High-temperature-resistant single-component silicone adhesive and preparation method thereof

Abstract

The invention discloses a high-temperature-resistant single-component silicone adhesive and a preparation method thereof, and belongs to the technical field of adhesives, the silicone adhesive is composed of polydimethylsiloxane, organic silicon resin, a filler, a catalyst and an additive, the silicone adhesive is prepared through a specific process, and the mechanical property, thermal stability and weather resistance of the silicone adhesive in a high-temperature environment are ensured. Wherein the modified organic silicon resin is used as a key component and is synthesized through a complex chemical process, so that the adhesive property and the temperature resistance of the adhesive are enhanced. Compared with the prior art, the silicone adhesive disclosed by the invention has higher tensile strength, bonding strength and durability in a severe environment, and meets the requirements on high-performance adhesives in industrial application.

Description

Technical Field

[0001] The present invention relates to the technical field of adhesives, and in particular to a high temperature resistant single-component silicone adhesive and a preparation method thereof. Background Art

[0002] With the rapid development of modern industrial technology, the demand for high-performance adhesives is growing, especially in the aerospace, automobile manufacturing, electronics and construction industries. The demand for adhesives that can maintain stable performance in high temperature environments is particularly urgent. As a sealant with excellent performance, silicone adhesive is widely used due to its excellent weather resistance, aging resistance and high temperature resistance. However, the performance of traditional silicone adhesives is often limited under extreme temperature conditions, especially in high temperature environments, such as decreased tensile strength and bonding strength, insufficient temperature resistance and weather resistance, which limits its use in a wider range of industrial applications.

[0003] Chinese invention patent CN110982480A discloses a one-component flame-retardant high-temperature resistant silicone sealant and its preparation method. The silicone sealant is prepared from the following raw materials by weight: 100 parts of base material, 15-40 parts of composite filler, 5-10 parts of ketoxime crosslinking agent, 0.1-1 parts of vulcanizing agent, and 0.5-2 parts of coupling agent; the base material is made of α,ω-dihydroxy polysiloxane containing phenyl and activated calcium carbonate; the composite filler is prepared from α,ω-dihydroxy polydimethylsiloxane, polyether silicone oil, iron oxide and aluminum hydroxide; the coupling agent is obtained by mixing the hydrolyzate of 3-aminopropyl triethoxysilane, aminophenyl trimethoxysilane and isocyanate propyl triethoxysilane with γ-(2,3-epoxypropoxy) propyl trimethoxysilane. The silicone sealant has excellent high temperature resistance and flame retardancy, high bonding strength and good insulation performance. However, the weather resistance, heat resistance and mechanical properties of the silicone sealant prepared by the invention still need to be improved. Summary of the invention

[0004] In view of the shortcomings of the prior art, the present invention aims to provide an improved high-temperature resistant one-component silicone adhesive and a preparation method thereof, by carefully selecting and proportioning various raw materials, including polydimethylsiloxane, silicone resin, heat-resistant filler, catalyst and various additives, and adopting a specific preparation process to ensure the mechanical properties, thermal stability and weather resistance of the silicone adhesive in a high-temperature environment, so as to meet the demand for high-performance adhesives in specific industrial applications.

[0005] In order to achieve the above-mentioned object of the invention, the present invention adopts the following technical solutions:

[0006] A method for preparing a high temperature resistant one-component silicone adhesive is as follows, in parts by weight:

[0007] S1. Raw material preparation: prepare 60-70 parts of polydimethylsiloxane, 15-20 parts of silicone resin, 10-15 parts of filler, 0.5-1 part of catalyst and 0.5-5 parts of additive, dry the prepared filler and remove moisture to ensure the stability of the formula;

[0008] S2, mixing polydimethylsiloxane and phenyltrimethoxysilane, and fully dispersing them using a high shear mixer to obtain a pretreated material;

[0009] S3, adding filler to the pretreated material prepared in step S2, and stirring until a uniform colloid is formed;

[0010] S4, adding tributyltin chloride and additives to the colloid prepared in step S3, mixing them evenly to obtain a mixture;

[0011] S5, degassing the mixture prepared in step S4, treating the mixture under a vacuum environment to remove bubbles, and obtaining an adhesive;

[0012] S6. Put the adhesive into a sealed container and store it in a cool and dry place to obtain a one-component silicone adhesive.

[0013] The polydimethylsiloxane has a viscosity of 30,000 to 400,000 mPa·s at 25° C.

[0014] The organic silicone resin is at least one of phenylsiloxane, fluorosilicone and modified organic silicone resin.

[0015] The filler is at least one of a heat-resistant inorganic filler and a reinforcing material; the heat-resistant inorganic filler is at least one of bauxite, aluminum silicate and silicon dioxide; the reinforcing material is at least one of glass fiber or carbon fiber.

[0016] The catalyst is butyltin chloride.

[0017] The additives include at least one of a modifier, an antioxidant, a rheology regulator, and a mildew preventer; wherein the modifier is at least one of a fluorinated silane or an amino silane.

[0018] The antioxidant is at least one of 2,6-di-tert-butyl-p-cresol, tri-tert-butyl-hydroxybenzene, and 2,2'-dihydroxy-4,4'-dimethylbenzophenone.

[0019] The rheology regulator is at least one of bentonite, titanium dioxide, diatomaceous earth powder, sodium carboxymethyl cellulose, methyl cellulose, guar gum or xanthan gum.

[0020] The mildew inhibitor is at least one of biphenyl and o-phenylphenol.

[0021] Preferably, the filler is a mixture of bauxite and glass fiber in a mass ratio of 2 to 4:1.

[0022] Preferably, the additive is composed of 3-aminopropyltriethoxysilane, 2,6-di-tert-butyl-p-cresol, methyl cellulose and biphenyl in a mass ratio of 4-6:1-3:1-3:1.

[0023] The preparation method of the modified silicone resin is as follows, in parts by weight:

[0024] Z1. Under a nitrogen atmosphere, first, 20 to 40 parts of 4,6-dichloro-1,3,5-triazine-2(1H)-one are added to 500 to 700 parts of toluene, and stirred at a temperature of 0 to 5°C to make it uniformly dispersed, 40 to 60 parts of 3-aminopropyltris(methoxyethoxyethoxy)silane and 30 to 50 parts of triethylamine are added to the solution, and then stirring is continued at room temperature for 20 to 30 hours. After the treatment is completed, the reaction solution is treated by suction filtration and rotary evaporation to obtain a pretreated product;

[0025] Z2, add 80-120 parts of di-1-adamantylphosphine chloride, 20-40 parts of triallylcarbinol, 15-25 parts of 1-(3-dimethylaminopropyl)-3-cyclohexylcarbodiimide and 10-20 parts of N-hydroxysulfonic acid succinimide to 2500-3500 parts of N,N-dimethylformamide, stir at 0-5°C for 2-4 hours, warm to room temperature, and stir overnight; after the treatment, distill under reduced pressure, dissolve the concentrate in 800-1200 parts of dichloromethane, add water, shake, separate the liquids, take the organic phase, dry it with anhydrous sodium sulfate, filter, take the filtrate, distill under reduced pressure, and vacuum dry it at 4-6°C for 5-15 hours to obtain a post-treated product;

[0026] Z3, adding 40 to 60 parts of the pre-treated product prepared in step Z1 and 20 to 40 parts of the post-treated product prepared in step Z2 to 400 to 600 parts of toluene, and stirring at 80 to 95° C. for 10 to 20 hours. After the treatment is completed, the product is washed with ethanol, filtered, washed with water and dried to obtain a functional agent;

[0027] Z4. Add 30 to 50 parts of the functional agent prepared in step Z3 to 400 to 600 parts of a 10 to 20 wt% sodium hypochlorite aqueous solution, and disperse evenly under stirring. Use 1 to 3 mol / L hydrochloric acid to adjust the pH value to 6.5 to 7.5, and continue stirring under this condition for 3 to 5 hours. After the treatment, wash with water and dry to obtain a modified silicone resin.

[0028] Preferably, the preparation method of the modified silicone resin is as follows, in parts by weight:

[0029] Z1. Under a nitrogen atmosphere, first, 20 to 40 parts of 4,6-dichloro-1,3,5-triazine-2(1H)-one are added to 500 to 700 parts of toluene, and stirred at a temperature of 0 to 5°C to make it uniformly dispersed, 40 to 60 parts of N-3-(triethoxysilyl)propyl-N-3-(trimethoxysilyl)propaneurea and 30 to 50 parts of triethylamine are added to the solution, and then stirring is continued at room temperature for 20 to 30 hours. After the treatment is completed, the reaction solution is treated by suction filtration and rotary evaporation to obtain a pretreated product;

[0030] Z2, add 80-120 parts of di-1-adamantylphosphine chloride, 20-40 parts of triallylcarbinol, 15-25 parts of 1-(3-dimethylaminopropyl)-3-cyclohexylcarbodiimide and 10-20 parts of N-hydroxysulfonic acid succinimide to 2500-3500 parts of N,N-dimethylformamide, stir at 0-5°C for 2-4 hours, warm to room temperature, and stir overnight; after the treatment, distill under reduced pressure, dissolve the concentrate in 800-1200 parts of dichloromethane, add water, shake, separate the liquids, take the organic phase, dry it with anhydrous sodium sulfate, filter, take the filtrate, distill under reduced pressure, and vacuum dry it at 4-6°C for 5-15 hours to obtain a post-treated product;

[0031] Z3, adding 40 to 60 parts of the pre-treated product prepared in step Z1 and 20 to 40 parts of the post-treated product prepared in step Z2 to 400 to 600 parts of toluene, and stirring at 80 to 95° C. for 10 to 20 hours. After the treatment is completed, the product is washed with ethanol, filtered, washed with water and dried to obtain a functional agent;

[0032] Z4. Add 30 to 50 parts of the functional agent prepared in step Z3 to 400 to 600 parts of a 10 to 20 wt% sodium hypochlorite aqueous solution, and disperse evenly under stirring. Use 1 to 3 mol / L hydrochloric acid to adjust the pH value to 6.5 to 7.5, and continue stirring under this condition for 3 to 5 hours. After the treatment, wash with water and dry to obtain a modified silicone resin.

[0033] The functions of each substance in the present invention are as follows:

[0034] As the main matrix component of silicone adhesive, polydimethylsiloxane provides the basic structure and performance of the adhesive, ensuring the flexibility and high temperature resistance of the adhesive.

[0035] Silicone resin enhances the high temperature resistance and bonding strength of silicone adhesive, and improves the chemical resistance and mechanical strength of adhesive.

[0036] Fillers improve the mechanical properties and temperature resistance of silicone adhesives, and reinforcing materials such as glass fiber or carbon fiber can improve the strength and heat resistance of adhesives.

[0037] Catalysts accelerate the curing process of silicone adhesives and improve the curing efficiency and bonding performance of adhesives.

[0038] Additives include modifiers, antioxidants, rheology regulators and mildew inhibitors, which are used to improve the various properties of silicone adhesives.

[0039] Modifiers (fluorinated silanes or amino silanes) enhance the bonding properties and heat resistance of silicone adhesives.

[0040] Antioxidants improve the aging resistance of silicone adhesive and extend its service life.

[0041] Rheology modifiers adjust the viscosity and fluidity of silicone rubber to facilitate construction and coating.

[0042] Anti-mold agents prevent silicone from growing mold in a humid environment and improve the product's mildew resistance.

[0043] 3-Aminopropyltriethoxysilane is used as one of the additives to enhance the bonding performance between silicone adhesive and substrate.

[0044] 4,6-Dichloro-1,3,5-triazine-2(1H)-one is used as a starting material in the preparation of modified silicone resin and participates in chemical reactions.

[0045] Triallyl carbinol is used as a reactant in the preparation of modified silicone resin, participating in the formation of a three-dimensional network structure and enhancing the cross-linking density of silicone glue.

[0046] 1-(3-Dimethylaminopropyl)-3-cyclohexylcarbodiimide is used as a crosslinking agent in the preparation of modified silicone resin to promote the crosslinking reaction between molecules.

[0047] N-Hydroxysulfonic acid succinimide is used as a coupling agent in the preparation of modified silicone resin to enhance the compatibility of silicone resin with other components.

[0048] The synergistic effect of these substances makes the silicone adhesive of the present invention have excellent high temperature resistance, good bonding performance and stable chemical properties, and is suitable for applications in various high temperature environments.

[0049] Compared with the prior art, it has the following beneficial effects:

[0050] 1) The one-component silicone adhesive of the present invention exhibits excellent mechanical properties, such as high tensile strength and bonding strength, under high temperature environments, which enables the adhesive to maintain structural integrity under extreme temperature conditions and is suitable for a wider range of industrial applications, especially in fields with high high temperature resistance requirements.

[0051] 2) Through the careful selection of raw materials and preparation process, the silicone adhesive of the present invention shows excellent thermal stability and good weather resistance in UV aging and wet heat cycle tests, which means that the product can maintain its performance and extend its service life under long-term exposure to harsh environmental conditions.

[0052] 3) The silicone adhesive of the present invention has a suitable viscosity range, which makes the adhesive easy to operate and shape, and is convenient for precise coating and construction in various applications, thereby improving construction efficiency and ease of use, while also reducing problems that may occur during the construction process, such as the generation of bubbles, thereby improving the processing performance of the product. DETAILED DESCRIPTION

[0053] Main sources of substances:

[0054] Polydimethylsiloxane, with a viscosity of 100,000 mPa·s at 25°C, Shandong Yousuo Chemical Technology Co., Ltd.

[0055] Cyanuric chloride, product number: 5125, Zhengzhou Quanfu Chemical Products Co., Ltd.

[0056] Bauxite, 325 mesh.

[0057] Glass fiber, length 19mm, diameter 14μm, breaking strength 1626Mpa.

[0058] Methyl cellulose, product number: 15-6, Henan Hongjia Chemical Products Co., Ltd.

[0059] 4,6-Dichloro-1,3,5-triazine-2(1H)-one, CAS number: 15791-08-9.

[0060] 3-Aminopropyltris(methoxyethoxyethoxy)silane, CAS number: 87794-64-7.

[0061] N-3-(triethoxysilyl)propyl-N-3-(trimethoxysilyl)propaneurea, CAS number: 24858-52-4.

[0062] The remaining raw materials in the examples and comparative examples of the present invention are all commercially available products.

[0063] The design idea of ​​the present invention is to provide a high-temperature resistant one-component silicone adhesive and a preparation method thereof, by carefully selecting and proportioning various raw materials, including polydimethylsiloxane, modified silicone resin, heat-resistant filler, catalyst and various additives, and adopting a specific preparation process, to ensure the mechanical properties, thermal stability and weather resistance of silicone adhesive in high temperature environment, thereby meeting the demand for high-performance adhesives in specific industrial applications.

[0064] Example 1

[0065] A method for preparing a high temperature resistant one-component silicone adhesive is as follows:

[0066] S1. Raw material preparation: 60 kg of polydimethylsiloxane, 15 kg of phenyltrimethoxysilane, 10 kg of filler, 0.5 kg of tributyltin chloride and 0.5 kg of additives. The filler is a mixture of bauxite and glass fiber in a mass ratio of 3:1. The additive is 3-aminopropyltriethoxysilane, 2,6-di-tert-butyl-p-cresol, methylcellulose and biphenyl in a mass ratio of 5:2:2:1. The prepared filler is dried to remove moisture to ensure the stability of the formula;

[0067] S2, mixing polydimethylsiloxane and phenyltrimethoxysilane, and fully dispersing them using a high shear mixer to obtain a pretreated material;

[0068] S3, adding filler to the pretreated material prepared in step S2, and stirring until a uniform colloid is formed;

[0069] S4, adding tributyltin chloride and additives to the colloid prepared in step S3, mixing them evenly to obtain a mixture;

[0070] S5, degassing the mixture prepared in step S4, treating the mixture under a vacuum environment to remove bubbles, and obtaining an adhesive;

[0071] S6. Put the adhesive into a sealed container and store it in a cool and dry place to obtain a one-component silicone adhesive.

[0072] Example 2

[0073] A method for preparing a high temperature resistant one-component silicone adhesive is as follows:

[0074] S1. Raw material preparation: 65 kg of polydimethylsiloxane, 17 kg of phenyltrimethoxysilane, 12 kg of filler, 0.6 kg of tributyltin chloride and 0.6 kg of additives. The filler is a mixture of bauxite and glass fiber in a mass ratio of 3:1. The additive is 3-aminopropyltriethoxysilane, 2,6-di-tert-butyl-p-cresol, methylcellulose and biphenyl in a mass ratio of 5:2:2:1. The prepared filler is dried to remove moisture to ensure the stability of the formula;

[0075] S2, mixing polydimethylsiloxane and phenyltrimethoxysilane, and fully dispersing them using a high shear mixer to obtain a pretreated material;

[0076] S3, adding filler to the pretreated material prepared in step S2, and stirring until a uniform colloid is formed;

[0077] S4, adding tributyltin chloride and additives to the colloid prepared in step S3, mixing them evenly to obtain a mixture;

[0078] S5, degassing the mixture prepared in step S4, treating the mixture under a vacuum environment to remove bubbles, and obtaining an adhesive;

[0079] S6. Put the adhesive into a sealed container and store it in a cool and dry place to obtain a one-component silicone adhesive.

[0080] Example 3

[0081] A method for preparing a high temperature resistant one-component silicone adhesive is as follows:

[0082] S1. Raw material preparation: 68 kg of polydimethylsiloxane, 18 kg of phenyltrimethoxysilane, 13 kg of filler, 0.8 kg of tributyltin chloride and 0.9 kg of additives. The filler is a mixture of bauxite and glass fiber in a mass ratio of 3:1. The additive is 3-aminopropyltriethoxysilane, 2,6-di-tert-butyl-p-cresol, methylcellulose and biphenyl in a mass ratio of 5:2:2:1. The prepared filler is dried to remove moisture to ensure the stability of the formula.

[0083] S2, mixing polydimethylsiloxane and phenyltrimethoxysilane, and fully dispersing them using a high shear mixer to obtain a pretreated material;

[0084] S3, adding filler to the pretreated material prepared in step S2, and stirring until a uniform colloid is formed;

[0085] S4, adding tributyltin chloride and additives to the colloid prepared in step S3, mixing them evenly to obtain a mixture;

[0086] S5, degassing the mixture prepared in step S4, treating the mixture under a vacuum environment to remove bubbles, and obtaining an adhesive;

[0087] S6. Put the adhesive into a sealed container and store it in a cool and dry place to obtain a one-component silicone adhesive.

[0088] Example 4

[0089] A method for preparing a high temperature resistant one-component silicone adhesive is as follows:

[0090] S1. Raw material preparation: 70 kg of polydimethylsiloxane, 20 kg of phenyltrimethoxysilane, 15 kg of filler, 1 kg of tributyltin chloride and 2 kg of additives. The filler is a mixture of bauxite and glass fiber in a mass ratio of 3:1. The additive is 3-aminopropyltriethoxysilane, 2,6-di-tert-butyl-p-cresol, methylcellulose and biphenyl in a mass ratio of 5:2:2:1. The prepared filler is dried to remove moisture to ensure the stability of the formula;

[0091] S2, mixing polydimethylsiloxane and phenyltrimethoxysilane, and fully dispersing them using a high shear mixer to obtain a pretreated material;

[0092] S3, adding filler to the pretreated material prepared in step S2, and stirring until a uniform colloid is formed;

[0093] S4, adding tributyltin chloride and additives to the colloid prepared in step S3, mixing them evenly to obtain a mixture;

[0094] S5, degassing the mixture prepared in step S4, treating the mixture under a vacuum environment to remove bubbles, and obtaining an adhesive;

[0095] S6. Put the adhesive into a sealed container and store it in a cool and dry place to obtain a one-component silicone adhesive.

[0096] Example 5

[0097] A method for preparing a high temperature resistant one-component silicone adhesive is as follows:

[0098] S1. Raw material preparation: 70 kg of polydimethylsiloxane, 20 kg of modified silicone resin, 15 kg of filler, 1 kg of tributyltin chloride and 2 kg of additives. The filler is a mixture of bauxite and glass fiber in a mass ratio of 3:1. The additive is 3-aminopropyltriethoxysilane, 2,6-di-tert-butyl-p-cresol, methylcellulose and biphenyl in a mass ratio of 5:2:2:1. The prepared filler is dried to remove moisture to ensure the stability of the formula;

[0099] S2, mixing polydimethylsiloxane and phenyltrimethoxysilane, and fully dispersing them using a high shear mixer to obtain a pretreated material;

[0100] S3, adding filler to the pretreated material prepared in step S2, and stirring until a uniform colloid is formed;

[0101] S4, adding tributyltin chloride and additives to the colloid prepared in step S3, mixing them evenly to obtain a mixture;

[0102] S5, degassing the mixture prepared in step S4, treating the mixture under a vacuum environment to remove bubbles, and obtaining an adhesive;

[0103] S6. Put the adhesive into a sealed container and store it in a cool and dry place to obtain a one-component silicone adhesive.

[0104] The preparation method of the modified silicone resin is as follows:

[0105] Z1. Under a nitrogen atmosphere, first, 30 g of 4,6-dichloro-1,3,5-triazine-2(1H)-one was added to 600 g of toluene, and stirred at 0°C to make it uniformly dispersed. 50 g of 3-aminopropyltris(methoxyethoxyethoxy)silane and 40 g of triethylamine were added to the solution, and then the stirring treatment was continued at room temperature for 24 hours. After the treatment was completed, the reaction solution was treated by suction filtration and rotary evaporation to obtain a pretreated product;

[0106] Z2, 100g of di-1-adamantylphosphine chloride, 30g of triallylcarbinol, 20g of 1-(3-dimethylaminopropyl)-3-cyclohexylcarbodiimide and 15g of N-hydroxysulfonic acid succinimide were added to 3000g of N, N-dimethylformamide, stirred at 0°C for 3 hours, warmed to room temperature, and stirred overnight; after the treatment was completed, the concentrate was distilled under reduced pressure, dissolved in 1000g of dichloromethane, water was added, shaken, separated, the organic phase was taken, dried over anhydrous sodium sulfate, filtered, the filtrate was taken, distilled under reduced pressure, and vacuum dried at 5°C for 10 hours to obtain a post-processed product;

[0107] Z3, adding 50g of the pre-treated product prepared in step Z1 and 30g of the post-treated product prepared in step Z2 to 500g of toluene, and stirring at 90°C for 15 hours. After the treatment is completed, the product is washed with ethanol, filtered, washed with water and dried to obtain a functional agent;

[0108] Z4. Add 40 g of the functional agent prepared in step Z3 to 500 g of a 15 wt% sodium hypochlorite aqueous solution and disperse evenly under stirring. Use 2 mol / L hydrochloric acid to adjust the pH value to 7, and continue stirring under this condition for 4 hours. After the treatment, wash with water and dry to obtain a modified silicone resin.

[0109] Example 6

[0110] The preparation method of a high temperature resistant one-component silicone adhesive is basically the same as that of Example 5, the only difference being that the preparation method of the modified silicone resin is different.

[0111] The preparation method of the modified silicone resin is as follows:

[0112] Z1. Under a nitrogen atmosphere, first add 30 g of 4,6-dichloro-1,3,5-triazine-2(1H)-one to 600 g of toluene, and stir at 0°C to make it uniformly dispersed, add 50 g of ureapropyltriethoxysilane and 40 g of triethylamine to the solution, and then continue stirring at room temperature for 24 hours. After the treatment is completed, the reaction solution is treated by suction filtration and rotary evaporation to obtain a pretreated product;

[0113] Z2, 100g of di-1-adamantylphosphine chloride, 30g of triallylcarbinol, 20g of 1-(3-dimethylaminopropyl)-3-cyclohexylcarbodiimide and 15g of N-hydroxysulfonic acid succinimide were added to 3000g of N, N-dimethylformamide, stirred at 0°C for 3 hours, warmed to room temperature, and stirred overnight; after the treatment was completed, the concentrate was distilled under reduced pressure, dissolved in 1000g of dichloromethane, water was added, shaken, separated, the organic phase was taken, dried over anhydrous sodium sulfate, filtered, the filtrate was taken, distilled under reduced pressure, and vacuum dried at 5°C for 10 hours to obtain a post-processed product;

[0114] Z3, adding 50g of the pre-treated product prepared in step Z1 and 30g of the post-treated product prepared in step Z2 to 500g of toluene, and stirring at 90°C for 15 hours. After the treatment is completed, the product is washed with ethanol, filtered, washed with water and dried to obtain a functional agent;

[0115] Z4. Add 40 g of the functional agent prepared in step Z3 to 500 g of a 15 wt% sodium hypochlorite aqueous solution and disperse evenly under stirring. Use 2 mol / L hydrochloric acid to adjust the pH value to 7, and continue stirring under this condition for 4 hours. After the treatment, wash with water and dry to obtain a modified silicone resin.

[0116] Example 7

[0117] The preparation method of a high temperature resistant one-component silicone adhesive is basically the same as that of Example 5, the only difference being that the preparation method of the modified silicone resin is different.

[0118] The preparation method of the modified silicone resin is as follows:

[0119] Z1. Under a nitrogen atmosphere, first, 30 g of 4,6-dichloro-1,3,5-triazine-2(1H)-one was added to 600 g of toluene, and stirred at 0°C to make it uniformly dispersed. 50 g of 3-[tri(2-ethoxyethoxy)silyl]propylamine and 40 g of triethylamine were added to the solution, and then the stirring treatment was continued at room temperature for 24 hours. After the treatment was completed, the reaction solution was treated by suction filtration and rotary evaporation to obtain a pretreated product;

[0120] Z2, 100g of di-1-adamantylphosphine chloride, 30g of triallylcarbinol, 20g of 1-(3-dimethylaminopropyl)-3-cyclohexylcarbodiimide and 15g of N-hydroxysulfonic acid succinimide were added to 3000g of N, N-dimethylformamide, stirred at 0°C for 3 hours, warmed to room temperature, and stirred overnight; after the treatment was completed, the concentrate was distilled under reduced pressure, dissolved in 1000g of dichloromethane, water was added, shaken, separated, the organic phase was taken, dried over anhydrous sodium sulfate, filtered, the filtrate was taken, distilled under reduced pressure, and vacuum dried at 5°C for 10 hours to obtain a post-processed product;

[0121] Z3, adding 50g of the pre-treated product prepared in step Z1 and 30g of the post-treated product prepared in step Z2 to 500g of toluene, and stirring at 90°C for 15 hours. After the treatment is completed, the product is washed with ethanol, filtered, washed with water and dried to obtain a functional agent;

[0122] Z4. Add 40 g of the functional agent prepared in step Z3 to 500 g of a 15 wt% sodium hypochlorite aqueous solution and disperse evenly under stirring. Use 2 mol / L hydrochloric acid to adjust the pH value to 7, and continue stirring under this condition for 4 hours. After the treatment, wash with water and dry to obtain a modified silicone resin.

[0123] Example 8

[0124] The preparation method of a high temperature resistant one-component silicone adhesive is basically the same as that of Example 5, the only difference being that the preparation method of the modified silicone resin is different.

[0125] The preparation method of the modified silicone resin is as follows:

[0126] Z1. Under a nitrogen atmosphere, first, 30 g of 4,6-dichloro-1,3,5-triazine-2(1H)-one was added to 600 g of toluene, and stirred at 0°C to make it uniformly dispersed. 50 g of 3-aminopropyltris(methoxyethoxyethoxy)silane and 40 g of triethylamine were added to the solution, and then the stirring treatment was continued at room temperature for 24 hours. After the treatment was completed, the reaction solution was treated by suction filtration and rotary evaporation to obtain a pretreated product;

[0127] Z2, 100g of di-1-adamantylphosphine chloride, 30g of 1,1-diallylethanol, 20g of 1-(3-dimethylaminopropyl)-3-cyclohexylcarbodiimide and 15g of N-hydroxysulfonic acid succinimide were added to 3000g of N,N-dimethylformamide, stirred at 0°C for 3 hours, warmed to room temperature, and stirred overnight; after the treatment, the concentrate was distilled under reduced pressure, dissolved in 1000g of dichloromethane, water was added, shaken, separated, the organic phase was taken, dried over anhydrous sodium sulfate, filtered, the filtrate was taken, distilled under reduced pressure, and vacuum dried at 5°C for 10 hours to obtain a post-processed product;

[0128] Z3, adding 50g of the pre-treated product prepared in step Z1 and 30g of the post-treated product prepared in step Z2 to 500g of toluene, and stirring at 90°C for 15 hours. After the treatment is completed, the product is washed with ethanol, filtered, washed with water and dried to obtain a functional agent;

[0129] Z4. Add 40 g of the functional agent prepared in step Z3 to 500 g of a 15 wt% sodium hypochlorite aqueous solution and disperse evenly under stirring. Use 2 mol / L hydrochloric acid to adjust the pH value to 7, and continue stirring under this condition for 4 hours. After the treatment, wash with water and dry to obtain a modified silicone resin.

[0130] Example 9

[0131] The preparation method of a high temperature resistant one-component silicone adhesive is basically the same as that of Example 5, the only difference being that the preparation method of the modified silicone resin is different.

[0132] The preparation method of the modified silicone resin is as follows:

[0133] Z1. Under a nitrogen atmosphere, first, 30 g of 4,6-dichloro-1,3,5-triazine-2(1H)-one was added to 600 g of toluene, and stirred at 0°C to make it uniformly dispersed. 50 g of 3-aminopropyltris(methoxyethoxyethoxy)silane and 40 g of triethylamine were added to the solution, and then the stirring treatment was continued at room temperature for 24 hours. After the treatment was completed, the reaction solution was treated by suction filtration and rotary evaporation to obtain a pretreated product;

[0134] Z2, 100g of di-1-adamantylphosphine chloride, 30g of (2-vinylcyclopropyl) methanol, 20g of 1-(3-dimethylaminopropyl)-3-cyclohexylcarbodiimide and 15g of N-hydroxysulfonic acid succinimide were added to 3000g of N, N-dimethylformamide, stirred for 3 hours at 0°C, warmed to room temperature, and stirred overnight; after the treatment was completed, the concentrate was distilled under reduced pressure, dissolved in 1000g of dichloromethane, water was added, oscillated, separated, the organic phase was taken, dried over anhydrous sodium sulfate, filtered, the filtrate was taken, distilled under reduced pressure, and vacuum dried at 5°C for 10 hours to obtain a post-processed product;

[0135] Z3, adding 50g of the pre-treated product prepared in step Z1 and 30g of the post-treated product prepared in step Z2 to 500g of toluene, and stirring at 90°C for 15 hours. After the treatment is completed, the product is washed with ethanol, filtered, washed with water and dried to obtain a functional agent;

[0136] Z4. Add 40 g of the functional agent prepared in step Z3 to 500 g of a 15 wt% sodium hypochlorite aqueous solution and disperse evenly under stirring. Use 2 mol / L hydrochloric acid to adjust the pH value to 7, and continue stirring under this condition for 4 hours. After the treatment, wash with water and dry to obtain a modified silicone resin.

[0137] Example 10

[0138] The preparation method of a high temperature resistant one-component silicone adhesive is basically the same as that of Example 5, the only difference being that the preparation method of the modified silicone resin is different.

[0139] The preparation method of the modified silicone resin is as follows:

[0140] Z1. Under a nitrogen atmosphere, first, 30 g of 4,6-dichloro-1,3,5-triazine-2(1H)-one was added to 600 g of toluene and stirred at 0°C to make it uniformly dispersed. 50 g of N-3-(triethoxysilyl)propyl-N-3-(trimethoxysilyl)propaneurea and 40 g of triethylamine were added to the solution, and then the stirring treatment was continued at room temperature for 24 hours. After the treatment was completed, the reaction solution was treated by suction filtration and rotary evaporation to obtain a pretreated product;

[0141] Z2, 100g of di-1-adamantylphosphine chloride, 30g of triallylcarbinol, 20g of 1-(3-dimethylaminopropyl)-3-cyclohexylcarbodiimide and 15g of N-hydroxysulfonic acid succinimide were added to 3000g of N, N-dimethylformamide, stirred at 0°C for 3 hours, warmed to room temperature, and stirred overnight; after the treatment was completed, the concentrate was distilled under reduced pressure, dissolved in 1000g of dichloromethane, water was added, shaken, separated, the organic phase was taken, dried over anhydrous sodium sulfate, filtered, the filtrate was taken, distilled under reduced pressure, and vacuum dried at 5°C for 10 hours to obtain a post-processed product;

[0142] Z3, adding 50g of the pre-treated product prepared in step Z1 and 30g of the post-treated product prepared in step Z2 to 500g of toluene, and stirring at 90°C for 15 hours. After the treatment is completed, the product is washed with ethanol, filtered, washed with water and dried to obtain a functional agent;

[0143] Z4. Add 40 g of the functional agent prepared in step Z3 to 500 g of a 15 wt% sodium hypochlorite aqueous solution and disperse evenly under stirring. Use 2 mol / L hydrochloric acid to adjust the pH value to 7, and continue stirring under this condition for 4 hours. After the treatment, wash with water and dry to obtain a modified silicone resin.

[0144] Comparative Example 1

[0145] The preparation method of a high temperature resistant one-component silicone adhesive is basically the same as that of Example 5, the only difference being that the preparation method of the modified silicone resin is different.

[0146] The preparation method of the modified silicone resin is as follows:

[0147] Z1. Under a nitrogen atmosphere, 30 g of cyanuric chloride was first added to 600 g of toluene, and stirred at 0 ° C to make it uniformly dispersed, 50 g of 3-aminopropyltris(methoxyethoxyethoxy)silane and 40 g of triethylamine were added to the solution, and then the stirring treatment was continued at room temperature for 24 hours. After the treatment was completed, the reaction solution was treated by suction filtration and rotary evaporation to obtain a pretreated product;

[0148] Z2, 100g of di-1-adamantylphosphine chloride, 30g of triallylcarbinol, 20g of 1-(3-dimethylaminopropyl)-3-cyclohexylcarbodiimide and 15g of N-hydroxysulfonic acid succinimide were added to 3000g of N, N-dimethylformamide, stirred at 0°C for 3 hours, warmed to room temperature, and stirred overnight; after the treatment was completed, the concentrate was distilled under reduced pressure, dissolved in 1000g of dichloromethane, water was added, shaken, separated, the organic phase was taken, dried over anhydrous sodium sulfate, filtered, the filtrate was taken, distilled under reduced pressure, and vacuum dried at 5°C for 10 hours to obtain a post-processed product;

[0149] Z3, adding 50g of the pre-treated product prepared in step Z1 and 30g of the post-treated product prepared in step Z2 to 500g of toluene, and stirring at 90°C for 15 hours. After the treatment is completed, the product is washed with ethanol, filtered, washed with water and dried to obtain a functional agent;

[0150] Z4. Add 40 g of the functional agent prepared in step Z3 to 500 g of a 15 wt% sodium hypochlorite aqueous solution and disperse evenly under stirring. Use 2 mol / L hydrochloric acid to adjust the pH value to 7, and continue stirring under this condition for 4 hours. After the treatment, wash with water and dry to obtain a modified silicone resin.

[0151] Comparative Example 2

[0152] The preparation method of a high temperature resistant one-component silicone adhesive is basically the same as that of Example 5, the only difference being that the preparation method of the modified silicone resin is different.

[0153] The preparation method of the modified silicone resin is as follows:

[0154] Z1. Under a nitrogen atmosphere, first, 30 g of 4,6-dichloro-1,3,5-triazine-2(1H)-one was added to 600 g of toluene, and stirred at 0°C to make it uniformly dispersed. 50 g of 3-aminopropyltriethoxysilane and 40 g of triethylamine were added to the solution, and then the stirring treatment was continued at room temperature for 24 hours. After the treatment was completed, the reaction solution was treated by suction filtration and rotary evaporation to obtain a pretreated product;

[0155] Z2, 100g of di-1-adamantylphosphine chloride, 30g of triallylcarbinol, 20g of 1-(3-dimethylaminopropyl)-3-cyclohexylcarbodiimide and 15g of N-hydroxysulfonic acid succinimide were added to 3000g of N, N-dimethylformamide, stirred at 0°C for 3 hours, warmed to room temperature, and stirred overnight; after the treatment was completed, the concentrate was distilled under reduced pressure, dissolved in 1000g of dichloromethane, water was added, shaken, separated, the organic phase was taken, dried over anhydrous sodium sulfate, filtered, the filtrate was taken, distilled under reduced pressure, and vacuum dried at 5°C for 10 hours to obtain a post-processed product;

[0156] Z3, adding 50g of the pre-treated product prepared in step Z1 and 30g of the post-treated product prepared in step Z2 to 500g of toluene, and stirring at 90°C for 15 hours. After the treatment is completed, the product is washed with ethanol, filtered, washed with water and dried to obtain a functional agent;

[0157] Z4. Add 40 g of the functional agent prepared in step Z3 to 500 g of a 15 wt% sodium hypochlorite aqueous solution and disperse evenly under stirring. Use 2 mol / L hydrochloric acid to adjust the pH value to 7, and continue stirring under this condition for 4 hours. After the treatment, wash with water and dry to obtain a modified silicone resin.

[0158] Comparative Example 3

[0159] The preparation method of a high temperature resistant one-component silicone adhesive is basically the same as that of Example 5, the only difference being that the preparation method of the modified silicone resin is different.

[0160] The preparation method of the modified silicone resin is as follows:

[0161] Z1. Under a nitrogen atmosphere, first, 30 g of 4,6-dichloro-1,3,5-triazine-2(1H)-one was added to 600 g of toluene, and stirred at 0°C to make it uniformly dispersed. 50 g of 3-aminopropyltris(methoxyethoxyethoxy)silane and 40 g of triethylamine were added to the solution, and then the stirring treatment was continued at room temperature for 24 hours. After the treatment was completed, the reaction solution was treated by suction filtration and rotary evaporation to obtain a pretreated product;

[0162] Z2, 100g di-1-adamantylphosphine chloride, 30g 5-hexene-1-ol, 20g 1-(3-dimethylaminopropyl)-3-cyclohexylcarbodiimide and 15gN-hydroxysulfonic acid succinimide were added to 3000g N, N-dimethylformamide, stirred for 3 hours at 0°C, warmed to room temperature, and stirred overnight; after the treatment, the concentrate was distilled under reduced pressure, dissolved in 1000g dichloromethane, water was added, oscillated, separated, the organic phase was taken, dried over anhydrous sodium sulfate, filtered, the filtrate was distilled under reduced pressure, and vacuum dried at 5°C for 10 hours to obtain a post-processed product;

[0163] Z3, adding 50g of the pre-treated product prepared in step Z1 and 30g of the post-treated product prepared in step Z2 to 500g of toluene, and stirring at 90°C for 15 hours. After the treatment is completed, the product is washed with ethanol, filtered, washed with water and dried to obtain a functional agent;

[0164] Z4. Add 40 g of the functional agent prepared in step Z3 to 500 g of a 15 wt% sodium hypochlorite aqueous solution and disperse evenly under stirring. Use 2 mol / L hydrochloric acid to adjust the pH value to 7, and continue stirring under this condition for 4 hours. After the treatment, wash with water and dry to obtain a modified silicone resin.

[0165] Test Example 1

[0166] Mechanical properties test

[0167] Tensile strength test

[0168] Equipment: Electronic universal material testing machine.

[0169] Sample preparation: Prepare standard tensile specimens (ASTM D638) in dog-bone shape;

[0170] The dimensions of each sample are: length: 150 mm, width: 10 mm, thickness: 3 mm;

[0171] The one-component silicone adhesive prepared in the examples and comparative examples was coated on a mold treated with a release agent and taken out after curing.

[0172] Test steps:

[0173] Step 1: Place the sample into the fixture of the electronic universal material testing machine;

[0174] Step 2: Stretch at a constant rate (e.g., 10 mm / min) and record the maximum stretching force;

[0175] Step 3: Calculate the tensile strength using the formula: tensile strength = maximum tensile force / initial cross-sectional area.

[0176] Bond strength test

[0177] Sample preparation: 13 groups were used, and each group consisted of two identical aluminum substrates (the silicone adhesive prepared in Examples 1 to 10 and Comparative Examples 1 to 3 was coated on the surface thereof and cured;

[0178] The dimensions of each sample are: width 10 mm, length 20 mm, thickness 3 mm.

[0179] Test steps:

[0180] Step 1: Fix two substrates in an overlapping manner on a shear tester;

[0181] Step 2: Apply shear force until the bonding surfaces separate;

[0182] Step 3: Record the maximum applied force and calculate the shear strength using the formula:

[0183] Bond strength = maximum shear force / bonding area.

[0184] Hardness test

[0185] Equipment: Shore A hardness tester;

[0186] Test steps:

[0187] Step 1: Place the hardness tester vertically on the surface of the cured silicone adhesive;

[0188] Step 2: Read the hardness value and take the average value after three measurements.

[0189] The test results are shown in Table 1.

[0190] Table 1

[0191]

[0192]

[0193] Test Example 2

[0194] Thermal performance test

[0195] Differential Scanning Calorimetry (DSC)

[0196] Equipment: Differential scanning calorimeter (DSC);

[0197] Sample preparation: Take 10 mg of the cured one-component silicone glue sample prepared in the examples and comparative examples;

[0198] Test steps:

[0199] Step 1: Place the sample in the DSC sample pan;

[0200] Step 2: Under nitrogen protection, perform heating and cooling cycles (usually from -80°C to 300°C);

[0201] Step 3: Record the heat flow changes and determine the glass transition temperature (Tg) and melting temperature (Tm).

[0202] The test results are shown in Table 2.

[0203] Table 2

[0204]

[0205]

[0206] Test Example 3

[0207] Weathering test

[0208] Ultraviolet (UV) aging test;

[0209] Equipment: UV aging test machine;

[0210] Sample preparation: The one-component silicone rubber prepared in the examples and comparative examples was processed into standard samples, the size of the standard samples being 100 mm×100 mm×3 mm;

[0211] Test steps:

[0212] Step 1: Place the samples prepared in the examples and comparative examples into a UV aging tester and set the UV illumination conditions (254 nm wavelength);

[0213] Step 2: Sampling after 200 hours;

[0214] Step 3: Test the hardness of the sample.

[0215] Damp heat cycle test

[0216] Equipment: Wet heat circulation box

[0217] Sample preparation: The one-component silicone rubber prepared in the examples and comparative examples was processed into standard samples, and the size of the standard samples was 100 mm×100 mm×3 mm;

[0218] Test steps:

[0219] Step 1: Place the sample in a wet heat cycle box and set the conditions (temperature: 40°C, humidity: 95% RH, cycle time: 1000 hours);

[0220] Step 2: Test the tensile strength of the sample.

[0221] The test results are shown in Table 3.

[0222] Table 3

[0223]

[0224] It can be seen from the data of Examples 1 to 4 that the one-component silicone adhesive prepared in Example 4 performs well in multiple performance tests, especially in tensile strength and bonding strength. It shows good deformation resistance; the tensile strength is as high as 2.9MPa, and the bonding strength also reaches 2.0MPa. These data are better than Examples 1 to 3, indicating that the silicone adhesive of Example 4 has significant advantages in mechanical properties. In addition, Example 4 also shows excellent thermal stability in thermal performance tests, with a glass transition temperature (Tg) as low as -69°C and a melting temperature (Tm) as high as 218°C, which means that the material can still maintain performance at extreme temperatures. In the weather resistance test, the hardness of the silicone adhesive of Example 4 only increased by 5 ShoreA units after ultraviolet aging, and the tensile strength only decreased by 10% after wet heat cycle aging, which further proves its durability in harsh environments. Therefore, the one-component silicone adhesive of Example 4 not only performs well in mechanical properties, but also has excellent thermal stability and weather resistance.

[0225] The reason why the 3-aminopropyl tris (methoxyethoxyethoxy) silane adopted in embodiment 5 performs best in tensile strength, bonding strength, temperature resistance and weather resistance is possible because of its unique molecular structure and chemical properties. This silane has amino and longer ethoxy chains, so that it can form chemical bonds with various resins and substrates, and can form silanols after hydrolysis, further acting on the substrate surface, and enhancing bonding properties. In addition, its longer ethoxy chain provides better flexibility and temperature resistance, which helps to keep the performance of adhesive at high temperatures. Meanwhile, the amino of 3-aminopropyl tris (methoxyethoxyethoxy) silane can be combined with other substances to form stable chemical bonds, and these bonds are still stable in a hot and humid environment, thereby improving the weather resistance of the material. Therefore, the structural characteristics of this silane make it have advantages in improving the mechanical properties and temperature resistance and weather resistance of the one-component silicone adhesive.

[0226] Triallylcarbinol has excellent tensile strength, adhesive strength, temperature resistance and weather resistance due to its unique structural characteristics. This compound contains three double bonds, which not only increases the cross-linking activity of the molecule, but also stabilizes the molecular structure and improves its reactivity due to the hyperconjugation effect. In the preparation of modified silicone resins, the multiple double bonds of triallylcarbinol can participate in cross-linking and polymerization reactions, thereby increasing the cross-linking density and the stability of the network structure. This high cross-linking density helps to enhance the bonding strength between the adhesive and the substrate and improve the overall mechanical properties of the material. At the same time, the introduction of triallylcarbinol increases the thermal stability and UV resistance of the adhesive, which is crucial for maintaining material performance under high temperature and UV irradiation environments. Therefore, these characteristics of triallylcarbinol make it more effective in improving the performance of silicone adhesives than other compounds containing unsaturated bonds such as 1,1-diallylethanol, (2-vinylcyclopropyl)methanol and 5-hexene-1-ol.

[0227] In the modified silicone resin preparation method of Example 5, the interaction between the various substances is reflected in their synergistic enhancement of the performance of silicone glue. 4,6-Dichloro-1,3,5-triazine-2(1H)-one reacts with 3-aminopropyltri(methoxyethoxyethoxy)silane and triethylamine to form a pre-treated material. In this step, the activity of the triazine ring and the nucleophilicity of the silane work together to promote the formation of silicon-oxygen bonds. Di-1-adamantylphosphine chloride acts with triallylcarbinol, 1-(3-dimethylaminopropyl)-3-cyclohexylcarbodiimide and N-hydroxysulfonic acid succinimide in N,N-dimethylformamide. In this process, the cross-linking between molecules is enhanced. In the subsequent steps, the pre-treated material and the post-treated material are mixed and heated in toluene, which further promotes the interaction and cross-linking between molecules, and finally the stability and activity of the modified silicone resin are ensured by adjusting the pH to neutral. The interaction between these substances acts together on the molecular structure of silicone glue, improving its high temperature resistance and mechanical strength.

[0228] The N-3-(triethoxysilyl)propyl-N-3-(trimethoxysilyl)propaneurea used in Example 10 performs better in tensile strength, bonding strength, temperature resistance and weather resistance than the 3-aminopropyltri(methoxyethoxyethoxy)silane used in Example 5. The possible reason is that the N-3-(triethoxysilyl)propyl-N-3-(trimethoxysilyl)propaneurea has two different silane groups, which enables it to form a stronger force with a variety of substrates. The presence of triethoxysilyl and trimethoxysilyl provides more sites, enhances the interaction with inorganic fillers and organic polymers, thereby improving the cohesion and bonding effect of the adhesive. In addition, this structure may also help to improve the thermal stability and weather resistance of the adhesive.

Claims

1. A method for preparing a high temperature resistant one-component silicone adhesive, characterized in that: The method is as follows, in parts by weight: S1. Raw material preparation: prepare 60-70 parts of polydimethylsiloxane, 15-20 parts of silicone resin, 10-15 parts of filler, 0.5-1 part of catalyst and 0.5-5 parts of additive, dry the prepared filler and remove moisture to ensure the stability of the formula; S2, mixing polydimethylsiloxane and phenyltrimethoxysilane, and fully dispersing them using a high shear mixer to obtain a pretreated material; S3, adding filler to the pretreated material prepared in step S2, and stirring until a uniform colloid is formed; S4, adding tributyltin chloride and additives to the colloid prepared in step S3, mixing them evenly to obtain a mixture; S5, degassing the mixture prepared in step S4, treating the mixture under a vacuum environment to remove bubbles, and obtaining an adhesive; S6. Put the adhesive into a sealed container and store it in a cool and dry place to obtain a single-component silicone adhesive; The organosilicon resin is a modified organosilicon resin; The preparation method of the modified silicone resin is as follows, in parts by weight: Z1. Under a nitrogen atmosphere, first, 20 to 40 parts of 4,6-dichloro-1,3,5-triazine-2(1H)-one are added to 500 to 700 parts of toluene, and stirred at a temperature of 0 to 5°C to make it uniformly dispersed, 40 to 60 parts of 3-aminopropyltris(methoxyethoxyethoxy)silane and 30 to 50 parts of triethylamine are added to the solution, and then stirring is continued at room temperature for 20 to 30 hours. After the treatment is completed, the reaction solution is treated by suction filtration and rotary evaporation to obtain a pretreated product; Z2, add 80-120 parts of di-1-adamantylphosphine chloride, 20-40 parts of triallylcarbinol, 15-25 parts of 1-(3-dimethylaminopropyl)-3-cyclohexylcarbodiimide and 10-20 parts of N-hydroxysulfonic acid succinimide to 2500-3500 parts of N,N-dimethylformamide, stir at 0-5°C for 2-4 hours, warm to room temperature, and stir overnight; after the treatment, distill under reduced pressure, dissolve the concentrate in 800-1200 parts of dichloromethane, add water, shake, separate the liquids, take the organic phase, dry it with anhydrous sodium sulfate, filter, take the filtrate, distill under reduced pressure, and vacuum dry it at 4-6°C for 5-15 hours to obtain a post-treated product; Z3, adding 40 to 60 parts of the pre-treated product prepared in step Z1 and 20 to 40 parts of the post-treated product prepared in step Z2 to 400 to 600 parts of toluene, and stirring at 80 to 95° C. for 10 to 20 hours. After the treatment is completed, the product is washed with ethanol, filtered, washed with water and dried to obtain a functional agent; Z4, add 30-50 parts of the functional agent prepared in step Z3 to 400-600 parts of 10-20wt% sodium hypochlorite aqueous solution, and disperse evenly under stirring, use 1-3 mol / L hydrochloric acid to adjust the pH value to 6.5-7.5, and continue stirring under this condition for 3-5 hours. After the treatment, wash with water and dry to obtain a modified silicone resin.

2. The method for preparing the high temperature resistant one-component silicone adhesive according to claim 1, characterized in that: The polydimethylsiloxane has a viscosity of 30,000 to 400,000 mPa·s at 25° C.

3. The method for preparing the high temperature resistant one-component silicone adhesive according to claim 1, characterized in that: The filler is at least one of a heat-resistant inorganic filler and a reinforcing material; the heat-resistant inorganic filler is at least one of bauxite, aluminum silicate and silicon dioxide; the reinforcing material is at least one of glass fiber or carbon fiber.

4. The method for preparing the high temperature resistant one-component silicone adhesive according to claim 1, characterized in that: The catalyst is butyltin chloride.

5. The method for preparing a high temperature resistant one-component silicone adhesive according to claim 1, characterized in that: The additive comprises at least one of a modifier, an antioxidant, a rheology regulator and a mildewproof agent; wherein the modifier is at least one of fluorinated silane or aminosilane; the antioxidant is at least one of 2,6-di-tert-butyl-p-cresol, tri-tert-butyl-hydroxybenzene and 2,2'-dihydroxy-4,4'-dimethylbenzophenone; the rheology regulator is at least one of bentonite, titanium dioxide, diatomaceous earth powder, sodium carboxymethyl cellulose, methyl cellulose, guar gum or xanthan gum; the mildewproof agent is at least one of biphenyl and o-phenylphenol.

6. The method for preparing a high temperature resistant one-component silicone adhesive according to claim 1 or 3, characterized in that: The filler is a mixture of bauxite and glass fiber in a mass ratio of 2 to 4:

1.

7. The method for preparing a high temperature resistant one-component silicone adhesive according to claim 1 or 5, characterized in that: The additive is composed of 3-aminopropyltriethoxysilane, 2,6-di-tert-butyl-p-cresol, methyl cellulose and biphenyl in a mass ratio of 4-6:1-3:1-3:

1.

8. A high temperature resistant one-component silicone adhesive, characterized in that: Prepared by the preparation method according to any one of claims 1 to 7.

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