High-weather-resistant water-resistant modified high-temperature-resistant adhesive

Abstract

The invention discloses a high-weather-resistant and water-resistant modified high-temperature-resistant adhesive, and belongs to the technical field of organic silicon adhesives. The preparation method comprises the following steps: mixing and stirring polysiloxane, polyvinyl acid ester, modified gas silicon, modified boron nitride, fluorine micro powder, oligomeric silsesquioxane, modified carbon nanotubes, carboxyl glycerol, zinc stearate, graphene, metal oxide, halloysite, butylated hydroxytoluene and dicyandiamide to obtain a component A; mixing polysilazane, a deoximation curing agent, a water removal agent, an adhesion promoter, cyclohexanone peroxide, a plasticizer and dithiobis (disilazane) phenol, and uniformly stirring to obtain a component B; and mixing the component A and the component B to obtain the double-component high-weather-resistant water-resistant modified high-temperature-resistant adhesive. The high-temperature-resistant adhesive can effectively solve the problems that an existing adhesive is insufficient in flexibility and poor in moisture resistance and thermal aging resistance, preparation is easy and convenient, and the obtained high-temperature-resistant adhesive has high flexibility, good moisture resistance, corrosion resistance, bacteriostasis, oil resistance and aging resistance, good stability and long storage life.

Description

TECHNICAL FIELD

[0001] The application relates to a high-weather-resistance water-resistance type modified high-temperature-resistant adhesive and belongs to the technical field of silicone adhesives. BACKGROUND

[0002] Products made of silicone materials have excellent performance and are various in types, and the development momentum is rapid. Nowadays, the new material field is increasingly dependent on silicone materials. Silicone rubber has good high and low temperature resistance, weather resistance and low compression permanent deformation rate and other advantages, and plays a great role in parts such as oil seals and rubber pipes. In the field of space transportation, high-temperature sealing conditions are usually involved, and the comprehensive performance of the adhesive stability and temperature resistance is strictly required. In addition, high-temperature conditions can easily lead to a decrease in bonding performance, bringing greater challenges to the development of high-temperature-resistant adhesives. For a long time, the high-temperature-resistant adhesive process is not mature, the technology is unstable, the stability of the obtained adhesive is general, the storage period is not long, and the high-temperature resistance is insufficient. This seriously restricts its use in many fields such as automobiles and transportation.

[0003] A high-adhesion lightweight heat-insulating high-temperature-resistant adhesive and a preparation method thereof are provided in Chinese Patent Publication No. CN117567980A, which are prepared from hydroxyl silicone oil, hollow microspheres, ceramic fibers and polysilazane. However, the prior art has insufficient flexibility, and lacks moisture resistance and heat aging resistance. According to the above-mentioned deficiencies, while ensuring the adhesion performance of the adhesive, the comprehensive performance of the adhesive is enhanced, which is the key and hot issue to be solved at present and in the future. Therefore, it is of great social value and economic benefit to provide a preparation method of a safe and reliable high-temperature-resistant adhesive with moisture resistance and aging resistance. SUMMARY

[0004] The purpose of the present application is to solve the problems of insufficient flexibility, lack of moisture resistance and heat aging resistance of existing high-temperature-resistant adhesives, and to provide a high-weather-resistance water-resistance type modified high-temperature-resistant adhesive. The high-temperature-resistant adhesive of the present application has high flexibility, and also has good moisture resistance, bacteriostasis, oil resistance and aging resistance. The obtained adhesive has good stability and a long storage period.

[0005] The purpose of the present application is achieved by the following technical solutions: In a first aspect, the present application provides a high-weather-resistance water-resistance type modified high-temperature-resistant adhesive, which is prepared from two components A and B. The A component is composed of the following raw materials in parts by weight: ; The B component is composed of the following raw materials in parts by weight:

[0007] .

[0008] As an embodiment of the present application, in the A component, the fluorine micropowder is one or more of polytetrafluoroethylene (PTFE), soluble polytetrafluoroethylene (PFA), and polyperfluoroethylene-propylene (FEP).

[0009] As an embodiment of the present application, in the A component, the metal oxide is one or more of tin dioxide, iron oxide, zinc oxide, and cerium oxide.

[0010] As an embodiment of the present application, in the A component, the modified fumed silica is fumed silica modified by trimethylchlorosilane and vinyltrimethoxysilane (A171 silane coupling agent). The modification aims to reduce the surface free energy and improve the thermal stability, bonding strength, bulk strength, and filler dispersibility in the system.

[0011] As an embodiment of the present application, in the A component, the preparation method of the modified fumed silica is as follows: dry fumed silica powder, trimethylchlorosilane, and vinyltrimethoxysilane (A171 silane coupling agent) are added to an acetone solution in a mass ratio of (5-8):1:2:100, continuously stirred at room temperature for 5-8 hours, taken out and filtered, and washed with anhydrous ethanol; then dried in a blast drying oven at 220-300℃ for 2-3 hours to obtain the modified fumed silica.

[0012] As an embodiment of the present application, in the A component, the modified carbon nanotube is a carbon nanotube modified by triethylbenzylammonium chloride. The modification aims to improve the dispersibility, mechanical properties, durability, and stability, and also has certain water resistance.

[0013] As an embodiment of the present application, in the A component, the preparation method of the modified carbon nanotube is as follows: triethylbenzylammonium chloride powder and carbon nanotubes are added to an N-methylpyrrolidone solution in a mass ratio of (0.05-0.07):1:20, ultrasonically dispersed and stirred at 100-130℃ for 2-3 hours, taken out and filtered, and repeatedly washed with anhydrous ethanol for 3-5 times; then dried in a blast drying oven at 220-300℃ for 5-8 hours to obtain the modified carbon nanotube.

[0014] As an embodiment of the present application, in the A component, the modified boron nitride is boron nitride modified by KH550. The modification aims to improve the mechanical properties and stability.

[0015] As an embodiment of the present application, in the A component, the preparation method of the modified boron nitride is as follows: boron nitride powder, KH550 are added into toluene solution at a mass ratio of (6-10):1:100, stirring is continued for 1-2 hours at 100-115℃, and then it is taken out, filtered, and washed repeatedly with anhydrous ethanol for 3-5 times; then it is dried in a blast drying oven at 220-300℃ for 2-3 hours to obtain the modified boron nitride.

[0016] As an embodiment of the present application, in the B component, the deoxime curing agent is one or more of methyl tributanone oxime silane, tetrabutyl tributanone oxime silane, and vinyl tributanone oxime silane.

[0017] As an embodiment of the present application, in the B component, the water removing agent is one or more of calcium oxide, magnesium sulfate, and polyacrylamide.

[0018] As an embodiment of the present application, in the B component, the adhesion promoter is one or a mixture of two or more of γ-aminopropyl triethoxysilane (KH-550), γ-glycidyl ether propyl trimethoxysilane (KH-560), and N-(β-aminoethyl)-γ-aminopropyl trimethoxysilane.

[0019] As an embodiment of the present application, in the B component, the plasticizer is one of diisodecyl phthalate, diisononyl phthalate, and dimethyl silicone oil.

[0020] As an embodiment of the present application, the mass ratio of the A component and the B component is 10-30:1. In some embodiments, the mass ratio of the A component and the B component is selected to be 20:1.

[0021] In a second aspect, the present application provides a preparation method of a high-weather-resistance and water-resistance type modified high-temperature-resistant adhesive, which comprises the following steps: S1, each component raw material of the A component is put into a kneader for high-speed mixing, and is dispersed and mixed at a stirring speed of 600-900 r / min for 2-4 h at 150-180℃ to obtain the A component, which is cooled to room temperature for standby; S2, each component raw material of the B component is stirred and mixed at a speed of 500-800 r / min under vacuum for 1-3 h to obtain the B component; S3, the A component and the B component are mixed at a mass ratio of 20:1 to obtain the two-component high-weather-resistance and water-resistance type modified high-temperature-resistant adhesive. As an embodiment of the present application, the step S3 further comprises a vacuum degassing step after uniform mixing. The time of the vacuum degassing can be 5-20 min.

[0022] Compared with the prior art, the present application has the following beneficial effects: 1) The high-weather-resistant water-resistant modified high-temperature-resistant adhesive provided by the application has a wide application range, high flexibility and bonding performance, and good moisture-proof corrosion-resistant, bacteriostatic, oil-resistant and anti-aging performance, good stability and long storage period. 2) The high-weather-resistant water-resistant modified high-temperature-resistant adhesive provided by the application does not need to be catalyzed by organic tin to realize rapid curing and forming of the silicone rubber; the high-temperature-resistant performance is reliable, the preparation method is simple, safe and reliable, raw materials are easy to obtain, and the process is simple. 3) The preparation method of the high-weather-resistant water-resistant modified high-temperature-resistant adhesive provided by the application is suitable for large-scale production and has good industrial prospects. DETAILED DESCRIPTION

[0023] The application will be described in detail below in combination with examples. The following examples will help those skilled in the art to further understand the application, but do not limit the application in any form. It should be pointed out that those skilled in the art can make some adjustments and improvements without departing from the concept of the application. These all belong to the protection scope of the application.

[0024] Example 1 Step one, respectively take each component raw material of A group according to the following table, put the raw material into the kneader and mix at high speed, heat to 150 DEG C and disperse at high speed, while stirring at a stirring speed of 700 r / min for 2h to obtain A component, and cool to room temperature for standby;

[0025] Step two, respectively take each component raw material of B group according to the following table, stir and mix under vacuum condition at a speed of 500 r / min for 1h to obtain B component;

[0026] Step three, mix A and B components according to the mass ratio of 20:1, adjust uniformly and vacuum degassing for 10 min to obtain the high-weather-resistant water-resistant modified high-temperature-resistant adhesive.

[0027] Example 2 Step one, respectively take each component raw material of A group according to the following table, put the raw material into the kneader and mix at high speed, heat to 160 DEG C and disperse at high speed, while stirring at a stirring speed of 800 r / min for 3h to obtain A component, and cool to room temperature for standby;

[0028] Step two, respectively take each component raw material of B group according to the following table, stir and mix under vacuum condition at a speed of 600 r / min for 2h to obtain B component, and the specific ratio is shown in the following table;

[0029] Step three, the two components A, B are mixed according to the mass ratio of 20:1, and then vacuum degassing for 10 min after uniform mixing to obtain the two-component high-weather-resistant water-resistant modified high-temperature-resistant adhesive.

[0030] Example 3 Step one, the raw materials of A component were weighed according to the following table, and then put into the kneader for high-speed mixing. The temperature was raised to 160°C and the mixture was dispersed at high speed while stirring at a speed of 700 r / min for 3 h to obtain the A component. Then it was cooled to room temperature for standby;

[0031] Step two, the raw materials of B component were weighed according to the following table, and then stirred and mixed at a speed of 600 r / min for 2 h under vacuum conditions to obtain the B component. The specific ratio is shown in the following table;

[0032] Step three, the two components A, B are mixed according to the mass ratio of 20:1, and then vacuum degassing for 10 min after uniform mixing to obtain the two-component high-weather-resistant water-resistant modified high-temperature-resistant adhesive.

[0033] Comparative Example 1 This comparative example relates to the preparation of high-temperature-resistant adhesive, and the specific preparation includes the following steps: according to the formula in Example 1, put into the stirrer at a speed of 500 rpm for 1 h to obtain A component. Then weigh 10 g of polysilazane, 1 g of KH560 silane coupling agent, 0.1 g of dibutyltin dilaurate, and 1.4 g of dimethyl silicone oil, and mix them at 500 r / min for 1 h to obtain B component. After uniform mixing of A and B components, vacuum degassing for 10 min, it can be used as room temperature vulcanized adhesive.

[0034] Comparative Example 2 This comparative example relates to the preparation of high-temperature-resistant adhesive, and the specific preparation includes the following steps: according to the formula in Example 1, put into the stirrer at a speed of 500 rpm for 1 h to obtain A component. Then weigh 5 g of vinyl tributylketoxime silane, 1 g of KH560 silane coupling agent, and 1.4 g of dimethyl silicone oil, and mix them at 500 r / min for 1 h to obtain B component. After uniform mixing of A and B components, vacuum degassing for 10 min, it can be used as room temperature vulcanized high-temperature-resistant adhesive.

[0035] Comparative Example 3 The comparative example relates to the preparation of high-temperature resistant adhesive, and the preparation specifically comprises the following steps: according to the formula in Example 1, the ingredients are put into a stirrer to stir at a speed of 500 rpm for 1 h to obtain component A. Then 5 g of tetraethyl orthosilicate, 0.1 g of dibutyltin dilaurate and 1 g of dimethyl silicone oil are weighed and mixed at a speed of 500 r / min for 1 h to obtain component B. After the two components A and B are uniformly mixed, vacuum degassing is performed for 10 min, and the high-temperature resistant adhesive at room temperature is obtained.

[0036] Comparative Example 4 The adhesive components and preparation method of the example are different from those of Example 1 in that no polyvinyl ester, carboxyl glycerol, zinc octadecanoate, dibutyl hydroxytoluene or bis-melamine is added in component A. The rest is the same as Example 1.

[0037] Comparative Example 5 The adhesive components and preparation method of the example are different from those of Example 1 in that no modified boron nitride, fluorine powder, Ph-poss, modified carbon nanotube, graphene or halloysite is added in component A. The rest is the same as Example 1.

[0038] Performance test The high-temperature resistant adhesives prepared in Examples 1-3 and Comparative Examples 1-5 are respectively tested for shear strength. The standard for testing the dry time is 13477.5-2002, the standard for testing the mechanical properties is GB / T7124, the standard for testing the high-temperature shear strength is GB / T444-88, the standard for testing the hot air aging is GB / T3512-2001, the hot aging condition is 300℃*12h, the water resistance is obtained by soaking in hot water at 90℃ for 8h. The oil resistance is tested according to the standard GB / T1690-2010, the test condition is 23℃*72h, and the oil is IRM903. The test results are shown in Table 1. Table 1: Performance test statistics table of modified high-temperature resistant adhesive

[0039] From the test results, it can be seen that examples 1-3 all have good surface dry time, elongation, shear strength and weather resistance. In addition, compared with the examples, comparative example 1 uses only one curing agent, and the mechanical properties are insufficient and the curing process needs to be accelerated by a catalyst. Compared with the examples, comparative example 2 does not add polysilazane and catalyst, resulting in a longer surface dry time and poor heat resistance. In comparative example 3, a commonly used ethyl silicate is used as a curing agent, and dibutyltin dilaurate is used as a catalyst, so the curing speed is too fast, and the high-temperature tensile shear strength and the tensile shear strength after heat aging decrease significantly. Compared with the examples, comparative example 4 adds polyvinyl ester, carboxyl glycerol, zinc octadecanoate, butylated hydroxytoluene, peroxide cyclohexanone, dithiobis-pentyl phenol and other substances, so that the adhesive elongation, shear strength and weather resistance are significantly improved. Compared with the examples, comparative example 5 adds various modified fillers, so that the mechanical properties, temperature resistance and moisture resistance are improved.

[0040] In summary, the present application discloses a high-weather-resistant and water-resistant modified high-temperature-resistant adhesive. The adhesive has high flexibility, good moisture resistance, corrosion resistance, antibacterial and anti-aging properties, and meets the high-temperature insulation working conditions, and has important application prospects in the field of aerospace.

[0041] The above specific description further describes the purpose, technical solutions and advantages of the application. It should be understood that the above description is only a specific embodiment of the application and is not used to limit the protection scope of the application. Any modification, equivalent replacement, improvement, etc. within the spirit and principles of the application should be included in the protection scope of the application.

Claims

1. A highly weather-resistant and water-resistant modified high-temperature adhesive, characterized in that, It is prepared from two components, A and B, wherein component A is composed of the following raw materials in parts by weight: ； Component B consists of the following raw materials in parts by weight: 。 2. The high weather-resistant and water-resistant modified high-temperature adhesive as described in claim 1, characterized in that, In component A, the modified gaseous silicon is prepared by adding dry gaseous silicon powder, trimethylchlorosilane, and vinyltrimethoxysilane to an acetone solution at a mass ratio of (5-8):1:2:100, stirring continuously at room temperature for 5-8 hours, filtering, and washing with anhydrous ethanol; then drying in a forced-air oven at 220-300℃ for 2-3 hours to obtain modified gaseous silicon.

3. The high weather-resistant and water-resistant modified high-temperature adhesive as described in claim 1, characterized in that, In component A, the modified boron nitride is prepared by adding boron nitride powder and KH550 to a toluene solution at a mass ratio of (6-10):1:100, stirring continuously for 1-2 hours at 100-115℃, filtering, and washing repeatedly with anhydrous ethanol 3-5 times; then drying in a forced-air oven at 220-300℃ for 2-3 hours to obtain modified boron nitride.

4. The high weather resistance and water resistance modified high temperature resistant adhesive as described in claim 1, characterized in that, In component A, the modified carbon nanotubes are prepared as follows: triethylbenzylammonium chloride powder and carbon nanotubes are added to an N-methylpyrrolidone solution at a mass ratio of (0.05-0.07):1:

20. The mixture is ultrasonically dispersed and stirred for 2-3 hours at 100-130°C. The mixture is then filtered and washed repeatedly with anhydrous ethanol 3-5 times. Subsequently, it is dried in a forced-air oven at 220-300°C for 5-8 hours to obtain the modified carbon nanotubes.

5. The high weather-resistant and water-resistant modified high-temperature adhesive as described in claim 1, characterized in that, In component A, the fluorinated micropowder is one or more of polytetrafluoroethylene, soluble polytetrafluoroethylene, and perfluoroethylene propylene. And / or, the metal oxide is one or more of tin dioxide, iron oxide, zinc oxide, and cerium oxide.

6. The high weather-resistant and water-resistant modified high-temperature adhesive as described in claim 1, characterized in that, In component B, the deoxime-based curing agent is one or more of methyltributanone oxime silane, tetrabutyltributanone oxime silane, and vinyltributanone oxime silane.

7. The high weather resistance and water resistance modified high temperature resistant adhesive as described in claim 1, characterized in that, In component B, the dehydrating agent is one or more of calcium oxide, magnesium sulfate, and polyacrylamide; And / or, the plasticizer is one of diisodecyl phthalate, diisononyl phthalate, and dimethyl silicone oil.

8. The high weather-resistant and water-resistant modified high-temperature adhesive as described in claim 1, characterized in that, In component B, the adhesion promoter is one or a mixture of two or more of γ-aminopropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, or N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane.

9. The high weather-resistant and water-resistant modified high-temperature adhesive as described in claim 1, characterized in that, In the adhesive, the mass ratio of components A to B is 10-30:

1.

10. A method for preparing a high weather-resistant and water-resistant modified high-temperature resistant adhesive according to any one of claims 1-9, characterized in that, The method includes the following steps: S1. Take each component of component A and put it into a kneader and mix at high speed. Under the conditions of 150-180℃, disperse and mix at a stirring speed of 600-900r / min for 2h-4h to obtain component A. Cool to room temperature for later use. S2. Take each component of component B and stir and mix them under vacuum at a speed of 500-800 r / min for 1-3 h to obtain component B; S3. Mix components A and B to obtain a two-component high weather-resistant and water-resistant modified high-temperature adhesive.

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