CN113527637A - Preparation and degradation method of thermosetting epoxy resin capable of being degraded by gamma ray irradiation - Google Patents
Preparation and degradation method of thermosetting epoxy resin capable of being degraded by gamma ray irradiation Download PDFInfo
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Abstract
A preparation method and a degradation method of thermosetting epoxy resin capable of being degraded by gamma ray irradiation belong to the technical field of gamma ray irradiation degradation of epoxy resin. The invention aims to solve the technical problems that the existing epoxy resin material has harsh degradation conditions and cannot give consideration to excellent service performance and degradation performance of the epoxy resin at the same time. The method of the invention is gamma-ray irradiation degradation; the degradation method is applied to degradation of thermosetting epoxy resin and epoxy resin composite materials. The invention introduces N-N bond or N-O bond connected with stable conjugated structure into the epoxy resin curing agent structure, and introduces the N-N bond or N-O bond into the epoxy resin cross-linked structure through cross-linking curing reaction, so that the N-N bond or N-O bond in the cross-linked network is preferentially broken under the condition of gamma ray irradiation, and the purpose of degrading the thermosetting epoxy resin is achieved. The gamma-ray irradiation degradation method really realizes zero energy consumption, and does not need harsh degradation conditions such as high temperature, high pressure, strong acid, strong alkali and the like.
Description
Technical Field
The invention belongs to the technical field of gamma-ray irradiation degradation of epoxy resin, and particularly relates to a preparation method and a degradation method of thermosetting epoxy resin capable of being degraded by gamma-ray irradiation.
Background
The advanced thermosetting resin-based composite material has excellent properties of light weight, high strength, high rigidity, high temperature resistance, corrosion resistance and the like, so that the advanced thermosetting resin-based composite material is widely applied to the industries of high-end sports, entertainment, automobiles and aerospace, and still rapidly expands new application fields. Epoxy resins, one of the three major thermosetting materials in the world, account for almost 70% of the global thermoset polymer market, and their importance is irreplaceable. According to statistics, the global market value of epoxy resin is more than 80 hundred million dollars in 2016, and China is the world with the largest capacity country, yield country and consumer market of epoxy resin. In 2017, the capacity of epoxy resin in China can reach 230 ten thousand tons, the yield can reach 130 ten thousand tons, and the consumption is about 150 ten thousand tons. However, epoxy resins, once cured and shaped, are difficult to reprocess and reuse like thermoplastic resins due to the limitations of their three-dimensional crosslinked network structure. In addition, the recovery of high-performance reinforcements with high value from epoxy resin composite materials is also a key problem to be solved urgently. Heretofore, as methods for industrially treating epoxy resin waste, energy recovery methods, physical pulverization recovery methods, and chemical recovery methods (high temperature, high pressure, supercritical fluid, etc.) have been mainly used. However, these conventional recycling methods often require harsh reaction conditions and have low degradation efficiency, and the properties, structures and orderliness of reinforcements such as recycled fibers are all significantly reduced, which greatly reduces their commercial value. In addition, researchers have introduced dynamic covalent bonds into the backbone or curing agent structure of epoxy resins, and achieved degradation of epoxy resins through cleavage of dynamic covalent bonds under stimuli such as light, heat, pH, and the like. However, the introduction of dynamic covalent bonds causes the mechanical property and the thermal property of the epoxy resin to be obviously reduced, and the application scenes of the epoxy resin are severely limited. Therefore, it is still a very urgent objective to develop a clean, low-energy, cost-effective degradation strategy while maintaining the high mechanical properties of epoxy resins.
Disclosure of Invention
The invention aims to solve the problems that the existing epoxy resin degradation method is harsh in condition and difficult to give consideration to excellent service performance and degradation performance, and provides a preparation method and a degradation method of thermosetting epoxy resin capable of being degraded by gamma ray irradiation and a composite material thereof.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a preparation method of thermosetting epoxy resin capable of being degraded by gamma ray irradiation comprises the following steps: the curing agent and the epoxy resin are subjected to thermosetting crosslinking to generate thermosetting epoxy resin which can be degraded by gamma ray irradiation; the weight ratio of the epoxy resin to the curing agent is 0.1-10: 1, the curing reaction temperature is 0-200 ℃;
the gamma ray irradiation degradable thermosetting epoxy resin contains the following breakable crosslinking structure:
the general molecular structure formula of the curing agent is as follows:
R1，R2，R4and R5Is alkylene, cycloalkylene, hydrocarbylenecycloalkylene, hydrocarbylenecycloalkylenealkylene, heterocycloalkylenealkylene, hydrocarbyleneheterocycloalkylenealkylene, cycloalkenylene, hydrocarbylenecycloalkenylene, hydrocarbylenecycloalkenylalkylene, heterocycloalkenylene, hydrocarbyleneheterocycloalkenylene, arylene, hydrocarbylenearylene, hydrocarbylenearylenealkylene, heteroarylene, hydrocarbyleneheteroarylenealkylene, secondary amine hydrocarbylene, secondary amine heterocycloalkylene secondary amine, secondary amine cycloalkylene secondary amine, secondary amine heterocycloalkylene secondary amine, or secondary amine cycloalkylene secondary amineOne of an amine group, a secondary amine heterocycloalkenylsecondary amine group, a secondary amine arylenesecondary amine group, a secondary amine heteroarylenesecondary amine group, a secondary amide cycloalkylenesecondary amide group, a secondary amide heterocycloalkylene secondary amide group, a secondary amide cycloalkylenesecondary amide group, a secondary amide heterocycloalkenylsecondary amide group, a secondary amide heteroarylenesecondary amide group, a secondary amide arylenesecondary amide group, a secondary amide heteroarylarylenesecondary amide group, an oxohydrocarbyloxy group, an oxocycloalkyloxy group, an oxocycloalkenyloxy group, an oxoaryloxy group; r1，R2，R4And R5May be the same or different;
R3is one of a hydrogen atom, an alkyl group, a cycloalkyl group, a heterocyclic group, a heterocycloalkyl group, an alkenyl group, a cycloalkenyl group, an aryl group, a heteroaryl group, an alkylheteroalkyl group, an alkynyl group, a hydrocarbylene group, a hydrocarbyleneheteroalkylene group, an alkenylene group, a hydrocarbyleneheteroalkylene group, an alkynylene group, or a hydrocarbyleneheteroalkynylene group.
The invention introduces the chemical bond (containing N-N bond or N-O bond with conjugated structure) which is preferentially degraded under the gamma-ray irradiation condition into the epoxy resin, thereby realizing the gamma-ray irradiation degradation of the epoxy resin.
Further, the preparation method of the curing agent specifically comprises the following steps: the molar ratio of the compound I to the compound II is 1-10: 1; performing click chemical reaction on the compound I and the compound II in a solvent to synthesize a compound III, wherein the light source absorption wavelength is 254-365 nm, a matched photoinitiator is selected according to the light source absorption wavelength, the concentration of the photoinitiator relative to the chemical I is 0.5-5 mol%, and the irradiation time is controlled to be 60-600 min; the molar ratio of the compound III to the chemical IV or the compound V is 1-10: 1; carrying out amine-aldehyde condensation reaction on the compound III and a chemical substance IV or a compound V in a solvent at the reaction temperature of 0-200 ℃ to synthesize a gamma-ray irradiation degradable epoxy resin curing agent containing a conjugated N-N bond or N-O bond; the compound I is H2N-R1-SH; the compound II is
The compound III is
The compound IV is H2N-NH-R4-NH-NH2(ii) a Chemical V is H2N-O-R5-O-NH2。
Further, the photoinitiator is at least one of 2-hydroxymethylphenylpropane-1-one, diethoxyacetophenone, 1-hydroxycyclohexylbenzophenone, 2-hydroxy-2-methyl-1-p-ethyl ether phenyl acetone and isopropyl thioxanthone; 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, diethyl ether, petroleum ether, isopropyl ether, tetrahydrofuran, chloroform, dioxane, pyridine, acetone, acetonitrile, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone and dimethyl sulfoxide.
Further, the epoxy resin includes at least one of glycidyl ether type epoxy resin, glycidyl ester type epoxy resin, glycidyl amine type epoxy resin, trifunctional epoxy resin, tetrafunctional epoxy resin, novolac type epoxy resin, o-cresol novolac epoxy resin, aliphatic epoxy resin, alicyclic epoxy resin, and nitrogen-containing epoxy resin.
Furthermore, in the preparation process, a reinforcement and an auxiliary material are added to obtain the epoxy resin composite material capable of being degraded by gamma ray irradiation.
Further, the reinforcement comprises at least one of carbon fibers, glass fibers, natural fibers, chemical fibers and fabrics made of fibrous materials, nanocarbon materials, boron nitride nanomaterials, metal nanoparticles, metal oxide nanoparticles, organic nanoparticles; the auxiliary material comprises at least one of an accelerant, a diluent, a plasticizer, a flexibilizer, a thickening agent, a coupling agent, a defoaming agent, a leveling agent, an ultraviolet absorbent, an antioxidant, a brightening agent, a fluorescent agent, a pigment and a filler.
A degradation method of the thermosetting epoxy resin capable of being degraded by gamma ray irradiation is specifically as follows: at room temperature, using60A Co gamma ray radiation source realizes the degradation of the thermosetting epoxy resin in a solvent; wherein the irradiation dose is 10 KGy-1000 KGy, and the irradiation dose rate is 500 Gy-20 KGy.
Further, 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, diethyl ether, petroleum ether, isopropyl ether, tetrahydrofuran, chloroform, dioxane, pyridine, acetone, acetonitrile, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone, and dimethyl sulfoxide.
Compared with the prior art, the invention has the beneficial effects that: the invention provides a method for degrading epoxy resin and an epoxy resin composite material thereof by gamma ray irradiation with zero energy consumption, high degradation efficiency and low cost, which guarantees the high-efficiency degradation of the epoxy resin and also considers excellent service performance. Gamma radiation is a readily available source of energy, which is penetrating electromagnetic radiation produced by radioactive decay of atomic nuclei, and thus has superior penetration, triggering both sensitive bond rupture at the surface and within the material. In this case, gamma irradiation has a higher degradation efficiency than other degradation techniques, and is therefore more suitable for degrading thermoset polymers of complex shape and large volume. The radiation consists of the shortest wavelength electromagnetic wave and then provides the highest photon energy (ranging from several keV to 8 Mev). However, such ultra-high energy electromagnetic radiation can break all chemical bonds while causing degradation and re-crosslinking of the polymer, so that in general gamma radiation only causes a decrease in the properties of the polymer, but not a controlled degradation process. The introduced conjugated structure can stabilize free radicals generated by the breakage of N-N bonds or N-O bonds, thereby preventing the re-crosslinking reaction from proceeding, leading the degradation process to be controllable and achieving the purpose of degrading the epoxy resin.
Meanwhile, the gamma-ray irradiation degradation technology is applied to degradation of epoxy resin matrix fiber reinforced composite materials, under the degradation condition provided by the invention, thermosetting epoxy resin matrix in the fiber reinforced composite materials is degraded into linear polymer with smaller molecular weight, the polymer can be dissolved in organic solvent, and the separation of the epoxy resin matrix and fibers can be realized through simple separation, so that the purpose of recycling and reusing the fiber reinforced materials is achieved. Because the low-dose gamma-ray irradiation almost has no damage to the strength of the fiber and other reinforcements, the recycled fiber reinforcements keep good structure, performance, order and the like. The gamma-ray irradiation degradation technology provided by the invention has zero energy consumption, avoids a degradation recovery method under severe conditions of high temperature, high pressure, strong acid, strong alkali and the like, does not generate secondary pollution sources to the environment, and is an economical and feasible industrial production route.
Through detection, the tensile strength of the degradable thermosetting epoxy resin prepared by the invention can reach 60-100 MPa, the bending strength can reach 100-130 MPa, the Tg is increased to be higher than 130 ℃, and the degradation rate of the degradable thermosetting epoxy resin can reach 100%.
Detailed Description
The technical solutions of the present invention are further described below with reference to the following examples, but the present invention is not limited thereto, and any modifications or equivalent substitutions may be made to the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.
The invention introduces N-N bond or N-O bond connected with stable conjugated structure into the epoxy resin curing agent structure, and introduces the N-N bond or N-O bond into the epoxy resin cross-linked structure through cross-linking curing reaction, so that the N-N bond or N-O bond in the cross-linked network is preferentially broken under the condition of gamma ray irradiation, and the purpose of degrading the thermosetting epoxy resin is achieved. The gamma-ray irradiation degradation method really realizes zero energy consumption, and does not need harsh degradation conditions such as high temperature, high pressure, strong acid, strong alkali and the like; and the gamma ray irradiation with super high penetrability can trigger sensitive chemical bonds to break on the surface and inside of the material at the same time, so that the degradation efficiency is higher than that of other degradation technologies.
Example 1: preparation of curing agent I
Curing agent I
12.51g of p-aminophenol, 13.21g of 4-vinylbenzaldehyde and 1 mol% of 2, 2-dimethoxy-2-phenylacetophenone (DMPA) were added to 500ml of LTHF, and after complete dissolution, the mixed solution was irradiated under a 365nm ultraviolet lamp, stirred at room temperature for 60min and then the solvent was removed in vacuo to obtain a crude product. 32.13g of the crude product and 19.14g of isophthalic dihydrazide were dissolved in methanol and reacted at 50 ℃ for 5 hours, whereupon a white precipitate was precipitated. Washing the precipitate with water, methanol and water for three times in sequence, and drying in vacuum to obtain pure curing agent I, wherein the yield is 70%.
1H-NMR(d-DMSO):11.58(s,2H),8.50(s,1H),7.75(m,4H),7.31(m,6H),6.67(d,2H),5.50(s,4H),3.12(m,4H),2.95(m,4H)
Example 2: preparation of curing agent II
Curing agent II
12.51g of p-aminophenol, 13.21g of 4-vinylbenzaldehyde and 1 mol% of 2, 2-dimethoxy-2-phenylacetophenone (DMPA) were added to 500ml of LTHF, and after complete dissolution, the mixed solution was irradiated under a 365nm ultraviolet lamp, stirred at room temperature for 60min and then the solvent was removed in vacuo to obtain a crude product. 32.13g of the crude product and 17.42g of adipic dihydrazide were dissolved in water and reacted at 50 ℃ for 5 hours, whereupon a white precipitate was precipitated. The precipitate was washed with water, methanol and water three times in sequence and dried under vacuum to give pure curing agent II in a yield of 72%.
1H-NMR(d-DMSO):11.07(s,2H),8.47(s,2H),7.82(d,4H),7.35(m,8H),6.67(m,4H),5.49(s,4H),3.12(m,4H),2.95(m,4H),2.34(m,4H),1.53(m,4H)
Example 3: preparation of curing agent III
Curing agent III
12.51g of p-aminophenol, 13.21g of 4-vinylbenzaldehyde and 1 mol% of 2, 2-dimethoxy-2-phenylacetophenone (DMPA) were added to 500ml of LTHF, and after complete dissolution, the mixed solution was irradiated under a 365nm ultraviolet lamp, stirred at room temperature for 60min and then the solvent was removed in vacuo to obtain a crude product. 32.13g of the crude product and 18.46g of O, O' -1, 3-propanediydroxylamine dihydrochloride were dissolved in water and reacted at 50 ℃ for 5 hours, whereupon a white precipitate was precipitated. Washing the precipitate with water, ethanol and water for three times in sequence, and drying in vacuum to obtain pure curing agent III with a yield of 72%.
1H-NMR(d-DMSO):8.44(s,2H),7.82(d,4H),7.38(m,4H),6.67(m,4H),5.20(s,4H),3.51(m,4H),3.12(m,4H),2.95(m,4H),1.79(m,4H)
Example 4: the curing agent I is crosslinked with epoxy resin to generate the gamma-ray irradiation degradable thermosetting resin I.
At room temperature, 33.25g of curing agent I and 50g of epoxy resin E51 are dissolved in 15ml of mixed solution of sodium hydroxide and sodium hydroxide, stirred uniformly and then transferred to a stainless steel mold coated with a release agent in advance, and the mixture is cured according to the procedure of 120 ℃ for 2h and 160 ℃ for 2 h. And cooling to room temperature to obtain the gamma-ray irradiation degradable epoxy resin I.
Example 5: curing agent II and epoxy resin are crosslinked to generate gamma-ray irradiation degradable thermosetting resin II
At room temperature, 35.76g of curing agent II and 50g of epoxy resin E51 were dissolved in 15mL of DMSO, stirred uniformly and transferred to a stainless steel mold previously coated with a release agent, and curing was carried out according to the procedure of 120 ℃ for 2h and 160 ℃ for 2 h. Cooling to room temperature to obtain the gamma-ray irradiation degradable epoxy resin II.
Example 6: curing agent III and epoxy resin are crosslinked to generate gamma-ray irradiation degradable thermosetting resin III
At room temperature, 32.10g of curing agent III and 50g of epoxy resin E51 are dissolved in 15ml of mixed solution of sodium hydroxide and sodium hydroxide, stirred uniformly and transferred to a stainless steel mold coated with a release agent in advance, and curing is carried out according to the procedure of 120 ℃ for 2h and 160 ℃ for 2 h. Cooling to room temperature to obtain the gamma-ray irradiation degradable epoxy resin III.
Detection example 1:
the viscosity and the gel time before curing, and the thermal and mechanical properties after curing of the degradable thermosetting epoxy resin i prepared in example 4, the degradable thermosetting epoxy resin ii prepared in example 5, and the degradable thermosetting epoxy resin iii prepared in example 6 were detected, and specific results are shown in table 1
TABLE 1
Example 7: gamma ray irradiation degradable thermosetting resin I
Under the condition of normal temperature, 1g of degradation type thermosetting resin I is placed in a 50mL glass bottle filled with DMSO solvent for use60Co gamma ray irradiation is carried out, 150KGy irradiation is carried out, and the degradation is complete, so that clear and transparent yellow solution is obtained.
Example 8: gamma ray irradiation degradable thermosetting resin I
Under the condition of normal temperature, 1g of degradation type thermosetting resin I is placed in a 50mL glass bottle filled with DMF solvent for use60Co gamma ray irradiation and 180KGy irradiation can degrade completely to obtain clear and transparent yellow solution.
Example 9: gamma ray irradiation degradable thermosetting resin I
At normal temperature1g of degradation type thermosetting resin I is placed in a 50mL glass bottle filled with methanol solvent for use60Co gamma ray irradiation, 400KGy irradiation, soaking in DMSO solvent for 5 hr to degrade completely to obtain clear and transparent yellow solution.
Example 10: gamma ray irradiation degradable thermosetting resin II
Under normal temperature conditions, 1g of the degradable thermosetting resin II was placed in a 50mL glass bottle containing DMSO solvent and used60Co gamma ray irradiation is carried out, 120KGy irradiation is carried out, and the degradation is complete, so that clear and transparent yellow solution is obtained.
Example 11: gamma ray irradiation degradable thermosetting resin II
Under normal temperature conditions, 1g of the degradable thermosetting resin II was placed in a 50mL glass bottle containing DMF solvent and used60Co gamma ray irradiation is carried out, 150KGy irradiation is carried out, and the degradation is complete, so that clear and transparent yellow solution is obtained.
Example 12: gamma ray irradiation degradable thermosetting resin II
Placing 1g of the degradable thermosetting resin II in a 50mL glass bottle containing methanol solvent at normal temperature, and using60Co gamma ray irradiation, placing the mixture into a DMSO solvent after 350KGy irradiation for soaking for 5h, and completely degrading to obtain a clear and transparent yellow solution.
Example 13: gamma ray irradiation degradable thermosetting resin III
Under normal temperature conditions, 1g of the degradable thermosetting resin III was placed in a 50mL glass bottle containing a DMSO solvent and used60Co gamma ray irradiation and 180KGy irradiation can degrade completely to obtain clear and transparent yellow solution.
Example 14: gamma ray irradiation degradable thermosetting resin III
1g of the degradable thermosetting resin III was placed in a 50mL glass bottle containing DMF solvent at room temperature and used60Co gamma ray irradiation is carried out, 230KGy irradiation is carried out, and the degradation is complete, so that clear and transparent yellow solution is obtained.
Example 15: gamma ray irradiation degradable thermosetting resin III
1g of the degradable thermosetting resin III was placed in a 50mL glass bottle containing a methanol solvent at ordinary temperature and used60Co gamma ray irradiation, 450KGy irradiation, soaking in DMSO solvent for 12 hr to degrade completely to obtain clear and transparent yellow solution.
Detection example 2:
and detecting the degradation performances of the degradable thermosetting resin I, the degradable thermosetting resin II and the degradable thermosetting resin III in different solvents. The specific results are shown in Table 2.
TABLE 2
Example 16: preparation of gamma-ray irradiation recyclable carbon fiber reinforced epoxy resin-based composite material plate I
The preparation of the carbon fiber reinforced epoxy resin matrix composite material plate I comprises two steps: preparing prepreg and compression molding. The first step is a prepolymer solution dipping 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 accomplished using hand lay-up and compression molding techniques. Firstly, after 25g of epoxy resin E51 and 16.25g of curing agent I are completely dissolved in 5ml of mixed solution of epoxy resin and epoxy resin, pouring the mixture into a mold paved with carbon fiber cloth, soaking the mixture for 30min at room temperature, and heating the mixture to 120 ℃ for precuring the mixture for 2h to obtain the carbon fiber prepreg. And then placing the carbon fiber prepreg on a flat hot press, curing and molding at the temperature of 160 ℃ for 2h under the pressure of 10MPa, and naturally cooling to room temperature to obtain the carbon fiber reinforced epoxy resin-based composite material plate I.
Example 17: preparation of gamma-ray irradiation recyclable carbon fiber reinforced epoxy resin matrix composite material plate II
The preparation of the carbon fiber reinforced epoxy resin matrix composite material plate II comprises two steps: preparing prepreg and compression molding. The first step is a prepolymer solution dipping 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 accomplished using hand lay-up and compression molding techniques. Firstly, after 25g of epoxy resin E51 and 17.15g of curing agent II are completely dissolved in 8mL of DMSO solution, pouring the mixture into a mold paved with carbon fiber cloth, soaking the mixture for 30min at room temperature, and heating the mixture to 120 ℃ for precuring for 2h to obtain the carbon fiber prepreg. And then placing the carbon fiber prepreg on a flat hot press, curing and molding the carbon fiber prepreg at the temperature of 160 ℃ for 2h under the pressure of 10MPa, and naturally cooling the carbon fiber prepreg to room temperature to obtain a recycled carbon fiber reinforced epoxy resin matrix composite plate II.
Example 18: preparation of gamma-ray irradiation recyclable carbon fiber reinforced epoxy resin matrix composite material plate III
The preparation of the carbon fiber reinforced epoxy resin matrix composite material plate III comprises two steps: preparing prepreg and compression molding. The first step is a prepolymer solution dipping 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 accomplished using hand lay-up and compression molding techniques. Firstly, after 25g of epoxy resin E51 and 15.40g of curing agent III are completely dissolved in 10ml of mixed solution of sodium chloride and sodium chloride, pouring the mixture into a mold paved with carbon fiber cloth, soaking the mixture for 30min at room temperature, and heating the mixture to 120 ℃ for precuring for 2h to obtain the carbon fiber prepreg. And then placing the carbon fiber prepreg on a flat hot press, curing and molding at the temperature of 160 ℃ for 2h under the pressure of 10MPa, and naturally cooling to room temperature to obtain a recycled carbon fiber reinforced epoxy resin matrix composite material plate III.
Example 19: gamma-ray irradiation recovery carbon fiber reinforced epoxy resin matrix composite material plate I
Placing 5g of the carbon fiber reinforced epoxy resin matrix composite material plate I in a 50mL glass bottle filled with a DMSO solvent at normal temperature, and using the glass bottle60And (3) irradiating by Co gamma rays, and separating the epoxy resin matrix from the composite material after irradiating 320KGy to obtain a clear and transparent yellow solution. The carbon fiber bundle was taken out, and the surface weave structure of the recovered fiber was well maintained.
Example 20: gamma-ray irradiation recovery carbon fiber reinforced epoxy resin matrix composite material plate I
Placing 5g of the carbon fiber reinforced epoxy resin-based composite material plate I in a 50mL glass bottle filled with DMF solvent at normal temperature, and using60Co gamma ray irradiation, after 380KGy irradiation, the epoxy resin matrix can be curedAnd separating the materials to obtain clear and transparent yellow solution. The carbon fiber bundle was taken out, and the surface weave structure of the recovered fiber was well maintained.
Example 21: gamma-ray irradiation recovery carbon fiber reinforced epoxy resin matrix composite material plate I
Placing 5g of the carbon fiber reinforced epoxy resin-based composite material plate I in a 50mL glass bottle filled with a methanol solvent at normal temperature, and using the carbon fiber reinforced epoxy resin-based composite material plate I60And (3) irradiating by Co gamma rays, and after 750KGy irradiation, putting the epoxy resin matrix into a DMSO solvent to soak for 10h, so that the epoxy resin matrix can be separated from the composite material, and a clear and transparent yellow solution is obtained. The carbon fiber bundle was taken out, and the surface weave structure of the recovered fiber was well maintained.
Example 22: gamma-ray irradiation degradation and recovery carbon fiber reinforced epoxy resin matrix composite material plate II
Placing 5g of carbon fiber reinforced epoxy resin matrix composite material plate II in a 50mL glass bottle filled with DMSO solvent at normal temperature for use60And (3) irradiating by Co gamma rays, wherein the epoxy resin matrix can be completely degraded after 700KGy irradiation, and a clear and transparent yellow solution is obtained. The carbon fiber bundle was taken out, and the surface weave structure of the recovered fiber was well maintained.
Example 23: gamma-ray irradiation degradation and recovery carbon fiber reinforced epoxy resin matrix composite material plate II
Placing 5g of carbon fiber reinforced epoxy resin matrix composite material plate II in a 50mL glass bottle filled with DMF solvent at normal temperature for use60And (3) irradiating by Co gamma rays, wherein the epoxy resin matrix can be completely degraded after being irradiated by 620KGy, and a clear and transparent yellow solution is obtained. The carbon fiber bundle was taken out, and the surface weave structure of the recovered fiber was well maintained.
Example 24: gamma-ray irradiation degradation and recovery carbon fiber reinforced epoxy resin matrix composite material plate II
Placing 5g of carbon fiber reinforced epoxy resin matrix composite material plate II in a 50mL glass bottle filled with methanol solvent at normal temperature for use60Co gamma ray irradiation, after 790KGy irradiation, the epoxy resin matrix is placed into DMSO to be soaked for 10h, and then the epoxy resin matrix can be completely degraded, so that clear and transparent yellow solution is obtained. Taking out carbonThe surface knitted structure of the fiber bundle and the recycled fiber is well maintained.
Example 25: gamma-ray irradiation degradation and recovery of carbon fiber reinforced epoxy resin matrix composite material plate III
Placing 5g of carbon fiber reinforced epoxy resin matrix composite material plate III in a 50mL glass bottle filled with DMSO solvent at normal temperature, and using60And (3) irradiating by Co gamma rays, wherein the epoxy resin matrix can be completely degraded after 750KGy irradiation, and a clear and transparent yellow solution is obtained. The carbon fiber bundle was taken out, and the surface weave structure of the recovered fiber was well maintained.
Example 26: gamma-ray irradiation degradation and recovery of carbon fiber reinforced epoxy resin matrix composite material plate III
Placing 5g of carbon fiber reinforced epoxy resin matrix composite material plate III in a 50mL glass bottle filled with DMF solvent at normal temperature, and using60And (3) irradiating by Co gamma rays, wherein the epoxy resin matrix can be completely degraded after 680KGy irradiation, and a clear and transparent yellow solution is obtained. The carbon fiber bundle was taken out, and the surface weave structure of the recovered fiber was well maintained.
Example 27: gamma-ray irradiation degradation and recovery of carbon fiber reinforced epoxy resin matrix composite material plate III
Placing 5g of carbon fiber reinforced epoxy resin matrix composite material plate III in a 50mL glass bottle filled with methanol solvent at normal temperature, and using60Co gamma ray irradiation, after 900KGy irradiation, the epoxy resin matrix is placed into DMSO to be soaked for 15h, and then the epoxy resin matrix can be completely degraded, so that a clear and transparent yellow solution is obtained. The carbon fiber bundle was taken out, and the surface weave structure of the recovered fiber was well maintained.
Claims (8)
1. A preparation method of thermosetting epoxy resin capable of being degraded by gamma ray irradiation is characterized by comprising the following steps: the method specifically comprises the following steps: the curing agent and the epoxy resin are subjected to thermosetting crosslinking to generate thermosetting epoxy resin which can be degraded by gamma ray irradiation; the weight ratio of the epoxy resin to the curing agent is 0.1-10: 1, the curing reaction temperature is 0-200 ℃;
the general molecular structure formula of the curing agent is as follows:
R1，R2，R4and R5Is alkylene, cycloalkylene, cycloalkylenealkylene, hydrocarbylenecycloalkylenealkylene, heterocycloalkylene, hydrocarbyleneheterocycloalkylene, hydrocarbyleneheterocycloalkenylalkylene, arylene, hydrocarbylenearylene, heteroarylene, hydrocarbyleneheteroarylene, secondary amine hydrocarbylene, secondary amine cycloalkylene secondary amine, secondary amine heterocycloalkylene secondary amine, secondary amine heteroarylene secondary amine, secondary amide hydrocarbylene secondary amide, secondary amide cycloalkylene secondary amide, secondary amide heterocycloalkylene secondary amide, secondary amide heterocycloalkylene alkylene, or cycloalkylene, One of secondary amide aromatic secondary amide group, secondary amide heteroaromatic secondary amide group, oxyalkylene group, oxacycloalkylene group, oxyalkylene group, oxacycloalkenylene group, oxyarylene group and oxyarylene group; r1，R2，R4And R5May be the same or different;
R3is one of a hydrogen atom, an alkyl group, a cycloalkyl group, a heterocyclic group, a heterocycloalkyl group, an alkenyl group, a cycloalkenyl group, an aryl group, a heteroaryl group, an alkylheteroalkyl group, an alkynyl group, a hydrocarbylene group, a hydrocarbyleneheteroalkylene group, an alkenylene group, a hydrocarbyleneheteroalkylene group, an alkynylene group, or a hydrocarbyleneheteroalkynylene group.
2. The method for preparing a thermosetting epoxy resin degradable by gamma ray irradiation according to claim 1, wherein: the preparation method of the curing agent comprises the following specific steps: the molar ratio of the compound I to the compound II is 1-10: 1; the compound I and the compound II are subjected to click chemical reaction in a solvent to synthesize a compound III, and a light sourceThe absorption wavelength is 254-365 nm, a matched photoinitiator is selected according to the light source absorption wavelength, the concentration of the photoinitiator relative to the chemical I is 0.5-5 mol%, and the irradiation time is controlled to be 60-600 min; the molar ratio of the compound III to the chemical IV or the compound V is 1-10: 1; carrying out amine-aldehyde condensation reaction on the compound III and a chemical substance IV or a compound V in a solvent at the reaction temperature of 0-200 ℃ to synthesize a curing agent; the compound I is H2N-R1-SH; the compound II is
The compound III is
The compound IV is H2N-NH-R4-NH-NH2(ii) a Chemical V is H2N-O-R5-O-NH2。
3. The method for preparing a thermosetting epoxy resin degradable by gamma ray irradiation according to claim 2, wherein: the photoinitiator is at least one of 2-hydroxymethyl phenyl propane-1-ketone, diethoxyacetophenone, 1-hydroxycyclohexyl benzophenone, 2-hydroxy-2-methyl-1-p-ethyl ether phenyl acetone and isopropyl thioxanthone; 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, diethyl ether, petroleum ether, isopropyl ether, tetrahydrofuran, chloroform, dioxane, pyridine, acetone, acetonitrile, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone and dimethyl sulfoxide.
4. The method for preparing a thermosetting epoxy resin degradable by gamma ray irradiation according to claim 1, wherein: the epoxy resin comprises at least one of glycidyl ether type epoxy resin, glycidyl ester type epoxy resin, glycidyl amine type epoxy resin, trifunctional epoxy resin, tetrafunctional group epoxy resin, phenolic aldehyde type epoxy resin, o-cresol formaldehyde epoxy resin, aliphatic epoxy resin, alicyclic epoxy resin and nitrogen-containing epoxy resin.
5. The method for preparing a thermosetting epoxy resin degradable by gamma ray irradiation according to claim 1, wherein: in the preparation process, the reinforcement and the auxiliary material are added to obtain the epoxy resin composite material capable of being degraded by gamma ray irradiation.
6. The method for preparing a thermosetting epoxy resin degradable by gamma ray irradiation according to claim 5, wherein: 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 particle, metal oxide nano particle and organic nano particle; the auxiliary material comprises at least one of an accelerant, a diluent, a plasticizer, a flexibilizer, a thickening agent, a coupling agent, a defoaming agent, a leveling agent, an ultraviolet absorbent, an antioxidant, a brightening agent, a fluorescent agent, a pigment and a filler.
7. A degradation method of thermosetting epoxy resin which can be degraded by gamma ray irradiation and prepared according to any one of claims 1 to 6, is characterized in that: the method specifically comprises the following steps: at room temperature, using60A Co gamma ray radiation source realizes the degradation of the thermosetting epoxy resin in a solvent; wherein the irradiation dose is 10 KGy-1000 KGy, and the irradiation dose rate is 500 Gy-20 KGy.
8. The degradation method of a thermosetting epoxy resin degradable by gamma ray irradiation according to claim 7, 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, diethyl ether, petroleum ether, isopropyl ether, tetrahydrofuran, chloroform, dioxane, pyridine, acetone, acetonitrile, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone and dimethyl sulfoxide.
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