Method for preparing thermosetting resin containing gamma ray irradiation sensitive groups

Abstract

The present invention discloses a method for preparing a thermosetting resin containing gamma-ray sensitive groups. The method comprises the following steps: Step 1: dissolving a monomer A containing two hydrazide groups, a monomer B containing two aldehyde groups or ketone groups, and a monomer C containing three aldehyde groups or ketone groups in a solvent; Step 2: uniformly mixing the solutions containing monomers A and B and reacting them to generate a linear prepolymer; Step 3: adding a solution of monomer C to the linear prepolymer and continuing the reaction; Step 4: pouring the reactants into a polytetrafluoroethylene mold, curing them, and vacuum drying them to obtain a thermosetting resin containing gamma-ray sensitive groups. The thermosetting resin prepared by this method can be rapidly cured at a suitable temperature, and the obtained thermosetting resin and a composite material prepared using the thermosetting resin as a matrix can be rapidly degraded under gamma-ray irradiation conditions, which has great economic and environmental advantages for the recycling and reuse of thermosetting resin-based composite materials.

Description

Technical Field

[0001] The present invention relates to a method for preparing a degradable and recyclable thermosetting resin, in particular to a method for preparing a thermosetting resin containing gamma ray radiation sensitive groups. Background Art

[0002] Advanced thermosetting resin-based composites, with their exceptional properties such as high modulus, high strength, high temperature resistance, and impact resistance, have led to their widespread application in a wide range of fields, including aerospace, wind power generation, and transportation. However, thermosetting resins, with their three-dimensional cross-linked network structure, are difficult to reprocess and reuse. The environmental pollution caused by waste thermosetting resins and the recycling of valuable, high-performance reinforcements in thermosetting resin composites are key challenges facing the industry. To date, the main industrial treatment methods for waste thermosetting resins include energy recovery, physical crushing, and chemical recycling. However, these traditional recycling methods fail to produce high-performance, structurally intact recycled fibers and other reinforcements, significantly reducing their commercial value. Researchers have engineered thermosetting resins using dynamic covalent bonds, exploiting the cleavage of these bonds in response to stimuli such as light, heat, and pH, to achieve degradation. However, the introduction of dynamic covalent bonds can significantly alter the mechanical and thermal properties of thermosetting resins, severely limiting their application. Therefore, the development of thermosetting resins with high strength, high modulus, and efficient degradation remains a pressing goal. Summary of the Invention

[0003] To address the above technical issues, the present invention provides a method for preparing a thermosetting resin containing gamma-ray-sensitive groups. The thermosetting resin prepared by this method can rapidly cure at a suitable temperature. The resulting thermosetting resin, as well as composite materials prepared using this thermosetting resin as a matrix, can rapidly degrade under gamma-ray irradiation conditions, offering significant economic and environmental advantages for the recycling and reuse of thermosetting resin-based composite materials.

[0004] The purpose of the present invention is achieved through the following technical solutions:

[0005] A method for preparing a thermosetting resin containing gamma ray radiation sensitive groups comprises the following steps:

[0006] Step 1: Dissolve monomer A containing two hydrazide groups, monomer B containing two aldehyde groups or ketone groups, and monomer C containing three aldehyde groups or ketone groups in a solvent respectively, wherein:

[0007] The monomer A is a dihydrazide compound, and the general molecular structure is as follows:

[0008]

[0009] wherein R1 is one of an alkyl group, a cycloalkyl group, a heterocyclyl group, a heterocycloalkyl group, an alkenyl group, a cycloalkenyl group, an aromatic group, a heteroaromatic group, an alkynyl group, an alkylene group, an alkylene heteroalkylene group, an alkenyl group, an alkylene heteroalkenylene group, an alkynylene group, or an alkylene heteroalkynylene group, preferably a methyl group; further, monomer A is one or more of isophthalic acid dihydrazide, terephthalic acid dihydrazide, adipic acid dihydrazide, succinic acid dihydrazide, and oxalohydrazide;

[0010] The monomer B is a dialdehyde or ketone compound, and the general molecular structure is as follows:

[0011]

[0012] wherein R2 is one of an alkyl group, a cycloalkyl group, a heterocyclic group, a heterocycloalkyl group, an alkenyl group, a cycloalkenyl group, an aromatic group, a heteroaromatic group, an alkane heteroalkyl group, an alkynyl group, an alkylene group, an alkylene heteroalkylene group, an alkenyl group, an alkylene heteroalkenylene group, an alkynyl group or an alkylene heteroalkynylene group, preferably a methyl group; R3 is one of a hydrogen atom, an alkyl group, a cycloalkyl group, a heterocyclic group, a heterocycloalkyl group, an alkenyl group, a cycloalkenyl group, an aromatic group, a heteroaromatic group, an alkane heteroalkyl group, an alkynyl group, an alkylene group, an alkylene heteroalkylene group, an alkenyl group, an alkylene heteroalkenylene group, an alkynyl group or an alkylene heteroalkynylene group, preferably a hydrogen atom; further, monomer B is terephthalaldehyde, o-phthalaldehyde, glyoxal , succinic dialdehyde, glutaraldehyde, divanillin-dimethylsilane, divanillin-phenyl phosphate, di-o-vanillin-dimethylsilane, di-o-vanillin-phenyl phosphate, divanillon-dimethylsilane, divanillon-phenyl phosphate or more; further, monomer B is terephthalaldehyde, o-phthalaldehyde, glyoxal, succinic dialdehyde, glutaraldehyde, divanillin-dimethylsilane, divanillin-phenyl phosphate, di-o-vanillin-dimethylsilane, di-o-vanillin-phenyl phosphate, divanillon-dimethylsilane, divanillon-phenyl phosphate or one or more;

[0013] The monomer C is a trialdehyde or ketone compound, and the general molecular structure is as follows:

[0014]

[0015] In the formula, R4 is one of cycloalkyl, heterocyclyl, heterocycloalkyl, alkenyl, cycloalkenyl, aromatic, heteroaromatic, preferably aromatic; R5 is one of hydrogen, alkyl, cycloalkyl, heterocyclyl, heterocycloalkyl, alkenyl, cycloalkenyl, aromatic, heteroaromatic, alkaneheteroalkyl, alkynyl, alkylene, alkyleneheteroalkylene, alkenylene, alkyleneheteroalkenylene, alkynylene or alkyleneheteroalkynylene, preferably hydrogen; further, monomer C It is one or more of trimesicaldehyde, biphenyl trimesicaldehyde, trimesicaldehyde, tri-o-vanillin phosphate, 2,4,6-tri-o-vanillin-1,3,5-triazine, tri-vanillin phosphate, 2,4,6-tri-o-vanillin-1,3,5-triazine, tri-o-vanillone phosphate, 2,4,6-tri-o-vanillonyl-1,3,5-triazine, tri-vanillone phosphate, 2,4,6-tri-o-vanillonyl-1,3,5-triazine, etc.;

[0016] The solvent is one or more of water, carbon tetrachloride, benzene, toluene, xylene, dichloromethane, carbon tetrachloride, methanol, ethanol, ethylene glycol, ethyl acetate, ether, petroleum ether, tetrahydrofuran, chloroform, dioxane, pyridine, acetone, acetonitrile, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, and dimethyl sulfoxide;

[0017] Step 2: uniformly mixing the solution containing monomer A and monomer B and reacting them at 0-200° C. for 2-12 hours to generate a linear prepolymer;

[0018] Step 3: Add the solution of monomer C to the linear prepolymer and continue to react at 0-200°C for 2-16 hours, wherein:

[0019] The molar number of the monomer A is the sum of the molar number of the monomer B and 1.5 times the molar number of the monomer C, and the molar ratio of the monomer B to the monomer C is 0:1 to 10:1;

[0020] The monomer A undergoes an amine-aldehyde condensation reaction with the monomer B and the monomer C in a solvent to synthesize a thermosetting resin containing a gamma-ray sensitive group;

[0021] Step 4: Pour the reactants into a polytetrafluoroethylene mold, solidify them, and vacuum dry them to obtain a thermosetting resin containing gamma-ray sensitive groups, wherein:

[0022] The vacuum drying temperature is 0-200° C., and the time is 8-24 hours.

[0023] The thermosetting resin containing gamma ray radiation sensitive groups contains the following breakable cross-linking structure:

[0024]

[0025] The thermosetting resin containing gamma ray radiation sensitive groups can be used as a matrix to prepare a degradable thermosetting resin composite material. The composite material is prepared from the thermosetting resin containing gamma ray radiation sensitive groups and a reinforcement. The specific preparation method is as follows:

[0026] Step 1: dissolving a monomer A containing two hydrazide groups, a monomer B containing two aldehyde groups or ketone groups, and a monomer C containing three aldehyde groups or ketone groups in a solvent respectively;

[0027] Step 2: Evenly mix the solution containing monomer A, monomer B and monomer C;

[0028] The molar number of the monomer A is the sum of the molar number of the monomer B and 1.5 times the molar number of the monomer C, and the molar ratio of the monomer B to the monomer C is 0:1 to 10:1;

[0029] Step 3: Place the mixed solution and reinforcement into a mold and solidify them by compression molding to obtain a thermosetting resin-based composite material containing gamma-ray sensitive groups, wherein:

[0030] The reinforcement comprises at least one of carbon fiber, glass fiber, natural fiber, chemical fiber and fabric made of fiber material, nano carbon material, boron nitride nano material, metal nano particles, metal oxide nano particles and organic nano particles;

[0031] The curing temperature is 0-200° C., the pressure is 0.1-10 MPa, and the curing time is 2-12 hours.

[0032] A method for degrading the thermosetting resin containing gamma-ray sensitive groups and the degradable thermosetting resin composite material comprises the following steps:

[0033] At room temperature, use 60 Coγ-rays are used as a radiation source to irradiate and degrade thermosetting resins and degradable thermosetting resin composites in a solvent, wherein:

[0034] The irradiation dose is 10 to 1000 KGy, and the irradiation dose rate is 500 Gy / h to 20 KGy / h;

[0035] The solvent is at least one of water, isopentane, n-pentane, petroleum ether, hexane, cyclohexane, cyclopentane, heptane, carbon tetrachloride, benzene, toluene, xylene, chlorobenzene, o-dichlorobenzene, dichloromethane, carbon tetrachloride, methanol, ethanol, ethylene glycol, propanol, isopropanol, butanol, isobutanol, tert-butanol, amyl alcohol, benzyl alcohol, ethyl acetate, ether, petroleum ether, isopropyl ether, tetrahydrofuran, chloroform, dioxane, pyridine, acetone, acetonitrile, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, and dimethyl sulfoxide.

[0036] Compared with the prior art, the present invention has the following advantages:

[0037] 1. The present invention provides a method for preparing a thermosetting resin containing gamma-ray-sensitive groups and a thermosetting resin composite thereof. These thermosetting resins and thermosetting resin composites exhibit excellent performance and can be efficiently degraded by gamma-ray irradiation, which is energy-efficient, cost-effective, and energy-efficient. Gamma rays possess exceptional penetrating power, triggering the rupture of sensitive bonds both on the surface and within the material. Gamma-ray irradiation offers greater degradation efficiency, making it particularly suitable for degrading complex and large thermosetting polymers. These rays, composed of electromagnetic waves of the highest frequency, deliver photon energies ranging from 1 keV to 8 MeV, capable of breaking all chemical bonds and simultaneously inducing polymer degradation and recrosslinking. Therefore, gamma-rays generally only cause degradation of polymer properties without inducing a controllable degradation process. The conjugated C=N structure introduced by the present invention stabilizes the free radicals generated by the rupture of N—N or N—O bonds, thereby preventing recrosslinking reactions and making the degradation process controllable, achieving the desired degradation of epoxy resins.

[0038] 2. The thermosetting resin containing gamma-irradiation-sensitive groups prepared by the present invention is applied to thermosetting resin-based fiber-reinforced composite materials. Under gamma ray irradiation, the thermosetting resin matrix in the fiber-reinforced composite material is degraded into linear polymers with low molecular weight. These polymers are soluble in organic solvents. A simple separation process can separate the thermosetting resin matrix from the fibers, thereby achieving the purpose of recovering and reusing the fiber reinforcement. Because low-dose gamma ray irradiation has little effect on the strength of the fiber reinforcement, the recovered fiber reinforcement maintains excellent structure, performance, and order.

[0039] 3. After testing, the tensile strength of the thermosetting resin containing gamma-ray sensitive groups prepared by the present invention reaches 30-90 MPa, the flexural strength reaches 50-120 MPa, the Tg reaches above 80-150°C, and the degradation rate of the degradable thermosetting epoxy resin reaches 100%. DETAILED DESCRIPTION

[0040] The technical solution of the present invention is further described below with reference to the embodiments, but is not limited thereto. Any modification or equivalent replacement of the technical solution of the present invention that does not depart from the spirit and scope of the technical solution of the present invention should be included in the scope of protection of the present invention.

[0041] Example 1: Preparation of Thermosetting Resin I Containing Gamma-Ray Radiation-Sensitive Groups

[0042] 4.355 g of adipic acid dihydrazide (25 mmol) was dissolved in 10 mL of ethanol, mixed and magnetically stirred at 25°C for 10 minutes, then 10 mL of an ethanol solution containing 1.341 g of terephthalaldehyde (10 mmol) was added. The reaction was continued with magnetic stirring for 2 hours, yielding a linear prepolymer with high viscosity. 10 mL of ethanol containing 5.011 g of trivanillin phosphate (10 mmol) was added to the reactor as a crosslinker. The prepolymer was poured into a polytetrafluoroethylene mold and allowed to react at 80°C for 16 hours. After curing, the mixture was vacuum-dried at 80°C for 12 hours to yield thermosetting resin I containing γ-ray sensitive groups. Its properties are shown in Table 1.

[0043] Example 2: Preparation of Thermosetting Resin II Containing γ-Ray Radiation Sensitive Groups

[0044] 11.323 g of adipic acid dihydrazide (65 mmol) was dissolved in 10 mL of ethanol, mixed and magnetically stirred at 25°C for 10 minutes, then 10 mL of an ethanol solution containing 6.707 g of terephthalaldehyde (50 mmol) was added. The reaction was continued with magnetic stirring for 2 hours, yielding a linear prepolymer with high viscosity. 10 mL of ethanol containing 5.011 g of trivanillin phosphate (10 mmol) was added to the reactor as a crosslinker. The mixture was poured into a polytetrafluoroethylene mold and the reaction continued at room temperature for 16 hours. After curing, the mixture was vacuum-dried at 80°C for 12 hours to yield thermosetting resin II containing γ-ray sensitive groups. Its properties are shown in Table 1.

[0045] Table 1

[0046] Example 1 Example 2 <![CDATA[T g (℃)]]> 132 121 <![CDATA[T d5％ (℃)]]> 324 312 Tensile strength (MPa) 83 76 Tensile elastic modulus (GPa) 3.2 2.3 Flexural strength (MPa) 123 119 Flexural modulus (GPa) 3.6 2.9 Elongation at break (%) 3.9 3.2

[0047] Example 3: Preparation of Thermosetting Resin III Containing γ-Ray Radiation Sensitive Groups

[0048] 12.622 g of isophthalic acid hydrazide (65 mmol) was dissolved in 10 mL of ethanol, mixed and magnetically stirred at 25°C for 10 minutes, then 10 mL of an ethanol solution containing 6.707 g of terephthalaldehyde (50 mmol) was added. The reaction was continued with magnetic stirring for 2 hours. A linear prepolymer with high viscosity was obtained after the reaction. 10 mL of ethanol containing 5.432 g of trivanillyl phosphate (10 mmol) was added to the reactor as a crosslinker. The mixture was poured into a polytetrafluoroethylene mold and the reaction continued at room temperature for 16 hours. After curing, the mixture was vacuum dried at 80°C for 12 hours to obtain thermosetting resin III containing gamma-ray sensitive groups.

[0049] Example 4: γ-ray irradiation of thermosetting resin I containing γ-ray sensitive groups

[0050] At room temperature, 1 g of the thermosetting resin I prepared in Example 1 was placed in a 50 mL glass bottle containing DMSO solvent. 60 Coγ-ray irradiation can completely degrade the product after 150KGy irradiation, and a clear and transparent yellow solution is obtained, with a degradation rate of 100%.

[0051] Example 5: γ-ray irradiation of thermosetting resin II containing γ-ray sensitive groups

[0052] At room temperature, 1 g of the thermosetting resin II prepared in Example 2 was placed in a 50 mL glass bottle containing DMSO solvent. 60 Coγ-ray irradiation can completely degrade the product after 120KGy irradiation, and a clear and transparent yellow solution is obtained, with a degradation rate of 100%.

[0053] Example 6: Preparation of γ-ray irradiation recyclable carbon fiber reinforced epoxy resin based composite material plate I

[0054] The preparation of carbon fiber-reinforced epoxy resin-based composite sheet I consists of two steps: prepreg preparation and compression molding. The first step involves prepolymer solution impregnation, where the resin content in the prepolymer is adjusted by the prepolymer concentration and the size of the carbon fibers. The second step is accomplished using hand lay-up and compression molding techniques. First, 4.355g of adipic acid dihydrazide (25mmol), 1.340g of terephthalaldehyde (10mmol), and 5.011g of trivanillin phosphate (10mmol) are completely dissolved in 5mL of DMSO solution. The mixture is then poured into a mold covered with carbon fiber cloth and allowed to soak at room temperature for 30 minutes. The prepreg is then heated to 40°C and precured for 2 hours to obtain the carbon fiber prepreg. The carbon fiber prepreg is then placed on a flat hot press and cured at 10MPa and 80°C for 2 hours. After cooling naturally to room temperature, the carbon fiber-reinforced epoxy resin-based composite sheet I is obtained.

[0055] Example 7: Gamma-ray irradiation recovery of carbon fiber reinforced epoxy resin based composite material plate 1

[0056] At room temperature, 5 g of the carbon fiber reinforced epoxy resin-based composite material plate 1 prepared in Example 6 was placed in a 50 mL glass bottle filled with DMSO solvent. 60 After irradiation with Coγ-rays at 320 kGy, the epoxy resin matrix was separated from the composite material, yielding a clear, transparent yellow solution. The carbon fiber bundles were removed, and the surface weave structure of the recycled fibers remained well-maintained, allowing for near-complete recovery of the carbon fibers at a recovery rate of 98%.

Claims

1. A method for preparing a thermosetting resin containing gamma ray sensitive groups, characterized in that The method comprises the following steps: Step 1: Dissolve monomer A containing two hydrazide groups, monomer B containing two aldehyde groups or ketone groups, and monomer C containing three aldehyde groups or ketone groups in a solvent respectively, wherein: The monomer A is a dihydrazide compound, and the general molecular structure is as follows: wherein R1 is one of alkyl, cycloalkyl, heterocyclyl, heterocycloalkyl, alkenyl, cycloalkenyl, aromatic, heteroaromatic, alkynyl, alkylene, alkyleneheteroalkylene, alkenylene, alkyleneheteroalkenylene, alkynylene, or alkyleneheteroalkynylene; The monomer B is a dialdehyde or ketone compound, and the general molecular structure is as follows: wherein R2 is one of an alkyl group, a cycloalkyl group, a heterocyclic group, a heterocycloalkyl group, an alkenyl group, a cycloalkenyl group, an aromatic group, a heteroaromatic group, an alkane heteroalkyl group, an alkynyl group, an alkylene group, an alkylene heteroalkylene group, an alkenyl group, an alkylene heteroalkylene group, an alkynyl group, or an alkylene heteroalkynylene group; and R3 is one of a hydrogen atom, an alkyl group, a cycloalkyl group, a heterocyclic group, a heterocycloalkyl group, an alkenyl group, a cycloalkenyl group, an aromatic group, a heteroaromatic group, an alkane heteroalkyl group, an alkynyl group, an alkylene group, an alkylene heteroalkylene group, an alkenyl group, an alkylene heteroalkynylene group, an alkynyl group, or an alkylene heteroalkynylene group; The monomer C is a trialdehyde or ketone compound, and the general molecular structure is as follows: wherein R4 is one of a cycloalkyl group, a heterocyclic group, a heterocycloalkyl group, an alkenyl group, a cycloalkenyl group, an aromatic group, or a heteroaromatic group; and R5 is one of a hydrogen atom, an alkyl group, a cycloalkyl group, a heterocyclic group, a heterocycloalkyl group, an alkenyl group, a cycloalkenyl group, an aromatic group, a heteroaromatic group, an alkynyl group, an alkylene group, an alkylene heteroalkylene group, an alkenyl group, an alkylene heteroalkenylene group, an alkynyl group, or an alkylene heteroalkynylene group; Step 2: uniformly mixing the solution containing monomer A and monomer B and reacting them at 0-200° C. for 2-12 hours to generate a linear prepolymer; Step 3: Add the solution of monomer C to the linear prepolymer and continue to react at 0-200°C for 2-16 hours, wherein: The molar number of the monomer A is the sum of the molar number of the monomer B and 1.5 times the molar number of the monomer C, and the molar ratio of the monomer B to the monomer C is 0:1 to 10:1; Step 4: Pour the reactants into a polytetrafluoroethylene mold, solidify them, and vacuum dry them to obtain a thermosetting resin containing gamma-ray sensitive groups, wherein: The thermosetting resin containing gamma ray radiation sensitive groups contains the following breakable cross-linking structure:

2. The method for preparing a thermosetting resin containing gamma ray sensitive groups according to claim 1, characterized in that The R1 is preferably a methyl group, R2 is preferably a methyl group, R3 is preferably a hydrogen atom, R4 is preferably an aromatic group, and R5 is preferably a hydrogen atom.

3. The method for preparing a thermosetting resin containing gamma ray sensitive groups according to claim 1, characterized in that The monomer A is one or more of isophthalic acid dihydrazide, terephthalic acid dihydrazide, adipic acid dihydrazide, succinic acid dihydrazide, and oxalohydrazide; the monomer B is one or more of terephthalic acid dihydrazide, o-phthalic acid dihydrazide, glyoxal, succinic acid dihydrazide, glutaraldehyde, divanillin-dimethylsilane, divanillin-phenyl phosphate, di-o-vanillin-dimethylsilane, di-o-vanillin-phenyl phosphate, divanillone-dimethylsilane, and divanillone-phenyl phosphate; the monomer C is one or more of trimesic acid aldehyde, biphenyl trimesic acid aldehyde, trimellitic acid aldehyde, tri-o-vanillin phosphate, 2,4,6-tri-o-vanillin-1,3,5-triazine, trivanillin phosphate, 2,4,6- One or more of trivanillin-1,3,5-triazine, tri-o-vanillin phosphate, 2,4,6-tri-o-vanillin-1,3,5-triazine, trivanillin phosphate, 2,4,6-trivanillin-1,3,5-triazine; the solvent is one or more of water, carbon tetrachloride, benzene, toluene, xylene, dichloromethane, carbon tetrachloride, methanol, ethanol, ethylene glycol, ethyl acetate, ether, petroleum ether, tetrahydrofuran, chloroform, dioxane, pyridine, acetone, acetonitrile, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, and dimethyl sulfoxide; the vacuum drying temperature is 0 to 200° C., and the time is 8 to 24 hours.

4. A method for degrading a thermosetting resin containing gamma ray sensitive groups prepared by the method according to any one of claims 1 to 3, characterized in that The method comprises the following steps: At room temperature, use 60 Coγ-rays are used as a radiation source to irradiate the thermosetting resin in a solvent, wherein: The irradiation dose is 10 to 1000 KGy, and the irradiation dose rate is 500 Gy / h to 20 KGy / h.

5. The method for degrading a thermosetting resin containing a gamma ray sensitive group according to claim 4, characterized in that The solvent is at least one of water, isopentane, n-pentane, petroleum ether, hexane, cyclohexane, cyclopentane, heptane, carbon tetrachloride, benzene, toluene, xylene, chlorobenzene, o-dichlorobenzene, dichloromethane, carbon tetrachloride, methanol, ethanol, ethylene glycol, propanol, isopropanol, butanol, isobutanol, tert-butanol, amyl alcohol, benzyl alcohol, ethyl acetate, ether, petroleum ether, isopropyl ether, tetrahydrofuran, chloroform, dioxane, pyridine, acetone, acetonitrile, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, and dimethyl sulfoxide.

6. Use of a material containing gamma-ray radiation sensitive groups prepared by the method according to any one of claims 1 to 3 as a matrix in a degradable thermosetting resin composite material.

7. A method for preparing the degradable thermosetting resin composite material according to claim 6, characterized in that The method comprises the following: Step 1: dissolving a monomer A containing two hydrazide groups, a monomer B containing two aldehyde groups or ketone groups, and a monomer C containing three aldehyde groups or ketone groups in a solvent respectively; Step 2: Evenly mix the solution containing monomer A, monomer B and monomer C; The molar number of the monomer A is the sum of the molar number of the monomer B and 1.5 times the molar number of the monomer C, and the molar ratio of the monomer B to the monomer C is 0:1 to 10:1; Step 3: Place the mixed solution and reinforcement into a mold and solidify them by compression molding to obtain a thermosetting resin-based composite material containing gamma-ray sensitive groups, wherein: The curing temperature is 0-200° C., the pressure is 0.1-10 MPa, and the curing time is 2-12 hours.

8. The method for preparing the degradable thermosetting resin composite material according to claim 7, characterized in that The reinforcement comprises at least one of carbon fiber, glass fiber, natural fiber, chemical fiber, fabric made of fiber material, nano carbon material, boron nitride nano material, metal nano particles, metal oxide nano particles, and organic nano particles.

9. A method for degrading a thermosetting resin composite material according to claim 6, characterized in that The method comprises the following: At room temperature, use 60 Coγ-rays are used as a radiation source to irradiate the composite material in a solvent, wherein: The irradiation dose is 10 to 1000 KGy, and the irradiation dose rate is 500 Gy / h to 20 KGy / h.

10. The method for degrading a thermosetting resin composite material according to claim 9, characterized in that The solvent is at least one of water, isopentane, n-pentane, petroleum ether, hexane, cyclohexane, cyclopentane, heptane, carbon tetrachloride, benzene, toluene, xylene, chlorobenzene, o-dichlorobenzene, dichloromethane, carbon tetrachloride, methanol, ethanol, ethylene glycol, propanol, isopropanol, butanol, isobutanol, tert-butanol, amyl alcohol, benzyl alcohol, ethyl acetate, ether, petroleum ether, isopropyl ether, tetrahydrofuran, chloroform, dioxane, pyridine, acetone, acetonitrile, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, and dimethyl sulfoxide.

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