several repeating units selected from the following units (A), together with their optical and geometric isomers, their acid or base salts, organic or mineral, and their solvates such as hydrates, or a composition comprising at least one such polymer: unit (A), units (A) in which: • Ri represents an (Ci-C4)alkyl group such as methyl, or a -C(O)-OR'4 group; • R2 and R3, whether identical or different, represent a hydrogen atom or a hydroxy group; R2 and R3 together form a connection, or R2 and R3 together form a saturated or unsaturated heterocycle, preferably saturated, comprising at least one oxygen atom, and comprising 3 to 6 links; • R4 and R'4, whether identical or different, represent i) a hydrogen atom, ii) a cationic counter ion M + , or iii) a hydrocarbon group, saturated or unsaturated, linear, branched or cyclic, aromatic or non-aromatic, comprising from 1 to 140 carbon atoms, said hydrocarbon group being further: o optionally substituted by one or more (di)(Ci-C4)(alkyl)amino groups; and / or optionally interrupted by one or more a') heteroatoms such as O, S, N(R a ), and Si(Rb)(Rc), b') S(O) r with r equal to 1 or 2, carbonyl, or c') the associations of a') with b'); Ra, Rb, Rc, identical or different, representing a hydrogen atom or a (C i-C4)alkyl group, it being understood that: - when R2 (and / or R3) represents a hydroxyl radical and R4 (and / or R'4) represents a hydrogen atom or a cationic counterion M +, then R2 and the -C(O)-OR4 group (and / or R3 and the -C(O)-OR'4 group) can together form a heterocycle with 5 or 6 members; and - when R4 and / or Rf represents a cationic counter ion M + , then the oxygen atom of the group -OR4 and / or R4' is in anionic form -O, and - the Ri of the different units (A), the R2 of the different units (A), the R3 of the different units (A), the R4 of the different units (A), and the R'4 of the different units (A), can be identical or different.

2. A process for treating a non-keratinized material according to claim 1, wherein at least one polymer is a homopolymer, a copolymer, and / or a mixture of at least one homopolymer and at least one copolymer.

3. A process for treating a non-keratinized material according to claim 1 or claim 2, wherein the polymer comprises: (i) several units selected from the units (A) as defined in claim 1, and (ii) one or more unit(s) chosen independently from the units (Al) to (Al 5), their optical isomers, geometric isomers, their acid or base salts, organic or mineral, their solvates such as hydrates and their mixtures: in which RI, R2, R3 and R4 are such as defined for Ri, R2, R3 and R4 respectively for units (A) in claim 1, X represents an oxygen atom, a sulfur atom, or an amino group N(Ra), with Ra representing a hydrogen atom or a (Ci-C4)alkyl group; RET, identical or different, represents a group resulting from the crosslinking of one or more reactive group(s) of at least one unit (A) with one or more crosslinking agents; and T represents the point of attachment of the group to the rest of the molecule; it being understood that the Ri, R2, R3, R4, R'4 of the different units (A) and RI, R2, R3 and R4 of the units (Al) to (A15) can be identical or different.

4. A process for treating a non-keratinized material according to any one of claims 1 to 3, wherein the units (A) are such that Ri represents a (Ci-C4)alkyl group such as methyl.

5. A process for treating a non-keratinized material according to any one of claims 1 to 4, wherein the units (A) are such that Ri represents a -C(O)-OR4' group with the R4, identical or different, representing i) a hydrogen atom, ii) a cationic counter ion M +, preferably an alkali or alkaline earth metal cation, or an ammonium cation, or iii) a hydrocarbon chain, saturated or unsaturated, linear or branched, non-cyclic or saturated or unsaturated cyclic, aromatic or non-aromatic, comprising from 1 to 30 carbon atoms; preferably comprising from 2 to 20 carbon atoms, preferably said hydrocarbon chain being saturated, acyclic, linear or branched, or cyclic; said hydrocarbon chain further being: • possibly substituted by one or more (di)(Ci-C4)(alkyl)amino groups; and / or • possibly interrupted by one or more a') heteroatoms such as O, S, N(R a ), and Si(Rb)(R c ), b') S(O) r with r being 1, 2 or 3, carbonyl, or c') associations of a') with b') such as the groups -C(O)-O-, -OC(O)-, amide -C(O)-N(R a )- or -N(R a )-C(O)-, urethane -N(R a )- C(O)-O- or -OC(O)- N(R a)-, urea - N(R a )-(CO)- N(R b )-, carbonate -OC(O)-O-, -[O-Si(R b (R c )] P - or -[(CR a 2)qO]p- , q being an integer between 1 and 4; with p between 1 and 200, in which R' represents a hydrogen atom, a (Ci-C4)alkyl group or S(O) r with r equal to 1, 2 or 3, R a , R b and R c , identical or different, represent a hydrogen atom or an (Cl-C4)alkyl group, particularly R a represents a hydrogen atom, R b and R c , being as defined previously, preferably represent a (Ci-C4)alkyl group such as methyl.

6. A process for treating a non-keratinized material according to any one of claims 1 to 5, wherein the units (A) are such that R2 and R3, whether identical or different, represent a hydrogen atom or a hydroxyl group, it being understood that R2 and R3 cannot simultaneously represent a hydrogen atom, preferably R2 and R3 represent a hydroxyl group; preferably the units (A) are units (B): units (B) wherein Ri and R4 are as defined in any one of claims 1 to 5, particularly units (B) are such that R4 represents a hydrogen atom or a cationic counterion M +, preferably an alkali or alkaline earth metal cation, or ammonium, a primary, secondary or tertiary (Ci-Cs)alkylamine which may comprise one or more nitrogen and / or oxygen atoms and may comprise several alcohol functions, it being understood that at least one of the nitrogen atoms is protonated so as to form an ammonium and that each of the amines is protonated, said units (B) being able to be in the form of cyclized units (Bl), particularly in acidic media: when Ri represents a -C(O)-OR'4 group, in particular carboxy or carboxylate -C(O)OM, then the units (B) are units (B'), said units (B') being able to cyclize, in particular in acidic medium, to lead to the bicyclic units (B'1):

7. A process for treating a non-keratinized material according to any one of claims 1 to 5, wherein the units (A) are such that R2 and R3 together form a bond; more particularly the units (A) are units (C): units (C), units (C) wherein Ri and Ri are as defined in any one of claims 1 to 4; particularly the units (C) are such that Ri represents a -C(O)-OR'4 group, in particular a carboxy or carboxylate -C(O)OM group + , M + being a cationic counter-ion as defined in any one of claims 1 to 4.

8. A process for treating a non-keratinized material according to any one of claims 1 to 5, wherein the units (A) are such that R2 and R3 together form a saturated or unsaturated heterocycle, preferably saturated, comprising at least one oxygen atom, and comprising 3 to 6 links, preferably 3 links, such as epoxy; in particular units (A) are units (D): units (D) wherein Ri and R4 are as defined in claim 1 or 3; in particular Ri represents a -C(O)-OR'4 group, notably carboxy or carboxylate -C(O)OM, M + being a cationic counter-ion as defined in any one of claims 1 to 4.

9. A process for treating a non-keratinized material according to any one of claims 1 to 8, wherein the polymer comprising units (A) and optionally units (Al) to (A15) further comprises one or more units resulting from the polymerization of one or more additional monomer(s) selected from i) (Ci-C4)(alkyl)acrylate of (Ci-C22)(cyclo)alkyl, preferably (meth)acrylate of (C5-C22)(cyclo)alkyl, and / or ii) (Ci-C4)(alkyl)acrylamide of (Ci-C22)(cyclo)alkyl, preferably (meth)acrylamide of (C5-C22)(cyclo)alkyl.

10. A process for treating a non-keratinized material according to any one of claims 1 to 9, wherein the polymer comprising units (A) and optionally units (Al) to (A15) further comprises one or more units resulting from the polymerization of one or more additional monomer(s) selected from monomers of formula (II): H2C=C(R6)-C(O)-E-R5, in which E represents an oxygen atom or N(R), preferably E represents an oxygen atom, with R representing a hydrogen atom or a (C1-C4)alkyl group such as methyl, and R-6 represents a hydrogen atom, a (C1-C4)alkyl group such as methyl, and R5 represents: - a (Ci-C22)alkyl group, preferably (Ci-C2o)alkyl, more preferably (Ci-Cio)alkyl, linear or branched, optionally interrupted by one or more oxygen atoms, preferably R5 represents a methyl, ethyl, n-propyl, i-propyl, n-butyl, s-butyl, t-butyl, n-hexyl, n-heptyl, 2-ethylhexyl, n-octyl, i-octyl, n-decyl, methoxyethyl, ethoxyethyl, methoxypropyl, isodecyl, lauryl, stearyl, hexadecyl, more preferably methyl, or - a (Cs-C22)cycloalkyl group, preferably (Cs-C2o)cycloalkyl, in particular cyclohexyl, norbomyl or isobomyl, preferably isobomyl, or - an aryl or aryl(Ci-C4)alkyl group such as benzyl; the additional monomer(s) being more preferentially chosen from among the monomers of formula (II'): H2C=C(Re)-C(O)-O-Rs , with Rs representing a linear or branched (Ci-C6)alkyl group such as methyl and Re representing a hydrogen atom or a (Ci-C4)alkyl group such as methyl.

11. A process for treating a non-keratinized material according to claim 9 or 10, wherein at least one copolymer further comprises units of formula (III): formula (III), wherein Re is as defined in claim 10 and A represents a hydroxy, amino, or OM group + with M + representing a cationic counter ion.

12. A process for treating a non-keratinized material according to any one of claims 1 to 11, wherein the polymer further comprises one or more units (Al) to (A15) as defined in claim 3, where RET represents a group resulting from the crosslinking of at least one hydroxy group and / or a -C(O)-OR'4 group and / or -C(O)-OR4 of a unit (A) with at least one crosslinker selected from: a) organic compounds comprising at least 2 heterocyclic groups comprising 3 to 10 links, preferably 3 links, and 1 to 3 heteroatoms such as O, S, N, and / or 1 to 3 carbonyl groups, preferably epoxide and / or aziridine heterocyclic groups; b) organic compounds comprising at least one electron-donating group such as a primary or secondary amine group, preferably at least two electron-donating groups such as hydroxyl or thiol; and c) (in)organic compounds comprising at least one phosphorus group -OP(O)(OH)2, -OP(O)(O'M +)2, -P(O)(OH)2 OR -P(O)(O'M + )2 with M + as defined in any one of claims 1 to 11.

13. A process for treating a non-keratinized material according to any one of claims 1 to 7, wherein the non-keratinized material is a metallic substrate or a non-metallic substrate, such as a substrate selected from the group consisting of wood, paper, mineral materials, non-keratinized organic materials, cellulosic materials, textile materials, inorganic materials, plastic materials and internal organs and / or mucous membranes of animals or humans.

14. A process for treating a non-keratinized material according to any one of claims 1 to 8, wherein the composition comprising at least one polymer is selected from the group consisting of superabsorbents, complexing agents, binders, electrolytes, thickeners, electrode separators, adhesives, paints, varnishes, detergents and oils.

15. Polymer comprising several repeating units selected from the units (A) as defined in any one of claims 1 to 14, selected from: 1) statistical, sequenced or gradient copolymers, comprising several identical repeating units selected from the units (A) as defined in any one of claims 1 and 4 to 8, and at least one of: one or more units selected from the units (Al) to (Al 5) as defined in claim 3, and / or one or more units resulting from the polymerization of one or more additional monomers as defined in any one of claims 9 to 11; 2) statistical, sequenced or gradient copolymers comprising at least two different repeating units selected from units (A) as defined in any one of claims 1 and 4 to 8, optionally one or more units selected from units (Al) to (Al 5) as defined in claim 3, and optionally one or more units resulting from the polymerization of one or more additional monomers as defined in any one of claims 9 to 11; 3) homopolymers comprising units (A) as defined in any one of claims 1 and 4 to 8 wherein Ri represents a -C(O)-OR'4 group, R2 and R3 together form a bond and R4 and R'4, preferably identical, each represent a linear or branched (C3-Cs)alkyl group other than i-propyl, n-butyl, and 2-ethylhexyl, such as t-butyl or n-octyl; or a (C3-Cio)cycloalkyl group other than cyclohexyl such as isobotyl, said homopolymers further being different from cis-cis-di-n-octylmuconate; 4) homopolymers comprising units (A) as defined in any one of claims 1 and 4 to 8 in which Ri represents a -C(O)-OR'4 group, and R2 and R3 together form a saturated or unsaturated heterocycle, preferably saturated, comprising at least one oxygen atom, and comprising 3 to 6 links, preferably 3 links, such as epoxy and R4 and R'4, preferably identical, are as defined in any one of claims 1 to 14; 5) homopolymers comprising units (A) in which R2 and R3, identical or different, represent a hydrogen atom or a hydroxy group, it being understood that R2 and R3 cannot simultaneously represent a hydrogen atom, preferably R2 and R3 represent a hydroxy group.

16. A process for preparing a polymer comprising several repeating units selected from the units (A) as defined in any one of claims 1 to 15, comprising the following steps i) to iii): i) The polymerization of a diene of formula (IC), one of its geometric isomers or a mixture of such dienes to obtain a polymer of formula (C): , preferably in the presence of at least one catalyst and / or initiator, in a solvent, preferably an organic solvent, in particular an aprotic solvent, at a temperature less than or equal to 120°C, wherein Ri and R4 are as defined in any one of claims 1 to 4; ii) the epoxidation of the polymer of formula (C) to form the polymer of formula (D): , preferably in the presence of at least one oxidizing agent selected from the group consisting of dioxygen, peroxides such as hydrogen peroxide H2O2, peracids, preferably aromatic, in particular (halo)perbenzoic acids, such as m-chloroperbenzoic acid, and / or at least one organic, organometallic, or enzymatic catalyst, such as titanium derivatives, manganese derivatives, aluminum derivatives, lipases that epoxidize unsaturates, peroxygenases, non-heme monooxygenases, halogenoperoxidases such as chloroperoxy dase, and cytochrome P450 monooxygenases; and iii) hydrolysis of the polymer of formula (D) to form one or more diol polymers of formula (B): in which Ri and R4 are as defined in any one of claims 1 to 4, preferably in water or in a mixture of water and at least one organic solvent.

17. Polymer obtained by a preparation process according to claim 16.

18. A process for degrading a polymer comprising several repeating units selected from the units (A) as defined in any one of claims 1 to 17 by oxidative degradation, preferably by contact with an alkali metal permanganate, such as potassium permanganate, or by ozonolysis, in particular by ozonolysis.

19. Compound with formula (Dl) , with X and RET as defined in claim 3.

Images