MONOMERS FOR THERMOSETTING OR ADHESIVE EPOXY RESINS

Abstract

The present invention relates to epoxy precursors, their preparation process and their use as monomers for the development of thermosetting resins or associated adhesives.

Description

Title of the invention: Monomers for thermosetting or adhesive epoxy resins FIELD OF INVENTION

[0001] The field of the present invention is that of the synthesis of epoxy precursors and their use as monomers for the preparation of thermosetting resins or associated adhesives. More specifically, the present invention relates to the use of polyfunctional phenolic aromatic compounds derived from renewable resources, and not from petroleum, natural gas, coal, or other fossil resources, exhibiting improved environmental and safety properties (HSE properties) and resulting in thermosetting resins that do not exhibit performance degradation in use. STATE OF THE ART

[0002] Nowadays, among polyfunctional phenolic aromatic compounds, one can cite in particular bisphenol A diglycidyl ether (DGEBA or BADGE), manufactured from bisphenol A (BPA) and epichlorohydrin (ECH). BPA is classified as a Carcinogenic, Mutagenic, and Reprotoxic (CMR), namely a category 2 reprotoxicant and an endocrine disruptor.

[0003] In recent years, several solutions have been implemented to develop compounds with a low environmental footprint and reduce their toxicity. For example, in 2007, Solvay presented the EPICEROL® process for the bio-based production of hydroxyethyl starch (HES) from glycerol. BPA, on the other hand, can be obtained by reacting phenol obtained by distilling forestry industry waste with acetone produced by fermentation (SuperSap® prepolymer from Entropy Resins).

[0004] However, the use of bio-based and renewable BPA does not change the hazardous nature of this substance, which remains classified as CMR regardless of its origin. Therefore, it is preferable to improve its properties with new, less polluting and non-toxic precursors for humans rather than implementing a "drop-in" product-for-product substitution that would retain the potential hazards of the products used.

[0005] Furthermore, in certain uses such as, for example, food contact (coatings for metal containers, tanks, etc.) or the rehabilitation of aging drinking water pipes by spray lining, the potential leaching of BPA from the degradation of thermosetting materials based on DGEBA is a concern for public authorities. (Rajarsarkka et al. Water Res. 2016, 103) , 133-140; Cantoni et al. Sci. Total Environ. 2021, 783, 146908; Lipke et al. Eur. J. Pharm. Biopharm. 2016,101, 1-8). TECHNICAL PROBLEM

[0006] The technical problem that the present invention aims to solve is therefore to obtain new polyfunctional epoxidized aromatic phenolic compounds from renewable resources that exhibit improved HSE properties. Summary of the invention

[0007] Thus, a first object of the invention is a compound of formula (I): r4 (0 in which: - Ri and R3, being identical, denote a group with the following formula (II): X2 (H) in which - E represents a single bond or a divalent hydrocarbon group in CrCi2 possibly including one or more heteroatoms; - Xi, X2 and X3, whether identical or different, represent a hydrogen atom, a Ci-C6 alkyl group or a C6-Ci4 aryl group, and / or - Xi and X3 or X2, or a carbon atom from the divalent hydrocarbon group of E and X3 or X2 can be linked together, with the carbon atoms of the epoxide group, to form a C4 to C8 carbocycle or a heterocycle having 5 to 8 links; - the symbol (*) represents the point of attachment of group (II) to the rest of the compound of formula (I); R5 represents -O-X4. with X4 representing a CrCi8 alkyl, a C6-Ci4 aryl, a C3-C7 cycloalkyl or a (C6-Ci4)aryl-(Ci-C6)alkyl; - R2, R4 and R6, whether identical or different, represent a hydrogen atom or an alkyl group in C1-C24.

[0008] A second object of the invention is a method for preparing a compound of formula (I) according to the invention, comprising a step b) of bringing the following compounds into contact: - a compound with the following formula (1-2): in which: (i-2) - Rf and R3' of formula (1-2), denote a -OH group; - R5 represents -O-X4, with X4 representing a CrCi8 alkyl, a C6-Ci4 aryl, a C3-C7 cycloalkyl or a (C6-Ci4)aryl-(Ci-C6)alkyl; - R2, R4 and R6, whether identical or different, represent a hydrogen atom or an alkyl group in Ci-C24;

[0009] - a compound of the following formula (II-l): X2 in which: - Y2 represents a function capable of reacting with an -OH group to form an ether bond; - E represents a single bond or divalent hydrocarbon group in C1-C12 possibly including one or more heteroatoms; - Xi, X2 and X3, whether identical or different, represent a hydrogen atom, a Ci-C6 alkyl group or a C6-Ci4 aryl group, and / or - Xi and X3 or X2, or a carbon atom from the divalent hydrocarbon group of E and X3 or X2 can be linked together, with the carbon atoms of the epoxide group, to form a C4 to C8 carbocycle or a heterocycle having 5 to 8 links.

[0010] A third object of the invention is a use of a compound of formula (I) according to the invention as a precursor of polymer materials, in particular thermosetting materials, or as an adhesive.

[0011] A fourth object of the invention is a process for preparing a thermosetting material comprising a polymerization step of a compound of formula (I) according to the invention, optionally the process further comprises a crosslinking step.

[0012] A fifth object of the invention is a thermosetting material that can be obtained by the preparation process described above. DEFINITIONS

[0013] In the present, unless expressly stated otherwise, all percentages (%) indicated are percentages (%) in moles.

[0014] Any interval of values ​​designated by the expression "between a and b" as well as by the expression "from a to b" means the domain of values ​​going from a to b (that is to say including the strict bounds a and b).

[0015] For the purposes of the present invention, "hydrocarbon chain" means a chain comprising one or more carbon atoms and one or more hydrogen atoms.

[0016] For the purposes of this invention, the term "Cx-Cy alkyl group" refers to a monovalent, saturated, linear or branched hydrocarbon chain comprising x to y carbon atoms, where x and y are integers. Examples of Ci-C6 alkyl groups include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isoamyl, neopentyl, and hexyl, preferably methyl, ethyl, propyl, or isopropyl. For example, C1-C12 alkyl groups include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isoamyl, neopentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, and dodecyl. Similarly, C1-C4 alkyl groups include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, and tert-butyl.

[0017] For the purposes of this invention, a "Cx-Cy cycloalkyl group" is defined as a saturated cyclic hydrocarbon chain comprising x to y cyclic carbon atoms. A cycloalkyl may be monocyclic or bicyclic, preferably monocyclic. Examples of C3-C7 cycloalkyls include cyclopropyl, cyclopentyl, cyclohexyl, and cycloheptyl groups.

[0018] The expression "C-Cj aryl" designates an aromatic hydrocarbon group comprising from i to j carbon atoms, i and j being integers. This group may comprise one or more fused rings. Advantageously, it is phenyl.

[0019] For the purposes of this invention, a "Cx-Cy carbocycle" is defined as a saturated or instanominated non-aromatic cyclic hydrocarbon group comprising x to y carbon atoms. A carbocycle may be monocyclic or polycyclic. When the carbocycle is polycyclic, it comprises at least 2, advantageously 2 or 3, rings These carbons can be bonded, bridged, or spiral. For example, they can be saturated carbon cycles, particularly at C3-C8. Examples include cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, and cyclooctane. They can also be unsaturated carbon cycles, meaning they contain at least one double or triple carbon-carbon bond, especially at C3-C8. Examples include cyclopropene, cyclobutene, cyclopentene, cyclohexene, 1,4-cyclohexadiene, cycloheptene, cycloheptyne, cyclooctene, and cyclooctyne.

[0020] For the purposes of this invention, a "heterocycle having x to y members" means a non-aromatic ring having x to y members, saturated or unsaturated, monocyclic or polycyclic (including rings), of which one or more, advantageously 1 to 4, more advantageously 1 or 2, cyclic atom(s) is / are a heteroatom, such as, for example, sulfur, nitrogen, or oxygen atoms, the other cyclic atoms being carbon atoms. Examples include the pyrrolidine, piperidine, piperazine, morpholine, pyrazolidine, imidazolidine, azepane, thiazolidine, isothiazolidine, oxazocane, thiazepane, and benzimidazolone groups.

[0021] For the purposes of this invention, "(C-Cj)aryl-(CX-Cy)alkyl" means a C-Cj aryl group, as defined above, linked to the rest of the molecule via a Cx-Cy alkyl group, as defined above. Examples include the benzyl and 1-phenylethyl groups.

[0022] By "heteroatom", we mean any atom other than carbon or hydrogen such as, for example, sulfur, nitrogen or oxygen atoms.

[0023] For the purposes of this invention, "halogen atom" or "halogen" means fluorine, chlorine, bromine and iodine atoms.

[0024] For the purposes of this invention, “stereoisomer” means a configurational isomer, and in particular a geometric or optical isomer.

[0025] Geometric isomers result from the different position of the substituents on a double bond which can then have a Z or E configuration.

[0026] Optical isomers result, in particular, from the different spatial positions of substituents on a carbon atom containing four different substituents. This carbon atom then constitutes a chiral or asymmetric center. Optical isomers include diastereomers and enantiomers. Optical isomers that are mirror images of each other but not superimposable are designated as "enantiomers." Optical isomers that are not mirror images of each other are designated as "diastereomers." A mixture containing equal amounts of two individual enantiomeric forms of opposite chirality is designated as a "racemic mixture."

[0027] According to the present invention, the disclosed compounds encompass all stereoisomers of said compounds.

[0028] For the purposes of this invention, "ambient temperature" means a temperature generally ranging from 15°C to 40°C, preferably from 20°C to 30°C, in particular around 25°C.

[0029] The compounds mentioned in the description may be of fossil origin or bio-based. In the latter case, they may be partially or totally derived from biomass or obtained from renewable raw materials derived from biomass. Similarly, the compounds mentioned may also come from the recycling of materials already used, that is to say, they may be partially or totally derived from a recycling process, or obtained from raw materials themselves derived from a recycling process.

[0030] In this description, "approximately" means that the value in question may be 10% lower or higher, in particular 5%, and in particular 1% higher, than the value indicated. DETAILED DESCRIPTION OF THE INVENTION

[0031] In the sense of the present invention, the various embodiments presented in the description as a whole can be used alone or in combination with each other, without limitation of combination. Compound of formula (I)

[0032] The object of the present invention relates to a compound of formula (I): R4 (O in which: - Ri and R3 are identical and denote a group according to the following formula (II): X2 E cr xi x< 0 (II) in which - E represents a single bond or a divalent hydrocarbon group in CrCi2 possibly including one or more heteroatoms; - Xi, X2 and X3, whether identical or different, represent a hydrogen atom, a Ci-C6 alkyl group or a C6-Ci4 aryl group, and / or - Xi and X3 or X2, or a carbon atom from the divalent hydrocarbon group of E and X3 or X2 can be linked together, with the carbon atoms of the epoxide group, to form a C4 to C8 carbocycle or a heterocycle having 5 to 8 links; - the symbol (*) represents the point of attachment of group (II) to the rest of the compound of formula (I); - R5 represents -O-X4 with X4 representing a CrCi8 alkyl, a C6-Ci4 aryl, a C3-C7 cycloalkyl or a (C6-Ci4)aryl-(Ci-C6)alkyl; - R2, R4 and R6, whether identical or different, represent a hydrogen atom or an alkyl group in CrC24.

[0033] Advantageously, R2, R4 and R6 represent, identical or different, a hydrogen atom or an alkyl group in CrCi2, preferably in Ci-C6, more preferably in Ci-C4. Preferably, R2, R4 and R6 represent a hydrogen atom.

[0034] E may represent a divalent hydrocarbon group in CrCi2, in particular in Ci-CiO, in particular in CrC8, preferably in Ci-C6, preferably in CrC4, typically in Ci or C2, optionally comprising one or more heteroatoms, in particular an alkyl group in CrCi2, in particular in Ci-CiO, in particular in CrC8, preferably in CrC6, preferably in CrC4, typically in Ci or C2, optionally comprising one or more heteroatoms. When present, the heteroatoms are preferably selected from S, O, and N, in particular from O and N, preferably are O. Preferably, E does not comprise any heteroatoms.

[0035] E can represent -(CH2)n- with n an integer equal to 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 or 12.

[0036] Preferably, Xb, X2, and X3, whether identical or different, represent a hydrogen atom or a Ci-C6 alkyl group. Advantageously, Xi represents a hydrogen atom. Advantageously, X2 and X3 each represent a hydrogen atom or a Ci-C6 alkyl group, such as a methyl group.

[0037] Advantageously, Xi represents a hydrogen atom and X2 and X3, identical or different, represent a hydrogen atom or a Ci-C6 alkyl, preferably a hydrogen atom or a Ci-C4 alkyl, preferably a hydrogen atom or a methyl.

[0038] According to one embodiment, Xb X2 and X3 represent a hydrogen atom.

[0039] According to another embodiment, Xi represents a hydrogen atom and X2 and X3, identical or different, represent a Ci-C6 alkyl, preferably a Ci-C4 alkyl, preferably a methyl.

[0040] When Xi and X3 or X2, or a carbon atom of the divalent hydrocarbon group of E and X3 or X2 are bonded together, with the carbon atoms of the epoxide group, to form a C4 to C8 carbocycle or a heterocycle having 5 to 8 links, the C4 to C8 carbocycle or the heterocycle having 5 to 8 links is advantageously saturated, and preferably is a C4 to C8 carbocycle, advantageously a cyclopentane, a cyclohexane or a cycloheptane, more preferably a cyclohexane.

[0041] Advantageously, X4 represents a CrCi2 alkyl, a phenyl, a cyclohexyl or a phenyl-(Ci-C6)alkyl, preferably a Ci-C6 alkyl, a phenyl or a benzyl, preferably a CrC4 alkyl, more preferably a methyl or an ethyl.

[0042] Advantageously, the compound according to the invention is a compound of formula (I) in which: - Ri and R3 are identical and denote a group of formula (II) in which: - E represents an alkyl in Ci-Ci2, preferably in CrC4, possibly comprising one or more heteroatoms; - Xb X2 and X3, identical or different, represent a hydrogen atom or an alkyl in Ci-C6; - the symbol (*) represents the point of attachment of group (II) to the rest of the compound of formula (I); - R5 represents -O-X4 with X4 representing an alkyl in CrCi8, preferably an alkyl in Ci-C6, preferably an alkyl in CrC4, more preferably a methyl or an ethyl; - R2, Rj and R6, whether identical or different, represent a hydrogen atom or an alkyl in CrCi2, preferably R2, R4 and R6 represent a hydrogen atom.

[0043] Even more advantageously, the compound of formula (I) is chosen in the group made up of and their mixtures.

[0044] Process for preparing a compound of formula (I)

[0045] In a first embodiment, the process for preparing a compound of formula (I) according to the invention comprises a step b) of bringing the following compounds into contact: - a compound with the following formula (1-2): in which: - Rf and R3' of formula (1-2), denote a -OH group; - R5 represents -O-X4 with X4 representing a Ci-Ci8 alkyl, a C6-CM aryl, a C3-C7 cycloalkyl, or a (C6-Ci4)aryl-(Ci-C6)alkyl; and - R2, Ri and R6 are identical to those of formula (I);

[0046] - a compound of the following formula (II-l): X2 in which: xX (11-1) - Y2 represents a function capable of reacting with an -OH group to form an ether bond, and - E, Xi, X2 and X3 are identical to those of formula (II).

[0047] In this embodiment, the compound of formula (1-2) can be prepared by an ether bond formation reaction to obtain the substituent R5 from the compound of formula (1-1) defined below.

[0048] Thus, the compound of formula (I) can be prepared by a preparation process comprising two successive ether bond formation reactions. The preparation process described below is suitable for preparing all kinds of compounds of formula (I).

[0049] The compound of formula (I) can therefore be prepared in two steps from the compound of formula (1-1): r4 (M) in which: - Rf, R3', R5' of formula (1-1), denote an -OH group, and - R2, R and R6 are identical to those of formula (I).

[0050] The compound of formula (Il) is preferably phloroglucinol.

[0051] The first step a) is a step of contacting the compound of formula (1-1) with a compound YrX4 in which - Yi represents a function capable of reacting with an -OH group for to form an etheric bond, and - X4 is as defined previously.

[0052] The functional groups Yi are well known to those skilled in the art. For example, Yi can represent an -OH group or a halogen atom, the halogen preferably being a bromine or chlorine atom. Preferably, Yi represents an -OH group.

[0053] The conditions of this step a) are a transposition of the usual conditions for ether bond formation reactions. This reaction can be carried out in an organic solvent, for example a polar and aprotic solvent such as tetrahydrofuran, or a nonpolar solvent such as toluene.

[0054] When Yi represents an -OH group, the compound YrX4 can also act as the solvent for the reaction, particularly when X4 represents a Ci-Ci8 alkyl group. Advantageously, when X4 represents a Ci-C6 alkyl group, YrX4 acts as the solvent, preferably when X4 represents a CrC4 alkyl group, and more preferably a methyl or ethyl group. YrX4 is therefore preferably methanol or ethanol.

[0055] The reaction can be carried out under acidic conditions, for example in the presence of a strong Brønsted acid such as sulfuric acid, and preferably at a temperature ranging from 0 to 90 °C, preferably from 20 °C to 70 °C, typically about 50 °C. The duration of the reaction can range from 1 hour to 40 hours.

[0056] Step a) can therefore be represented by the following diagram. + Y1-X4

[0057] Step a) therefore leads to obtaining a compound of formula (1-2) in which: - Rf and R3' are identical to those of formula (1-1), - R5 represents -O-X4 with X4 representing a CrCi8 alkyl, an aryl at C6 -Ci4, a C3-C7 cycloalkyl or a (C6-Ci4)aryl-(Ci-C6)alkyl, and - R2, R4 and R6 are identical to those of formula (I).

[0058] Step b), which is the second step when step a) is implemented, is a step of contacting the compound of formula (1-2) as defined above with a compound of formula (II-1) as follows: X2 as defined previously. xA (IM)

[0059] This step therefore leads to obtaining a compound of formula (I) according to the invention.

[0060] The Y2 functional groups are well known to those skilled in the art. For example, Y2 can represent an -OH group or a halogen atom, the halogen preferably being a bromine or chlorine atom. Preferably, Y2 represents a chlorine or bromine atom.

[0061] The conditions of this step b) are a transposition of the usual conditions for ether bond formation reactions, which are not necessarily identical to those of step a). This reaction can be carried out in an organic solvent, for example, a polar and aprotic solvent such as tetrahydrofuran (THF), dimethylformamide (DMF), or acetonitrile. The compound of formula (II-l) can also act as a solvent when it is in liquid form under the reaction conditions. Preferably, when E represents a -CH2- group, Xb, X2, and X3 represent a hydrogen atom, and Y2 represents a chlorine or bromine atom, then the compound of formula (II-l) also acts as a solvent.

[0062] The reaction can be carried out at a temperature ranging from 20 to 150 °C, preferably from 50 °C to 120 °C, typically about 90 °C. The duration of the reaction can range from 15 minutes to 10 hours, typically about 2 hours.

[0063] According to a second embodiment, the compound of formula (I) can be prepared by a process comprising an epoxidation step of a compound of formula (1-3) defined below, this step thus yielding a compound of formula (I). This epoxidation step is preferably preceded by an ether bond formation step to obtain the ether functions of the groups of formula (II), thus yielding the compound of formula (1-3). This step is advantageously preceded by an ether bond formation step to form the ether bond of the R5 group to obtain the compound (1-1).

[0064] The compound of formula (I) can be prepared in three steps from the compound of formula (1-1): R. ' as defined previously. r4 (1-1)

[0065] The first step a') is identical to step a) as defined previously. Step a') yields a compound of formula (1-2) with the following formula: R / 'P 1 5s K3 r4 (1-2) in which Rf, R2, Rf, R4, R5 and R6 are as defined previously.

[0066] Step b'), which is the second step when step a' is implemented, is a step of contacting the compound of formula (1-2) with a compound according to the following formula (II-2): X1 Y2x rA / X3 E X2 (1I-2) in which: - Y2 represents a function capable of reacting with an -OH group to form an ether bond as defined previously, and - E, Xb X2 and X3 are as defined previously.

[0067] The conditions of this step b') are a transposition of the usual conditions for ether bond formation reactions. This reaction can be carried out in an organic solvent, for example a polar and aprotic solvent such as tetrahydrofuran, or a nonpolar solvent such as toluene.

[0068] Step b') can be carried out with a compound molar ratio of formula (1-2):compound according to formula (II-2) ranging from 1.9 to 5, preferably ranging from 2 to 4, typically ranging from 2.1 to 2.4.

[0069] Step b') can therefore be represented by the following diagram. (1-2) (11-2) (1-3)

[0070] Step a) therefore leads to obtaining a compound of formula (1-3) in which: - Ri” and R3” are identical and designate a group according to the following formula (II-3): ^2 (H-3) in which: - E, Xb X2 and X3 are as defined previously; - the symbol (*) represents the attachment point of the group of formula (II-3) to the remainder of the compound of formula (1-3); - R2, R4, R5 and R6 are identical to those of formula (I).

[0071] Step c'), which is the third step when steps a') and b') are carried out, is a step of contacting the compound of formula (1-3) as defined above with an epoxidizing agent. In the context of the present invention, the epoxidizing agent is a compound or a mixture of compounds that allows the transformation of the C=C double bond of the compound of formula (1-3) into an epoxide function. This step therefore leads to obtaining a compound of formula (I) as defined above.

[0072] Epoxidizing agents are numerous and well known to those skilled in the art. For example, metachloroperbenzoic acid (MCPBA) is an epoxidizing agent. The conditions of this epoxidation step c') are a transposition of the usual conditions for epoxidation reactions. This reaction can be carried out in an organic solvent, preferably polar and aprotic, such as dichloromethane, and preferably at room temperature. The reaction time can range from 1 hour to 50 hours.

[0073] In all embodiments, the compound (I) thus obtained can be separated from the reaction medium by methods well known to those skilled in the art, such as, for example, by extraction, evaporation of the solvent or by precipitation and filtration. The same applies to the compound of formula (1-2) obtained at the end of step a) or a') and to the compound (1-3) obtained at the end of step b').

[0074] The compounds can also be purified if necessary by techniques well known to those skilled in the art, such as by recrystallization if the compound is crystalline, by distillation, by silica gel column chromatography or by high-performance liquid chromatography (HPLC).

[0075] Use of a compound of formula (I) and process for preparing thermosetting materials

[0076] Compounds of formula (I) are particularly interesting precursors for the preparation of polymeric materials, and especially thermosetting polymeric materials. A thermosetting material is a polymeric material obtained by a polymerization step that renders the material irreversibly rigid. This hardening is due to extensive cross-linking between the polymer chains.

[0077] Crosslinking is a chemical reaction that creates covalent chemical bonds between polymer chains that are not initially covalently linked. This reaction is generally initiated by heat, pressure, changes in pH, or radiation, and most often requires a crosslinking agent. The crosslinking of linear or branched polymer chains is accompanied by an increase in the molecular dimensions of the chains, particularly their molar masses, and leads to the formation of a network of crosslinked polymers.

[0078] Thermosetting polymers have very good mechanical properties, in particular strength, and can also be used as an adhesive.

[0079] Thus, another object of the invention relates to the use of a compound of formula (I) for the preparation of a thermosetting material. Also, another object of the invention relates to a process for preparing a thermosetting material comprising a polymerization step of a compound of formula (I).

[0080] This polymerization can be carried out with at least one monomer M different from the compound of formula (I). This monomer M has at least two reactive functional groups that can react with the epoxide groups present in the compound of formula (I). These functional groups are well known to those skilled in the art. For example, amine, amide, carboxylic acid, and derivative functional groups such as acid anhydrides, isocyanates, polymercaptans, and phenols may be mentioned.

[0081] Monomer M can preferably be chosen from diamines such as urea and its derivatives, dicyandiamide or aliphatic diamines with a cyclohexyl center such as isophorone diamine or those marketed under the name Priamine 1071 or Priamine 1075.

[0082] The monomer M can be chosen from acid anhydrides, aromatic amines, cycloaliphatic amines, primary aliphatic amines and carboxylic acids.

[0083] The following acid anhydrides may be cited: hexahydrophthalic anhydride, succinic anhydride, maleic anhydride, chlorendic anhydride, nadic anhydride, tetrachlorophthalic anhydride, pyromellitic dianhydride, 1,2,3,4 cyclopentanetetracarboxylic acid dianhydride, glutaric anhydride, phthalic anhydride, and aliphatic acid polyanhydrides such as polyazelaic polyanhydride or polysebatic polyanhydride.

[0084] The following aromatic amines may be cited: 4,4'-aminodiphenylsulfone, also called DDS; 4,4'-methylene-bis(2,6-diethylaniline); 4,4'-(phenylenediisopropyl)-bis(2,6-dipropylaniline); 4,4'-methylene-bis(2-isopropyl-6-methylaniline), also called M-MIPA; 4,4'-methylene-bis(2,6-diethylaniline), also called M-DEA; 4,4'-methylene-bis(3-chloro-2,6-diethylaniline), also called M-CDEA; 4,4'-(phenylenediisopropyl)-bis(2,6-dimethylaniline); 4,4'-(phenylenediisopropyl)-bis(2,6-diethylaniline); 4,4'-(phenylenediisopropyl)-bis(2,6-dipropylaniline), 4,4'-(phenylenediisopropyl)-bis(2,6-diisopropylaniline), 4,4'-(phenylenediisopropyl)-bis(2,6-dimethyl-3-chloroaniline), 4,4'-(phenylenediisopropyl)-bis(2,6-diethyl-3-chloroaniline), 4,4'-(phenylenediisopropyl)-bis(2,6-dipropyl-3-chloroaniline), 4,4'-(phenylenediisopropyl)-bis(2,6-diisopropyl-3-chloroaniline), 3,3'-(phenylenediisopropyl)-bis(2,6-dimethylaniline),3,3'-(phenylenediisopropyl)-bis(2,6-diethylaniline), 3,3'-(phenylenediisopropyl)-bis(2,6-dipropylaniline), 3,3'-(phenylenediisopropyl)-bis(2,6-dimethyl-3-chloroaniline), 3,3'-(phenylenediisopropyl)-bis(2,6-diethyl-3-chloroaniline), 3,3'-(phenylenediisopropyl)-bis(2,6-dipropyl-3-chloroaniline), 3,3'-(phenylenediisopropyl)-bis(2,6-diisopropylaniline), and 3,3'-(phenylenediisopropyl)-bis(2,6-diisopropyl-3-chloroaniline).

[0085] The following cycloaliphatic amines may be cited: 1,3-cyclohexanediamine, 1,4-cyclohexanediamine, 1,3-bis(aminomethyl)cyclohexane, 1,4-bis(aminomethyl)cyclohexane, bis(aminomethyl)norbomane, 4,4'-diamino dicyclohexylmethane also called PACM, 3,3'-dimethyl-4,4'-dicyclohexylmethane also called MACM, isophorone diamine also called IPDA, and menthane diamine.

[0086] Examples of primary aliphatic amines include: ethylenediamine, diethylenetriamine, triethylenetetramine, piperazinoethylethylenediamine, aminoethyldiaminoethylpiperazine, aminoethylpiperazinoethylethylenediamine, aminoethylpiperazine, aminoethylethanolamine (AEEA marketed by Dow Chemical), and polyetheramine-type amino monomers prepared from oxide ethylene, propylene oxide, or ethylene oxide / propylene oxide mixture (such as the Jeffamines series marketed by Huntsman), 4,7,10-trioxatridecan-1,13-diamine, polytetrahydrofuranamine (marketed by BASF), polyamidoamines, polyaminoimidazolines, unbranched or hyperbranched polyethyleneimines (PEI), and polyalkyleneamines.

[0087] The following carboxylic acids may be cited: carboxylic acids comprising 2 to 40 carbon atoms, such as linear diacids (glutaric, adipic, pimelic, suberic, azelaic, sebacic, dodecanedioic and their higher mass homologues) as well as their mixtures, or fatty acid derivatives, trimers (oligomers of 3 identical or different monomers) and mixtures of fatty acid dimers and trimers, in particular of vegetable origin. These compounds result from the oligomerization of unsaturated fatty acids such as: undecylenic, myristoleic, palmitoleic, oleic, linoleic, linolenic, ricinoleic, eicosenoic, docosenoic acids, which are usually found in pine, rapeseed, corn, sunflower, soybean, grapeseed, flaxseed, jojoba oils, as well as eicosapentaenoic and docosahexaenoic acids which are found in fish oils.We can also mention aromatic carboxylic acids comprising 2 to 40 carbon atoms, such as aromatic diacids like phthalic acid, trimellitic acid, terephthalic acid or naphthalenedicarboxylic acid.

[0088] This polymerization step of a compound of formula (I) can lead directly to a thermosetting material or it can lead to obtaining a mainly linear polymer chain which will subsequently have to undergo an additional crosslinking step in order to obtain the thermosetting sand material.

[0089] Optionally, the preparation process includes an additional crosslinking step with a crosslinking agent, also called a hardening agent.

[0090] The compound of formula (I) is divalent, indeed it has two groups of formula (II) and therefore two epoxide functions.

[0091] When the monomer M is trivalent, the monomer M and the compound of formula (I) are introduced in a molar proportion (I):M ranging from 6:1 to 1:6, preferably ranging from 5:1 to 1:5, even more preferably from 4:1 to 1:4, typically about 3:1.

[0092] When the monomer M is divalent, the monomer M and the compound of formula (I) are introduced in a molar proportion (I):M ranging from 6:1 to 1:6, preferably ranging from 4:1 to 1:4, even more preferably from 3:1 to 1:2, typically about 2:1.

[0093] Advantageously, the monomer M and the compound of formula (I) are introduced in a molar proportion equivalent to the reactive function of monomer M such that defined above: epoxide functions of the compound of formula (I) (proportion abbreviated as Mr:(I)r) ranging from 0.8:1 to 1:0.8, preferably from 0.9:1 to 1:0.9, typically about 1:1.

[0094] The reaction can take place in an organic solvent, more preferably polar, in a mass quantity ranging from 0% to 1000% by mass of the mass of the monomers involved, preferably ranging from 5% to 500% by mass of the mass of the monomers involved, more preferably ranging from 10% to 50% by mass of the mass of the monomers involved.

[0095] In the case where the solvent is a polar organic solvent, it is preferably aprotic, chosen by those skilled in the art as capable of solubilizing the monomer(s) and possibly the polymer produced, and with a boiling point sufficiently high to carry out the reaction under the required conditions, such as, for example, dimethyl sulfoxide, tetrahydrofuran, dichloromethane, acetone, racetonitrile, trifluorotoluene, or diphenyl ether. When this solvent is miscible with water, the solvent may consist of a mixture of the aprotic solvent with water, for example, a dimethyl sulfoxide / water mixture.

[0096] The polymerization reaction can be carried out at a temperature ranging from 20 °C to 220 °C, preferably from 40 °C to 200 °C, preferably from 50 °C to 160 °C or from 60 °C to 120 °C, more preferably from 70 °C to 100 °C, typically about 80 °C. The reaction time can range from 10 minutes to 4 hours, typically about 60 minutes.

[0097] At the end of the process according to the invention, the polymer produced can be recovered in a known manner, stored where appropriate, and possibly processed for its subsequent uses by techniques known to those skilled in the art.

[0098] The polymer thus obtained can have a glass transition temperature (Tg) ranging from 0°C to 200°C, preferably from 20°C to 200°C. The Tg can be measured by any method known to those skilled in the art, in particular that described in the examples.

[0099] Another object of the invention relates to a polymer obtainable by the polymerization step of a compound of formula (I) as defined above. Optionally, the polymer has undergone the additional crosslinking step as defined above. Those skilled in the art can determine the structure of the polymer obtained based on the nature of the monomers M, the compounds of formula (I), and optionally the crosslinking agents used. This polymer is preferably a thermosetting material. The polymer thus obtained can have a glass transition temperature (Tg) ranging from 0°C to 250°C, preferably from 20°C to 250°C, and preferably from 20°C to 200°C.

[0100] Another object of the invention relates to the use of a compound of formula (I) as a precursor of polymeric materials, in particular thermosetting materials, or as an adhesive. It is understood that, when used as an adhesive, the compound of formula (I) must be brought into contact with a crosslinking agent to achieve the desired effect.

[0101] The aforementioned features of the present invention, as well as others, will be better understood upon reading the following description of several examples of embodiments of the invention, given by way of illustration and not limitation. EXAMPLES

[0102] The following examples illustrate particular embodiments of the invention without limiting its scope.

[0103] The following abbreviations are used in the examples: AHEW - amine hydrogen equivalent weight d - diameter DCM - dichloromethane DMF - dimethylformamide HMBC - heteronuclear multiple-bond correlation HSQC – heteronuclear single quantum coherence 1 - length MCPBA - metachloroperbenzoic acid TA - ambient temperature TMBAC - trimethylbenzylammonium chloride TMS - tetramethylsilane THF - tetrahydrofuran v / v - volume / volume 1. Materials and methods 1.1. Characterization of molecules

[0104] Structural analysis and determination of the molar purities of the synthetic molecules are performed by NMR analysis. The spectra are acquired on a Bruker Avance 3400 MHz spectrometer equipped with a BBFO-zgrad 5 mm broadband probe. The quantitative ¹H NMR experiment uses a single 30° pulse sequence and a 3-second repetition delay between each of the 64 acquisitions. The samples are solubilized in a deuterated solvent, deuterated chloroform (CDC13), unless otherwise specified. The deuterated solvent is also used for the lock signal. For example, calibration is performed on the proton signal of CDC13 deuterated at 7.20 ppm relative to a TMS reference at 0 ppm. The ¹H NMR spectrum coupled with the 2D HSQC ¹H / ¹³C and HMBC ¹H / ¹³C experiments allows the Structural determination of molecules. Molar quantifications are performed from the quantitative 1D 'H NMR spectrum.

[0105] The ERETIC quantification method consists of measuring the mass percentage of one or more species present in a sample by external calibration, using as a standard a reference tube of triphenyl phosphate (TPP) at 48.5 mmol / L in acetone-d6. A quantitative ¹H NMR spectrum with a single 30° pulse is recorded with a 62-second recyclability interval (RI) between each of the 16 scans. The sample to be analyzed is precisely weighed and dissolved in a precise volume of the deuterated solvent appropriate for the sample (approximately 10 mg / mL). A series of ¹H NMR spectra with a single 30° pulse, with the same number of scans (generally 8), the same general relativity (GR), and different RIs (generally 5 / 10 / 15, or even 20 seconds), are recorded and then superimposed to ensure the quantitative nature of the measurement. A 1H NMR spectrum with a single 30° pulse is then recorded on the same tube using the adapted DI (from the previous test) at 64 or 128 scans.The TPP signal is integrated onto the reference spectrum, which counts for 15 protons and is recorded as "Define as ERETIC reference". The most isolated and resolved signal(s) of each species identified on the sample spectrum are also integrated. Using the ERETIC (Calculate Concentration) module of Topspin, it is necessary to enter the precise volume of solvent used, the number of protons assigned to each of the integrated signals, and the molar mass of each species corresponding to the integrated signals. The concentration of the species in the sample is calculated directly by this module. This value is compared to the theoretical concentration (mmol / L) calculated using the sample weight, the solvent volume, and the molar masses of each species.

[0106] x ^'expected

[0107] with

[0108] C [ mnwl ] __ mIM * Expected! L 1 V

[0109] where m = weighed mass [mg]; M = molar mass [^7]; V = volume of solvent [l] 1.2. Chemical Compounds

[0110] All compounds are from a commercial source (Sigma-Aldrich). [YES] 2. Synthesis of compound A (2.2'-(((5-ethoxy-1.3-phenylene)bis(oxy ))bis(methylene))bis(oxirane)))

[0112] The synthesis of compound A is carried out in two steps starting from phloroglucinol.

[0113] 2.1 Synthesis of compound Al (5-ethoxybenzene-L3-diol) HO. ^OH HO. ..c. OH 11 Y Y EtOH, HgSO* J T ô. OH j (A-1)

[0114] Under argon protection, a suspension of phloroglucinol (20.00 g; 159 mmol) in anhydrous ethanol (240 mL) is stirred at room temperature (20-22 °C) to obtain a pale yellow solution. Concentrated sulfuric acid (30 mL) is added dropwise over 20-25 minutes. The temperature of the mixture is gradually raised to 50-55 °C. Then, still under argon protection, the mixture is refluxed for 20 hours. The ethanol is then evaporated under vacuum (Tbain = 50 °C, 20 mbar) and the residue is carefully poured into distilled water (300 mL). The aqueous phase is extracted with ethyl acetate (3 x 120 mL). The collected organic phases are washed with distilled water (2x70 mL) and concentrated under reduced pressure (Tbain = 40°C, 25 mbar) to obtain an orange-brown oil.The product of interest is isolated by silica column chromatography (230-400 mesh, 1 = 40 cm, d = 4.5 cm) using a gradient of ethyl acetate and petroleum ether (v / v, 1:3 to 1:2 to 1:1). After evaporation (Tbain = 40 °C, 8 mbar), a yellow oil is obtained that partially crystallizes upon prolonged storage. For further purification, the crude oil is mixed with distilled water (30 mL) and vigorously stirred at room temperature for 10-15 minutes. The resulting precipitate is filtered, washed with distilled water (3 x 10 mL), and air-dried. An off-white solid (7.860 g; 51 mmol) is obtained. Yield: 32%, melting point: 84-85 °C, purity: 93% (H NMR). .

[0115]

[0116] CH2“CH3 ss [Tables 1 Nê ô 'H (ppm) ô 13C (ppm) 1 5.92 95.8 2 / 157.3 3 5.92 94.9 4 / 160.8 5 3.81 63.7 6 1.25 14.6 2.2. Synthesis of compound A

[0117] 1. TM B AC (A)

[0118] TMBAC (1.368 g, 7.33 mmol) is added to a mixture of 5-ethoxybenzene-1,3-diol (compound Al; 5.650 g, 36.6 mmol) and epichlorohydrin (102 g, 1099 mmol). The reaction mixture is heated to Tbain = 90 °C for 1 hour. An aqueous solution of NaOH (7.33 g NaOH in 29.32 g water) is then added, and the biphasic mixture is heated to Tbain = 90 °C for another hour. The aqueous phase is then separated, while the organic phase is washed with brine (30 mL) and then with distilled water (2 x 30 mL). After separation and concentration under reduced pressure (Tbain = 50 °C, 25 mbar), a yellow-orange oil is obtained. The target product is isolated by silica column chromatography (230-400 mesh, 1 = 27 cm, d = 4.5 cm) by eluting with a mixture of ethyl acetate and petroleum ether (v / v, 1:1) without gradient.The fractions of interest are collected and concentrated under reduced pressure (Tbain = 40 °C, 5 mbar) to produce a transparent oil (4.606 g, 17.30 mmol). Yield: 47%, purity: 92% (H-NMR). NMR attribution (CDC13):

[0119] O.. ch2-ch3 2 1

[0120] [Tables2 Nê ô 'H (ppm) ô 13C (ppm) 1 1.31 14.7 2 3.90 63.5 3 / 160.7 4 6.04 94.4 5 / 160.2 6 6.04 94.0 7 3.81 and 4.11 68.7 3. Synthesis of compound B (2.2'-(((5-methoxy-1.3-phenylene)bis(oxy

[0121] ))bis(methylene))bis(oxirane))) O (B)

[0122]

[0123]

[0124] The synthesis of compound A is carried out in two steps from phloroglucinol. 3.1. Synthesis of compound Bl (5-methoxybenzene-L3-diol) HO. .OH HO. ,OH ■ Y MeOH, H2SO4 OH O . (B-1) The product (Bl) (5-methoxybenzene-l,3-diol, CAS 2174-64-3) is commercial or can be synthesized from phloroglucinol according to the procedure described in the article Angewandte Chemie, International Edition 2014, 53, 7832-7837. 3.2. Synthesis of compound B

[0125] (8-1) (B)

[0126] TMBAC (1.106 g, 5.92 mmol) is added to a mixture of 5-methoxybenzene-1,3-diol (compound Bl; 4.15 g, 29.6 mmol) and epichlorohydrin (82 g, 888 mmol). The reaction mixture is heated to Tbain = 90 °C for 1 hour. An aqueous solution of NaOH (5.92 g NaOH in 29.6 g water) is then added, and the resulting biphasic mixture is heated to Tbain = 90 °C for another hour. The aqueous phase is then separated, while the organic phase is washed with brine (30 mL) and then with distilled water (2 x 30 mL). After separation and concentration under reduced pressure (Tbain = 50 °C, 5 mbar), a yellow-orange oil is obtained. The target product is isolated by silica column chromatography (230-400 mesh, length 22 cm, diameter 4.5 cm) by eluting with a mixture of ethyl acetate and petroleum ether (v / v, 2:1) without gradient.The fractions of interest are collected and concentrated under reduced pressure (Tbain = 40 °C, 5 mbar) to produce a slightly yellowish oil. After 48 hours at room temperature, this oil partially crystallizes. A mixture of ethyl acetate and petroleum ether (v / v, 1:1, 10 mL, at 0 °C) is then added, and the resulting suspension is stirred at 1–3 °C for 10–12 minutes. The precipitate is filtered, washed with a mixture of ethyl acetate and petroleum ether (v / v, 1:1, 2 x 5 mL, at 0 °C), and air-dried. A white solid (0.467 g, 1.85 mmol) is obtained. Yield: 6%, melting point: 61–62 °C, purity: 96% (¹H NMR). NMR attribution (CDC13):

[0127]

[0128] [Tables 3 Nê ô 'H (ppm) ô 13C (ppm) 1 3.70 55.4 2 / 161.5 3 6.06 94.1 4 / 160.3 5 6.06 94.1 6 3.84 and 4.12 68.8 7 3.24-3.30 50.0 8 2.68 and 2.83 44.7

[0129] 4. Synthesis of compound C [3,3'-(((5-ethoxy-1,3-phenylene)bis(oxy )bis(methylene))bis(2,2-dimethyloxirane)1 (C)

[0130] The synthesis of compound C is carried out in two steps from phloroglucinol and compound (C-2) of the following formula: O (C-2)

[0131] The compound (C-2) can be prepared in two steps from isoprene.

[0132] 4.1. Synthesis of compound C-1 (l-bromo-3-methylbut-2-ene) Br21 AcOH 0°C, 48h (C-1)

[0133] The product Cl, l-bromo-3-methylbut-2-ene, CAS [870-63-3] is commercial or can be synthesized from isoprene according to the procedure described in the article Journal of the Chemical Society, Perkin Transactions I, 1985, 2307-2326.

[0134] 4,2, Synthesis of compound C-2 (3-(bromomethyl)-2,2-dimethyloxirane) MCPBA, DCM O Br (C-2)

[0135] The compound C-2, 3-(bromomethyl)-2,2-dimethyloxirane can be obtained according to the procedure described in the article Organic Process Research & Development 2005, 9, 278-287. NMR attribution (CDC13):

[0136] Br O CH-— ' ch3

[0137] 4 [Tables 4 Nê ô 'H (ppm) ô 13C (ppm) 1 3.13 and 3.37 29.6 2 2.94 62.0 3 / 60.1 4 1.17 and 1.21 18.0 and 24.3 4.3. Synthesis of compound Al (5-ethoxybenzene-L3-diol) XOH

[0138] "'Y ÊtOH <H2SO4 T O. OH (A-1)

[0139]

[0140]

[0141] The synthesis of compound Al from phloroglucinol is described in section 2.1 of the examples. 4.4. Synthesis of compound C ooo HO. ,OH xv । ,O. ...-Y. i , XyJ<C’2> Z 'W O. MeCN (A-1) (C) A solution of 5-ethoxybenzene-1,3-diol (compound Al; 0.848 g, 5.50 mmol) and 3-(bromomethyl)-2,2-dimethyloxirane (compound C-2; 2.179 g, 13.20 mmol) in anhydrous acetonitrile (30 mL) is degassed by bubbling with argon for 8–10 minutes. Potassium carbonate (2.281 g, 16.50 mmol) is then added in a single portion. Still under argon protection, the reaction mixture is refluxed for 8 hours. Once complete, inorganic salts are filtered and washed with acetone (2 × 10 mL). The permeate is concentrated under reduced pressure (Tbain = 40 °C, 10 mbar) to yield a brown oil. The target product is isolated by silica column chromatography (230-400 mesh, 1 = 20 cm, d = 1.5 cm) by eluting with a mixture of ethyl acetate and petroleum ether (v / v, 1:3) without a gradient. The fractions of interest are collected and concentrated under reduced pressure (Tbain = 40 °C, 5 mbar) to to obtain a colorless and transparent oil (0.671 g, 2.08 mmol). Yield: 38%, mass purity: greater than 90% (H-NMR). NMR attribution (CDC13): i ox ch?~ch3 2 1

[0143] [Tables 5 Nê ô 'H (ppm) ô 13C (ppm) 1 1.33 14.7 2 3.93 63.5 3 / 160.8 4 6.07 94.2 5 / 160.4 6 6.07 94.5 7 3.97 and 4.01 67.0 8 3.06 60.5 9 / 58.2 10 1.28 and 1.33 18.9 and 24.6

[0144] 5. Synthesis of compound D (2.2'-(((5-ethoxy-L3-phenylene)bis(oxy))bis(ethane- 2,l-diyl))bis(oxirane))

[0145] The synthesis of compound D is carried out in two steps starting from phloroglucinol and of the compound (Dl) with the following formula:

[0146] The compound (Dl) can be prepared in one step from 4-bromo-l-butene.

[0147] 5.1. Synthesis of compound Dl (l-bromo-3-methylbut-2-ene) Br MCPBA O. -------* R DCM (D-1)

[0148] The compound Dl, 2-(2-bromoethyl)oxirane, can be obtained according to the procedure described in the article Organic & Biomolecular Chemistry 2021,19, 8578-8585. NMR attribution (CDC13):

[0149]

[0150]

[0151]

[0152] The synthesis of compound Al from phloroglucinol is described in section 2.1 of the examples. 5.3. Synthesis of compound D o. K2CO3 MeCN O (A-1) 'D^

[0154] A solution of 5-ethoxybenzene-1,3-diol (compound Al; 1.00 g, 6.49 mmol) and 2-(2-bromoethyl)oxirane (compound Dl; 2.35 g, 15.58 mmol) in anhydrous acetonitrile (35 mL) is degassed by bubbling with argon for 8-10 minutes. Then, potassium carbonate (2.69 g, 19.47 mmol) is added in a single portion. Still under argon protection, the reaction mixture is refluxed for 8 hours. Once complete, inorganic salts are filtered and washed with acetone (2 x 12 mL). The permeate is concentrated under reduced pressure (Tbain = 40 °C, 10 mbar) to yield a brown oil. The target product is isolated by silica column chromatography (230–400 mesh, 23 cm length, 1.5 cm diameter) by eluting with a mixture of ethyl acetate and petroleum ether (v / v, 1:3) without a gradient. The fractions of interest are collected and concentrated under reduced pressure (Tbain = 40 °C, 5 mbar) to obtain a colorless and transparent oil (0.82 g, 2.79 mmol). Yield: 43%, mass purity: greater than 89% (¹H NMR). NMR attribution (CDC13): î %......CH^ 2 1

[0156] [Tables? Nê ô 'H (ppm) ô 13C (ppm) 1 1.32 14.7 2 3.91 63.5 3 / 160.6 4 6.05 94.1 5 / 160.3 6 6.05 94.3 7 4.03 64.6 8 1.94 and 2.10 32.4 9 3.09-3.15 49.6 10 2.45 and 2.70 47.0

[0157] 6. Synthesis of compound E ((L3.5-tris(2-(2-oxiran-2-yl)ethoxy)benzene) O

[0158] The synthesis of compound E is carried out in one step from phloroglucinol and compound (Dl). ... o, ,o.. ,.0,,,-.,.,0 HO. , ,OH 1 ' ' ' "Br v Tl "T "T NaH, DMF Ô . , ,. ,,O OH '

[0159] A solution of 2-(2-bromoethyl)oxirane (compound Dl; 0.838 g; 5.55 mmol) in anhydrous DMF (10 mL) is stirred at room temperature by bubbling with argon for 8–10 minutes. Phloroglucinol (0.2 g; 1.59 mmol) is added in one portion, and the reaction mixture is cooled to 0°C. Under argon protection, NaH (60% mineral oil dispersion; 0.213 g; 8.88 mmol) is added in several portions over 15 minutes. The resulting medium is stirred at 0°C for 30 minutes and at 80°C for an additional 5 hours. Once complete, the reaction mixture is mixed with distilled water (100 mL) and extracted with ethyl acetate (2 × 40 mL). The combined organic phases are concentrated under reduced pressure (Tbain = 33°C, 5 mbar) to produce a yellow-orange oil. The target product is isolated by silica column chromatography (1 = 25 cm, d = 2 cm) by eluting with a mixture of DCM and ethyl acetate (5:1, v / v).The fractions of interest are combined and evaporated again under reduced pressure (Tbain = 30°C, 5 mbar). A transparent oil (0.065 g; 0.19 mmol) is obtained. Yield 12%, purity: 93% (1H NMR). NMR attribution (CDC13):

[0161] [Tables8 Nê ô 'H (ppm) ô 13C (ppm) 1 2.53 and 2.78 46.9 2 3.09 49.5 3 1.92 and 2.08 32.2 4 4.03 64.5 5 / 160.7 6 6.08 94.2 7. Synthesis of compound F (1.3.5-tris((3-methyloxiran-2-yl)methoxy)benzene)

[0162]

[0163] The synthesis of compound F is carried out in two steps starting from phloroglucinol and compound (Fl) with the following formula:

[0164]

[0165] The compound (Fl) can be prepared in one step from 4-bromo-l-butene. 7.1. Synthesis of compound Fl (2-bromomethyl)-3-methyloxirane)

[0166] The compound Fl, (2-bromomethyl)-3-methyloxirane, can be obtained, for example, according to the procedure described in the article Tetrahedron Letters 2003, 44, 3075-3080. NMR attribution (CDC13):

[0167]

[0168] [Tables9 Nê ô 'H (ppm) ô 13C (ppm) 1 3.24 and 3.34 32.4 2 2.92 58.2 3 2.87 56.6 4 1.28 17.3 7.2. Synthesis of compound F

[0169] O. HO Br -------------------------------------->- T K2CO3. MeCN OH

[0170] A solution of phloroglucinol (1.01 g, 8.0 mmol) and 2-(bromomethyl)-3-methyloxirane (compound Fl; 4.59 g, 30.4 mmol) in anhydrous acetonitrile (40 mL) was degassed by bubbling argon for 10 minutes. Potassium carbonate (4.49 g, 32.5 mmol) was then added in a single portion. Still under argon protection, the reaction mixture was refluxed for 12 hours. Once this was complete, inorganic salts were filtered and washed with acetone (2 x 20 mL). The permeate was concentrated under reduced pressure (Tbain = 40°C, 5 mbar) to yield an orange-brown oil. The target product is isolated by silica column chromatography (230-400 mesh, 25 cm length, 1.5 cm diameter) by eluting with a mixture of ethyl acetate and petroleum ether (v / v, 1:3) without a gradient. The fractions of interest are collected and concentrated under reduced pressure (Tbain = 40°C, 5 mbar) to obtain a colorless and transparent oil (0.73 g, 2.17 mmol).Yield: 27%, purity: greater than 91% (H-NMR). NMR attribution (CDC13):

[0171]

[0172] [Tables 10] Nê ô 'H (ppm) ô 13C (ppm) 1 1.26 17.2 2 2.87 55.0 3 2.95 57.3 4 3.91 and 4.05 67.2 5 / 160.5 6 6.07 94.4 8. Evaluation of the properties of the compound (A)

[0173] The properties of compound (A) with respect to DGEBA were evaluated in thermosetting materials. Various amine derivatives (crosslinking agents) were combined with this new monomer to study its thermal properties in formulations and thus compare them to DGEBA-based formulations: • Priamine 1071 (pf < -30 °C, AHEW = 140 g / eq), • DICY (dicyandiamide) (mp = 208-211 °C, AHEW = 21 g / eq), • IPDA (isophorone diamine) (mp = 10 °C, AHEW = 42.575 g / eq).

[0174] The thermal properties protocol for formulation was carried out as follows.

[0175] The monomer was weighed with the corresponding diamine (1 equivalent with respect to the reactive functions). The mixture was dissolved in a DMSO:water mixture (% mass = 74:26) at a mass concentration between 10 and 12%. The DMSO was added to the mixture followed by the water. After homogenization, the mixture was then placed in a vacuum oven (5 mbar) with a slight nitrogen flow at 120 °C for 60 to 100 minutes (preheating step). A portion of the material obtained after preheating was taken to continue the second part of the reaction in the DSC (aluminum crucible with reaction temperature < decomposition temperature), under helium at 40 mL / min at 80 or 210 °C for 60 minutes. The glass transition temperature (Tg) of the material obtained is then measured by DSC, under helium at 40 mL / min, according to the following method: 1. Cooling from 25°C to -150°C at -50°C / min, 2. Isotherm at -150 °C for 18 min, 3. Heating from -150 °C to +250 °C at 50 °C / min, 4. Isotherm at -150 °C for 18 min, 5. Heating from -150 °C to +250 °C at 50 °C / min.

[0176] The Tg was measured on ramp no. 5.

[0177] Several tests were carried out by varying the monomer used, the crosslinking agent (the diamine) used, and certain reaction conditions. These tests are summarized in the table below.

[0178] [Tables II] Test 1 2 3 4 5 6 Monomer Compound (A) according to the invention DGEBA Diamine Priamine 1071 DICY IPDA Priamine 1071 DICY IPDA molar equivalent diamine molecule:monomer 1:2 1:2 Molar equivalent function (NH: epoxide) 1:1 1:1 Dispersion solvents (% mass:% mass) DMSO:Water = 74:26 C mass, reactants (%) 12.6 9.8 10.4 12 12 12 Preheating time (min) 100 60 Preheating temperature (°C) 120 120 Reaction time (min) 60 60 Reaction temperature (°C) 200 210 Tg (°C) 23 125 98 24 140 100

[0179] The glass transition temperature of materials prepared from compound (A) compared to those prepared from DGEBA is similar, regardless of the crosslinking agent (Priamine 1071, DICY, and IPDA). These results demonstrate that the use of the monomers according to the invention makes it possible to obtain thermosetting materials with properties equivalent to those obtained with a reference monomer such as DGEBA, without the drawback of being derived from bisphenol A, and thus exhibiting improved HSE properties for the precursor of compound (A). The variety of glass transition temperatures obtained makes it possible to consider the use of thermosetting materials derived from these monomers in all kinds of application fields.

Claims

1. Demands Compound of formula (I): Ri in which: - Ri and R3, being identical, denote a group with the following formula (II): X2 (II) in which - E represents a single bond or a divalent hydrocarbon group in CrCi2 possibly including one or more heteroatoms; - Xi, X2 and X3, whether identical or different, represent a hydrogen atom, a Ci-C6 alkyl group or a C6-Ci4 aryl group, and / or - Xi and X3 or X2, or a carbon atom from the divalent hydrocarbon group of E and X3 or X2 can be linked together, with the carbon atoms of the epoxide group, to form a C4 to C8 carbocycle or a heterocycle having 5 to 8 links; - the symbol (*) represents the point of attachment of group (II) to the rest of the compound of formula (I); R5 represents -O-X4. with X4 representing a Ci-Ci8 alkyl, a C6-Ci4 aryl, a C3-C7 cycloalkyl or a (C6-Ci4)aryl-(Ci-C6) alkyl; - R2, R4 and R6, whether identical or different, represent a hydrogen atom or an alkyl in C1-C24.

2. Compound according to claim 1, characterized in that R2, R4 and R6, identical or different, represent a hydrogen atom or an alkyl in CrCi2, preferably a hydrogen atom or an alkyl in Ci-C6, preferably a hydrogen atom or an alkyl in C1-C4, more preferably a hydrogen atom.

3. Compound according to claim 1 or 2, characterized in that E represents a divalent hydrocarbon group in C1-C12, in particular in C1-C10, in particular in Ci-C8, preferably in Ci-C6, preferably in C1-C4, typically in Ci or C2, optionally comprising one or more heteroatoms.

4. Compound according to any one of claims 1 to 3, characterized in that X4 represents a CrCi2 alkyl, a phenyl, a cyclohexyl or a phenyl-(Ci-C6)alkyl, preferably a Ci-C6 alkyl, a phenyl or a benzyl, preferably a C1-C4 alkyl, more preferably a methyl or an ethyl.

5. Compound according to any one of claims 1 to 4, characterized in that Xb X2 and X3, identical or different, represent a hydrogen atom or a Ci-C6 alkyl, preferably Xi represents a hydrogen atom and X2 and X3, identical or different, represent a hydrogen atom or a Ci-C6 alkyl, such as a methyl.

6. Composed according to any one of claims 1 to 5, chosen from the group consisting of (HAS) (C) , and their mixtures. (D)

7. A process for preparing a compound of formula (I) according to any one of claims 1 to 6, comprising a step b) of contacting the following compounds: - a compound of the following formula (1-2):

8. in which: Ry *4 (i-2) - R / and R3' of formula (1-2), denote a -OH group; - R5 represents -O-X4, with X4 representing a CrCi8 alkyl, a C6-Ci4 aryl, a C3-C7 cycloalkyl, or a (C6-Ci4)aryl-(Ci-C6)alkyl; and - R2, R4 and R6, whether identical or different, represent an atom of hydrogen or an alkyl in Ci-C24; - a compound of the following formula (II-l): X2 in which: O (11-1) - Y2 represents a function capable of reacting with an -OH group to form an ether bond; - E represents a single bond or divalent hydrocarbon group in CrCi2 possibly including one or more heteroatoms; - Xi, X2 and X3, whether identical or different, represent a hydrogen atom, a Ci-C6 alkyl group or a C6-Ci4 aryl group, and / or - Xi and X3 or X2, or a carbon atom from the divalent hydrocarbon group of E and X3 or X2 can be linked together, with the carbon atoms of the epoxide group, to form a C4 to C8 carbocycle or a heterocycle having 5 to 8 links. A process according to claim 7, further comprising a step a) preceding step b), step a) being a step of bringing the following compounds into contact: - a compound with the following formula (1-1) in which: - R / , R3' and R5' denote an -OH group, and - R2, R4 and R6, whether identical or different, represent an atom of hydrogen or a C1-C24 alkyl; - a Y1-X4 compound in which

9.

10.

11. - Y1 represents a function capable of reacting with a group -OH to form an ether bond, and - X4 representing a CrCi8 alkyl, a C6-Ci4 aryl, a C3-C7 cycloalkyl or a (C6-Ci4)aryl-(Ci-C6)alkyl. Use of a compound of formula (I) according to any one of claims 1 to 6 as a precursor of polymeric materials, in particular thermosetting materials, or as an adhesive. A process for preparing a thermosetting material comprising a step of polymerizing a compound of formula (I) according to any one of claims 1 to 6; optionally, the process further comprises a crosslinking step. Thermosetting material that can be obtained by the process according to claim 10.