Preparation method of thermosetting resin containing gamma ray irradiation sensitive group

Abstract

The invention discloses a preparation method of thermosetting resin containing gamma ray irradiation sensitive groups. The method comprises the following steps: step 1, respectively 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; 2, uniformly mixing the solution containing the monomer A and the monomer B, and reacting to generate a linear prepolymer; 3, adding a solution of a monomer C into the linear prepolymer, and continuously reacting; and 4, pouring the reactant into a polytetrafluoroethylene mold, curing, and carrying out vacuum drying to obtain the thermosetting resin containing the gamma ray irradiation sensitive group. The thermosetting resin prepared by the method can be rapidly cured at a proper temperature, the obtained thermosetting resin and a composite material prepared by taking the thermosetting resin as a matrix can be rapidly degraded under a gamma ray irradiation condition, and the method has huge economic and environmental advantages for recycling of the thermosetting resin-based composite material.

Description

Technical Field

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

[0002] Advanced thermosetting resin-based composites have excellent properties such as high modulus, high strength, high temperature resistance, and impact resistance, and have therefore been widely used in aerospace, wind power generation, transportation, and other fields. Thermosetting resins with three-dimensional network cross-linked structures are difficult to reprocess and reuse. The environmental pollution caused by waste thermosetting resins and the recycling and reuse of high-value high-performance reinforcements in thermosetting resin composites are key problems that the industry generally pays attention to. So far, the industrial treatment methods for waste thermosetting resins mainly include energy recovery, physical crushing recovery, and chemical recovery. However, these traditional recycling methods cannot obtain high-performance, structurally intact reinforcements such as recycled fibers, which greatly reduces their commercial value. Researchers construct thermosetting resins through dynamic covalent bonds and use the cleavage of dynamic covalent bonds under light, heat, pH, and other stimuli to achieve the degradation of thermosetting resins. However, the introduction of dynamic covalent bonds may cause significant changes in the mechanical and thermal properties of thermosetting resins, which seriously limits the application scenarios of thermosetting resins. Therefore, the development of a high-strength, high-modulus, and efficiently degradable thermosetting resin remains a very urgent goal. Summary of the invention

[0003] In order to solve the above technical problems, the present invention provides a method for preparing a thermosetting resin containing a gamma-ray irradiation sensitive group. The thermosetting resin prepared by the method can be quickly cured at a suitable temperature, and the obtained thermosetting resin and the composite material prepared with the thermosetting resin as a matrix can be quickly degraded under gamma-ray irradiation conditions, which has great economic and environmental advantages for the recycling and reuse of thermosetting resin-based composite materials.

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

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

[0006] 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, wherein:

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

[0008]

[0009] In the formula, R1 is one of alkyl, cycloalkyl, heterocyclyl, heterocyclylalkyl, alkenyl, cycloalkenyl, aromatic, heteroaromatic, alkane heteroalkyl, alkynyl, alkylene, alkylene heteroalkylene, alkenylene, alkylene heteroalkenylene, alkynylene or alkylene heteroalkynylene, preferably methyl; 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 heterocyclic alkyl 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 heteroalkenylene group, preferably a methyl group; R3 is one of a hydrogen atom, an alkyl group, a cycloalkyl group, a heterocyclic group, a heterocyclic alkyl 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 heteroalkenylene 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, divanillone-dimethylsilane, divanillone-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, divanillone-dimethylsilane, divanillone-phenyl phosphate 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, heterocyclic, heterocycloalkyl, alkenyl, cycloalkenyl, aromatic, heteroaromatic, preferably aromatic; R5 is one of hydrogen, alkyl, cycloalkyl, heterocyclic, heterocycloalkyl, alkenyl, cycloalkenyl, aromatic, heteroaromatic, alkane-heteroalkyl, alkynyl, alkylene, alkylene-heteroalkylene, alkenylene, alkylene-heteroalkylene, alkynylene or alkylene-heteroalkynylene, 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-vanillin-1,3,5-triazine, tri-o-vanillone phosphate, 2,4,6-tri-o-vanillone-1,3,5-triazine, tri-vanillone phosphate, 2,4,6-tri-vanillone-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 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 and vacuum dry to obtain a thermosetting resin containing gamma-ray sensitive groups, wherein:

[0022] The vacuum drying is carried out at a temperature of 0 to 200° C. and for a time of 8 to 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 irradiation sensitive groups can be used as a matrix to prepare a degradable thermosetting resin composite material. The composite material is prepared from a thermosetting resin containing gamma-ray irradiation 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, mixing the solutions containing monomer A, monomer B and monomer C uniformly;

[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: Put the mixed solution and the reinforcement into a mold, and solidify them by compression molding to obtain a thermosetting resin-based composite material containing gamma-ray radiation 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 for irradiation to achieve degradation of 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 a gamma-ray irradiation sensitive group and a thermosetting resin composite material thereof. The thermosetting resin and the thermosetting resin composite material thereof have excellent performance and can be efficiently degraded by gamma-ray irradiation with zero energy consumption, high degradation efficiency and low cost. Gamma rays have super strong penetrability and can trigger sensitive bonds to break simultaneously on the surface and inside of the material. Gamma-ray irradiation technology has a more efficient degradation efficiency and is therefore more suitable for degrading thermosetting polymers with complex shapes and large volumes. The ray is composed of electromagnetic waves with the highest frequency, and then provides photon energy of up to 1keV to 8Mev, which can break all chemical bonds and cause degradation and re-crosslinking of the polymer. Therefore, under normal circumstances, gamma rays will only cause the performance of the polymer to deteriorate, but will not cause a controllable degradation process. The conjugated C=N structure introduced by the present invention can stabilize the free radicals generated by the breakage of the N-N bond or the N-O bond, thereby preventing the re-crosslinking reaction from proceeding, making the degradation process controllable, and achieving the purpose of degrading epoxy resin.

[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 a small molecular weight. The polymer can be dissolved in an organic solvent. After a simple separation, the thermosetting resin matrix and the fiber can be separated, thereby achieving the purpose of recycling and reusing the fiber reinforcement. Since low-dose gamma ray irradiation has almost no damage to the strength of the fiber and other reinforcements, the recycled fiber reinforcement maintains good structure, performance, orderliness, etc.

[0039] 3. According to the test, 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 in conjunction with the embodiments, but is not limited thereto. Any modification or equivalent replacement of the technical solution of the present invention without departing from the spirit and scope of the technical solution of the present invention should be included in the protection scope 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 min, and then 10 mL of ethanol solution containing 1.341 g of terephthalaldehyde (10 mmol) was added, and the magnetic stirring reaction was continued for 2 h. After the reaction, a linear prepolymer with high viscosity was obtained. 10 mL of ethanol solvent containing 5.011 g of trivanillin phosphate (10 mmol) was added to the reactor as a crosslinking agent, poured into a polytetrafluoroethylene mold and reacted at 80 ° C for 16 h. After curing, it was vacuum dried at 80 ° C for 12 h to obtain a thermosetting resin I containing a γ-ray irradiation sensitive group, and its performance indicators are shown in Table 1.

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

[0044] 11.323g of adipic acid dihydrazide (65mmol) was dissolved in 10mL of ethanol, mixed and magnetically stirred at 25℃ for 10min, then 10mL of ethanol solution containing 6.707g of terephthalaldehyde (50mmol) was added, and the reaction was continued with magnetic stirring for 2h. After the reaction, a linear prepolymer with high viscosity was obtained. 10mL of ethanol solvent containing 5.011g of trivanillin phosphate (10mmol) was added to the reactor as a crosslinking agent, and poured into a polytetrafluoroethylene mold and continued to react at room temperature for 16h. After curing, vacuum drying was performed at 80℃ for 12h to obtain a thermosetting resin II containing a γ-ray irradiation sensitive group, and its performance indicators 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 Bending 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 Gamma-Ray Radiation Sensitive Groups

[0048] Dissolve 12.622g of isophthalic acid hydrazide (65mmol) in 10mL of ethanol, mix and stir magnetically for 10min at 25℃, then add 10mL of ethanol solution containing 6.707g of terephthalaldehyde (50mmol), continue to stir magnetically for 2h, and obtain a linear prepolymer with high viscosity after the reaction. Add 10mL of ethanol solvent containing 5.432g of trivanillin phosphate (10mmol) as a crosslinking agent to the reactor, pour into a polytetrafluoroethylene mold and continue to react at room temperature for 16h. After curing, vacuum dry at 80℃ for 12h to obtain a thermosetting resin III containing a γ-ray irradiation sensitive group.

[0049] Example 4: γ-ray irradiation of thermosetting resin I containing γ-ray irradiation 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 filled with DMSO solvent. 60 Coγ-ray irradiation can completely degrade the product after 150KGy irradiation to obtain a clear and transparent yellow solution with a degradation rate of 100%.

[0051] Example 5: γ-ray irradiation of thermosetting resin II containing γ-ray irradiation 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 filled with DMSO solvent. 60 Coγ-ray irradiation can completely degrade the product after 120KGy irradiation to obtain a clear and transparent yellow solution with a degradation rate of 100%.

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

[0054] The preparation of carbon fiber reinforced epoxy resin-based composite sheet Ⅰ is divided into two steps: preparation of prepreg and compression molding. The first step is the prepolymer solution impregnation method, and the resin content in the prepolymer is adjusted by the prepolymer concentration and the size of the carbon fiber. The second step is completed by hand paste and compression molding technology. 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 DMSO solution, poured into a mold with a flat carbon fiber cloth, soaked at room temperature for 30min, heated to 40℃ for precuring for 2h, and obtained a carbon fiber prepreg. Then the carbon fiber prepreg is placed on a flat hot press, 10MPa, 80℃2h curing molding, and naturally cooled to room temperature to obtain a carbon fiber reinforced epoxy resin-based composite sheet Ⅰ.

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

[0056] Under normal temperature conditions, 5 g of the carbon fiber reinforced epoxy resin-based composite material plate prepared in Example 6 was placed in a 50 mL glass bottle filled with DMSO solvent. 60 After Coγ-ray irradiation, the epoxy resin matrix can be separated from the composite material after irradiation of 320KGy, and a clear and transparent yellow solution is obtained. The carbon fiber bundle is taken out, and the surface weaving structure of the recycled fiber is well maintained. The carbon fiber can be basically completely recycled, with a recovery rate of 98%.

Claims

1. A method for preparing a thermosetting resin containing a gamma-ray sensitive group, characterized in that 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 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, alkane-heteroalkyl, alkynyl, alkylene, alkylene-heteroalkylene, alkenylene, alkylene-heteroalkenylene, alkynylene, or alkylene-heteroalkynylene; 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 heterocyclic alkyl 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 heteroalkenylene group; and R3 is one of a hydrogen atom, an alkyl group, a cycloalkyl group, a heterocyclic group, a heterocyclic alkyl 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 heteroalkenylene group; The monomer C is a trialdehyde or ketone compound, and the general molecular structure is as follows: In the formula, R4 is one of cycloalkyl, heterocyclic, heterocycloalkyl, alkenyl, cycloalkenyl, aromatic, heteroaromatic, and R5 is one of hydrogen, alkyl, cycloalkyl, heterocyclic, heterocycloalkyl, alkenyl, cycloalkenyl, aromatic, heteroaromatic, alkane-heteroalkyl, alkynyl, alkylene, alkylene-heteroalkylene, alkenylene, alkylene-heteroalkenylene, alkynylene, or alkylene-heteroalkynylene; Step 2, uniformly mixing the solution containing monomer A and monomer B and reacting 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 and vacuum dry 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 a gamma-ray sensitive group 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 a gamma-ray sensitive group 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 oxaloylhydrazide; the monomer B is one or more of terephthalaldehyde, o-phthalaldehyde, 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 trimesic acid aldehyde, biphenyl trimesic acid aldehyde, trimellitic acid aldehyde, tri-o-vanillin phosphate, 2,4,6-tri-o-vanillin-1,3,5-triazine, tri-vanillin 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 and degrade thermosetting resins 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, mixing the solutions containing monomer A, monomer B and monomer C uniformly; 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: Put the mixed solution and the reinforcement into a mold, and solidify them by compression molding to obtain a thermosetting resin-based composite material containing gamma-ray irradiation 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 includes 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.

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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