Radiation-resistant epoxy resin composite material and preparation method thereof

Abstract

The invention provides a radiation-resistant epoxy resin composite material and a preparation method thereof, and the method comprises the following steps: (1) uniformly mixing soluble cerium salt, an organic ligand and a solvent to obtain a precursor solution; (2) carrying out hydrothermal reaction on the precursor solution to obtain a cerium organic complex; and (3) mixing the cerium organic complex with epoxy resin, and then adding a curing agent for curing to obtain the radiation-resistant epoxy resin composite material. The prepared irradiation-resistant epoxy resin composite material has irradiation resistance, and effectively reduces the damage of epoxy resin in the gamma ray irradiation process.

Description

Technical Field

[0001] The invention relates to the technical field of high-performance resins, and in particular to a radiation-resistant epoxy resin composite material and a preparation method thereof. Background Art

[0002] In the field of deep space exploration, the harsh environment faced by spacecraft places extremely high demands on the performance of materials. In particular, for the protection of sensitive electronic equipment and organisms inside spacecraft, gamma-ray shielding is particularly important. Epoxy resin, as a widely used polymer material, has been widely used in structural materials and electronic packaging of spacecraft due to its excellent mechanical properties, chemical stability and good adhesion. However, the free radicals generated in the epoxy resin system after being exposed to gamma rays will destroy its own cross-linked structure, reduce mechanical properties, and have irreversible effects on spacecraft. Therefore, it is urgent to provide a radiation-resistant epoxy resin composite material and a preparation method thereof. Summary of the invention

[0003] The embodiment of the present invention provides a radiation-resistant epoxy resin composite material and a preparation method thereof. The radiation-resistant epoxy resin composite material has radiation resistance and effectively reduces the damage of the epoxy resin during gamma ray irradiation.

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

[0005] (1) mixing a soluble cerium salt, an organic ligand and a solvent to obtain a precursor solution;

[0006] (2) subjecting the precursor solution to a hydrothermal reaction to obtain a cerium organic complex;

[0007] (3) After mixing the cerium organic complex and the epoxy resin, a curing agent is added to perform 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 ammonium cerium nitrate.

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

[0013] Preferably, step (1) comprises:

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

[0015] (12) dissolving the organic ligand in an organic solvent to obtain a second solution; the solvent comprises 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 50-150° C., and the reaction time is 0.5-3 h.

[0019] Preferably, step (3) comprises:

[0020] (31) heating and melting the epoxy resin, and then adding the heated and molten epoxy resin and the cerium organic complex into a three-roll mill for mixing to obtain a premix;

[0021] (32) Adding the curing agent to the premix for curing to obtain the radiation-resistant epoxy resin composite material.

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

[0023] The rotation speed ratio of the feed roller and the discharge roller of the three-roller machine 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:(3-3.5).

[0027] Preferably, the curing adopts gradient temperature rise: the starting temperature is 100-150°C, the ending temperature is 200-250°C, the temperature rise gradient is 10-20°C, the temperature rise rate is 1-4°C / min, and the insulation time of each gradient stage is 1-3h.

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

[0029] Preferably, the radiation-resistant epoxy resin composite material comprises epoxy resin and a cerium organic complex, and the mass ratio of the epoxy resin to the 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 the present invention has rich Ce elements and has phenolic hydroxyl functional groups at the structural defect positions. The cerium element can control the formation of oxygen vacancies through valence state transition, thereby capturing and removing free radicals generated during gamma irradiation. At the same time, the covalent bond defects formed by the phenolic hydroxyl functional groups can also remove and capture free radicals. Therefore, the synergistic effect of the two can effectively inhibit the segment degradation of epoxy resin during irradiation.

[0032] The radiation-resistant epoxy resin composite material added with defective cerium organic complex prepared by the present invention has a tensile strength of 85.1MPa, a Young's modulus of 1.72GPa and an elongation at break of 4.45% before irradiation, which is 62.1% higher than the tensile strength, 20.3% higher than the Young's modulus and 20.3% higher than the pure epoxy resin that has not been irradiated; after irradiation, the radiation-resistant epoxy resin composite material added with defective cerium organic complex has a tensile strength of 73.8MPa, a Young's modulus of 1.69GPa and an elongation at break of 4.23%, which is 82.6% higher than the tensile strength, 28.0% higher than the Young's modulus and 18.83% higher than the pure epoxy resin that has been irradiated. Obviously, the radiation-resistant epoxy resin composite material prepared by the present invention can effectively avoid the reduction of mechanical properties caused by the degradation of epoxy resin molecular chain segments during the irradiation process. BRIEF DESCRIPTION OF THE DRAWINGS

[0033] In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings required for use in the embodiments or the description of the prior art will be briefly introduced below. Obviously, the drawings described below are some embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying creative work.

[0034] Figure 1 It is a flow chart of a method for preparing a radiation-resistant epoxy resin composite material provided by one embodiment of the present invention;

[0035] Figure 2 It is the infrared spectra of the cerium organic complexes provided in Example 1, Example 2 and Comparative Example 3 of the present invention. DETAILED DESCRIPTION

[0036] In order to make the purpose, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the present invention will be clearly and completely described in combination with the embodiments of the present invention. Obviously, the described embodiments are part of the embodiments of the present invention, rather than all the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making creative work are within the scope of protection of the present invention.

[0037] The present invention provides a method for preparing a radiation-resistant epoxy resin composite material, such as Figure 1 As shown, the preparation method comprises the following steps:

[0038] (1) mixing a soluble cerium salt, an organic ligand and a solvent to obtain a precursor solution;

[0039] (2) subjecting the precursor solution to a hydrothermal reaction to obtain a cerium organic complex;

[0040] (3) After the cerium organic complex and the epoxy resin are mixed, 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 is any one or a mixture of any several in any proportion.

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

[0044] In the present invention, 5-hydroxyisophthalic acid is introduced as a defect agent to obtain a cerium organic complex with structural defects having a Ce element and a phenolic hydroxyl functional group. The synergistic effect of the Ce element and the phenolic hydroxyl at the structural defect position can effectively remove the free radicals generated by the epoxy resin during the gamma irradiation process, thereby effectively inhibiting the segment degradation of the epoxy resin.

[0045] According to some preferred embodiments, the molar ratio of the soluble cerium salt to the 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, 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 is the ratio of molar concentration.

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

[0047] According to some preferred embodiments, the molar ratio of 5-hydroxyisophthalic acid to 1,3,5-benzenetricarboxylic acid is (0.1-0.9):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 the present invention, it has been experimentally 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 the epoxy resin molecular segments during the irradiation process; however, if the amount of 5-hydroxyisophthalic acid is too large, it will lead to an unstable system structure, which will change itself during the irradiation process, resulting in structural changes, thereby affecting the scavenging and capture of free radicals.

[0049] Specifically, the cerium organic complex prepared by the present invention is a spherical structure with a diameter of 200 to 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) comprises:

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

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

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

[0054] According to some more 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 mesitylene acid and 5-hydroxyisophthalic acid are dissolved in N,N-dimethylformamide (DMF) to obtain a second solution, and then the second solution is introduced into the first solution, stirred and mixed to obtain a precursor solution.

[0056] According to some preferred embodiments, in step (2): the temperature of the hydrothermal reaction is 50-150°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 0.5-3h (for example, it can be 0.5h, 1h, 1.5h, 2h, 2.5h or 3h).

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

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

[0059] (31) heating and melting the epoxy resin, and then adding the heated and molten epoxy resin and the cerium organic complex into a three-roll mill for mixing to obtain a premix;

[0060] (32) A curing agent is added to the premix for curing 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, 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 rotational speed ratio of the feed roller and the discharge roller of the three-roll mill is 1:(1-5) (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:(1-3) (for example, it can be 1:1, 1:1.5, 1:2, 1:2.5 or 1:3).

[0063] In the present invention, the epoxy resin is heated and melted to reduce the viscosity of the epoxy resin to 5-10 Pa·s, which is more conducive to fully mixing the epoxy resin and the cerium organic complex, so as to avoid leakage on a three-roll mill due to too low viscosity and to avoid the problem of being difficult to disperse evenly due to too high viscosity. At the same time, the heated and melted epoxy resin and the cerium organic complex are ground and dispersed by a three-roll mill, so that the cerium organic complex is evenly dispersed in the epoxy resin.

[0064] More specifically, the cerium organic complex is better dispersed by controlling the number of grinding times of the slurry on the three-roll mill. The more grinding times, the more dispersed the cerium organic complex is, so as to solve the agglomeration problem of the cerium organic complex. Preferably, the grinding times are 10 to 20 times, and the heated and molten epoxy resin and the cerium organic complex are all slowly added to the three-roll mill for full grinding, which is regarded as one grinding; and because after each grinding, as the temperature decreases, the viscosity of the premix will increase and affect the grinding effect, so after each grinding, the product collected at the discharge roller needs to be placed in an oil bath pot (for example, 80°C) to heat the product for a period of time, so as to reduce the viscosity of the slurry, so as to achieve 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 and cured to obtain a radiation-resistant epoxy resin composite material. In this way, by heating the premix and then adding the curing agent, the two can be fully mixed.

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

[0067] The mass ratio of the epoxy resin to the cerium organic complex is 100:(0.05-0.5) (for example, 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 the epoxy resin matrix to the curing agent is 1:(3-3.5) (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 may be at least one of the group consisting of glycidyl ethers, glycidyl esters and glycidyl amines. The curing agent may be at least one of the group consisting of diaminodiphenylmethane DDM, 4,4'-dioxydiphenylsulfone DDS and dicyandiamide DICY.

[0070] In the present invention, it is experimentally 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 is too low, and the radiation resistance of the prepared radiation-resistant epoxy resin composite material is poor; if the mass ratio of epoxy resin to cerium organic complex is less than 100:0.5, the amount of cerium organic complex is too high, although it can further improve the anti-γ-ray radiation performance, 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, the curing adopts a gradient temperature increase: the starting temperature is 100-150°C (for example, it can be 100°C, 106°C, 110°C, 115°C, 120°C, 125°C, 130°C, 135°C, 140°C, 148°C or 150°C), the end temperature is 200-250°C (for example, it can be 200°C, 206°C, 210°C, 215°C, 220°C, 225°C, 230°C, 235°C, 240°C, 246°C or 250°C), and the temperature increase gradient is 10 The temperature is 400-200 ℃ (for example, it can be 10 ℃, 10.5 ℃, 11 ℃, 12 ℃, 13 ℃, 14 ℃, 15 ℃, 16 ℃, 17 ℃, 18 ℃, 19 ℃ or 20 ℃), the heating rate is 1-4 ℃ / min (for example, it can be 1 ℃ / min, 1.5 ℃ / min, 2 ℃ / min, 2.5 ℃ / min, 3 ℃ / min, 3.5 ℃ / min or 4 ℃ / min), and the insulation time of each gradient stage is 1-3 h (for example, it can be 1 h, 1.5 h, 2 h, 2.5 h or 3 h).

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

[0073] In order to more clearly illustrate the technical solution and advantages of the present invention, a radiation-resistant epoxy resin composite material and a preparation method thereof are described in detail below through several embodiments.

[0074] Example 1

[0075] Preparation of organic cerium complexes:

[0076] Dissolve 0.2 mol of cerium ammonium nitrate in 400 mL of deionized water to obtain a first solution; dissolve 0.035 mol of 1,3,5-benzenetricarboxylic acid and 0.0175 mol of 5-hydroxyisophthalic acid in 600 mL of N,N-dimethylformamide (DMF) to obtain a second solution; introduce the second solution into the first solution, stir at 30°C to obtain a precursor solution. The precursor solution was placed at 100°C for a hydrothermal reaction for 0.5 h, then washed with tetrahydrofuran (THF) and acetone, centrifuged, and then vacuum dried to obtain a cerium organic complex. Among them, the infrared spectrum of the cerium organic complex is shown in the figure below: Figure 2 shown.

[0077] Preparation of radiation-resistant epoxy resin composites:

[0078] The bisphenol A epoxy resin is heated to 100° C., and then the heated and molten epoxy resin is added to a three-roll mill, and the cerium organic complex prepared above (the mass ratio of the epoxy resin matrix to the cerium organic complex is 100:0.2) is put into the three-roll mill, and the three-roll mill is rolled at a speed ratio of 1:1 and a gap ratio of 1:1 until the cerium organic complex is observed to be fully and evenly mixed with the epoxy resin matrix to obtain a premix;

[0079] The premix was placed in an oil bath and heated to 140°C, and a curing agent DDS was added in a mass ratio of 1:3. The mixture was fully stirred for 1 hour to obtain a mixed solution. The mixed solution was placed in a vacuum drying oven at 40°C for heat preservation and bubbling for 30 minutes, and then poured into a mold. The mold was then placed in an oven with an initial temperature of 100°C and programmed to heat. The end temperature was 200°C, the temperature gradient was 10°C, each gradient temperature was maintained for 1 hour, and the heating rate was 1°C / min to obtain a radiation-resistant epoxy resin composite material.

[0080] Example 2

[0081] Preparation of organic cerium complexes:

[0082] Dissolve 0.2 mol of cerium ammonium nitrate in 400 mL of deionized water to obtain a first solution; dissolve 0.4 mol of 1,3,5-benzenetricarboxylic acid and 0.2 mol of 5-hydroxyisophthalic acid in 600 mL of N,N-dimethylformamide (DMF) to obtain a second solution; introduce the second solution into the first solution, stir at 30°C to mix, and obtain a precursor solution. The precursor solution was placed at 150°C for a hydrothermal reaction for 0.5 h, then washed with tetrahydrofuran (THF) and acetone, centrifuged, and then vacuum dried to obtain a cerium organic complex. Among them, the infrared spectrum of the cerium organic complex is shown in the figure below: Figure 2 shown.

[0083] Preparation of radiation-resistant epoxy resin composites:

[0084] The bisphenol A epoxy resin is heated to 80° C., and then the heated and molten epoxy resin is added to a three-roll mill, and the cerium organic complex prepared above (the mass ratio of the epoxy resin matrix to the cerium organic complex is 100:0.2) is put into the three-roll mill, and the three-roll mill is rolled at a speed ratio of 1:5 and a gap ratio of 1:1 until the cerium organic complex is observed to be fully and evenly mixed with the epoxy resin matrix to obtain a premix;

[0085] The premix was placed in an oil bath and heated to 140°C, and a curing agent DDS was added in a mass ratio of 1:3. The mixture was fully stirred for 1 hour to obtain a mixed solution. The mixed solution was placed in a vacuum drying oven at 40°C for heat preservation and bubbling for 30 minutes, and then poured into a mold. The mold was then placed in an oven with an initial temperature of 100°C and programmed to heat. The end temperature was 200°C, the temperature gradient was 10°C, each gradient temperature was maintained for 1 hour, and the heating rate was 1°C / min to obtain a radiation-resistant epoxy resin composite material.

[0086] Example 3

[0087] Preparation of organic cerium complexes:

[0088] Dissolve 0.2 mol of cerium ammonium nitrate in 400 mL of deionized water to obtain a first solution; dissolve 1.33 mol of 1,3,5-benzenetricarboxylic acid and 0.67 mol of 5-hydroxyisophthalic acid in 600 mL of N,N-dimethylformamide (DMF) to obtain a second solution; introduce the second solution into the first solution, stir at 30°C to mix, and obtain a precursor solution. Place the precursor solution at 100°C for a hydrothermal reaction for 0.5 h, then wash with tetrahydrofuran (THF) and acetone, centrifuge, and vacuum dry to obtain a cerium organic complex.

[0089] Preparation of radiation-resistant epoxy resin composites:

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

[0091] The premix was placed in an oil bath and heated to 140°C, and a curing agent DDS was added in a mass ratio of 1:3. The mixture was fully stirred for 1 hour to obtain a mixed solution. The mixed solution was placed in a vacuum drying oven at 40°C for heat preservation and bubbling for 30 minutes, and then poured into a mold. The mold was then placed in an oven with an initial temperature of 100°C and programmed to heat. The end temperature was 200°C, the temperature gradient was 10°C, each gradient temperature was maintained for 1 hour, and the heating rate was 1°C / min to obtain a radiation-resistant epoxy resin composite material.

[0092] Example 4

[0093] Preparation of organic cerium complexes:

[0094] 2 mol of cerium ammonium nitrate was dissolved in 400 mL of deionized water to obtain a 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 a second solution; the second solution was introduced into the first solution, stirred at 30°C to obtain a precursor solution. The precursor solution was placed at 100°C for a hydrothermal reaction for 0.5 h, then washed with tetrahydrofuran (THF) and acetone, centrifuged and vacuum dried to obtain a cerium organic complex.

[0095] Preparation of radiation-resistant epoxy resin composites:

[0096] The bisphenol A epoxy resin is heated to 100° C., and then the heated and molten epoxy resin is added to a three-roll mill, and the cerium organic complex prepared above (the mass ratio of the epoxy resin matrix to the cerium organic complex is 100:0.2) is put into the three-roll mill, and the three-roll mill is rolled at a speed ratio of 1:3 and a gap ratio of 1:3 until the cerium organic complex is observed to be fully and evenly mixed with the epoxy resin matrix to obtain a premix;

[0097] The premix was placed in an oil bath and heated to 140°C, and a curing agent DDS was added in a mass ratio of 1:3. The mixture was fully stirred for 1 hour to obtain a mixed solution. The mixed solution was placed in a vacuum drying oven at 40°C for heat preservation and bubbling for 30 minutes, and then poured into a mold. The mold was then placed in an oven with an initial temperature of 100°C and programmed to heat. The end temperature was 200°C, the temperature gradient was 10°C, each gradient temperature was maintained for 1 hour, and the heating rate was 1°C / min to obtain a radiation-resistant epoxy resin composite material.

[0098] Example 5

[0099] Preparation of organic cerium complexes:

[0100] Dissolve 0.2 mol of cerium ammonium nitrate in 400 mL of deionized water to obtain a first solution; dissolve 0.035 mol of 1,3,5-benzenetricarboxylic acid and 0.0175 mol of 5-hydroxyisophthalic acid in 600 mL of N,N-dimethylformamide (DMF) to obtain a second solution; introduce the second solution into the first solution, stir at 30°C to mix, and obtain a precursor solution. Place the precursor solution at 50°C for a hydrothermal reaction for 3 hours, then wash with tetrahydrofuran (THF) and acetone, centrifuge, and vacuum dry to obtain a cerium organic complex.

[0101] Preparation of radiation-resistant epoxy resin composites:

[0102] The bisphenol A epoxy resin is heated to 100° C., and then the heated and molten epoxy resin is added to a three-roll mill, and the prepared cerium organic complex (the mass ratio of the epoxy resin matrix to the cerium organic complex is 100:0.05) is placed in the three-roll mill, and the three-roll mill is rolled at a speed ratio of 1:1 and a gap ratio of 1:1 until the cerium organic complex is observed to be fully and evenly mixed with the epoxy resin matrix to obtain a premix;

[0103] The premix was placed in an oil bath and heated to 140°C, and a curing agent DDS was added at a mass ratio of 1:3.5. The mixture was fully stirred for 1 hour to obtain a mixed solution. The mixed solution was placed in a vacuum drying oven at 40°C for heat preservation and bubbling for 30 minutes, and then poured into a mold. The mold was then placed in an oven with an initial temperature of 100°C and programmed to rise in temperature with an end temperature of 200°C and a temperature rise gradient of 20°C. Each gradient temperature was maintained for 3 hours, and the heating rate was 2°C / min to obtain 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 the epoxy resin matrix to the cerium organic complex is 100:0.5.

[0106] Example 7

[0107] Preparation of organic cerium complexes:

[0108] Dissolve 0.2 mol of cerium ammonium nitrate in 400 mL of deionized water to obtain a first solution; dissolve 0.035 mol of 1,3,5-benzenetricarboxylic acid and 0.0175 mol of 5-hydroxyisophthalic acid in 600 mL of N,N-dimethylformamide (DMF) to obtain a second solution; introduce the second solution into the first solution, stir at 30°C to mix, and obtain a precursor solution. Place the precursor solution at 100°C for a hydrothermal reaction for 0.5 h, then wash with tetrahydrofuran (THF) and acetone, centrifuge, and vacuum dry to obtain a cerium organic complex.

[0109] Preparation of radiation-resistant epoxy resin composites:

[0110] The bisphenol A epoxy resin is heated to 100° C., and then the heated and molten epoxy resin is added to a three-roll mill, and the cerium organic complex prepared above (the mass ratio of the epoxy resin matrix to the cerium organic complex is 100:0.2) is put into the three-roll mill, and the three-roll mill is rolled at a speed ratio of 1:1 and a gap ratio of 1:1 until the cerium organic complex is observed to be fully and evenly mixed with the epoxy resin matrix to obtain a premix;

[0111] The premix was placed in an oil bath and heated to 140°C, and a curing agent DDS was added in a mass ratio of 1:3. The mixture was fully stirred for 1 hour to obtain a mixed solution. The mixed solution was placed in a vacuum drying oven at 40°C for heat preservation and bubbling for 30 minutes, and then poured into a mold. The mold was then placed in an oven with an initial temperature of 100°C and programmed to heat. The end temperature was 200°C, the temperature gradient was 10°C, each gradient temperature was maintained for 1 hour, and the heating rate was 1°C / min to obtain a radiation-resistant epoxy resin composite material.

[0112] Example 7

[0113] Example 7 is substantially 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 substantially 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 substantially 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 substantially the same as Example 1, except that the cerium organic complex prepared in Example 1 is not added to the bisphenol A epoxy resin.

[0120] Comparative Example 2

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

[0122] Specifically, bisphenol A epoxy resin was heated to 100°C, and then the heated and molten epoxy resin was added to a three-roll mill, and the cerium oxide (epoxy resin matrix and cerium oxide CeO 2 The mass ratio of cerium oxide to epoxy resin matrix is ​​100:0.2) and put into the three-roll mill, and roll at a speed ratio of 1:1 and a gap ratio of 1:1 until the cerium oxide is observed to be fully and evenly mixed with the epoxy resin matrix to obtain a premix;

[0123] The premix was placed in an oil bath and heated to 140°C, and a curing agent DDS was added in a mass ratio of 1:3. The mixture was fully stirred for 1 hour to obtain a mixed solution. The mixed solution was placed in a vacuum drying oven at 40°C for heat preservation and bubbling for 30 minutes, and then poured into a mold. The mold was then placed in an oven with an initial temperature of 100°C and programmed to rise in temperature with an end temperature of 200°C and a temperature rise gradient of 10°C. Each gradient temperature was maintained for 1 hour, and a heating rate of 1°C / min was obtained to obtain an epoxy resin composite material.

[0124] Comparative Example 3

[0125] Comparative Example 3 is substantially the same as Example 1, except that 5-hydroxyisophthalic acid was not added when preparing the cerium organic complex. Figure 2 shown.

[0126] Comparative Example 4

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

[0128] The radiation-resistant epoxy resin composite materials and epoxy resin composite materials 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 the radiation-resistant epoxy resin composite material and the epoxy resin composite material at room temperature were tested in accordance with the GB / T 2567-2008 standard, using the US INSTRON 5967 electronic universal testing machine, wherein the radiation-resistant epoxy resin composite material was prepared into a standard dumbbell-shaped sample for testing before irradiation, and the test loading rate was 2 mm / min. The radiation-resistant epoxy resin composite material was prepared into a standard dumbbell-shaped sample under the condition of an irradiation dose of 800 kGy, and the irradiated sample was tested. Among them, at least 5 samples of each radiation-resistant epoxy resin composite material were prepared and tested separately.

[0130] Table 1

[0131]

[0132] As shown in Table 1, the radiation-resistant epoxy resin composite material prepared by the present invention still has excellent mechanical properties under the condition of an irradiation dose of 800 kGy, and effectively avoids the reduction of mechanical properties caused by the degradation of epoxy resin molecular segments during irradiation. Compared with Comparative Example 1, the tensile strength, Young's modulus and elongation at break before and after irradiation are significantly improved in Example 1. In Comparative Example 2, cerium oxide is used instead of cerium organic complex. Although it can improve the mechanical properties and radiation resistance of pure epoxy resin, its radiation resistance is still lower than that of Example 1. Similarly, since 5-hydroxyisophthalic acid is not added in Comparative Example 3, the cerium organic complex prepared does not have a phenolic hydroxyl functional group, so its radiation resistance is still lower than that of Example 1. Compared with Comparative Example 4, since more cerium organic complexes are added in Comparative Example 4, although the radiation resistance is further improved, the mechanical properties of the prepared radiation-resistant epoxy resin composite material are affected.

[0133] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, rather than to limit them; although the present invention has been described in detail with reference to the above embodiments, those skilled in the art should understand that they can still modify the technical solutions described in the above embodiments, or replace some of the technical features therein by equivalents; and these modifications or replacements do not make the essence of the corresponding technical solutions deviate from the spirit and scope of the technical solutions of the embodiments of the present invention. The parts not described in detail in the present invention are well-known technologies of those skilled in the art.

Claims

1. A method for preparing a radiation-resistant epoxy resin composite material, characterized in that: The preparation method comprises: (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; (3) After mixing the cerium organic complex and the epoxy resin, a curing agent is added to perform curing to obtain the radiation-resistant epoxy resin composite material.

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; and / or, The organic ligands are 1,3,5-benzenetricarboxylic acid and 5-hydroxyisophthalic acid.

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); preferably, the soluble cerium salt is ammonium cerium nitrate.

4. The preparation method according to claim 2, characterized in that: The molar ratio of 5-hydroxyisophthalic acid to 1,3,5-benzenetricarboxylic acid is (0.1-0.9):

1.

5. The preparation method according to claim 1, characterized in that: Step (1) comprises: (11) dissolving the soluble cerium salt in deionized water to obtain a first solution; (12) dissolving the organic ligand in an organic solvent to obtain a second solution; the solvent comprises deionized water and the organic solvent; preferably, 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° C., and the reaction time is 0.5-3 h.

7. The preparation method according to claim 1, characterized in that: Step (3) includes: (31) heating and melting the epoxy resin, and then adding the heated and molten epoxy resin and the cerium organic complex into a three-roll mill for mixing to obtain a premix; (32) Adding the curing agent to the premix for curing 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 to 150° C. The rotation speed ratio of the feed roller and the discharge roller of the three-roller machine 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 cerium organic complex is 100:(0.05-0.5); The mass ratio of the epoxy resin to the curing agent is 1:(3-3.5); and / or, The curing adopts gradient heating: the starting temperature is 100-150°C, the ending temperature is 200-250°C, the heating gradient is 10-20°C, the heating rate is 1-4°C / min, and the insulation time of each gradient stage is 1-3h.

10. A radiation-resistant epoxy resin composite material, characterized in that: The method is prepared by any one of claims 1 to 9.

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