Epoxide resin composition containing isosorbide epoxide and its use in stabilizing fibrous or porous materials

Abstract

The present invention provides a compound of formula (A) (I): [Formula 1] isosorbide epoxide of formula JPEG2023500516000009.jpg62128 (wherein n is an integer of 0 to 300); - (B) an epoxide having at least three epoxy functional groups; The present invention relates to a curable composition comprising the composition and a curing agent (D) selected from polyamines, and to an epoxy resin formed by crosslinking the crosslinkable mixture. The present invention also relates to a method for stabilizing a fibrous or porous material, comprising vacuum impregnation of the material with the curable composition, and to the use of isosorbide epoxide (A) in a curable composition to stabilize a fibrous or porous material.

Description

[Background technology]

[0001] The present invention relates to the field of epoxy resins, and more particularly to epoxy resins used to stabilize or reinforce fibrous or porous materials by impregnation.

[0002] The use of solid wood components generally involves dealing with wood deterioration: indeed, changes in temperature and humidity over time can cause the component to deform, discolor, or even fragment to the point where it becomes unusable.

[0003] It would therefore be necessary to be able to stabilize this solid wood in order to retain its appearance and shape over time.

[0004] The stabilization must be complete, pigmentable, and economically justifiable.

[0005] To impregnate solid components without causing any aesthetic problems, existing methods use harmful or even banned products such as creosote, which have not yet found an economical equivalent, or are surface impregnations that penetrate the wood only a few millimeters.

[0006] Wood used in flooring or building materials can be stabilized by heat treatment (torrefaction).

[0007] In arts and crafts (cutlery, jewellery, luxury items, archery, musical instruments, arms, etc.), stabilisation is carried out by autoclaving with unsaturated polyester or acrylic resins, the former of which poses problems due to the release of volatile organic compounds (VOCs), and the latter in terms of workability. Furthermore, the epoxides suitable for this type of process are based on bisphenol A (BPA), which should preferably be eliminated due to its toxicity.

[0008] Furfurylation methods are also used, but are limited to certain varieties and certain colors (brown).

[0009] There is therefore a need to be able to provide compositions that are capable of stabilizing fibrous or porous materials, in particular solid wood, completely to its core, without containing toxic products or products prone to emitting VOCs.

[0010] Following extensive research, the applicant has discovered that this objective can be achieved by means of an epoxy resin composition based on isosorbide epoxide.

[0011] Other features and advantages of the present invention will become apparent from the following detailed description. Summary of the Invention

[0012] A first object of the present invention relates to an epoxy prepolymer composition, the composition comprising: - (A) Formula (I): [ka] (wherein n is an integer of 0 to 300), containing isosorbide epoxide of (B) comprises an epoxide having at least two epoxy functional groups.

[0013] A second object of the present invention relates to a curable composition comprising the epoxy prepolymer composition of the present invention and a curing agent (D) chosen from polyamines.

[0014] A third object of the present invention relates to epoxy resins obtainable by polymerization of the curable compositions of the present invention.

[0015] A fourth object of the present invention relates to a method for stabilizing a fibrous or porous material comprising vacuum impregnation of said material with a curable composition according to the invention.

[0016] A fifth object of the present invention is to provide a compound of formula (I) in a curable composition for stabilizing fibrous or porous materials by vacuum impregnation: [ka] (wherein n is an integer of 0 to 300 as described above) The present invention relates to the use of isosorbide epoxide. DETAILED DESCRIPTION OF THE INVENTION

[0017] In this patent application, the expression "... to..." should be understood to include the boundary values.

[0018] The epoxy prepolymer composition of the present invention comprises: - (A) Formula (I): [ka] (wherein n is an integer of 0 to 300), containing isosorbide epoxide of (B) comprises an epoxide having at least two epoxy functional groups, in particular at least three epoxy functional groups.

[0019] In the present invention, the epoxy prepolymer composition has the following formula (I): [ka] (wherein n is an integer of 0 to 300, particularly 0 to 10, more particularly 0 to 5).

[0020] The epoxide (A) can be prepared according to the method described in application WO2015 / 110758A1.

[0021] Unlike bisphenol A, it has the advantage of being bio-derived and is not an endocrine disruptor.

[0022] By "isosorbide epoxide (A)" is intended to mean a single isosorbide epoxide of formula (I) or a mixture of different isosorbide epoxides in which the R substituent and / or the subscript n differ from one another. In the case of a mixture of different isosorbide epoxides, R varies as specified in formula (I) and / or n varies from 0 to 300, preferably from 0 to 10, and even more preferentially from 0 to 5.

[0023] The subscript n ranges from 0 to 300, and may specifically be equal to 290, 280, 270, 260, 250, 240, 230, 220, 210, 200, 190, 180, 170, 160, 150, 140, 130, 120, 110, 100, 90, 80, 70, 60, 50, 40, 30, 20, 10, 9, 8, 7, 6, 5, 4, 3, 2, or 1.

[0024] In one embodiment, the subscript n is between 0 and 290, between 0 and 280, between 0 and 270, between 0 and 260, between 0 and 250, between 0 and 240, between 0 and 230, between 0 and 220, between 0 and 210, between 0 and 200, between 0 and 190, between 0 and 180, between 0 and 170, between 0 and 160, between 0 and 150, between 0 and 140, between 0 and 130, between 0 and 120, between 0 and 110, between 0 and 100, between 0 and 90, between 0 and 80, between 0 and 70, between 0 and 60, between 0 and 50, between 0 and 40, between 0 and 30, between 0 and 20, between 0 and 10, between 0 and 9, between 0 and 8, between 0 and 7, between 0 and 6, between 0 and 5.

[0025] In one embodiment, the subscript n is from 1 to 290, from 1 to 280, from 1 to 270, from 1 to 260, from 1 to 250, from 1 to 240, from 1 to 230, from 1 to 220, from 1 to 210, from 1 to 200, from 1 to 190, from 1 to 180, from 1 to 170, from 1 to 160, from 1 to 150, from 1 to 140, from 1 to 130, from 1 to 120, from 1 to 110, from 1 to 100, from 1 to 90, from 1 to 80, from 1 to 70, from 1 to 60, from 1 to 50, from 1 to 40, from 1 to 30, from 1 to 20, from 1 to 10, from 1 to 9, from 1 to 8, from 1 to 7, from 1 to 6, from 1 to 5.

[0026] In one embodiment, the subscript n is from 2 to 290, from 2 to 280, from 2 to 270, from 2 to 260, from 2 to 250, from 2 to 240, from 2 to 230, from 2 to 220, from 2 to 210, from 2 to 200, from 2 to 190, from 2 to 180, from 2 to 170, from 2 to 160, from 2 to 150, from 2 to 140, from 2 to 130, from 2 to 120, from 2 to 110, from 2 to 100, from 2 to 90, from 2 to 80, from 2 to 70, from 2 to 60, from 2 to 50, from 2 to 40, from 2 to 30, from 2 to 20, from 2 to 10, from 2 to 9, from 2 to 8, from 2 to 7, from 2 to 6, or from 2 to 5.

[0027] In one embodiment, the subscript n is from 3 to 290, from 3 to 280, from 3 to 270, from 3 to 260, from 3 to 250, from 3 to 240, from 3 to 230, from 3 to 220, from 3 to 210, from 3 to 200, from 3 to 190, from 3 to 180, from 3 to 170, from 3 to 160, from 3 to 150, from 3 to 140, from 3 to 130, from 3 to 120, from 3 to 110, from 3 to 100, from 3 to 90, from 3 to 80, from 3 to 70, from 3 to 60, from 3 to 50, from 3 to 40, from 3 to 30, from 3 to 20, from 3 to 10, from 3 to 9, from 3 to 8, from 3 to 7, from 3 to 6, or from 3 to 5.

[0028] In one embodiment, the subscript n is from 4 to 290, from 4 to 280, from 4 to 270, from 4 to 260, from 4 to 250, from 4 to 240, from 4 to 230, from 4 to 220, from 4 to 210, from 4 to 200, from 4 to 190, from 4 to 180, from 4 to 170, from 4 to 160, from 4 to 150, from 4 to 140, from 4 to 130, from 4 to 120, from 4 to 110, from 4 to 100, from 4 to 90, from 4 to 80, from 4 to 70, from 4 to 60, from 4 to 50, from 4 to 40, from 4 to 30, from 4 to 20, from 4 to 10, from 4 to 9, from 4 to 8, from 4 to 7, from 4 to 6, or from 4 to 5.

[0029] In one embodiment, the subscript n is from 5 to 290, from 5 to 280, from 5 to 270, from 5 to 260, from 5 to 250, from 5 to 240, from 5 to 230, from 5 to 220, from 5 to 210, from 5 to 200, from 5 to 190, from 5 to 180, from 5 to 170, from 5 to 160, from 5 to 150, from 5 to 140, from 5 to 130, from 5 to 120, from 5 to 110, from 5 to 100, from 5 to 90, from 5 to 80, from 5 to 70, from 5 to 60, from 5 to 50, from 5 to 40, from 5 to 30, from 5 to 20, from 5 to 10, from 5 to 9, from 5 to 8, from 5 to 7, or from 5 to 6.

[0030] In one embodiment, the subscript n is 10 to 290, 10 to 280, 10 to 270, 10 to 260, 10 to 250, 10 to 240, 10 to 230, 10 to 220, 10 to 210, 10 to 200, 10 to 190, 10 to 180, 10 to 170, 10 to 160, 10 to 150, 10 to 140, 10 to 130, 10 to 120, 10 to 110, 10 to 100, 10 to 90, 10 to 80, 10 to 70, 10 to 60, 10 to 50, 10 to 40, 10 to 30, or 10 to 20.

[0031] The epoxide (A) typically has a viscosity of 500 mPa.s to 10,000 mPa.s, in particular 1,000 mPa.s to 8,000 mPa.s, more particularly 2,000 mPa.s to 6,000 mPa.s, and even more particularly 3,000 mPa.s to 5,000 mPa.s, measured at 25°C in a Brookfield viscometer.

[0032] By using a mixture of different isosorbide epoxides in the composition, it is possible to adjust in particular the mechanical properties of the composition.

[0033] The equivalent weight of the epoxide functional group in the isosorbide epoxide (A) is 120 to 1500 g / eq, particularly 150 to 300 g / eq, more particularly 160 to 250 g / eq. More specifically, the equivalent weight of the epoxide functional group in the isosorbide epoxide (A) is about 180 g / eq.

[0034] The proportion of epoxide (A) in the epoxy prepolymer composition is 15% to 75% by weight, in particular 15% to 60% by weight, more particularly 15% to 55% by weight, more particularly 15% to 50% by weight, and even more particularly 20% to 50% by weight, relative to the total weight of the composition.

[0035] In the present invention, the epoxy prepolymer composition comprises a second epoxide (B) having at least two epoxy functional groups, in particular at least three epoxy functional groups.

[0036] The epoxide (B) has the advantage of reducing the water uptake of the epoxy resin cured by polymerization with the curing agent.

[0037] It is chosen from polyglycidyl ethers, in particular diglycidyl ethers, triglycidyl ethers or tetraglycidyl ethers, more particularly triglycidyl ethers or tetraglycidyl ethers, more particularly triglycidyl ethers.

[0038] Epoxide (B) is advantageously chosen from trimethylolpropane triglycidyl ether, trimethylolethane triglycidyl ether, p-aminophenol triglycidyl ether, m-aminophenol triglycidyl ether, polyoxypropylene glycol triglycidyl ether, pentaerythritol tetraglycidyl ether, tetraglycidylmethylenedianiline, or sorbitol polyglycidyl ether. Preferably, epoxide (B) is trimethylolpropane triglycidyl ether.

[0039] The equivalent weight of the epoxide functional groups in epoxide (B) is 120 to 500 g / eq, in particular 130 to 350 g / eq, more particularly 140 to 250 g / eq, and even more particularly, the equivalent weight of the epoxide functional groups in epoxide (B) is about 160 g / eq.

[0040] The proportion of epoxide (B) in the epoxy prepolymer composition is 20% to 85% by weight, more specifically 25% to 80% by weight, more specifically 30% to 75% by weight, more specifically 35% to 70% by weight, more specifically 40% to 60% by weight, relative to the total weight of the composition.

[0041] The weight ratio of epoxide (A) to epoxide (B) is 0.3 to 1.0, in particular 0.3 to 0.8, more specifically 0.4 to 0.7, and even more specifically 0.5 to 0.6.

[0042] In certain embodiments, the epoxy prepolymer composition of the present invention further comprises a reactive diluent (C) selected from monoepoxides.

[0043] The viscosity of the epoxy prepolymer composition can be adjusted by adding the reactive diluent (C) to the epoxy resin composition of the present invention.

[0044] In a preferred embodiment, the viscosity of the epoxy prepolymer composition is less than 500 mPa.s, preferentially less than 400 mPa.s, more particularly less than 350 mPa.s at the temperature of impregnation of the wood.

[0045] Viscosity was measured from 0 to 200 seconds using an Anton Paar MCR501 instrument equipped with a CP25 cone plate. -1 The measurement can be carried out with a velocity gradient of

[0046] Examples of monoepoxides suitable as diluents in the present invention are monoglycidyl ethers. In particular, the reactive diluent (C) is selected, alone or in mixture, from alkyl glycidyl ethers, aryl glycidyl ethers, or carboxylic acid glycidyl ethers.

[0047] Examples of alkyl glycidyl ethers include n-butyl glycidyl ether, octyl glycidyl ether, decyl glycidyl ether, dodecyl glycidyl ether, tridecyl glycidyl ether, tetradecyl glycidyl ether, pentadecyl glycidyl ether, and also 2-ethylhexyl glycidyl ether.

[0048] Aryl glycidyl ethers include, for example, phenyl glycidyl ether, o-cresyl glycidyl ether, or 4-(tert-butyl)phenyl glycidyl ether.

[0049] An example of the carboxylic acid glycidyl ether is neodecanoic acid glycidyl ether.

[0050] In certain embodiments, the reactive diluent (C) is selected from a mixture of dodecyl glycidyl ether and tetradecyl glycidyl ether (C12-C14), a mixture of octyl glycidyl ether and decyl glycidyl ether (C8-C10), a mixture of tridecyl glycidyl ether and pentadecyl glycidyl ether (C13-C15), or a mixture of octyl glycidyl ether and tetradecyl glycidyl ether (C8-C14). Even more specifically, the reactive diluent (D) is a mixture of dodecyl glycidyl ether and tetradecyl glycidyl ether (C12-C14).

[0051] The proportion of the reactive diluent (C) in the epoxy resin composition is 0 to 10% by weight, in particular 2 to 8% by weight, more particularly 3 to 7% by weight, based on the total weight of the composition. More particularly, the proportion of the reactive diluent (C) in the epoxy resin composition is 5% by weight, based on the total weight of the composition.

[0052] The epoxy prepolymer compositions of the present invention may further comprise one or more additives such as dyes, especially pigments or soluble dyes, or catalysts of the Lewis acid, tertiary amine, or imidazole type.

[0053] In fact, as described below, the epoxy prepolymer composition of the present invention can be crosslinked (cured) by contacting it with a curing agent (D) to form an epoxy resin. Depending on the mixture of epoxy prepolymers, it may be necessary to add a catalyst to initiate or accelerate the polymerization reaction.

[0054] The epoxy prepolymer composition of the present invention can be prepared by simply mixing the components that make it up.

[0055] A second object of the present invention relates to a curable composition comprising the epoxy prepolymer composition of the present invention and a curing agent (D) chosen from polyamines.

[0056] "Curable composition" is intended to mean a liquid mixture that can be polymerized to form a crosslinked (cured) resin.

[0057] Thus, the function of the curing agent (D) is to react with the epoxides (A) and (B) and optionally the epoxide (C) of the epoxy prepolymer composition of the present invention to form a hardened epoxy resin by polymerization.

[0058] For the purposes of the present invention, "polyamine" is intended to mean compounds such as amines, amidoamines, polyamides, and polyetheramines having at least two amine functional groups.

[0059] Therefore, the curing agent (D) is linear aliphatic diamines such as 1,2-diaminomethane, 1,3-diaminopropane, butane-1,4-diamine, pentane-1,5-diamine, 1,6-diaminohexane, or 1,12-diaminododecane; cycloaliphatic diamines such as isophoronediamine (IPDA), 4,4'-diaminodicyclohexylmethane (PACM), 1,2-diaminocyclohexane (DACH), menthanediamine or 1,3-bis(aminomethyl)cyclohexane (1,3BAC), aromatic diamines such as 4,4'-methylenebis(2,6-diethylaniline) (MDEA), 4,4'-diaminodiphenyl sulfone (DDS), 9,9-bis(4-aminophenyl)fluorene (BAFL), diethyltoluenediamine (DETDA), dimethylthiotoluenediamine (DMTDA), 4,4'-methylenebis(2-ethylaniline) (MOEA), m-xylenediamine, m-phenylenediamine or 4,4'-diaminodiphenylmethane, - Triamines such as diethylenetriamine (DTA), - tetramines such as triethylenetetramine, - pentamines such as tetraethylenepentamine, - dimeric fatty acid diamines, such as Priamine® 1074 from Croda; polyetheramines such as poly(oxypropylene) diamine (Jeffamine® D-230 from Huntsman Petrochemical LLC) or poly(oxypropylene) triamine (Jeffamine® T-403 from Huntsman Petrochemical LLC), or any other polyamine, such as polyethyleneimine (for example Lupasol® FG from BASF), dipropenediamine, diethylaminopropylamine, N-aminoethylpiperazine, dicyandiamide (Dicy), - or mixtures thereof.

[0060] In a particular embodiment, the curing agent (D) is selected from poly(di- or tri-)etheramines such as Jeffamine® from Huntsman, for example Jeffamine D-230 or Jeffamine T-403, or mixtures thereof.

[0061] The epoxy / amine systems formed by the curable compositions of the present invention may be stoichiometric or may contain an excess of amine functionality or an excess of epoxy functionality.

[0062] Thus, the ratio of the number of -NH groups of the curing agent (D) to the number of epoxy groups of the epoxy prepolymer composition is 1:2 to 2:1, in particular 2:3 to 3:2, more particularly equal to 1:1 (stoichiometric mixture).

[0063] Another object of the present invention is the epoxy resin obtained by polymerization of the curable composition of the present invention.

[0064] Polymerization may be spontaneously initiated or may actually require heat or the presence of a catalyst in the curable composition.

[0065] Another object of the present invention is a method for stabilizing a fibrous or porous material comprising vacuum impregnation of said material with a curable composition comprising the epoxy prepolymer composition of the invention as described above and a curing agent (D) as described above.

[0066] Some curing agents (D) can react directly at ambient temperature, in which case the curable composition is formed just before impregnation, preferably under a vacuum pressure cycle.

[0067] The method of the present invention allows the material to retain its appearance and resist deformation over time.

[0068] The method of the present invention also allows the material to be densified, thereby increasing its mechanical strength.

[0069] To completely impregnate the material, ie, throughout the entire substance, the material is preferably impregnated by submerging it in a bath of the curable composition.

[0070] In the method of the present invention, the material is treated in one or more cycles, each cycle alternating between vacuum and pressure phases.

[0071] The cycle is advantageously carried out in an autoclave.

[0072] During the vacuum phase, the medium is subjected to a pressure below atmospheric pressure, in particular in the range of 0.01 bar to 0.9 bar, for a time t1. The negative pressure thus created makes it possible to remove all or part of the air or water contained in the spaces present in the material (degassing), allowing the material to absorb the curable composition inside.

[0073] The vacuum phase is followed by a pressure phase at a pressure ranging from 2 bar to 30 bar for a time t2. The applied pressure allows the composition to penetrate into the spaces within the material, even to its deepest parts, thus ensuring good diffusion of the composition into the core of the wood.

[0074] The cycle is carried out at temperatures ranging from 20°C to 80°C.

[0075] Depending on the properties of the material, times t1 and t2 vary, but generally, they range independently from 5 seconds to 1 hour, in particular from 1 minute to 30 minutes, in particular from 5 minutes to 20 minutes.

[0076] The pressure applied will also vary depending on the properties of the material being processed.

[0077] In one embodiment, the temperature at which the cycles are carried out is increased with each successive cycle.

[0078] For example, the first cycle may be carried out at about 30°C, followed by a second cycle at 45°C, followed by a third cycle at 60°C.

[0079] The time required for polymerization of the curable composition must be longer than the time required to carry out the impregnation under vacuum of the fibrous or porous material.

[0080] In practice, the polymerization time of the curable composition of the present invention is 3 to 6 hours, particularly 4 to 5 hours.

[0081] The fibrous or porous materials that can be stabilized by the curable composition of the present invention are not particularly limited. - wood such as birch, poplar, beech, elm, ash, maple, laurel, horse chestnut, palm, raffia or oak, - Animal horns such as sheep, blesbok, buffalo, impala, kudu, springbok, zebu or wildebeest horns; - animal bones, in particular those of ostriches, camels, giraffes, kudus, zebras, zebu cattle or mammoths; - deer antlers, in particular those of red deer or sambar deer or roe deer; - selected from animal teeth or tusks, in particular ivory, in particular mammoth ivory or teeth;

[0082] The porous material is selected from inorganic materials, in particular natural inorganic materials such as pearl or coral, or composite materials.

[0083] The method of the present invention can be used to stabilize a variety of materials made from fibrous or porous materials, such as, for example, all or part of a musical instrument or knife handle.

[0084] Another object of the present invention is to provide a curable composition for stabilizing fibrous or porous materials by vacuum impregnation. Formula (I): [ka] (wherein n is an integer of 0 to 300 as described above) is used.

[0085] Stabilization allows, among other things, the material to retain its appearance and to reduce deformation of the material over time.

[0086] Stabilization also has the effect of densifying the material and thereby increasing its mechanical strength. [Example]

[0087] Stabilization of beech wood:

[0088] 5 kg of beech wood with the following composition by weight: - 40% epoxidized isosorbide having a viscosity equal to 4500 mPa.s at 25 ° C in a Brookfield viscometer, - 55% trimethylolpropane triglycidyl ether (TMPTE), and - submerged in a vessel containing 8 L of a curable composition of the present invention having 5% of a C12-C14 fatty chain epoxy diluent; Jeffamine® hardener was added to it in different amounts depending on the type of hardener: - Jeffamine® D-230, 34 phr / epoxy resin; - Jeffamine® T-403, 47 phr / epoxy resin; "phr" means "per hundred parts resin").

[0089] The container containing the resin and wood is brought to 30°C in an autoclave.

[0090] After reaching temperature, a vacuum of 0.2 bar is applied for 15 minutes, followed by a pressure of 12 bar for 5 minutes.

[0091] This pressure-vacuum cycle is repeated two more times at 45°C and then 60°C.

[0092] The density of wood treated in this way increased by an average of 8% compared to treatment with the epoxide resin DER332, and the torsional modulus (fiber matrix interlocking) increased by an average of 9.2% compared to treatment with the epoxide resin and 16.4% compared to treatment with the isophthalic polyester compound Polynt1133 (Cray Valley).

Claims

1. 1. An epoxy prepolymer composition comprising: (A) Formula (I): 【Chemical 1】 wherein n is an integer from 0 to 300; (B) an epoxide having at least three epoxy functional groups, The composition, wherein the epoxide (B) is selected from trimethylolpropane triglycidyl ether, trimethylolethane triglycidyl ether, p-aminophenol triglycidyl ether, m-aminophenol triglycidyl ether, polyoxypropylene triol triglycidyl ether, pentaerythritol tetraglycidyl ether, tetraglycidylmethylenedianiline, and sorbitol polyglycidyl ether.

2. 2. The composition according to claim 1, wherein the equivalent weight of the epoxide functional group in the isosorbide epoxide (A) is 120 to 1500 g / eq.

3. The ratio of isosorbide epoxide (A) in the epoxy prepolymer composition is 3. The composition according to claim 1, wherein the amount of the active ingredient is from 15% to 75% by weight relative to the total weight of the composition.

4. 4. The composition according to claim 1, wherein the isosorbide epoxide (A) has a viscosity of 500 mPa s to 10,000 mPa s measured at 25°C with a Brookfield viscometer.

5. 5. The composition according to claim 1, wherein the epoxide (B) is trimethylolpropane triglycidyl ether.

6. 6. The composition according to claim 1, wherein the equivalent weight of epoxide functional groups in the epoxide (B) is from 120 to 500 g / eq.

7. 7. The composition according to claim 1, wherein the proportion of epoxide (B) in the epoxy prepolymer composition is between 20% and 85% by weight relative to the total weight of the composition.

8. 8. Composition according to claim 1, characterized in that the weight ratio of isosorbide epoxide (A) to epoxide (B) is between 0.3 and 1.

0.

9. The composition according to any one of claims 1 to 8, characterized in that it further comprises a reactive diluent (C) chosen from monoepoxides.

10. 10. The composition of claim 9, wherein the reactive diluent (C) is selected from alkyl glycidyl ethers, aryl glycidyl ethers, or carboxylic acid glycidyl ethers.

11. 11. The composition according to claim 9 or 10, characterized in that the proportion of the reactive diluent (C) in the epoxy prepolymer composition is 2% by weight to 8% by weight relative to the total weight of the composition.

12. 12. The composition according to any one of claims 1 to 11, characterized in that the composition further comprises one or more additives selected from pigments, soluble dyes, Lewis acids, tertiary amines, and imidazole type catalysts.

13. A curable composition comprising the epoxy prepolymer composition of any one of claims 1 to 12 and a curing agent (D) selected from polyamines.

14. The curing agent (D) - linear aliphatic diamines, - cycloaliphatic diamines, aromatic diamines, - triamines, - tetramines, - pentamines, - dimeric fatty acid diamines, - polyetheramines, polyethyleneimine, dipropenediamine, diethylaminopropylamine, N-aminoethylpiperazine or dicyandiamide, - or mixtures thereof The curable composition according to claim 13, characterized in that it is selected from

15. The curable composition according to claim 13 or 14, characterized in that the ratio of the number of -NH groups of the curing agent (D) to the number of epoxy groups of the epoxy prepolymer composition is 1:2 to 2:

1.

16. An epoxy resin obtained by polymerization of the curable composition according to any one of claims 13 to 15.

17. A method for stabilizing a fibrous or porous material comprising vacuum impregnation of the material with a curable composition according to any one of claims 13 to 15.

18. 18. The stabilization method of claim 17, wherein the impregnation is performed by immersing the material in a bath of the curable composition.

19. 19. A stabilization method according to claim 17 or 18, characterized in that the material is treated in one or more cycles, each cycle alternating between vacuum and pressure phases.

20. 20. The stabilization method according to any one of claims 17 to 19, characterized in that the impregnation under vacuum is carried out at a temperature ranging from 20°C to 80°C.

21. The vacuum phase is t １ The pressure phase is carried out by exposing the mixture to a pressure in the range of 0.01 to 0.9 bar for a period of time of t ２ 21. The stabilization method according to any one of claims 17 to 20, characterized in that it is carried out at a pressure in the range of 2 to 30 bar for a period of time.

22. The time t １ and t ２ 22. The stabilization method according to claim 21, wherein, independently of one another, the time periods are in the range of 5 seconds to 1 hour.

23. 20. The method of claim 19, wherein the temperature at which the cycles are carried out is increased with each successive cycle.

24. 20. The method of claim 19, wherein the first cycle is carried out at 30°C, the second cycle at 45°C, and the third cycle at 60°C.

25. The fibrous material is - wood, - Animal horns, - Animal bones, - deer antlers, - Animal teeth or tusks, The stabilization method according to any one of claims 17 to 24, characterized in that the compound is selected from the group consisting of:

26. The stabilization method according to any one of claims 17 to 25, characterized in that the porous material is selected from inorganic materials or composite materials.

27. A stabilization method according to any one of claims 17 to 26, characterized in that the fibrous or porous material is selected from the following objects: all or part of a musical instrument or a knife handle.

28. Use of the epoxy prepolymer composition according to any one of claims 1 to 12 in a curable composition for stabilising fibrous or porous materials by impregnation under vacuum.

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