Preparation method of high-temperature-resistant and corrosion-resistant alloy rubber

Abstract

The invention discloses a preparation method of high-temperature-resistant and corrosion-resistant alloy rubber, and relates to the technical field of rubber. Silicone oil and organic aluminum are combined to form an organic silicon-aluminum structure capable of absorbing free radicals generated by heat, then low-melting-point bismuth alloy, boron nitride, modified silicone oil and silicone rubber are mixed, and through vulcanization pressing, the bismuth alloy and boron nitride form a network structure and are connected with a rubber base material to form a heat dissipation channel. The high-temperature resistance of the rubber is further enhanced; 3, 4-dichloro-6-nitroaniline, 2, 6-nonadienol and 2-hydroxy-4-(methylacryloyloxy) benzophenone react to form a benzotriazole structure to effectively absorb ultraviolet rays, benzophenone is introduced, a multi-benzene-ring structure is constructed, the ultraviolet ray absorption capacity is greatly improved, the ultraviolet aging resistance of rubber is improved, then the benzotriazole structure is grafted to the surface of rubber, and the ultraviolet aging resistance of the rubber is improved. Double bonds are polymerized to form an anti-ultraviolet protective film, so that the anti-ultraviolet aging performance of the rubber is enhanced.

Description

Technical Field

[0001] The present invention relates to the technical field of rubber, and specifically to a preparation method of a high-temperature resistant and corrosion-resistant alloy rubber. Background Art

[0002] The rubber industry is one of the important basic industries of the national economy. It not only provides daily-use and medical light industrial rubber products that are indispensable in people's daily lives, but also provides various rubber production equipment or rubber components for heavy industries and emerging industries such as mining, transportation, construction, machinery, and electronics.

[0003] Silicone rubber is a semi-organic and semi-inorganic polymer material. The main chain of the molecule is composed of Si-O-Si linkages and has relatively excellent corrosion resistance. However, at high temperatures, silicone rubber usually undergoes two reactions: main chain degradation and side group oxidation. Among them, main chain degradation includes unzipping degradation initiated by end groups and main chain thermogravimetric rearrangement degradation. With the continuous progress of technologies in various fields, the requirements for the high-temperature resistance performance of silicone rubber materials are getting higher and higher, and the existing silicone rubber compounding systems can no longer meet the increasingly stringent usage conditions. In addition, the ultraviolet intensity is relatively high in low-latitude coastal areas and high-altitude areas. Rubber used in these areas is easily irradiated by high-intensity ultraviolet rays and is extremely prone to photoaging degradation, resulting in a serious reduction in the service life of the rubber. Summary of the Invention

[0004] The purpose of the present invention is to provide a high-temperature resistant and corrosion-resistant alloy rubber and its preparation method to solve the problems existing in the prior art.

[0005] To solve the above technical problems, the present invention provides the following technical solution: A preparation method of a high-temperature resistant and corrosion-resistant alloy rubber, including the following preparation steps: (1) Mix phenyl silicone rubber, boron nitride, modified silicone oil, bismuth alloy, and curing agent bis(2,5-dimethyl-2,5-di(t-butylperoxy)hexane) in a mass ratio of 40-60:9-18:2-8:12-22:1-3 for 10-30 min. After standing for 12 h, place it between two smooth and flat metal templates, and use a flat vulcanizing machine to press it at 75-85 °C and a pressure of 5-10 MPa for 10-30 s to form a circular thin film with a thickness of 0.05-0.20 mm. Then vulcanize it at 60-65 °C and a pressure of 0.5-2 MPa for 30-50 min to obtain the rubber; (2) Mix polystyrene triethanolamine resin and 2,6-nonadienol at a mass ratio of 0.5 - 1.5:15.8, soak for 6 - 8 h, then add 3,4-dichloro-6-nitroaniline which is 5.2 - 15.7 times the mass of the polystyrene triethanolamine resin and sodium hydroxide which is 5 times the mass of the polystyrene triethanolamine resin, place in a water bath at 60 - 62 °C, react for 3 - 5 h, then distill at a vacuum of -0.08 MPa and 40 °C for 1 - 2 h, add deionized water which is 10 - 15 times the mass of the polystyrene triethanolamine resin, stir at 200 - 300 rpm for 30 min, filter by suction, take the filtrate, wash the filtrate with deionized water until the pH of the washing liquid is 7, rinse with ethanol at 50 °C for 5 - 15 min, then wash with deionized water 6 times, and dry at 40 °C for 24 h to obtain intermediate A; (3) Mix intermediate A, hydrochloric acid with a mass fraction of 36.5%, and deionized water at a mass ratio of 2.2:4 - 5:20, stir at 30 °C and 60 rpm for 25 - 40 min, cool to 0 - 5 °C, add an aqueous sodium nitrite solution which is 2.5 - 3.0 times the mass of intermediate A at a rate of 0.1 - 0.3 mL / min, react for 30 - 60 min, add urea until the starch-iodide test paper turns blue to obtain a diazonium salt solution; Mix 2-hydroxy-4-(methacryloyloxy)benzophenone, distilled water, and sodium hydroxide with a mass fraction of 5% at a mass ratio of 0.2:10:0.1 - 0.2, stir to dissolve, then at 0 - 5 °C, add the diazonium salt solution at a rate of 0.3 - 0.5 mL / min until the molar ratio of the diazonium salt to 2-hydroxy-4-(methacryloyloxy)benzophenone is 1:1, react for 1 - 2 h, maintain the pH at 4 during this period, centrifuge at 3000 - 4000 rpm for 5 - 10 min, pour out the supernatant, wash the precipitate with distilled water 3 times, and vacuum dry at 40 °C for 24 h to obtain intermediate B; (4) Mix intermediate B, ethanol, and sodium hydroxide at a mass ratio of 1:15:0.10 - 0.12, stir to dissolve, then react at 25 - 35 °C for 20 - 30 min, add sodium dithionite which is 0.1 - 0.2 times the mass of the intermediate in three portions, continue to react for 1 - 1.5 h, then add hydrochloric acid with a mass fraction of 36.5% which is 0.2 times the mass of intermediate B, let stand for 10 - 15 min, filter by suction, take the filter cake, wash with absolute ethanol 4 times, and dry at 40 °C for 24 h to obtain the modifier; (5) After the rubber is activated, place ethyl acetate, triethylamine, and activated rubber at a mass ratio of 10 - 20:0.6 - 1.3:1 in an ice-water bath at 0 °C, stir evenly, then under stirring at 300 - 400 rpm, add a mixed solution of 3-bromo-4-fluorobenzoyl bromide which is 3.5 - 4.4 times the mass of the activated rubber, raise the temperature to 35 °C, react for 5 - 7 h, then filter by suction, take the filtrate, place it in deionized water, ethanol, and acetone in turn for ultrasonic cleaning for 10 min, repeat 3 times to obtain pre-modified rubber; (6) Mix cuprous iodide, tetramethylethylenediamine, and anhydrous dimethyl sulfoxide in a mass ratio of 0.01:0.1:2.2. Under a nitrogen atmosphere, stir at 60 - 80 rpm for 30 min. Add cesium carbonate that is 2 - 3 times the mass of cuprous iodide and a modifier that is 10 - 15 times the mass of cuprous iodide. Stir at 80 - 120 rpm for 4 h at room temperature. Then add pre-modified rubber that is 15 - 20 times the mass of cuprous iodide and anhydrous dimethyl sulfoxide that is 117 times the mass of cuprous iodide, and continue the reaction for 48 - 55 h. Filter by suction, take the filtrate, wash it, and dry it at 40 °C for 24 h to obtain intermediate C; (7) Mix triisobutylaluminum, toluene, intermediate C, and tris(pentafluorophenyl)borane in a mass ratio of 0.005:15 - 20:8:0.0001. React at 55 - 60 °C for 1 - 2 h, then add a hydrochloric acid ethanol solution that is 2 - 3 times the mass of intermediate C. Let it stand for 20 - 30 min, filter by suction, take the filtrate, and dry it at 40 °C for 24 h to obtain a high-temperature and corrosion-resistant alloy rubber.

[0006] Furthermore, the preparation method of the modified silicone oil in step (1) is as follows: Mix bis(epoxy-terminated) silicone oil with a number-average molecular weight of 8000 and isopropyl alcohol in a mass ratio of 1:0.4. After stirring evenly, add an organoaluminum isopropanol solution that is 1.5 - 3.3 times the mass of bis(epoxy-terminated) silicone oil. The mass ratio of organoaluminum to isopropyl alcohol in the organoaluminum isopropanol solution is 1:2. React at 80 °C for 4 - 6 h, and then distill at a vacuum of -0.06 MPa and 55 °C for 1 - 2 h.

[0007] Furthermore, the preparation method of the organoaluminum is as follows: Mix acetylacetone, m-dimethylaminobenzene, p-toluenesulfonic acid, and toluene in a mass ratio of 4:4 - 5.5:0.05 - 0.1:58 - 63. After stirring and dissolving, react at 90 - 105 °C for 4 - 6 h, then place it in an ice-water bath. Add a trimethylaluminum - n-hexane solution that is 1.5 - 2.2 times the mass of acetylacetone. The mass ratio of trimethylaluminum to n-hexane in the trimethylaluminum - n-hexane solution is 1:2 - 3. Remove the ice-water bath, stir at 30 - 60 rpm at room temperature for 12 h, then distill at a vacuum of -0.06 MPa and 80 °C for 4 - 6 h, and freeze at -18 °C for 1 - 1.5 h.

[0008] Furthermore, the composition of the bismuth alloy in step (1) by mass fraction includes 47.22% bismuth, 26.7% lead, 9.7% cadmium, and 13.61% tin; the melting point of the bismuth alloy is 70 °C.

[0009] Further, the preparation method of the polystyrene triethanolamine resin described in step (2) is as follows: Mix chloromethyl polystyrene resin and toluene at a mass ratio of 5:17.4, soak for 8 h, add diethanolamine which is 1.2 times the mass of the chloromethyl polystyrene resin, place it in an oil bath at 110 °C, stir at 700 rpm for 2.5 h, cool to room temperature, add deionized water which is 3 times the mass of the chloromethyl polystyrene resin, stir at the same speed for 30 min, filter, take the solid, wash it 3 times with deionized water, extract it with ethanol in a Soxhlet extractor for 20 h, and dry it at a vacuum of -0.08 MPa and 40 °C for 8 h.

[0010] Further, in the sodium nitrite aqueous solution described in step (3), the mass ratio of sodium nitrite to deionized water in the sodium nitrite aqueous solution is 5.3:24.

[0011] Further, the activation treatment described in step (5) is as follows: Place the rubber in a low-temperature plasma processor, under an oxygen atmosphere, treat it at 400 W for 300 - 450 s to obtain activated rubber.

[0012] Further, in the 3-bromo-4-fluorobenzoyl bromide mixture described in step (5), the mass ratio of 3-bromo-4-fluorobenzoyl bromide to ethyl acetate is 9.3:18.

[0013] Further, the washing treatment described in step (6) is as follows: Wash it 3 times successively with saturated brine and deionized water.

[0014] Further, the concentration of the hydrochloric acid ethanol solution described in step (7) is 0.1 mol / L.

[0015] Compared with the prior art, the beneficial effects achieved by the present invention are as follows: The present invention uses the methylamine of m,m-dimethylaminobenzene to react with acetylacetone to generate a β-ketoimine structure, and utilizes this structure to complex with aluminum ions. Then, the remaining unreacted methylamine of m,m-dimethylaminobenzene reacts with the epoxy groups of the bis-terminal epoxy silicone oil to form an aluminum-silicone oil complex, which is kneaded with silicone rubber to improve the high-temperature resistance of the rubber. At the same time, the organoaluminum complex structure in the silicone oil molecular chain can absorb the free radicals generated by heat, improving the thermal stability of the rubber, thereby enhancing the anti-aging performance of the rubber; and during the kneading process, bismuth alloy and boron nitride are added. Through vulcanization and pressing, the low-melting bismuth alloy is heated to a molten state, infiltrates boron nitride, and becomes fibrous with the tensile orientation generated by pressing, binding boron nitride, so that the bismuth alloy and boron nitride are connected inside the rubber to form a heat conduction network structure, improving the heat dissipation performance of the rubber, thereby enhancing the high-temperature resistance of the rubber.

[0016] The present invention utilizes the reaction between the chloro group of 3,4-dichloro-6-nitroaniline and the hydroxyl group of 2,6-nonadienol. Subsequently, the diazonium salt of 3,4-dichloro-6-nitroaniline is coupled with 2-hydroxy-4-(methacryloyloxy)benzophenone to form an azo structure, which is then reduced to form a benzotriazole structure, effectively absorbing ultraviolet light. At the same time, 2,3',4,6-tetrahydroxybenzophenone contains a benzene ring benzophenone, and its phenolic hydroxyl group forms an intramolecular hydrogen bond with the ketone carbonyl group. Moreover, the polybenzene ring structure of 3,4-dichloro-6-nitroaniline and 2,3',4,6-tetrahydroxybenzophenone also greatly increases the ultraviolet absorption ability, improving the anti-ultraviolet aging performance of the rubber. Under the crosslinking action of 3-bromo-4-fluorobenzoyl bromide, the modifier is grafted onto the surface of the plasma-activated rubber, and double bonds polymerize to form an anti-ultraviolet protective film, enhancing the anti-ultraviolet aging performance of the rubber. Detailed implementation manners

[0017] The following will describe the technical solutions in the embodiments of the present invention clearly and completely in conjunction with the embodiments of the present invention. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all of the embodiments. All other embodiments obtained by those of ordinary skill in the art based on the embodiments of the present invention without creative efforts shall fall within the protection scope of the present invention.

[0018] In order to more clearly illustrate the method provided by the present invention, the following embodiments are used for detailed description. The test methods for each index of the high-temperature resistant and corrosion-resistant alloy rubber prepared in the following embodiments are as follows: Anti-ultraviolet aging: Take the same-sized examples and comparative examples, use a gallium lamp to simulate ultraviolet light, the ultraviolet light wavelength is 200~780nm, the peak value is 420nm, and the irradiation intensity is 300 μW / cm 2 , irradiate for 240d, and calculate the tensile strength retention rate and elongation retention rate with reference to GB / T528.

[0019] High temperature resistance: Take the same-sized examples and comparative examples and refer to GB / T3512, place them in a hot air aging oven at 250°C for 72h, and measure various properties after aging.

[0020] Example 1 (1) Mix acetylacetone, m-dimethylaminobenzene, p-toluenesulfonic acid, and toluene according to a mass ratio of 4:4:0.05:58. After stirring and dissolving, react at 90°C for 4h, then place it in an ice-water bath, and add a trimethylaluminum-n-hexane solution that is 1.5 times the mass of acetylacetone. The mass ratio of trimethylaluminum to n-hexane in the trimethylaluminum-n-hexane solution is 1:2. Remove the ice-water bath, stir at 30 rpm at room temperature for 12h, distill at a vacuum of -0.06 MPa and 80°C for 4h, and freeze at -18°C for 1h to obtain organoaluminum; (2) Mix the bis - terminal epoxy silicone oil with a number - average molecular weight of 8000 and isopropyl alcohol at a mass ratio of 1:0.4. After stirring evenly, add an aluminum isopropoxide solution 1.5 times the mass of the bis - terminal epoxy silicone oil. The mass ratio of aluminum to isopropyl alcohol in the aluminum isopropoxide solution is 1:2. React at 80 °C for 4 h, then distill at a vacuum of - 0.06 MPa and 55 °C for 1 h to obtain the modified silicone oil; (3) Knead phenyl silicone rubber, boron nitride, modified silicone oil, bismuth alloy, and curing agent bis - 25 at a mass ratio of 40:9:2:12:1 for 10 min. After standing for 12 h, place it between two smooth and flat metal templates. Use a flat vulcanizing machine to press at 75 °C and a pressure of 5 MPa for 10 s to form a circular thin film with a thickness of 0.05 mm. Then vulcanize at 60 °C and a pressure of 0.5 MPa for 30 min to obtain the rubber; (4) Mix chloromethylated polystyrene resin and toluene at a mass ratio of 5:17.4. After soaking for 8 h, add diethanolamine 1.2 times the mass of the chloromethylated polystyrene resin. Place it in an oil bath at 110 °C and stir at 700 rpm for 2.5 h. Then cool to room temperature, add deionized water 3 times the mass of the chloromethylated polystyrene resin, stir at the same speed for 30 min, filter, take the solid, wash it 3 times with deionized water, place it in a Soxhlet extractor and extract with ethanol for 20 h, and dry at a vacuum of - 0.08 MPa and 40 °C for 8 h to obtain polystyrene triethanolamine resin; (5) Mix polystyrene triethanolamine resin and 2,6 - nonadienol at a mass ratio of 0.5:15.8. After soaking for 6 h, add 3,4 - dichloro - 6 - nitroaniline 5.2 times the mass of the polystyrene triethanolamine resin and sodium hydroxide 5 times the mass of the polystyrene triethanolamine resin. Place it in a water bath at 60 °C and react for 3 h. Then distill at a vacuum of - 0.08 MPa and 40 °C for 1 h. Add deionized water 10 times the mass of the polystyrene triethanolamine resin, stir at 200 rpm for 30 min, filter, take the filtrate, wash the filtrate with deionized water until the pH of the washing liquid is 7, rinse with ethanol at 50 °C for 5 min, then wash with deionized water 6 times, and dry at 40 °C for 24 h to obtain intermediate A; (6) Mix intermediate A, hydrochloric acid with a mass fraction of 36.5%, and deionized water at a mass ratio of 2.2:4:20, stir at 30 °C and 60 rpm for 25 min, cool to 0 °C, and add an aqueous sodium nitrite solution 2.5 times the mass of intermediate A at a rate of 0.1 mL / min. The mass ratio of sodium nitrite to deionized water in the aqueous sodium nitrite solution is 5.3:24. React for 30 min, add urea to the solution until the starch-iodide test paper turns blue to obtain a diazonium salt solution; Mix 2-hydroxy-4-(methacryloyloxy)benzophenone, distilled water, and sodium hydroxide with a mass fraction of 5% at a mass ratio of 0.2:10:0.1, stir to dissolve, and at 0 °C, add the diazonium salt solution at a rate of 0.3 mL / min until the molar ratio of the diazonium salt to 2-hydroxy-4-(methacryloyloxy)benzophenone is 1:1. React for 1 h, maintain the pH at 4 during this period, centrifuge at 3000 rpm for 5 min, pour out the supernatant, wash the precipitate with distilled water 3 times, and vacuum dry at 40 °C for 24 h to obtain intermediate B; (7) Mix intermediate B, ethanol, and sodium hydroxide at a mass ratio of 1:15:0.1, stir to dissolve, react at 25 °C for 20 min, add sodium dithionite 0.1 times the mass of the intermediate in three portions, continue to react for 1 h, then add hydrochloric acid with a mass fraction of 36.5% 0.2 times the mass of intermediate B, let stand for 10 min, filter by suction, take the filter cake, wash it 4 times with absolute ethanol, and dry at 40 °C for 24 h to obtain the modifier; (8) Place the rubber in a low-temperature plasma processor and treat it at 400 W for 300 s in an oxygen atmosphere to obtain activated rubber; Place ethyl acetate, triethylamine, and activated rubber at a mass ratio of 10:0.6:1 in an ice-water bath at 0 °C, stir evenly, and under stirring at 300 rpm, add a mixed solution of 3-bromo-4-fluorobenzoyl bromide 3.5 times the mass of the activated rubber. The mass ratio of 3-bromo-4-fluorobenzoyl bromide to ethyl acetate in the mixed solution of 3-bromo-4-fluorobenzoyl bromide is 9.3:18. Heat up to 35 °C and react for 5 h, then filter by suction, take the filtrate, and ultrasonically clean it in deionized water, ethanol, and acetone for 10 min each, repeat 3 times to obtain pre-modified rubber; (9) Mix copper(I) iodide, tetramethylethylenediamine, and anhydrous dimethyl sulfoxide at a mass ratio of 0.01:0.1:2.2, stir at 60 rpm for 30 min under a nitrogen atmosphere, add cesium carbonate 2 times the mass of copper(I) iodide and the modifier 10 times the mass of copper(I) iodide, stir at 80 rpm at room temperature for 4 h, add pre-modified rubber 15 times the mass of copper(I) iodide and anhydrous dimethyl sulfoxide 117 times the mass of copper(I) iodide, continue to react for 48 h, filter by suction, take the filtrate, wash it 3 times with saturated brine and deionized water in sequence, and dry at 40 °C for 24 h to obtain intermediate C; (10) Mix triisobutylaluminum, toluene, intermediate C, and tris(pentafluorophenyl)borane at a mass ratio of 0.005:15:8:0.0001. After reacting at 55 °C for 1 h, add a 0.1 mol / L hydrochloric acid ethanol solution that is 2 times the mass of intermediate C, let it stand for 20 min, filter by suction, take the filtrate, and dry it at 40 °C for 24 h to obtain a high-temperature and corrosion-resistant alloy rubber.

[0021] Example 2 (1) Mix acetylacetone, m-dimethylaminobenzene, p-toluenesulfonic acid, and toluene at a mass ratio of 4:4.8:0.08:60.5. After stirring and dissolving, react at 97 °C for 5 h, then place it in an ice-water bath, and add a trimethylaluminum-n-hexane solution that is 1.85 times the mass of acetylacetone. The mass ratio of trimethylaluminum to n-hexane in the trimethylaluminum-n-hexane solution is 1:2.5. Remove the ice-water bath, stir at 45 rpm at room temperature for 12 h, then distill at a vacuum of -0.06 MPa and 80 °C for 5 h, and freeze at -18 °C for 1.2 h to obtain organoaluminum. (2) Mix a bis-terminal epoxy silicone oil with a number-average molecular weight of 8000 and isopropanol at a mass ratio of 1:0.4. After stirring evenly, add an organoaluminum isopropanol solution that is 2.4 times the mass of the bis-terminal epoxy silicone oil. The mass ratio of organoaluminum to isopropanol in the organoaluminum isopropanol solution is 1:2. React at 80 °C for 5 h, then distill at a vacuum of -0.06 MPa and 55 °C for 1.5 h to obtain a modified silicone oil. (3) Knead phenyl silicone rubber, boron nitride, modified silicone oil, bismuth alloy, and vulcanizing agent bis-25 at a mass ratio of 50:13.5:4:17:2 for 20 min, let it stand for 12 h, then place it between two smooth and flat metal templates, use a flat vulcanizing machine, press at 80 °C and a pressure of 7.5 MPa for 20 s to form a circular thin film with a thickness of 0.1 m, and then vulcanize at 62 °C and a pressure of 1.2 MPa for 40 min to obtain rubber. (4) Mix chloromethylated polystyrene resin and toluene at a mass ratio of 5:17.4, soak for 8 h, add diethanolamine that is 1.2 times the mass of chloromethylated polystyrene resin, place it in an oil bath at 110 °C, stir at 700 rpm for 2.5 h, then cool to room temperature, add deionized water that is 3 times the mass of chloromethylated polystyrene resin, stir at the same speed for 30 min, filter, take the solid, wash it 3 times with deionized water, extract it with ethanol in a Soxhlet extractor for 20 h, and dry it at a vacuum of -0.08 MPa and 40 °C for 8 h to obtain polystyrene triethanolamine resin. (5) Mix polystyrene triethanolamine resin and 2,6-nonadienol at a mass ratio of 1:15.8. After soaking for 7 h, add 3,4-dichloro-6-nitroaniline which is 10.4 times the mass of the polystyrene triethanolamine resin and sodium hydroxide which is 5 times the mass of the polystyrene triethanolamine resin. Place it in a water bath at 61 °C and react for 4 h. Then, distill at a vacuum of -0.08 MPa and 40 °C for 1.5 h. Add deionized water which is 12.5 times the mass of the polystyrene triethanolamine resin, stir at 250 rpm for 30 min, filter by suction, take the filter residue, wash the filter residue with deionized water until the pH of the washing liquid is 7, rinse with ethanol at 50 °C for 10 min, then wash with deionized water 6 times, and dry at 40 °C for 24 h to obtain intermediate A; (6) Mix intermediate A, hydrochloric acid with a mass fraction of 36.5%, and deionized water at a mass ratio of 2.2:4.5:20. Stir at 30 °C and 60 rpm for 32 min, then cool to 2 °C. Add an aqueous sodium nitrite solution which is 2.7 times the mass of intermediate A at a rate of 0.2 mL / min. The mass ratio of sodium nitrite to deionized water in the aqueous sodium nitrite solution is 5.3:24. React for 45 min, then add urea until the starch-potassium iodide test paper turns blue to obtain a diazonium salt solution. Mix 2-hydroxy-4-(methacryloyloxy)benzophenone, distilled water, and sodium hydroxide with a mass fraction of 5% at a mass ratio of 0.2:10:0.15. After stirring and dissolving, at 2 °C, add the diazonium salt solution at a rate of 0.4 mL / min until the molar ratio of the diazonium salt to 2-hydroxy-4-(methacryloyloxy)benzophenone is 1:1. React for 1.5 h, maintaining the pH at 4 during this period. Centrifuge at 3500 rpm for 8 min, pour out the supernatant, wash the precipitate with distilled water 3 times, and vacuum dry at 40 °C for 24 h to obtain intermediate B; (7) Mix intermediate B, ethanol, and sodium hydroxide at a mass ratio of 1:15:0.11. After stirring and dissolving, react at 30 °C for 25 min, then add sodium dithionite which is 0.15 times the mass of the intermediate in three portions and continue to react for 1.2 h. Then add hydrochloric acid with a mass fraction of 36.5% which is 0.2 times the mass of intermediate B, let it stand for 12 min, filter by suction, take the filter cake, wash it with absolute ethanol 4 times, and dry at 40 °C for 24 h to obtain the modifier; (8) Place the rubber in a low-temperature plasma treatment instrument and treat it at 400 W for 375 s in an oxygen atmosphere to obtain activated rubber. Mix ethyl acetate, triethylamine, and activated rubber at a mass ratio of 15:0.95:1 in an ice-water bath at 0 °C. After stirring evenly, under stirring at 350 rpm, add a mixed solution of 3-bromo-4-fluorobenzoyl bromide which is 3.95 times the mass of the activated rubber. The mass ratio of 3-bromo-4-fluorobenzoyl bromide to ethyl acetate in the mixed solution of 3-bromo-4-fluorobenzoyl bromide is 9.3:18. Heat up to 35 °C and react for 6 h. Then filter by suction, take the filter residue, and place it in deionized water, ethanol, and acetone for ultrasonic cleaning for 10 min each, repeating 3 times to obtain pre-modified rubber; (9) Mix cuprous iodide, tetramethylethylenediamine, and anhydrous dimethyl sulfoxide in a mass ratio of 0.01:0.1:2.2. Stir at 70 rpm for 30 min under a nitrogen atmosphere. Add cesium carbonate 2.5 times the mass of cuprous iodide and a modifier 12.5 times the mass of cuprous iodide. Stir at 100 rpm for 4 h at room temperature. Then add pre-modified rubber 17.5 times the mass of cuprous iodide and anhydrous dimethyl sulfoxide 117 times the mass of cuprous iodide, and continue the reaction for 51.5 h. Perform suction filtration, take the filtrate, wash it 3 times successively with saturated brine and deionized water, and then dry it at 40 °C for 24 h to obtain intermediate C; (10) Mix triisobutylaluminum, toluene, intermediate C, and tris(pentafluorophenyl)borane in a mass ratio of 0.005:17.5:8:0.0001. React at 57 °C for 1.5 h, then add a 0.1 mol / L hydrochloric acid ethanol solution 2.5 times the mass of intermediate C, let it stand for 25 min, perform suction filtration, take the filtrate, and dry it at 40 °C for 24 h to obtain a high-temperature and corrosion-resistant alloy rubber.

[0022] Example 3 (1) Mix acetylacetone, m-dimethylaminobenzene, p-toluenesulfonic acid, and toluene in a mass ratio of 4:5.5:0.1:63. After stirring and dissolving, react at 105 °C for 6 h, then place it in an ice-water bath and add a trimethylaluminum-n-hexane solution 2.2 times the mass of acetylacetone. The mass ratio of trimethylaluminum to n-hexane in the trimethylaluminum-n-hexane solution is 1:3. Remove the ice-water bath and stir at 60 rpm for 12 h at room temperature. Then distill at a vacuum of -0.06 MPa and 80 °C for 6 h, and freeze at -18 °C for 1.5 h to obtain organoaluminum; (2) Mix bis(epoxy)silicone oil with a number-average molecular weight of 8000 and isopropyl alcohol in a mass ratio of 1:0.4. After stirring evenly, add an organoaluminum isopropyl alcohol solution 3.3 times the mass of bis(epoxy)silicone oil. The mass ratio of organoaluminum to isopropyl alcohol in the organoaluminum isopropyl alcohol solution is 1:2. React at 80 °C for 6 h, then distill at a vacuum of -0.06 MPa and 55 °C for 2 h to obtain modified silicone oil; (3) Knead phenyl silicone rubber, boron nitride, modified silicone oil, bismuth alloy, and vulcanizing agent bis-25 in a mass ratio of 60:18:8:22:3 for 30 min. Let it stand for 12 h, then place it between two smooth and flat metal templates. Use a flat vulcanizer to press at 85 °C and a pressure of 10 MPa for 30 s to form a circular thin film with a thickness of 0.2 mm, and then vulcanize at 65 °C and a pressure of 2 MPa for 50 min to obtain rubber; (4) Mix chloromethylated polystyrene resin and toluene at a mass ratio of 5:17.4, soak for 8 h, add diethanolamine which is 1.2 times the mass of the chloromethylated polystyrene resin, place it in an oil bath at 110 °C, stir at 700 rpm for 2.5 h, cool to room temperature, add deionized water which is 3 times the mass of the chloromethylated polystyrene resin, stir at the same speed for 30 min, filter, take the solid, wash it 3 times with deionized water, place it in a Soxhlet extractor and extract with ethanol for 20 h, dry at a vacuum of -0.08 MPa and 40 °C for 8 h to obtain polystyrene triethanolamine resin; (5) Mix polystyrene triethanolamine resin and 2,6-nonadienol at a mass ratio of 1.5:15.8, soak for 8 h, add 3,4-dichloro-6-nitroaniline which is 15.7 times the mass of the polystyrene triethanolamine resin and sodium hydroxide which is 5 times the mass of the polystyrene triethanolamine resin, place it in a water bath at 62 °C, react for 5 h, distill at a vacuum of -0.08 MPa and 40 °C for 2 h, add deionized water which is 15 times the mass of the polystyrene triethanolamine resin, stir at 300 rpm for 30 min, filter by suction, take the filtrate, wash the filtrate with deionized water until the pH of the washing liquid is 7, rinse with ethanol at 50 °C for 15 min, then wash with deionized water 6 times, dry at 40 °C for 24 h to obtain intermediate A; (6) Mix intermediate A, hydrochloric acid with a mass fraction of 36.5%, and deionized water at a mass ratio of 2.2:5:20, stir at 30 °C and 60 rpm for 40 min, cool to 5 °C, add an aqueous sodium nitrite solution which is 3 times the mass of intermediate A at a rate of 0.3 mL / min. The mass ratio of sodium nitrite to deionized water in the aqueous sodium nitrite solution is 5.3:24, react for 60 min, add urea until the starch-potassium iodide test paper turns blue to obtain a diazonium salt solution; Mix 2-hydroxy-4-(methacryloyloxy)benzophenone, distilled water, and sodium hydroxide with a mass fraction of 5% at a mass ratio of 0.2:10:0.2, stir to dissolve, at 5 °C, add the diazonium salt solution at a rate of 0.5 mL / min until the molar ratio of the diazonium salt to 2-hydroxy-4-(methacryloyloxy)benzophenone is 1:1, react for 2 h, maintain the pH at 4 during this period, centrifuge at 4000 rpm for 10 min, pour out the supernatant, wash the precipitate 3 times with distilled water, and dry in vacuum at 40 °C for 24 h to obtain intermediate B; (7) Mix intermediate B, ethanol, and sodium hydroxide at a mass ratio of 1:15:0.12, stir to dissolve, react at 35 °C for 30 min, add sodium dithionite which is 0.2 times the mass of the intermediate in three portions, continue to react for 1.5 h, add hydrochloric acid with a mass fraction of 36.5% which is 0.2 times the mass of intermediate B, let it stand for 15 min, filter by suction, take the filter cake, wash it 4 times with absolute ethanol, and dry at 40 °C for 24 h to obtain the modifier; (8) Place the rubber in a low-temperature plasma processor and treat it for 450 s at 400 W in an oxygen atmosphere to obtain activated rubber. Place ethyl acetate, triethylamine, and the activated rubber in an ice-water bath at 0 °C in a mass ratio of 20:1.3:1. After stirring evenly, add a mixed solution of 3-bromo-4-fluorobenzoyl bromide that is 4.4 times the mass of the activated rubber while stirring at 400 rpm. The mass ratio of 3-bromo-4-fluorobenzoyl bromide to ethyl acetate in the mixed solution of 3-bromo-4-fluorobenzoyl bromide is 9.3:18. Raise the temperature to 35 °C and react for 7 h. Then, perform suction filtration, take the filtrate, and ultrasonically clean it in deionized water, ethanol, and acetone for 10 min each, repeating 3 times to obtain pre-modified rubber. (9) Mix cuprous iodide, tetramethylethylenediamine, and anhydrous dimethyl sulfoxide in a mass ratio of 0.01:0.1:2.2. Stir at 80 rpm for 30 min under a nitrogen atmosphere, add cesium carbonate that is 3 times the mass of cuprous iodide and a modifier that is 15 times the mass of cuprous iodide. Stir at 120 rpm for 4 h at room temperature, add pre-modified rubber that is 20 times the mass of cuprous iodide and anhydrous dimethyl sulfoxide that is 117 times the mass of cuprous iodide, and continue to react for 55 h. Then, perform suction filtration, take the filtrate, wash it 3 times with saturated brine and deionized water in sequence, and dry it at 40 °C for 24 h to obtain intermediate C. (10) Mix triisobutylaluminum, toluene, intermediate C, and tris(pentafluorophenyl)borane in a mass ratio of 0.005:20:8:0.0001. React at 60 °C for 2 h, then add a 0.1 mol / L hydrochloric acid ethanol solution that is 3 times the mass of intermediate C, let it stand for 30 min, perform suction filtration, take the filtrate, and dry it at 40 °C for 24 h to obtain a high-temperature and corrosion-resistant alloy rubber.

[0023] Comparative Example 1 The difference between Comparative Example 1 and Example 2 is that steps (1) and (2) are absent, and step (3) is modified as follows: Knead phenyl silicone rubber, boron nitride, bis(epoxy) silicone oil with a number-average molecular weight of 8000, bismuth alloy, and vulcanizing agent bis-25 in a mass ratio of 50:13.5:4:17:2 for 20 min. After standing for 12 h, place it between two smooth and flat metal templates, and use a flat vulcanizer to press it at 80 °C and a pressure of 7.5 MPa for 20 s to form a circular thin film with a thickness of 0.1 m. Then, vulcanize it at 62 °C and a pressure of 1.2 MPa for 40 min to obtain rubber. The remaining steps are the same as in Example 2.

[0024] Comparative Example 2 The difference between Comparative Example 2 and Example 2 lies in step (3). Modify step (3) as follows: Knead phenyl silicone rubber, boron nitride, modified silicone oil, and vulcanizing agent bis-25 in a mass ratio of 50:13.5:4:2 for 20 min. After standing for 12 h, vulcanize it at 62 °C and a pressure of 1.2 MPa for 40 min to obtain rubber. The remaining steps are the same as in Example 2.

[0025] Comparative Example 3 The difference between Comparative Example 3 and Example 2 lies in the difference in step (3). Step (3) is changed to: Mix phenyl silicone rubber, boron nitride, modified silicone oil, bismuth alloy, and vulcanizing agent bis(2,5-dimethyl-2,5-di(t-butylperoxy)hexane) at a mass ratio of 50:13.5:4:17:2 for 20 min. After standing for 12 h, vulcanize at 80 °C for 40 min to obtain rubber. The remaining steps are the same as those in Example 2.

[0026] Comparative Example 4 The difference between Comparative Example 4 and Example 2 is that steps (4), (5), and (10) are absent. Step (6) is changed to: Mix 3,4-dichloro-6-nitroaniline, hydrochloric acid with a mass fraction of 36.5%, and deionized water at a mass ratio of 2.2:4.5:20, stir at 30 °C and 60 rpm for 32 min, cool to 2 °C, and add an aqueous sodium nitrite solution 2.7 times the mass of 3,4-dichloro-6-nitroaniline at a rate of 0.2 mL / min. The mass ratio of sodium nitrite to deionized water in the aqueous sodium nitrite solution is 5.3:24, react for 45 min, add urea to the solution until the starch-iodide test paper turns blue to obtain a diazonium salt solution; Mix 2-hydroxy-4-(methacryloyloxy)benzophenone, distilled water, and sodium hydroxide with a mass fraction of 5% at a mass ratio of 0.2:10:0.15, stir to dissolve, and at 2 °C, add the diazonium salt solution at a rate of 0.4 mL / min until the molar ratio of the diazonium salt to 2-hydroxy-4-(methacryloyloxy)benzophenone is 1:1, react for 1.5 h, maintain the pH at 4 during this period, centrifuge at 3500 rpm for 8 min, pour out the supernatant, wash the precipitate 3 times with distilled water, and vacuum dry at 40 °C for 24 h to obtain intermediate B. The remaining steps are the same as those in Example 2.

[0027] Comparative Example 5 The difference between Comparative Example 5 and Example 2 is that steps (6) and (7) are absent. Step (9) is changed to: Mix copper iodide, tetramethylethylenediamine, and anhydrous dimethyl sulfoxide at a mass ratio of 0.01:0.1:2.2, stir at 70 rpm for 30 min under a nitrogen atmosphere, add cesium carbonate 2.5 times the mass of copper iodide and intermediate A 12.5 times the mass of copper iodide, stir at 100 rpm for 4 h at room temperature, add pre-modified rubber 17.5 times the mass of copper iodide and anhydrous dimethyl sulfoxide 117 times the mass of copper iodide, continue to react for 51.5 h, filter by suction, take the filtrate, wash it 3 times with saturated brine and deionized water in sequence, and dry at 40 °C for 24 h to obtain intermediate C. The remaining steps are the same as those in Example 2.

[0028] Effect Example The following Table 1 shows the performance analysis results of the high-temperature and corrosion-resistant alloy rubbers of Examples 1 to 3 and Comparative Examples 1 to 5 of the present invention.

[0029] Table 1 From the comparison of the thermal aging experimental data between the examples and the comparative examples, it can be found that the present invention combines silicone oil and organoaluminum to form an organosilicon-aluminum structure, which absorbs free radicals generated by heat, improves the thermal stability of the rubber, and thus improves the high-temperature resistance of the rubber. Then, low-melting-point bismuth alloy, boron nitride, modified silicone oil, and silicone rubber are kneaded, and through vulcanization and pressing, the bismuth alloy and boron nitride form a network structure, which is connected to the rubber base material to form a heat dissipation channel, improving the heat dissipation performance of the rubber, and thus enhancing the high-temperature resistance of the rubber. From the comparison of the photoaging experimental data between the examples and the comparative examples, it can be found that the present invention uses 3,4-dichloro-6-nitroaniline, 2,6-nonadienol, and 2-hydroxy-4-(methacryloyloxy) benzophenone to react to form a benzotriazole structure, which effectively absorbs ultraviolet rays, and introduces benzophenone to construct a polybenzene ring structure, greatly increasing the ultraviolet absorption ability, improving the anti-ultraviolet aging performance of the rubber, and then grafting it onto the rubber surface, and the double bonds polymerize to form an anti-ultraviolet protective film, enhancing the anti-ultraviolet aging performance of the rubber.

[0030] For those skilled in the art, it is obvious that the present invention is not limited to the details of the above exemplary embodiments, and without departing from the spirit or basic characteristics of the present invention, the present invention can be implemented in other specific forms. Therefore, from any point of view, the embodiments should be regarded as exemplary and non-limiting. The scope of the present invention is defined by the appended claims rather than the above description. Therefore, all changes falling within the meaning and scope of the equivalent elements of the claims are intended to be included in the present invention. Any reference signs in the claims should not be regarded as limiting the claimed claim.

Claims

1. A preparation method of a high-temperature resistant and corrosion-resistant alloy rubber, characterized in that, It includes the following preparation steps: (1) Mix acetylacetone, m-dimethylaminobenzene, p-toluenesulfonic acid, and toluene at a mass ratio of 4:4.8:0.08:60.

5. After stirring and dissolving, react at 97°C for 5 h, then place it in an ice-water bath. Add a trimethylaluminum-n-hexane solution that is 1.85 times the mass of acetylacetone. The mass ratio of trimethylaluminum to n-hexane in the trimethylaluminum-n-hexane solution is 1:2.

5. Remove the ice-water bath and stir at 45 rpm at room temperature for 12 h. Then distill at a vacuum of -0.06 MPa and 80°C for 5 h, and freeze at -18°C for 1.2 h to obtain organoaluminum; (2) Mix bis-terminal epoxy silicone oil with a number-average molecular weight of 8000 and isopropyl alcohol at a mass ratio of 1:0.

4. After stirring evenly, add an organoaluminum isopropyl alcohol solution that is 2.4 times the mass of bis-terminal epoxy silicone oil. The mass ratio of organoaluminum to isopropyl alcohol in the organoaluminum isopropyl alcohol solution is 1:

2. React at 80°C for 5 h, then distill at a vacuum of -0.06 MPa and 55°C for 1.5 h to obtain modified silicone oil; (3) Knead phenyl silicone rubber, boron nitride, modified silicone oil, bismuth alloy, and vulcanizing agent bis-25 at a mass ratio of 50:13.5:4:17:2 for 20 min. After standing for 12 h, place it between two smooth and flat metal templates. Use a flat vulcanizing machine to press at 80°C and a pressure of 7.5 MPa for 20 s to form a circular thin film with a thickness of 0.1 m. Then vulcanize at 62°C and a pressure of 1.2 MPa for 40 min to obtain rubber; (4) Mix chloromethylated polystyrene resin and toluene at a mass ratio of 5:17.

4. After soaking for 8 h, add diethanolamine that is 1.2 times the mass of chloromethylated polystyrene resin. Place it in an oil bath at 110°C and stir at 700 rpm for 2.5 h. Then cool to room temperature, add deionized water that is 3 times the mass of chloromethylated polystyrene resin, stir at the same speed for 30 min, filter, take the solid, wash it 3 times with deionized water, place it in a Soxhlet extractor and extract with ethanol for 20 h, and dry at a vacuum of -0.08 MPa and 40°C for 8 h to obtain polystyrene triethanolamine resin; (5) Mix polystyrene triethanolamine resin and 2,6-nonadienol at a mass ratio of 1:15.

8. After soaking for 7 h, add 3,4-dichloro-6-nitroaniline that is 10.4 times the mass of polystyrene triethanolamine resin and sodium hydroxide that is 5 times the mass of polystyrene triethanolamine resin. Place it in a water bath at 61°C and react for 4 h. Then distill at a vacuum of -0.08 MPa and 40°C for 1.5 h. Add deionized water that is 12.5 times the mass of polystyrene triethanolamine resin, stir at 250 rpm for 30 min, filter, take the filtrate, wash the filtrate with deionized water until the pH of the washing solution is 7, rinse with ethanol at 50°C for 10 min, then wash with deionized water 6 times, and dry at 40°C for 24 h to obtain intermediate A; (6) Mix intermediate A, hydrochloric acid with a mass fraction of 36.5%, and deionized water in a mass ratio of 2.2:4.5:20, stir at 30 °C and 60 rpm for 32 min, cool to 2 °C, and add an aqueous sodium nitrite solution 2.7 times the mass of intermediate A at a rate of 0.2 mL / min. The mass ratio of sodium nitrite to deionized water in the aqueous sodium nitrite solution is 5.3:

24. React for 45 min, add urea to the solution until the starch-iodide test paper turns blue to obtain a diazonium salt solution; Mix 2-hydroxy-4-(methacryloyloxy)benzophenone, distilled water, and sodium hydroxide with a mass fraction of 5% in a mass ratio of 0.2:10:0.15, stir to dissolve, and at 2 °C, add the diazonium salt solution at a rate of 0.4 mL / min until the molar ratio of the diazonium salt to 2-hydroxy-4-(methacryloyloxy)benzophenone is 1:

1. React for 1.5 h, maintain the pH at 4 during this period, centrifuge at 3500 rpm for 8 min, pour out the supernatant, wash the precipitate 3 times with distilled water, and vacuum dry at 40 °C for 24 h to obtain intermediate B; (7) Mix intermediate B, ethanol, and sodium hydroxide in a mass ratio of 1:15:0.11, stir to dissolve, react at 30 °C for 25 min, add sodium dithionite 0.15 times the mass of the intermediate in three portions, continue to react for 1.2 h, then add hydrochloric acid with a mass fraction of 36.5% 0.2 times the mass of intermediate B, let stand for 12 min, filter by suction, take the filter cake, wash it 4 times with absolute ethanol, and dry at 40 °C for 24 h to obtain the modifier; (8) Place the rubber in a low-temperature plasma treatment instrument, treat it at 400 W for 375 s in an oxygen atmosphere to obtain activated rubber; Place ethyl acetate, triethylamine, and activated rubber in an ice-water bath at 0 °C in a mass ratio of 15:0.95:1, stir evenly, and under stirring at 350 rpm, add a mixed solution of 3-bromo-4-fluorobenzoyl bromide 3.95 times the mass of the activated rubber. The mass ratio of 3-bromo-4-fluorobenzoyl bromide to ethyl acetate in the mixed solution of 3-bromo-4-fluorobenzoyl bromide is 9.3:

18. Raise the temperature to 35 °C, react for 6 h, then filter by suction, take the filtrate, and ultrasonically clean it in deionized water, ethanol, and acetone for 10 min each, repeat 3 times to obtain pre-modified rubber; (9) Mix copper(I) iodide, tetramethylethylenediamine, and anhydrous dimethyl sulfoxide in a mass ratio of 0.01:0.1:2.2, stir at 70 rpm for 30 min under a nitrogen atmosphere, add cesium carbonate 2.5 times the mass of copper(I) iodide and the modifier 12.5 times the mass of copper(I) iodide, stir at 100 rpm at room temperature for 4 h, add pre-modified rubber 17.5 times the mass of copper(I) iodide and anhydrous dimethyl sulfoxide 117 times the mass of copper(I) iodide, continue to react for 51.5 h, filter by suction, take the filtrate, wash it 3 times with saturated brine and deionized water in sequence, and dry at 40 °C for 24 h to obtain intermediate C; (10) Mix triisobutylaluminum, toluene, intermediate C, and tris(pentafluorophenyl)borane in a mass ratio of 0.005:17.5:8:0.0001. After reacting at 57 °C for 1.5 h, add a 0.1 mol / L hydrochloric acid ethanol solution that is 2.5 times the mass of intermediate C, let it stand for 25 min, filter by suction, take the filtrate, and dry it at 40 °C for 24 h to obtain a high-temperature and corrosion-resistant alloy rubber.

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