A radiation-resistant epoxy resin composite material and its preparation method

Abstract

This invention provides a radiation-resistant epoxy resin composite material and its preparation method. The method includes: (1) mixing a soluble cerium salt, an organic ligand, and a solvent to obtain a precursor solution; (2) subjecting the precursor solution to a hydrothermal reaction to obtain a cerium organic complex; and (3) mixing the cerium organic complex with epoxy resin, then adding a curing agent for curing to obtain the radiation-resistant epoxy resin composite material. The radiation-resistant epoxy resin composite material prepared by this invention has radiation resistance, effectively reducing the damage to epoxy resin during γ-ray irradiation.

Description

Technical Field

[0001] This invention relates to the field of high-performance resin technology, and in particular to a radiation-resistant epoxy resin composite material and its preparation method. Background Technology

[0002] In the field of deep space exploration, the harsh environment faced by spacecraft places extremely high demands on the performance of materials. Gamma-ray shielding is particularly important for protecting sensitive electronic equipment and biological organisms inside spacecraft. Epoxy resin, as a widely used polymer material, is extensively used in spacecraft structural materials and electronic packaging due to its excellent mechanical properties, chemical stability, and good adhesion. However, the free radicals generated in epoxy resin systems after exposure to gamma rays can destroy their cross-linked structure, reduce mechanical properties, and have irreversible effects on spacecraft. Therefore, there is an urgent need to provide a radiation-resistant epoxy resin composite material and its preparation method. Summary of the Invention

[0003] This invention provides a radiation-resistant epoxy resin composite material and its preparation method. The radiation-resistant epoxy resin composite material has radiation resistance and effectively reduces the damage to epoxy resin during γ-ray irradiation.

[0004] In a first aspect, the present invention provides a method for preparing a radiation-resistant epoxy resin composite material, the method comprising the following steps:

[0005] (1) Mix the soluble cerium salt, organic ligand and solvent to obtain the precursor solution;

[0006] (2) The precursor solution is subjected to a hydrothermal reaction to obtain a cerium organic complex;

[0007] (3) After mixing the cerium organic complex and epoxy resin, a curing agent is added for curing to obtain the radiation-resistant epoxy resin composite material.

[0008] Preferably, the soluble cerium salt is at least one of cerium nitrate and cerium ammonium nitrate.

[0009] Preferably, the organic ligand is 1,3,5-benzenetricarboxylic acid and 5-hydroxyisophthalic acid.

[0010] Preferably, the molar ratio of the soluble cerium salt to the organic ligand in the precursor solution is (0.1-1):(0.1-1).

[0011] More preferably, the soluble cerium salt is cerium ammonium nitrate.

[0012] Preferably, the molar ratio of 5-hydroxyisophthalic acid to 1,3,5-benzenetricarboxylic acid is (0.1 to 0.9):1.

[0013] Preferably, step (1) includes:

[0014] (11) Dissolve the soluble cerium salt in deionized water to obtain a first solution;

[0015] (12) Dissolve the organic ligand in an organic solvent to obtain a second solution; the solvent includes deionized water and the organic solvent.

[0016] (13) Add the second solution to the first solution and mix well to obtain the precursor solution.

[0017] More preferably, the organic solvent is N,N-dimethylformamide.

[0018] Preferably, in step (2): the temperature of the hydrothermal reaction is 50 to 150°C, and the reaction time is 0.5 to 3 hours.

[0019] Preferably, step (3) includes:

[0020] (31) The epoxy resin is heated and melted, and then the heated and melted epoxy resin and the cerium organic complex are added to a three-roll mill for mixing to obtain a premix.

[0021] (32) The curing agent is added to the premix and cured to obtain the radiation-resistant epoxy resin composite material.

[0022] Preferably, the heating and melting temperature is 80–150°C;

[0023] The ratio of the rotational speeds of the feed roller and the discharge roller of the three-roll mill is 1:(1-5), and the gap ratio is 1:(1-3).

[0024] Preferably, in step (3):

[0025] The mass ratio of the epoxy resin to the cerium organic complex is 100:(0.05~0.5);

[0026] The mass ratio of the epoxy resin matrix to the curing agent is 1:(3 to 3.5).

[0027] Preferably, the curing process employs a gradient heating method: the initial temperature is 100–150°C, the final temperature is 200–250°C, the heating gradient is 10–20°C, the heating rate is 1–4°C / min, and the holding time for each gradient stage is 1–3 hours.

[0028] In a second aspect, the present invention provides a radiation-resistant epoxy resin composite material, which is prepared by any of the preparation methods described in the first aspect above.

[0029] Preferably, the radiation-resistant epoxy resin composite material comprises epoxy resin and cerium organic complex, wherein the mass ratio of epoxy resin to cerium organic complex is 100:(0.05-0.5).

[0030] Compared with the prior art, the present invention has at least the following beneficial effects:

[0031] The defective cerium organic complex prepared by this invention has abundant Ce element and phenolic hydroxyl functional groups at the structural defect sites. The cerium element can control the formation of oxygen vacancies through valence state transitions, thereby capturing and scavenging free radicals generated during gamma irradiation. At the same time, the covalent bond defects formed by the phenolic hydroxyl functional groups can also achieve the scavenging and capture of free radicals. Therefore, the synergistic effect of the two can effectively inhibit the segmental degradation of epoxy resin during irradiation.

[0032] The radiation-resistant epoxy resin composite material with defective cerium organic complexes prepared by this invention, compared with unmodified pure epoxy resin, exhibits the following characteristics before irradiation: Before irradiation, the tensile strength of the radiation-resistant epoxy resin composite material with defective cerium organic complexes is 85.1 MPa, the Young's modulus is 1.72 GPa, and the elongation at break is 4.45%, which are 62.1% higher than the tensile strength, 20.3% higher Young's modulus, and 20.3% higher elongation at break compared with the same unirradiated pure epoxy resin. After irradiation, the tensile strength of the radiation-resistant epoxy resin composite material with defective cerium organic complexes is 73.8 MPa, the Young's modulus is 1.69 GPa, and the elongation at break is 4.23%, which are 82.6% higher than the tensile strength, 28.0% higher Young's modulus, and 18.83% higher elongation at break compared with the same irradiated pure epoxy resin. Obviously, the radiation-resistant epoxy resin composite material prepared by this invention effectively avoids the reduction in mechanical properties caused by the degradation of epoxy resin molecular chain segments during irradiation. Attached Figure Description

[0033] To more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are some embodiments of the present invention. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.

[0034] Figure 1 This is a flowchart of a method for preparing a radiation-resistant epoxy resin composite material according to an embodiment of the present invention;

[0035] Figure 2 These are infrared spectra of cerium organic complexes provided in Embodiments 1, 2 and 3 of the present invention. Detailed Implementation

[0036] To make the objectives, technical solutions, and advantages of the embodiments of the present invention clearer, the technical solutions of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention. Obviously, the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments obtained by those skilled in the art based on the embodiments of the present invention without creative effort are within the scope of protection of the present invention.

[0037] This invention provides a method for preparing radiation-resistant epoxy resin composite materials, such as... Figure 1 As shown, the preparation method includes the following steps:

[0038] (1) Mix the soluble cerium salt, organic ligand and solvent to obtain the precursor solution;

[0039] (2) The precursor solution was subjected to a hydrothermal reaction to obtain a cerium organic complex;

[0040] (3) After mixing the cerium organic complex and epoxy resin, a curing agent is added for curing to obtain a radiation-resistant epoxy resin composite material.

[0041] According to some preferred embodiments, the soluble cerium salt is at least one of cerium nitrate and cerium ammonium nitrate.

[0042] It should be noted that "at least one" means any one or more of them mixed in any proportion.

[0043] According to some preferred embodiments, the organic ligands are 1,3,5-benzenetricarboxylic acid and 5-hydroxyisophthalic acid.

[0044] In this invention, 5-hydroxyisophthalic acid is introduced as a defect agent to obtain a cerium organic complex with structural defects. The complex has Ce element and phenolic hydroxyl functional groups. The synergistic effect of Ce element and phenolic hydroxyl groups at the structural defect sites can effectively scavenge free radicals generated by epoxy resin during gamma irradiation, thereby effectively inhibiting the segmental degradation of epoxy resin.

[0045] According to some preferred embodiments, the molar ratio of soluble cerium salt to organic ligand in the precursor solution is (0.1-1):(0.1-1) (for example, it can be 0.1:0.1, 0.1:0.2, 0.1:0.3, 0.1:0.4, 0.1:0.5, 0.1:0.6, 0.1:0.7, 0.1:0.8, 0.1:0.9, 0.1:1, etc.). (0.5:0.1, 0.5:0.2, 0.5:0.3, 0.5:0.4, 0.5:0.5, 0.5:0.6, 0.5:0.7, 0.5:0.8, 0.5:0.9, 0.5:1, 1:0.1, 1:0.2, 1:0.3, 1:0.4, 1:0.5, 1:0.6, 1:0.7, 1:0.8, or 1:0.9). It should be noted that the molar ratio refers to the molar concentration ratio.

[0046] According to some preferred embodiments, the soluble cerium salt is cerium ammonium nitrate.

[0047] According to some preferred embodiments, the molar ratio of 5-hydroxyisophthalic acid to 1,3,5-benzenetricarboxylic acid is (0.1 to 0.9):1 (for example, it can be 0.1:1, 0.2:1, 0.3:1, 0.4:1, 0.5:1, 0.6:1, 0.7:1, 0.8:1 or 0.9:1).

[0048] In this invention, experiments have confirmed that if the amount of 5-hydroxyisophthalic acid in the organic ligand is too small, it is difficult to effectively inhibit the degradation of epoxy resin molecular chain segments during irradiation; however, if the amount of 5-hydroxyisophthalic acid is too large, it will lead to structural instability, which will change itself during irradiation, resulting in structural changes, and thus affecting the scavenging and capture of free radicals.

[0049] Specifically, the cerium organic complex prepared by this invention has a spherical structure with a diameter of 200-500 nm (for example, it can be 200 nm, 205 nm, 210 nm, 215 nm, 225 nm, 230 nm, 240 nm, 250 nm, 260 nm, 300 nm, 325 nm, 350 nm, 375 nm, 400 nm, 425 nm, 450 nm, 475 nm or 500 nm).

[0050] According to some preferred embodiments, step (1) includes:

[0051] (11) Dissolve the soluble cerium salt in deionized water to obtain the first solution;

[0052] (12) Dissolve the organic ligand in an organic solvent to obtain a second solution; the solvent includes deionized water and an organic solvent;

[0053] (13) Add the second solution to the first solution and mix well to obtain the precursor solution.

[0054] According to some preferred embodiments, the organic solvent is N,N-dimethylformamide.

[0055] Specifically, a certain amount of soluble cerium salt is dissolved in deionized water to obtain a first solution. A certain amount of mesitylenic acid and 5-hydroxyisophthalic acid are dissolved in N,N-dimethylformamide (DMF) to obtain a second solution. The second solution is then introduced into the first solution and stirred to obtain a precursor solution.

[0056] According to some preferred embodiments, in step (2): the temperature of the hydrothermal reaction is 50 to 150°C (for example, it can be 50°C, 55°C, 60°C, 70°C, 80°C, 90°C, 100°C, 110°C, 120°C, 130°C, 140°C, 145°C or 150°C), and the reaction time is 0.5 to 3 hours (for example, it can be 0.5 hours, 1 hour, 1.5 hours, 2 hours, 2.5 hours or 3 hours).

[0057] Specifically, after the hydrothermal reaction of the precursor solution is completed, it is allowed to cool naturally to room temperature and then centrifuged, washed, and dried to obtain the cerium organic complex.

[0058] According to some preferred embodiments, step (3) includes:

[0059] (31) The epoxy resin is heated and melted, and then the heated and melted epoxy resin and cerium organic complex are added to a three-roll mill for mixing to obtain a premix.

[0060] (32) Add a curing agent to the premix and cure it to obtain a radiation-resistant epoxy resin composite material.

[0061] According to some preferred embodiments, the heating and melting temperature is 80 to 150°C (for example, it can be 80°C, 85°C, 90°C, 95°C, 100°C, 105°C, 110°C, 115°C, 120°C, 125°C, 130°C, 135°C, 140°C, 145°C or 150°C).

[0062] The ratio of the rotational speeds of the feed roller and the discharge roller of the three-roll mill is 1:(1 to 5) (for example, it can be 1:1, 1:1.5, 1:2, 1:2.5, 1:3, 1:3.5, 1:4, 1:4.5 or 1:5), and the gap ratio is 1:(1 to 3) (for example, it can be 1:1, 1:1.5, 1:2, 1:2.5 or 1:3).

[0063] In this invention, heating and melting the epoxy resin reduces its viscosity to 5–10 Pa·s, which facilitates thorough mixing of the epoxy resin and the cerium organic complex. This avoids leakage on the three-roll mill due to excessively low viscosity, and also prevents uneven dispersion due to excessively high viscosity. Simultaneously, the three-roll mill is used to grind and disperse the heated and molten epoxy resin and the cerium organic complex, ensuring that the cerium organic complex is uniformly dispersed within the epoxy resin.

[0064] More specifically, the cerium organic complex is better dispersed by controlling the number of grinding cycles on a three-roll mill. The more grinding cycles, the more dispersed the cerium organic complex, thus solving the problem of cerium organic complex agglomeration. Preferably, the number of grinding cycles is 10 to 20. The heated and molten epoxy resin and cerium organic complex are slowly added to the three-roll mill for thorough grinding, which is considered one grinding cycle. Furthermore, since the viscosity of the premix increases with the decrease in temperature after each grinding cycle, affecting the grinding effect, after each grinding cycle, the product collected at the discharge roller needs to be placed in an oil bath (e.g., at 80°C) and heated for a period of time to reduce the viscosity of the slurry, thereby achieving the purpose of better dispersing the cerium organic complex in the next grinding process.

[0065] It should be noted that in step (32), after the premix is ​​heated, a curing agent is added, mixed thoroughly, and then cured to obtain a radiation-resistant epoxy resin composite material. Thus, by heating the premix before adding the curing agent, the two materials can be thoroughly mixed.

[0066] According to some preferred embodiments, in step (3):

[0067] The mass ratio of epoxy resin to cerium organic complex is 100:(0.05 to 0.5) (for example, it can be 100:0.05, 100:0.055, 100:0.06, 100:0.07, 100:0.08, 100:0.09, 100:0.1, 100:0.15, 100:0.2, 100:0.25, 100:0.3, 100:0.35, 100:0.4, 100:0.45, 100:0.48, 100:0.5);

[0068] The mass ratio of epoxy resin matrix to curing agent is 1:(3 to 3.5) (for example, it can be 1:3, 1:3.05, 1:3.1, 1:3.2, 1:3.3, 1:3.4 or 1:3.5).

[0069] It should be noted that the epoxy resin can be at least one of the group consisting of glycidyl ethers, glycidyl esters, and glycidyl amines. The curing agent can be at least one of the group consisting of diaminodiphenylmethane (DDM), 4,4'-dioxydiphenyl sulfone (DDS), and dicyandiamine (DICY).

[0070] In this invention, experiments have confirmed that if the mass ratio of epoxy resin to cerium organic complex is greater than 100:0.05, the amount of cerium organic complex used is too low, resulting in poor radiation resistance of the prepared radiation-resistant epoxy resin composite material. If the mass ratio of epoxy resin to cerium organic complex is less than 100:0.5, the amount of cerium organic complex used is too high. Although this can further improve the resistance to gamma ray irradiation, it will cause the cerium organic complex to agglomerate, affecting the mechanical properties of the prepared radiation-resistant epoxy resin composite material.

[0071] According to some preferred embodiments, curing employs a gradient temperature increase: the initial temperature is 100–150°C (e.g., 100°C, 106°C, 110°C, 115°C, 120°C, 125°C, 130°C, 135°C, 140°C, 148°C, or 150°C), and the final temperature is 200–250°C (e.g., 200°C, 206°C, 210°C, 215°C, 220°C, 225°C, 230°C, 235°C, 240°C, 246°C, or 250°C), with a temperature gradient of 10°C. The temperature range is 1-20℃ (e.g., 10℃, 10.5℃, 11℃, 12℃, 13℃, 14℃, 15℃, 16℃, 17℃, 18℃, 19℃ or 20℃), the heating rate is 1-4℃ / min (e.g., 1℃ / min, 1.5℃ / min, 2℃ / min, 2.5℃ / min, 3℃ / min, 3.5℃ / min or 4℃ / min), and the holding time for each gradient stage is 1-3h (e.g., 1h, 1.5h, 2h, 2.5h or 3h).

[0072] The present invention also provides a radiation-resistant epoxy resin composite material, which is prepared by the preparation method provided in the present invention.

[0073] To more clearly illustrate the technical solution and advantages of the present invention, the following detailed description of a radiation-resistant epoxy resin composite material and its preparation method is provided through several embodiments.

[0074] Example 1

[0075] Preparation of cerium organic complexes:

[0076] 0.2 mol of cerium ammonium nitrate was dissolved in 400 mL of deionized water to obtain the first solution. 0.035 mol of 1,3,5-benzenetricarboxylic acid and 0.0175 mol of 5-hydroxyisophthalic acid were dissolved in 600 mL of N,N-dimethylformamide (DMF) to obtain the second solution. The second solution was added to the first solution and stirred at 30 °C to obtain the precursor solution. The precursor solution was subjected to a hydrothermal reaction at 100 °C for 0.5 h, followed by washing with tetrahydrofuran (THF) and acetone, centrifugation, and vacuum drying to obtain the cerium organic complex. The infrared spectrum of the cerium organic complex is shown below. Figure 2 As shown.

[0077] Preparation of radiation-resistant epoxy resin composite materials:

[0078] Bisphenol A type epoxy resin was heated to 100°C, and then the heated and molten epoxy resin was added to a three-roll mill. The cerium organic complex (the mass ratio of epoxy resin matrix to cerium organic complex was 100:0.2) prepared above was also placed into the three-roll mill. Under the conditions of a speed ratio of 1:1 and a gap ratio of 1:1, the mill was rolled until it was observed that the cerium organic complex was fully and uniformly mixed with the epoxy resin matrix to obtain a premix.

[0079] The premix was heated to 140°C in an oil bath, and DDS curing agent was added at a mass ratio of 1:3. After stirring thoroughly for 1 hour, a mixture was obtained. The mixture was then placed in a vacuum drying oven at 40°C for heat preservation and defoaming for 30 minutes. The mixture was then poured into a mold, and the mold was placed in an oven with an initial temperature of 100°C for programmed temperature rise, ending at 200°C. The temperature gradient was 10°C, and each gradient temperature was held for 1 hour. The heating rate was 1°C / min, resulting in a radiation-resistant epoxy resin composite material.

[0080] Example 2

[0081] Preparation of cerium organic complexes:

[0082] 0.2 mol of cerium ammonium nitrate was dissolved in 400 mL of deionized water to obtain the first solution. 0.4 mol of 1,3,5-benzenetricarboxylic acid and 0.2 mol of 5-hydroxyisophthalic acid were dissolved in 600 mL of N,N-dimethylformamide (DMF) to obtain the second solution. The second solution was added to the first solution and stirred at 30 °C to obtain the precursor solution. The precursor solution was subjected to a hydrothermal reaction at 150 °C for 0.5 h, followed by washing with tetrahydrofuran (THF) and acetone, centrifugation, and vacuum drying to obtain the cerium organic complex. The infrared spectrum of the cerium organic complex is shown below. Figure 2 As shown.

[0083] Preparation of radiation-resistant epoxy resin composite materials:

[0084] Bisphenol A type epoxy resin was heated to 80°C, and then the heated and molten epoxy resin was added to a three-roll mill. The cerium organic complex (the mass ratio of epoxy resin matrix to cerium organic complex was 100:0.2) prepared above was also placed into the three-roll mill. Under the conditions of a speed ratio of 1:5 and a gap ratio of 1:1, the mill was rolled until it was observed that the cerium organic complex was fully and uniformly mixed with the epoxy resin matrix to obtain a premix.

[0085] The premix was heated to 140°C in an oil bath, and DDS curing agent was added at a mass ratio of 1:3. After stirring thoroughly for 1 hour, a mixture was obtained. The mixture was then placed in a vacuum drying oven at 40°C for heat preservation and defoaming for 30 minutes. The mixture was then poured into a mold, and the mold was placed in an oven with an initial temperature of 100°C for programmed temperature rise, ending at 200°C. The temperature gradient was 10°C, and each gradient temperature was held for 1 hour. The heating rate was 1°C / min, resulting in a radiation-resistant epoxy resin composite material.

[0086] Example 3

[0087] Preparation of cerium organic complexes:

[0088] 0.2 mol of cerium ammonium nitrate was dissolved in 400 mL of deionized water to obtain the first solution. 1.33 mol of 1,3,5-benzenetricarboxylic acid and 0.67 mol of 5-hydroxyisophthalic acid were dissolved in 600 mL of N,N-dimethylformamide (DMF) to obtain the second solution. The second solution was added to the first solution and stirred at 30 °C to obtain the precursor solution. The precursor solution was subjected to a hydrothermal reaction at 100 °C for 0.5 h, followed by washing with tetrahydrofuran (THF) and acetone, centrifugation, and vacuum drying to obtain the cerium organic complex.

[0089] Preparation of radiation-resistant epoxy resin composite materials:

[0090] Bisphenol A type epoxy resin is heated to 100°C, and then the heated and molten epoxy resin is added to a three-roll mill. The cerium organic complex (the mass ratio of epoxy resin matrix to cerium organic complex is 100:0.2) prepared above is also placed into the three-roll mill. Under the conditions of a speed ratio of 1:2 and a gap ratio of 1:1, the mill is rolled until the cerium organic complex is observed to be fully and uniformly mixed with the epoxy resin matrix to obtain a premix.

[0091] The premix was heated to 140°C in an oil bath, and DDS curing agent was added at a mass ratio of 1:3. After stirring thoroughly for 1 hour, a mixture was obtained. The mixture was then placed in a vacuum drying oven at 40°C for heat preservation and defoaming for 30 minutes. The mixture was then poured into a mold, and the mold was placed in an oven with an initial temperature of 100°C for programmed temperature rise, ending at 200°C. The temperature gradient was 10°C, and each gradient temperature was held for 1 hour. The heating rate was 1°C / min, resulting in a radiation-resistant epoxy resin composite material.

[0092] Example 4

[0093] Preparation of cerium organic complexes:

[0094] 2 mol of cerium ammonium nitrate was dissolved in 400 mL of deionized water to obtain the first solution. 0.133 mol of 1,3,5-benzenetricarboxylic acid and 0.067 mol of 5-hydroxyisophthalic acid were dissolved in 600 mL of N,N-dimethylformamide (DMF) to obtain the second solution. The second solution was added to the first solution and stirred at 30 °C to obtain the precursor solution. The precursor solution was subjected to a hydrothermal reaction at 100 °C for 0.5 h, followed by washing with tetrahydrofuran (THF) and acetone, centrifugation, and vacuum drying to obtain the cerium organic complex.

[0095] Preparation of radiation-resistant epoxy resin composite materials:

[0096] Bisphenol A type epoxy resin is heated to 100°C, and then the heated and molten epoxy resin is added to a three-roll mill. The cerium organic complex (the mass ratio of epoxy resin matrix to cerium organic complex is 100:0.2) prepared above is also placed into the three-roll mill. Under the conditions of a speed ratio of 1:3 and a gap ratio of 1:3, the mill is rolled until it is observed that the cerium organic complex is fully and uniformly mixed with the epoxy resin matrix to obtain a premix.

[0097] The premix was heated to 140°C in an oil bath, and DDS curing agent was added at a mass ratio of 1:3. After stirring thoroughly for 1 hour, a mixture was obtained. The mixture was then placed in a vacuum drying oven at 40°C for heat preservation and defoaming for 30 minutes. The mixture was then poured into a mold, and the mold was placed in an oven with an initial temperature of 100°C for programmed temperature rise, ending at 200°C. The temperature gradient was 10°C, and each gradient temperature was held for 1 hour. The heating rate was 1°C / min, resulting in a radiation-resistant epoxy resin composite material.

[0098] Example 5

[0099] Preparation of cerium organic complexes:

[0100] 0.2 mol of cerium ammonium nitrate was dissolved in 400 mL of deionized water to obtain the first solution. 0.035 mol of 1,3,5-benzenetricarboxylic acid and 0.0175 mol of 5-hydroxyisophthalic acid were dissolved in 600 mL of N,N-dimethylformamide (DMF) to obtain the second solution. The second solution was added to the first solution and stirred at 30 °C to obtain the precursor solution. The precursor solution was subjected to a hydrothermal reaction at 50 °C for 3 h, followed by washing with tetrahydrofuran (THF) and acetone, centrifugation, and vacuum drying to obtain the cerium organic complex.

[0101] Preparation of radiation-resistant epoxy resin composite materials:

[0102] Bisphenol A type epoxy resin is heated to 100°C, and then the heated and molten epoxy resin is added to a three-roll mill. The cerium organic complex (the mass ratio of epoxy resin matrix to cerium organic complex is 100:0.05) prepared above is also placed into the three-roll mill. Under the conditions of a speed ratio of 1:1 and a gap ratio of 1:1, the mill is rolled until it is observed that the cerium organic complex is fully and uniformly mixed with the epoxy resin matrix to obtain a premix.

[0103] The premix was heated to 140°C in an oil bath, and DDS curing agent was added at a mass ratio of 1:3.5. After stirring thoroughly for 1 hour, a mixture was obtained. The mixture was then placed in a vacuum drying oven at 40°C for heat preservation and defoaming for 30 minutes. The mixture was then poured into a mold, and the mold was placed in an oven with an initial temperature of 100°C for programmed temperature rise, ending at 200°C. The temperature gradient was 20°C, and each gradient temperature was maintained for 3 hours. The heating rate was 2°C / min, resulting in a radiation-resistant epoxy resin composite material.

[0104] Example 6

[0105] Example 6 is the same as Example 5, except that the mass ratio of epoxy resin matrix to cerium organic complex is 100:0.5.

[0106] Example 7

[0107] Preparation of cerium organic complexes:

[0108] 0.2 mol of cerium ammonium nitrate was dissolved in 400 mL of deionized water to obtain the first solution. 0.035 mol of 1,3,5-benzenetricarboxylic acid and 0.0175 mol of 5-hydroxyisophthalic acid were dissolved in 600 mL of N,N-dimethylformamide (DMF) to obtain the second solution. The second solution was added to the first solution and stirred at 30 °C to obtain the precursor solution. The precursor solution was subjected to a hydrothermal reaction at 100 °C for 0.5 h, followed by washing with tetrahydrofuran (THF) and acetone, centrifugation, and vacuum drying to obtain the cerium organic complex.

[0109] Preparation of radiation-resistant epoxy resin composite materials:

[0110] Bisphenol A type epoxy resin was heated to 100°C, and then the heated and molten epoxy resin was added to a three-roll mill. The cerium organic complex (the mass ratio of epoxy resin matrix to cerium organic complex was 100:0.2) prepared above was also placed into the three-roll mill. Under the conditions of a speed ratio of 1:1 and a gap ratio of 1:1, the mill was rolled until it was observed that the cerium organic complex was fully and uniformly mixed with the epoxy resin matrix to obtain a premix.

[0111] The premix was heated to 140°C in an oil bath, and DDS curing agent was added at a mass ratio of 1:3. After stirring thoroughly for 1 hour, a mixture was obtained. The mixture was then placed in a vacuum drying oven at 40°C for heat preservation and defoaming for 30 minutes. The mixture was then poured into a mold, and the mold was placed in an oven with an initial temperature of 100°C for programmed temperature rise, ending at 200°C. The temperature gradient was 10°C, and each gradient temperature was held for 1 hour. The heating rate was 1°C / min, resulting in a radiation-resistant epoxy resin composite material.

[0112] Example 7

[0113] Example 7 is basically the same as Example 1, except that the composition of the second solution is different. Specifically, 0.0276 mol of 1,3,5-benzenetricarboxylic acid and 0.0249 mol of 5-hydroxyisophthalic acid are dissolved in 600 mL of N,N-dimethylformamide (DMF) to obtain the second solution.

[0114] Example 8

[0115] Example 8 is basically the same as Example 1, except that the composition of the second solution is different. Specifically, 0.0477 mol of 1,3,5-benzenetricarboxylic acid and 0.0048 mol of 5-hydroxyisophthalic acid are dissolved in 600 mL of N,N-dimethylformamide (DMF) to obtain the second solution.

[0116] Example 9

[0117] Example 9 is basically the same as Example 1, except that the composition of the second solution is different. Specifically, 0.0375 mol of 1,3,5-benzenetricarboxylic acid and 0.015 mol of 5-hydroxyisophthalic acid are dissolved in 600 mL of N,N-dimethylformamide (DMF) to obtain the second solution.

[0118] Comparative Example 1

[0119] Comparative Example 1 is basically the same as Example 1, except that the cerium organic complex prepared in Example 1 was not added to the bisphenol A type epoxy resin.

[0120] Comparative Example 2

[0121] Comparative Example 2 is basically the same as Example 1, except that cerium oxide is used instead of cerium organic complex.

[0122] Specifically, bisphenol A type epoxy resin is heated to 100°C, and then the heated and molten epoxy resin is added to a three-roll mill. The cerium oxide (the mass ratio of epoxy resin matrix to cerium oxide CeO2 is 100:0.2) prepared above is also placed into the three-roll mill. Under the conditions of a speed ratio of 1:1 and a gap ratio of 1:1, the mill is rolled until it is observed that the cerium oxide is fully and uniformly mixed with the epoxy resin matrix to obtain a premix.

[0123] The premix was heated to 140°C in an oil bath, and DDS curing agent was added at a mass ratio of 1:3. After stirring thoroughly for 1 hour, a mixture was obtained. The mixture was then placed in a vacuum drying oven at 40°C for heat preservation and defoaming for 30 minutes. The mixture was then poured into a mold, and the mold was placed in an oven with an initial temperature of 100°C for programmed temperature rise, ending at 200°C. The temperature gradient was 10°C, and each gradient temperature was held for 1 hour. The heating rate was 1°C / min, resulting in an epoxy resin composite material.

[0124] Comparative Example 3

[0125] Comparative Example 3 is essentially the same as Example 1, except that 5-hydroxyisophthalic acid was not added during the preparation of the cerium organic complex. The infrared spectrum of the cerium organic complex is shown below. Figure 2 As shown.

[0126] Comparative Example 4

[0127] Comparative Example 4 is basically the same as Example 1, except that the mass ratio of epoxy resin to cerium organic complex is 100:0.6.

[0128] The radiation-resistant epoxy resin composites and epoxy resin composites obtained in the examples and comparative examples were subjected to performance tests, and the test data are shown in Table 1.

[0129] Specifically, the tensile properties of radiation-resistant epoxy resin composites and epoxy resin composites at room temperature were tested according to GB / T 2567-2008 standard using an INSTRON 5967 electronic universal testing machine (USA). Before irradiation, standard dumbbell-shaped samples of the radiation-resistant epoxy resin composites were prepared and tested at a loading rate of 2 mm / min. Then, standard dumbbell-shaped samples of the radiation-resistant epoxy resin composites were irradiated at a dose of 800 kGy, and the irradiated samples were tested. At least five samples of each radiation-resistant epoxy resin composite were prepared and tested separately.

[0130] Table 1

[0131]

[0132] As shown in Table 1, the radiation-resistant epoxy resin composite material prepared in this invention still exhibits excellent mechanical properties under an irradiation dose of 800 kGy, effectively avoiding the reduction in mechanical properties caused by the degradation of epoxy resin molecular chain segments during irradiation. Compared with Comparative Example 1, Example 1 showed significant improvements in tensile strength, Young's modulus, and elongation at break before and after irradiation. In Comparative Example 2, cerium oxide was used instead of cerium organic complexes, which improved the mechanical properties and radiation resistance of pure epoxy resin, but its radiation resistance was still lower than that of Example 1. Similarly, in Comparative Example 3, since 5-hydroxyisophthalic acid was not added, the cerium organic complex prepared did not have phenolic hydroxyl functional groups, and therefore its radiation resistance was still lower than that of Example 1. Compared with Comparative Example 4, Example 1 showed improved radiation resistance due to the addition of more cerium organic complexes, but this affected the mechanical properties of the prepared radiation-resistant epoxy resin composite material.

[0133] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, and not to limit them. Although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art should understand that modifications can still be made to the technical solutions described in the foregoing embodiments, or equivalent substitutions can be made to some of the technical features; and these modifications or substitutions do not cause the essence of the corresponding technical solutions to deviate from the spirit and scope of the technical solutions of the embodiments of the present invention. The parts of the present invention not described in detail are techniques known to those skilled in the art.

Claims

1. A method for preparing a radiation-resistant epoxy resin composite material, characterized in that, The preparation method includes: (1) A soluble cerium salt, an organic ligand and a solvent are mixed to obtain a precursor solution; the organic ligand is 1,3,5-benzenetricarboxylic acid and 5-hydroxyisophthalic acid; the molar ratio of 5-hydroxyisophthalic acid and 1,3,5-benzenetricarboxylic acid is (0.1~0.9):1; (2) The precursor solution is subjected to a hydrothermal reaction to obtain a cerium organic complex; (3) After mixing the cerium organic complex and epoxy resin, a curing agent is added for curing to obtain the radiation-resistant epoxy resin composite material; the mass ratio of the epoxy resin and the cerium organic complex is 100:(0.05~0.5).

2. The preparation method according to claim 1, characterized in that, The soluble cerium salt is at least one of cerium nitrate and cerium ammonium nitrate.

3. The preparation method according to claim 1, characterized in that, The molar ratio of the soluble cerium salt to the organic ligand in the precursor solution is (0.1~1):(0.1~1).

4. The preparation method according to claim 1, characterized in that, The soluble cerium salt is cerium ammonium nitrate.

5. The preparation method according to claim 1, characterized in that, Step (1) includes: (11) Dissolve the soluble cerium salt in deionized water to obtain a first solution; (12) Dissolve the organic ligand in an organic solvent to obtain a second solution; the organic solvent is N,N-dimethylformamide; (13) Add the second solution to the first solution and mix well to obtain the precursor solution.

6. The preparation method according to claim 1, characterized in that, In step (2): the temperature of the hydrothermal reaction is 50~150℃ and the reaction time is 0.5~3h.

7. The preparation method according to claim 1, characterized in that, Step (3) includes: (31) The epoxy resin is heated and melted, and then the heated and melted epoxy resin and the cerium organic complex are added to a three-roll mill for mixing to obtain a premix; (32) The curing agent is added to the premix and cured to obtain the radiation-resistant epoxy resin composite material.

8. The preparation method according to claim 7, characterized in that: The heating and melting temperature is 80~150℃; The ratio of the rotational speeds of the feed roller and the discharge roller of the three-roll mill is 1:(1~5), and the gap ratio is 1:(1~3).

9. The preparation method according to any one of claims 1 to 8, characterized in that, In step (3): The mass ratio of the epoxy resin to the curing agent is 1:(3~3.5).

10. The preparation method according to any one of claims 1 to 8, characterized in that, In step (3): The curing process employs a gradient heating method: the initial temperature is 100~150℃, the final temperature is 200~250℃, the heating gradient is 10~20℃, the heating rate is 1~4℃ / min, and the holding time for each gradient stage is 1~3h.

11. A radiation-resistant epoxy resin composite material, characterized in that, It is prepared by any of the preparation methods described in claims 1 to 10.

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