Weather-resistant high-tack adhesive formulation and method of making same

Abstract

The application relates to the technical field of adhesives, and discloses a weather-resistant high-adhesion adhesive preparation and a preparation method thereof. The weather-resistant high-adhesion adhesive preparation is prepared by the following steps: preparing an antioxidant modified hydrogen-containing MQ silicone resin by grafting an antioxidant on a hydrogen-containing MQ silicone resin, and adding the antioxidant modified hydrogen-containing MQ silicone resin, methyl vinyl silicone rubber, KH550, antioxidant modified silicon dioxide and phenolic resin into EPDM-g-MAH-containing EPDM rubber base glue; the antioxidant modified hydrogen-containing MQ silicone resin, the antioxidant modified silicon dioxide and the methyl vinyl silicone rubber improve the temperature resistance, weather resistance and anti-aging performance of the material; the phenolic resin improves the bonding performance of the material; the KH550 and the EPDM-g-MAH serve as compatibilizers to improve the compatibility between the components; and the prepared adhesive preparation has excellent weather resistance and bonding performance.

Description

Technical Field

[0001] This invention relates to the field of adhesive technology, specifically to a weather-resistant, high-tack adhesive formulation and its preparation method. Background Technology

[0002] Ethylene propylene diene monomer (EPDM) rubber is a general-purpose synthetic rubber obtained by coordination polymerization of ethylene and propylene as the main raw materials, with a small amount of non-conjugated dienes under the action of an initiator. EPDM rubber has a saturated main chain and a small number of double bonds on the side chains. Therefore, it can be vulcanized using sulfur vulcanization systems to improve production efficiency, and it also has excellent heat resistance and aging resistance. However, due to its special molecular structure, the rubber compound has weak chemical reactivity and low surface energy, resulting in poor adhesive properties.

[0003] Rubber is prone to oxidation during processing, storage, and use, especially under the influence of heat, oxygen, light, and mechanical force. This oxidation causes degradation or cross-linking of the molecular chains, leading to decreased performance and shortened lifespan—a phenomenon known as aging. To delay or prevent oxidation, antioxidants or anti-aging agents are typically added. Anti-aging agents can be broadly classified into two categories: free radical inhibitors, which react with alkyl radicals, hydroxyl radicals, and peroxide radicals generated during auto-oxidation, interrupting the free radical chain reaction; and peroxide decomposers, which decompose hydroperoxides generated during rubber auto-oxidation without generating free radicals, thus delaying and preventing rubber aging. Adding anti-aging agents to EPDM rubber can slow down the oxidation process, ensuring the material's processing, use, and storage, extending its service life, and further improving its heat resistance in high-temperature environments.

[0004] In summary, solving the problem of poor adhesive performance of EPDM and improving the weather resistance of EPDM have become the focus of attention. Summary of the Invention

[0005] The purpose of this invention is to overcome the shortcomings of existing technologies and provide a weather-resistant, high-adhesion adhesive formulation and its preparation method. This invention involves preparing an antioxidant-modified hydrogen-containing MQ silicone resin by grafting an antioxidant onto it. This modified hydrogen-containing MQ silicone resin is then added to a tereethylene propylene diene monomer (EPDM) rubber-based adhesive containing EPDM-g-MAH, along with methyl vinyl silicone rubber, KH550, antioxidant-modified silica, and phenolic resin. The antioxidant-modified hydrogen-containing MQ silicone resin, antioxidant-modified silica, and methyl vinyl silicone rubber improve the material's temperature resistance, weather resistance, and anti-aging properties; the phenolic resin enhances the material's adhesive properties; and KH550 and EPDM-g-MAH act as compatibilizers to improve the compatibility between the components. The resulting adhesive formulation exhibits excellent weather resistance and adhesive properties.

[0006] To achieve the above objectives, the technical solution adopted by the present invention is as follows:

[0007] A method for preparing a weather-resistant, high-tack adhesive formulation includes the following steps:

[0008] Step (1): Mix 1,1,3,3-tetramethyldisiloxane and tetraethyl orthosilicate to obtain the reactant. Add ethanol, water and hydrogen chloride aqueous solution and continue to mix evenly. After the reaction is completed, purify to obtain hydrogen-containing MQ silicone resin.

[0009] Step (2): In a nitrogen atmosphere, allyl glycidyl ether and Karstedt catalyst are mixed, stirred and kept warm, and an isopropanol solution of hydrogen-containing MQ silicone resin is added dropwise. After the addition is complete, the reaction is carried out. After the reaction is completed, the color is removed, filtered, and distilled under reduced pressure to obtain epoxy-modified hydrogen-containing MQ silicone resin.

[0010] Epoxy-modified hydrogen-containing MQ silicone resin, p-aminodiphenylamine, and hexafluoroisopropanol were mixed and reacted. After the reaction was completed, the mixture was distilled under reduced pressure to obtain antioxidant-modified hydrogen-containing MQ silicone resin.

[0011] Step (3): Mix EPDM-g-MAH with EPDM to obtain EPDM base rubber; mix EPDM base rubber with antioxidant-modified hydrogen-containing MQ silicone resin, methyl vinyl silicone rubber, KH550, antioxidant-modified silica, phenolic resin and vulcanizing agent dicumyl peroxide to obtain weather-resistant high-tack adhesive formulation.

[0012] Preferably, in step (1): the molar ratio of 1,1,3,3-tetramethyldisiloxane and tetraethyl orthosilicate is 0.9:1; the mass ratio of reactants, ethanol, water, and 36wt% hydrogen chloride aqueous solution is 100:3-10:30:10; the hydrogen chloride aqueous solution is 36wt% hydrogen chloride aqueous solution; the reaction conditions are: reaction at 30-50℃ for 1-3h.

[0013] Preferably, in step (1), the purification operation includes: adding xylene and stirring for 10 min, letting stand for 12 h, taking the organic phase, adding sodium bicarbonate to neutralize to neutral, filtering, taking the filtrate, and removing the solvent xylene by vacuum distillation.

[0014] Preferably, in step (2), the mass ratio of allyl glycidyl ether, Karstedt catalyst, and hydrogen-containing MQ silicone resin is 104-105:1:100; the isopropanol solution of hydrogen-containing MQ silicone resin is prepared by mixing hydrogen-containing MQ silicone resin and isopropanol in a mass ratio of 1:3.

[0015] Preferably, in step (2), when preparing epoxy-modified hydrogen-containing MQ silicone resin, the stirring and heat preservation conditions are: stirring and heat preservation at 55-65℃ for 10-20 min in a nitrogen atmosphere; the dropping conditions are: dropping at 55-65℃ for 1 h in a nitrogen atmosphere; and the reaction conditions are: heating to 80-85℃ at a heating rate of 10℃ / h in a nitrogen atmosphere and reacting for 6-7 h.

[0016] Preferably, in step (2), when preparing the antioxidant-modified hydrogen-containing MQ silicone resin, the mass ratio of epoxy-modified hydrogen-containing MQ silicone resin, p-aminodiphenylamine, and hexafluoroisopropanol is 1:1.8-2:2-3; the reaction conditions are: stirring at 120-140℃ for 8-24 hours.

[0017] Preferably, in step (3): the mass ratio of EPDM-g-MAH to EPDM is 20:2-2.5; the mass ratio of EPDM base rubber, antioxidant-modified hydrogen-containing MQ silicone resin, methyl vinyl silicone rubber, KH550, antioxidant-modified silica, phenolic resin, and vulcanizing agent dicumyl peroxide is 70:5-10:20-25:2.5-3:4-5:5-7:2-2.5.

[0018] Preferably, in step (3), the antioxidant-modified silica is prepared by the following steps:

[0019] Antioxidant GM, KH590 and toluene were mixed evenly, and triethylamine catalyst was added dropwise. After the reaction was completed, the mixture was rotary evaporated to obtain antioxidant-modified silane coupling agent.

[0020] Nano-silica and 25 vol% ethanol aqueous solution were mixed, ultrasonically dispersed, pH value was adjusted, antioxidant-modified silane coupling agent was added, and the reaction continued. After the reaction was completed, the mixture was filtered, washed, and dried to obtain antioxidant-modified silica.

[0021] Preferably, in step (3), when preparing the antioxidant-modified silane coupling agent: the molar ratio of antioxidant GM to KH590 is 1-1.2:1; the mass of toluene added is 2-5 times the sum of the masses of antioxidant GM and KH590; the mass of triethylamine catalyst added is 8-12% of the sum of the masses of antioxidant GM and KH590; the reaction conditions are: reaction at 40-50℃ for 4-5 hours in a nitrogen atmosphere.

[0022] Preferably, in step (3), when preparing antioxidant-modified silica, the mass ratio of the nano silica, 25 vol% ethanol aqueous solution, and antioxidant-modified silane coupling agent is 10:60-80:3-4; the reaction conditions are as follows: continue the reaction for 3-4 hours in a nitrogen atmosphere, at a pH of 4 and a temperature of 50-60°C.

[0023] Preferably, a weather-resistant high-viscosity adhesive preparation is prepared using the preparation method of the weather-resistant high-viscosity adhesive preparation described above.

[0024] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0025] This invention prepares an antioxidant-modified hydrogen-containing MQ silicone resin by grafting an antioxidant onto it. This modified MQ silicone resin is then added to an EPDM-g-MAH-based ethylene propylene diene monomer (EPDM) rubber compound along with methyl vinyl silicone rubber, KH550, antioxidant-modified silica, and phenolic resin. The antioxidant-modified hydrogen-containing MQ silicone resin, antioxidant-modified silica, and methyl vinyl silicone rubber improve the material's temperature resistance, weather resistance, and anti-aging properties. The phenolic resin enhances the material's adhesive properties. KH550 and EPDM-g-MAH act as compatibilizers, improving the compatibility between the components. The resulting adhesive formulation exhibits excellent weather resistance and adhesive properties.

[0026] In this invention, a hydrogen-containing MQ silicone resin is prepared by hydrolysis and condensation reaction of tetramethyldisiloxane with tetramethyldisiloxane. Then, an epoxy-modified hydrogen-containing MQ silicone resin is obtained by hydrosilylation reaction of the carbon-carbon double bond of allyl glycidyl ether with the Si-H bond of the hydrogen-containing MQ silicone resin. Finally, an antioxidant, p-aminodiphenylamine, is grafted onto the epoxy-modified hydrogen-containing MQ silicone resin through a ring-opening reaction between the epoxy group and the amino group, thus preparing an antioxidant-modified hydrogen-containing MQ silicone resin, which effectively inhibits the migration of the antioxidant. In this invention, an antioxidant-modified silane coupling agent is prepared by Michael addition reaction of thiol-alkene between antioxidant GM and KH590. This agent is used to modify the surface of silica, not only introducing antioxidant components onto the silica surface but also improving the compatibility and dispersibility of silica in the matrix.

[0027] This invention uses antioxidant-modified hydrogen-containing MQ silicone resin and antioxidant-modified silica as synergistic anti-aging components, methyl vinyl silicone rubber as a temperature-resistant component, phenolic resin as a tackifying component, and EPDM-g-MAH and KH550 as compatibilizers. These components comprehensively improve the weather resistance, anti-aging properties, and adhesive properties of EPDM rubber. Among them, EPDM-g-MAH has excellent compatibility with EPDM rubber, and KH550 has good compatibility with organosilicon resins (including antioxidant-modified hydrogen-containing MQ silicone resin and methyl vinyl silicone rubber). During mixing, the carboxyl functional groups of EPDM-g-MAH and the amino functional groups of KH550 react, using chemical bonds to improve the compatibility between organosilicon resin and EPDM rubber, which plays a positive additive role in improving the adhesive properties of the material. Attached Figure Description

[0028] Figure 1This is a bar chart showing the tensile strength retention rate of Examples 1-5 and Comparative Examples 1-2 in the mechanical properties and weather resistance tests of this invention.

[0029] Figure 2 This is a line graph showing the adhesive strength of Examples 1-5 and Comparative Examples 1-2 in the adhesive performance test of this invention. Detailed Implementation

[0030] The present invention will be further illustrated below through specific embodiments. The following embodiments are specific implementations of the present invention, but the implementation of the present invention is not limited to the following embodiments. Any changes, modifications, substitutions, combinations, or simplifications made without departing from the spirit and principle of the present invention shall be considered equivalent substitutions and are included within the protection scope of the present invention.

[0031] Example 1

[0032] This embodiment discloses a method for preparing a weather-resistant, high-viscosity adhesive formulation, comprising the following steps:

[0033] Step (1): Mix 1,1,3,3-tetramethyldisiloxane and tetraethyl orthosilicate to obtain the reactant. Add ethanol, water and 36wt% hydrogen chloride aqueous solution and continue to mix evenly. React at 30℃ for 3h. After the reaction is completed, add xylene and stir for 10min. Let stand for 12h, take the organic phase, add sodium bicarbonate to neutralize to neutral, filter, take the filtrate, and remove the solvent xylene by vacuum distillation to obtain hydrogen-containing MQ silicone resin.

[0034] The molar ratio of 1,1,3,3-tetramethyldisiloxane to tetraethyl orthosilicate is 0.9:1; the mass ratio of reactants, ethanol, water, and 36wt% aqueous hydrogen chloride solution is 100:3:30:10.

[0035] Step (2): In a nitrogen atmosphere, allyl glycidyl ether and Karstedt catalyst are mixed and stirred at 65°C for 10 min. An isopropanol solution of hydrogen-containing MQ silicone resin is added dropwise over 1 h. After the addition is complete, the temperature is increased to 80°C at a rate of 10°C / h and reacted for 7 h. After the reaction is complete, activated carbon is added for decolorization for 1 h. The mixture is filtered and the solvent is removed by vacuum distillation to obtain epoxy-modified hydrogen-containing MQ silicone resin.

[0036] The mass ratio of allyl glycidyl ether, Karstedt catalyst, and hydrogen-containing MQ silicone resin is 104:1:100; the isopropanol solution of hydrogen-containing MQ silicone resin is prepared by mixing hydrogen-containing MQ silicone resin and isopropanol in a mass ratio of 1:3.

[0037] Epoxy-modified hydrogen-containing MQ silicone resin, p-aminodiphenylamine, and hexafluoroisopropanol were mixed in a mass ratio of 1:1.8:2 and stirred at 120°C for 24 hours. After the reaction was completed, the solvent hexafluoroisopropanol was removed by vacuum distillation to obtain antioxidant-modified hydrogen-containing MQ silicone resin.

[0038] Step (3): Mix EPDM-g-MAH with EPDM-g-MAH at a mass ratio of 20:2 to obtain EPDM-g-MAH base rubber; mix EPDM-g-MAH base rubber with antioxidant-modified hydrogen-containing MQ silicone resin, methyl vinyl silicone rubber, KH550, antioxidant-modified silica, phenolic resin, and vulcanizing agent dicumyl peroxide at a mass ratio of 70:5:20:2.5:4:5:2 to obtain weather-resistant high-viscosity adhesive formulation.

[0039] The antioxidant-modified silica is prepared by the following steps:

[0040] Antioxidant GM, KH590, and toluene were mixed evenly, and triethylamine catalyst was added dropwise. The mixture was reacted at 40°C for 5 hours under a nitrogen atmosphere. After the reaction was completed, the solvent toluene was removed by rotary evaporation to obtain an antioxidant-modified silane coupling agent. The molar ratio of antioxidant GM to KH590 was 1.2:1; the mass of toluene added was twice the sum of the masses of antioxidant GM and KH590; and the mass of triethylamine catalyst added was 10% of the sum of the masses of antioxidant GM and KH590.

[0041] Nano-silica and 25 vol% ethanol aqueous solution were mixed and ultrasonically dispersed for 10 min. Hydrogen chloride aqueous solution was added to adjust the pH to 4. Antioxidant-modified silane coupling agent was added, and the mixture was reacted at 50°C for 4 h in a nitrogen atmosphere. After the reaction was completed, the mixture was filtered, washed, and dried at 50°C for 24 h to obtain antioxidant-modified silica. The mass ratio of nano-silica, 25 vol% ethanol aqueous solution, and antioxidant-modified silane coupling agent was 10:60:3.

[0042] Example 2

[0043] This embodiment discloses a method for preparing a weather-resistant, high-viscosity adhesive formulation, comprising the following steps:

[0044] Step (1): Mix 1,1,3,3-tetramethyldisiloxane and tetraethyl orthosilicate to obtain the reactant. Add ethanol, water and 36wt% hydrogen chloride aqueous solution and continue to mix evenly. React at 30℃ for 3h. After the reaction is completed, add xylene and stir for 10min. Let stand for 12h, take the organic phase, add sodium bicarbonate to neutralize to neutral, filter, take the filtrate, and remove the solvent xylene by vacuum distillation to obtain hydrogen-containing MQ silicone resin.

[0045] The molar ratio of 1,1,3,3-tetramethyldisiloxane to tetraethyl orthosilicate is 0.9:1; the mass ratio of reactants, ethanol, water, and 36wt% aqueous hydrogen chloride solution is 100:6:30:10.

[0046] Step (2): In a nitrogen atmosphere, allyl glycidyl ether and Karstedt catalyst are mixed and stirred at 65°C for 10 min. An isopropanol solution of hydrogen-containing MQ silicone resin is added dropwise over 1 h. After the addition is complete, the temperature is increased to 83°C at a rate of 10°C / h and the reaction is carried out for 6.5 h. After the reaction is completed, activated carbon is added for decolorization for 1 h. The mixture is filtered and the solvent is removed by vacuum distillation to obtain epoxy-modified hydrogen-containing MQ silicone resin.

[0047] The mass ratio of allyl glycidyl ether, Karstedt catalyst, and hydrogen-containing MQ silicone resin is 104:1:100; the isopropanol solution of hydrogen-containing MQ silicone resin is prepared by mixing hydrogen-containing MQ silicone resin and isopropanol in a mass ratio of 1:3.

[0048] Epoxy-modified hydrogen-containing MQ silicone resin, p-aminodiphenylamine, and hexafluoroisopropanol were mixed in a mass ratio of 1:1.85:2.5 and stirred at 120°C for 24 hours. After the reaction was completed, the solvent hexafluoroisopropanol was removed by vacuum distillation to obtain antioxidant-modified hydrogen-containing MQ silicone resin.

[0049] Step (3): Mix EPDM-g-MAH with EPDM-g-MAH at a mass ratio of 20:2.2 to obtain EPDM-g-MAH base rubber; mix EPDM-g-MAH base rubber with antioxidant-modified hydrogen-containing MQ silicone resin, methyl vinyl silicone rubber, KH550, antioxidant-modified silica, phenolic resin, and vulcanizing agent dicumyl peroxide at a mass ratio of 70:6:22:2.6:4.3:5.5:2.2 to obtain weather-resistant high-viscosity adhesive formulation;

[0050] The antioxidant-modified silica is prepared by the following steps:

[0051] Antioxidant GM, KH590, and toluene were mixed evenly, and triethylamine catalyst was added dropwise. The mixture was reacted at 45°C for 4.5 hours under a nitrogen atmosphere. After the reaction was completed, the solvent toluene was removed by rotary evaporation to obtain an antioxidant-modified silane coupling agent. The molar ratio of antioxidant GM to KH590 was 1.2:1; the mass of toluene added was twice the sum of the masses of antioxidant GM and KH590; and the mass of triethylamine catalyst added was 10% of the sum of the masses of antioxidant GM and KH590.

[0052] Nano-silica and 25 vol% ethanol aqueous solution were mixed and ultrasonically dispersed for 10 min. Hydrogen chloride aqueous solution was added to adjust the pH to 4. Antioxidant-modified silane coupling agent was added, and the mixture was reacted at 50°C for 4 h in a nitrogen atmosphere. After the reaction was completed, the mixture was filtered, washed, and dried at 50°C for 24 h to obtain antioxidant-modified silica. The mass ratio of nano-silica, 25 vol% ethanol aqueous solution, and antioxidant-modified silane coupling agent was 10:60:3.

[0053] Example 3

[0054] This embodiment discloses a method for preparing a weather-resistant, high-viscosity adhesive formulation, comprising the following steps:

[0055] Step (1): Mix 1,1,3,3-tetramethyldisiloxane and tetraethyl orthosilicate to obtain the reactant. Add ethanol, water and 36wt% hydrogen chloride aqueous solution and continue to mix evenly. React at 30℃ for 3h. After the reaction is completed, add xylene and stir for 10min. Let stand for 12h, take the organic phase, add sodium bicarbonate to neutralize to neutral, filter, take the filtrate, and remove the solvent xylene by vacuum distillation to obtain hydrogen-containing MQ silicone resin.

[0056] The molar ratio of 1,1,3,3-tetramethyldisiloxane to tetraethyl orthosilicate is 0.9:1; the mass ratio of reactants, ethanol, water, and 36wt% aqueous hydrogen chloride solution is 100:6:30:10.

[0057] Step (2): In a nitrogen atmosphere, allyl glycidyl ether and Karstedt catalyst are mixed and stirred at 65°C for 10 min. An isopropanol solution of hydrogen-containing MQ silicone resin is added dropwise over 1 h. After the addition is complete, the temperature is increased to 83°C at a rate of 10°C / h and the reaction is carried out for 6.5 h. After the reaction is completed, activated carbon is added for decolorization for 1 h. The mixture is filtered and the solvent is removed by vacuum distillation to obtain epoxy-modified hydrogen-containing MQ silicone resin.

[0058] The mass ratio of allyl glycidyl ether, Karstedt catalyst, and hydrogen-containing MQ silicone resin is 104.5:1:100; the isopropanol solution of hydrogen-containing MQ silicone resin is prepared by mixing hydrogen-containing MQ silicone resin and isopropanol in a mass ratio of 1:3.

[0059] Epoxy-modified hydrogen-containing MQ silicone resin, p-aminodiphenylamine, and hexafluoroisopropanol were mixed in a mass ratio of 1:1.9:2.5 and stirred at 120°C for 24 hours. After the reaction was completed, the solvent hexafluoroisopropanol was removed by vacuum distillation to obtain antioxidant-modified hydrogen-containing MQ silicone resin.

[0060] Step (3): Mix EPDM-g-MAH with EPDM-g-MAH at a mass ratio of 20:2.3 to obtain EPDM-g-MAH base rubber; mix EPDM-g-MAH base rubber with antioxidant-modified hydrogen-containing MQ silicone resin, methyl vinyl silicone rubber, KH550, antioxidant-modified silica, phenolic resin, and vulcanizing agent dicumyl peroxide at a mass ratio of 70:8:23:2.8:4.5:6:2.3 to obtain weather-resistant high-viscosity adhesive formulation;

[0061] The antioxidant-modified silica is prepared by the following steps:

[0062] Antioxidant GM, KH590, and toluene were mixed evenly, and triethylamine catalyst was added dropwise. The mixture was reacted at 45°C for 4.5 hours under a nitrogen atmosphere. After the reaction was completed, the solvent toluene was removed by rotary evaporation to obtain an antioxidant-modified silane coupling agent. The molar ratio of antioxidant GM to KH590 was 1.2:1; the mass of toluene added was twice the sum of the masses of antioxidant GM and KH590; and the mass of triethylamine catalyst added was 10% of the sum of the masses of antioxidant GM and KH590.

[0063] Nano-silica and 25 vol% ethanol aqueous solution were mixed and ultrasonically dispersed for 10 min. Hydrogen chloride aqueous solution was added to adjust the pH to 4. Antioxidant-modified silane coupling agent was added, and the mixture was reacted at 50°C for 4 h in a nitrogen atmosphere. After the reaction was completed, the mixture was filtered, washed, and dried at 50°C for 24 h to obtain antioxidant-modified silica. The mass ratio of nano-silica, 25 vol% ethanol aqueous solution, and antioxidant-modified silane coupling agent was 10:60:3.

[0064] Example 4

[0065] This embodiment discloses a method for preparing a weather-resistant, high-viscosity adhesive formulation, comprising the following steps:

[0066] Step (1): Mix 1,1,3,3-tetramethyldisiloxane and tetraethyl orthosilicate to obtain the reactant. Add ethanol, water and 36wt% hydrogen chloride aqueous solution and continue to mix evenly. React at 30℃ for 3h. After the reaction is completed, add xylene and stir for 10min. Let stand for 12h, take the organic phase, add sodium bicarbonate to neutralize to neutral, filter, take the filtrate, and remove the solvent xylene by vacuum distillation to obtain hydrogen-containing MQ silicone resin.

[0067] The molar ratio of 1,1,3,3-tetramethyldisiloxane to tetraethyl orthosilicate is 0.9:1; the mass ratio of reactants, ethanol, water, and 36wt% aqueous hydrogen chloride solution is 100:6:30:10.

[0068] Step (2): In a nitrogen atmosphere, allyl glycidyl ether and Karstedt catalyst are mixed and stirred at 65°C for 10 min. An isopropanol solution of hydrogen-containing MQ silicone resin is added dropwise over 1 h. After the addition is complete, the temperature is increased to 83°C at a rate of 10°C / h and the reaction is carried out for 6.5 h. After the reaction is completed, activated carbon is added for decolorization for 1 h. The mixture is filtered and the solvent is removed by vacuum distillation to obtain epoxy-modified hydrogen-containing MQ silicone resin.

[0069] The mass ratio of allyl glycidyl ether, Karstedt catalyst, and hydrogen-containing MQ silicone resin is 105:1:100; the isopropanol solution of hydrogen-containing MQ silicone resin is prepared by mixing hydrogen-containing MQ silicone resin and isopropanol in a mass ratio of 1:3.

[0070] Epoxy-modified hydrogen-containing MQ silicone resin, p-aminodiphenylamine, and hexafluoroisopropanol were mixed in a mass ratio of 1:1.95:2.5 and stirred at 120°C for 24 hours. After the reaction was completed, the solvent hexafluoroisopropanol was removed by vacuum distillation to obtain antioxidant-modified hydrogen-containing MQ silicone resin.

[0071] Step (3): Mix EPDM-g-MAH with EPDM-g-MAH at a mass ratio of 20:2.4 to obtain EPDM-g-MAH base rubber; mix EPDM-g-MAH base rubber with antioxidant-modified hydrogen-containing MQ silicone resin, methyl vinyl silicone rubber, KH550, antioxidant-modified silica, phenolic resin, and vulcanizing agent dicumyl peroxide at a mass ratio of 70:9:24:2.9:4.8:6.5:2.4 to obtain weather-resistant high-viscosity adhesive formulation;

[0072] The antioxidant-modified silica is prepared by the following steps:

[0073] Antioxidant GM, KH590, and toluene were mixed evenly, and triethylamine catalyst was added dropwise. The mixture was reacted at 45°C for 4.5 hours under a nitrogen atmosphere. After the reaction was completed, the solvent toluene was removed by rotary evaporation to obtain an antioxidant-modified silane coupling agent. The molar ratio of antioxidant GM to KH590 was 1.2:1; the mass of toluene added was twice the sum of the masses of antioxidant GM and KH590; and the mass of triethylamine catalyst added was 10% of the sum of the masses of antioxidant GM and KH590.

[0074] Nano-silica and 25 vol% ethanol aqueous solution were mixed and ultrasonically dispersed for 10 min. Hydrogen chloride aqueous solution was added to adjust the pH to 4. Antioxidant-modified silane coupling agent was added, and the mixture was reacted at 50°C for 4 h in a nitrogen atmosphere. After the reaction was completed, the mixture was filtered, washed, and dried at 50°C for 24 h to obtain antioxidant-modified silica. The mass ratio of nano-silica, 25 vol% ethanol aqueous solution, and antioxidant-modified silane coupling agent was 10:60:3.

[0075] Example 5

[0076] This embodiment discloses a method for preparing a weather-resistant, high-viscosity adhesive formulation, comprising the following steps:

[0077] Step (1): Mix 1,1,3,3-tetramethyldisiloxane and tetraethyl orthosilicate to obtain the reactant. Add ethanol, water and 36wt% hydrogen chloride aqueous solution and continue to mix evenly. React at 30℃ for 3h. After the reaction is completed, add xylene and stir for 10min. Let stand for 12h, take the organic phase, add sodium bicarbonate to neutralize to neutral, filter, take the filtrate, and remove the solvent xylene by vacuum distillation to obtain hydrogen-containing MQ silicone resin.

[0078] The molar ratio of 1,1,3,3-tetramethyldisiloxane to tetraethyl orthosilicate is 0.9:1; the mass ratio of reactants, ethanol, water, and 36wt% aqueous hydrogen chloride solution is 100:10:30:10.

[0079] Step (2): In a nitrogen atmosphere, allyl glycidyl ether and Karstedt catalyst are mixed and stirred at 65°C for 10 min. An isopropanol solution of hydrogen-containing MQ silicone resin is added dropwise over 1 h. After the addition is complete, the temperature is increased to 85°C at a rate of 10°C / h and reacted for 6 h. After the reaction is complete, activated carbon is added for decolorization for 1 h. The mixture is filtered and the solvent is removed by vacuum distillation to obtain epoxy-modified hydrogen-containing MQ silicone resin.

[0080] The mass ratio of allyl glycidyl ether, Karstedt catalyst, and hydrogen-containing MQ silicone resin is 105:1:100; the isopropanol solution of hydrogen-containing MQ silicone resin is prepared by mixing hydrogen-containing MQ silicone resin and isopropanol in a mass ratio of 1:3.

[0081] Epoxy-modified hydrogen-containing MQ silicone resin, p-aminodiphenylamine, and hexafluoroisopropanol were mixed in a mass ratio of 1:2:3 and stirred at 120°C for 24 hours. After the reaction was completed, the solvent hexafluoroisopropanol was removed by vacuum distillation to obtain antioxidant-modified hydrogen-containing MQ silicone resin.

[0082] Step (3): Mix EPDM-g-MAH with EPDM-g-MAH at a mass ratio of 20:2.5 to obtain EPDM-g-MAH base rubber; mix EPDM-g-MAH base rubber with antioxidant-modified hydrogen-containing MQ silicone resin, methyl vinyl silicone rubber, KH550, antioxidant-modified silica, phenolic resin, and vulcanizing agent dicumyl peroxide at a mass ratio of 70:10:25:3:5:7:2.5 to obtain weather-resistant high-viscosity adhesive formulation.

[0083] The antioxidant-modified silica is prepared by the following steps:

[0084] Antioxidant GM, KH590, and toluene were mixed evenly, and triethylamine catalyst was added dropwise. The mixture was reacted at 50°C for 4 hours under a nitrogen atmosphere. After the reaction was completed, the solvent toluene was removed by rotary evaporation to obtain an antioxidant-modified silane coupling agent. The molar ratio of antioxidant GM to KH590 was 1.2:1; the mass of toluene added was twice the sum of the masses of antioxidant GM and KH590; and the mass of triethylamine catalyst added was 10% of the sum of the masses of antioxidant GM and KH590.

[0085] Nano-silica and 25 vol% ethanol aqueous solution were mixed and ultrasonically dispersed for 10 min. Hydrogen chloride aqueous solution was added to adjust the pH to 4. Antioxidant-modified silane coupling agent was added, and the mixture was reacted at 50°C for 4 h in a nitrogen atmosphere. After the reaction was completed, the mixture was filtered, washed, and dried at 50°C for 24 h to obtain antioxidant-modified silica. The mass ratio of nano-silica, 25 vol% ethanol aqueous solution, and antioxidant-modified silane coupling agent was 10:60:3.

[0086] Comparative Example 1

[0087] This comparative example discloses a method for preparing an adhesive formulation, comprising the following steps:

[0088] Step (1): Mix 1,1,3,3-tetramethyldisiloxane and tetraethyl orthosilicate to obtain the reactant. Add ethanol, water and 36wt% hydrogen chloride aqueous solution and continue to mix evenly. React at 30℃ for 3h. After the reaction is completed, add xylene and stir for 10min. Let stand for 12h, take the organic phase, add sodium bicarbonate to neutralize to neutral, filter, take the filtrate, and remove the solvent xylene by vacuum distillation to obtain hydrogen-containing MQ silicone resin.

[0089] The molar ratio of 1,1,3,3-tetramethyldisiloxane to tetraethyl orthosilicate is 0.9:1; the mass ratio of reactants, ethanol, water, and 36wt% aqueous hydrogen chloride solution is 100:3:30:10.

[0090] Step (2): Mix EPDM-g-MAH with EPDM-g-MAH at a mass ratio of 20:2 to obtain EPDM-g-MAH base rubber; mix EPDM-g-MAH base rubber with hydrogen-containing MQ silicone resin, methyl vinyl silicone rubber, KH550, antioxidant-modified silica, phenolic resin, and vulcanizing agent dicumyl peroxide at a mass ratio of 70:5:20:2.5:4:5:2 to obtain adhesive formulation;

[0091] The antioxidant-modified silica is prepared by the following steps:

[0092] Antioxidant GM, KH590, and toluene were mixed evenly, and triethylamine catalyst was added dropwise. The mixture was reacted at 40°C for 5 hours under a nitrogen atmosphere. After the reaction was completed, the solvent toluene was removed by rotary evaporation to obtain an antioxidant-modified silane coupling agent. The molar ratio of antioxidant GM to KH590 was 1.2:1; the mass of toluene added was twice the sum of the masses of antioxidant GM and KH590; and the mass of triethylamine catalyst added was 10% of the sum of the masses of antioxidant GM and KH590.

[0093] Nano-silica and 25 vol% ethanol aqueous solution were mixed and ultrasonically dispersed for 10 min. Hydrogen chloride aqueous solution was added to adjust the pH to 4. Antioxidant-modified silane coupling agent was added, and the mixture was reacted at 50°C for 4 h in a nitrogen atmosphere. After the reaction was completed, the mixture was filtered, washed, and dried at 50°C for 24 h to obtain antioxidant-modified silica. The mass ratio of nano-silica, 25 vol% ethanol aqueous solution, and antioxidant-modified silane coupling agent was 10:60:3.

[0094] Comparative Example 2

[0095] This comparative example discloses a method for preparing an adhesive formulation, comprising the following steps:

[0096] Step (1): Mix 1,1,3,3-tetramethyldisiloxane and tetraethyl orthosilicate to obtain the reactant. Add ethanol, water and 36wt% hydrogen chloride aqueous solution and continue to mix evenly. React at 30℃ for 3h. After the reaction is completed, add xylene and stir for 10min. Let stand for 12h, take the organic phase, add sodium bicarbonate to neutralize to neutral, filter, take the filtrate, and remove the solvent xylene by vacuum distillation to obtain hydrogen-containing MQ silicone resin.

[0097] The molar ratio of 1,1,3,3-tetramethyldisiloxane to tetraethyl orthosilicate is 0.9:1; the mass ratio of reactants, ethanol, water, and 36wt% aqueous hydrogen chloride solution is 100:3:30:10.

[0098] Step (2): In a nitrogen atmosphere, allyl glycidyl ether and Karstedt catalyst are mixed and stirred at 65°C for 10 min. An isopropanol solution of hydrogen-containing MQ silicone resin is added dropwise over 1 h. After the addition is complete, the temperature is increased to 80°C at a rate of 10°C / h and reacted for 7 h. After the reaction is complete, activated carbon is added for decolorization for 1 h. The mixture is filtered and the solvent is removed by vacuum distillation to obtain epoxy-modified hydrogen-containing MQ silicone resin.

[0099] The mass ratio of allyl glycidyl ether, Karstedt catalyst, and hydrogen-containing MQ silicone resin is 104:1:100; the isopropanol solution of hydrogen-containing MQ silicone resin is prepared by mixing hydrogen-containing MQ silicone resin and isopropanol in a mass ratio of 1:3.

[0100] Epoxy-modified hydrogen-containing MQ silicone resin, p-aminodiphenylamine, and hexafluoroisopropanol were mixed in a mass ratio of 1:1.8:2 and stirred at 120°C for 24 hours. After the reaction was completed, the solvent hexafluoroisopropanol was removed by vacuum distillation to obtain antioxidant-modified hydrogen-containing MQ silicone resin.

[0101] Step (3): Mix EPDM rubber, antioxidant-modified hydrogen-containing MQ silicone resin, methyl vinyl silicone rubber, antioxidant-modified silica, phenolic resin, and vulcanizing agent dicumyl peroxide in a mass ratio of 79.5:5:20:4:5:2 to obtain an adhesive formulation.

[0102] The antioxidant-modified silica is prepared by the following steps:

[0103] Antioxidant GM, KH590, and toluene were mixed evenly, and triethylamine catalyst was added dropwise. The mixture was reacted at 40°C for 5 hours under a nitrogen atmosphere. After the reaction was completed, the solvent toluene was removed by rotary evaporation to obtain an antioxidant-modified silane coupling agent. The molar ratio of antioxidant GM to KH590 was 1.2:1; the mass of toluene added was twice the sum of the masses of antioxidant GM and KH590; and the mass of triethylamine catalyst added was 10% of the sum of the masses of antioxidant GM and KH590.

[0104] Nano-silica and 25 vol% ethanol aqueous solution were mixed and ultrasonically dispersed for 10 min. Hydrogen chloride aqueous solution was added to adjust the pH to 4. Antioxidant-modified silane coupling agent was added, and the mixture was reacted at 50°C for 4 h in a nitrogen atmosphere. After the reaction was completed, the mixture was filtered, washed, and dried at 50°C for 24 h to obtain antioxidant-modified silica. The mass ratio of nano-silica, 25 vol% ethanol aqueous solution, and antioxidant-modified silane coupling agent was 10:60:3.

[0105] In the above examples and comparative examples: the platinum content in the Karstedt catalyst was 2000 ppm; the grade of EPDM-g-MAH was TRD-358EP, and the maleic anhydride grafting rate was 1.2; the grade of EPDM rubber was IP4520; the grade of methyl vinyl silicone rubber was MVQ-110-2; the particle size of nano silica was 50-100 nm; and the phenolic resin was p-tert-octylphenolic resin SL-1801.

[0106] Test case

[0107] The adhesive properties of the adhesive formulations prepared in Examples 1-5 and Comparative Examples 1-2 were tested; the specific test results are shown in Table 1:

[0108] Table 1

[0109] Sample 1 Sample 2 Sample 3 Sample 4 Sample 5 Sample 6 Sample 7 Bond strength (KN / m) 0.59 0.62 0.67 0.73 0.76 0.59 0.51

[0110] The testing of the indicators in Table 1 is based on the following standards: Adhesive performance is represented by adhesive strength. The test method is as follows: The adhesive preparations prepared in Examples 1-5 and Comparative Examples 1-2 are mixed to form a mixed film, which is then cut into strips 100 mm long and 20 mm wide. One side of the strip is covered with adhesive tape, and the other side is used as the bonding surface. The bonding surfaces of the two strips are then bonded together and held under pressure of 30 MPa for 5 hours to obtain samples 1-7. The samples 1-7 are then subjected to a peel test using an electronic tensile testing machine at a speed of 50 mm / min, and the adhesive strength is calculated.

[0111] As can be seen from the test results in Table 1, the adhesive formulation prepared by this invention has excellent adhesive properties. This is due to the addition of tackifying components phenolic resin and compatibilizers EPDM-g-MAH and KH550. Phenolic resin is polar and plays a tackifying role. During mixing, the carboxyl functional groups of EPDM-g-MAH and the amino functional groups of KH550 react, using chemical bonds to improve the compatibility between silicone resin and EPDM rubber, which has a positive additive effect on improving the adhesive properties of the material.

[0112] Sample 7 prepared from Comparative Example 2 did not contain EPDM-g-MAH and KH550. The lack of compatibilizers improved the compatibility of the components in the material, resulting in decreased compatibility of the components and thus affecting the adhesive performance of the material. Therefore, the adhesive performance of Comparative Example 2 was not as good as that of the Example.

[0113] The adhesive formulations prepared in Examples 1-5 and Comparative Examples 1-2 were tested for mechanical properties and weather resistance. The vulcanization conditions for all tests were: vulcanization at 160°C for 30 min. Specific test results are shown in Table 2.

[0114] Table 2

[0115] Tensile strength (MPa) Tensile strength retention rate (%) Example 1 7.9 93.4 Example 2 8.2 94.1 Example 3 8.5 94.8 Example 4 8.8 95.5 Example 5 9.2 96.3 Comparative Example 1 7.8 85.8 Comparative Example 2 6.7 93.1

[0116] The tests for each indicator in Table 2 were conducted according to the following standards: Tensile strength was measured according to standard GB / T529-2009 "Determination of Tensile Stress-Strain Properties of Vulcanized Rubber or Thermoplastic Rubber"; Weather resistance was expressed by the tensile strength retention rate, and the test method was: a thermo-oxidative aging test was conducted according to standard GB3512-1983 "Rubber Hot Air Aging Test Method", with a test temperature of 100℃ and a test time of 5 days. After the test, the tensile strength change rate was calculated.

[0117] As can be seen from the test results in Table 2, the adhesive formulation prepared by the present invention has excellent weather resistance. This is because the antioxidant grafted with hydrogen-containing MQ silicone resin and the antioxidant modified silica are used as synergistic anti-aging components, and the methyl vinyl silicone rubber is used as a temperature-resistant component. The three components comprehensively improve the weather resistance of the adhesive formulation, and the compatibility between the components is good.

[0118] Comparative Example 1 did not modify the hydrogen-containing MQ silicone resin with antioxidants, and lacked the effect of antioxidant components in improving the weather resistance of the material. Therefore, the weather resistance of Comparative Example 1 was lower than that of the Example.

[0119] Comparative Example 2 did not contain EPDM-g-MAH and KH550, and lacked compatibilizers to improve the compatibility of the components in the material. Therefore, the mechanical properties of Comparative Example 2 were not as good as those of the Example.

[0120] It should be noted that the embodiments described above are only for explaining the present invention and do not constitute any limitation on the present invention. The present invention has been described with reference to typical embodiments, but it should be understood that the words used therein are descriptive and explanatory terms, not limiting terms. Modifications can be made to the present invention within the scope of the claims, and revisions can be made to the present invention without departing from the scope and spirit of the present invention. Although the present invention described herein relates to specific methods, materials, and embodiments, it does not mean that the present invention is limited to the specific examples disclosed herein; on the contrary, the present invention can be extended to all other methods and applications with the same function.

Claims

1. A method for preparing a weather-resistant, high-viscosity adhesive formulation, characterized in that, Includes the following steps: Step (1): In a nitrogen atmosphere, allyl glycidyl ether and Karstedt catalyst are mixed, stirred and kept warm, and an isopropanol solution of hydrogen-containing MQ silicone resin is added dropwise. After the addition is complete, the reaction is carried out. After the reaction is completed, the color is removed, filtered, and distilled under reduced pressure to obtain epoxy-modified hydrogen-containing MQ silicone resin. Epoxy-modified hydrogen-containing MQ silicone resin, p-aminodiphenylamine, and hexafluoroisopropanol were mixed and reacted. After the reaction was completed, the mixture was distilled under reduced pressure to obtain antioxidant-modified hydrogen-containing MQ silicone resin. Step (2): Mix EPDM-g-MAH with EPDM to obtain EPDM base rubber; mix EPDM base rubber with antioxidant-modified hydrogen-containing MQ silicone resin, methyl vinyl silicone rubber, KH550, antioxidant-modified silica, phenolic resin and dicumyl peroxide to obtain weather-resistant high-viscosity adhesive formulation. The mass ratio of EPDM-g-MAH to EPDM is 20:2-2.5; the mass ratio of EPDM base rubber, antioxidant-modified hydrogen-containing MQ silicone resin, methyl vinyl silicone rubber, KH550, antioxidant-modified silica, phenolic resin, and dicumyl peroxide is 70:5-10:20-25:2.5-3:4-5:5-7:2-2.

5.

2. The method for preparing a weather-resistant high-viscosity adhesive formulation according to claim 1, characterized in that, In step (1), the hydrogen-containing MQ silicone resin is prepared by the following steps: 1,1,3,3-Tetramethyldisiloxane and tetraethyl orthosilicate were mixed to obtain the reactant. Ethanol, water, and aqueous hydrogen chloride solution were added and mixed thoroughly. After the reaction was completed, the mixture was purified to obtain hydrogen-containing MQ silicone resin.

3. The method for preparing a weather-resistant high-viscosity adhesive formulation according to claim 2, characterized in that, In step (1), when preparing the hydrogen-containing MQ silicone resin: the molar ratio of 1,1,3,3-tetramethyldisiloxane and tetraethyl orthosilicate is 0.9:1; the mass ratio of reactants, ethanol, water, and 36wt% hydrogen chloride aqueous solution is 100:3-10:30:10; the hydrogen chloride aqueous solution is 36wt% hydrogen chloride aqueous solution; the reaction conditions are: reacting at 30-50℃ for 1-3 hours.

4. The method for preparing a weather-resistant high-tack adhesive formulation according to claim 1, characterized in that, In step (1), when preparing epoxy-modified hydrogen-containing MQ silicone resin, the mass ratio of allyl glycidyl ether, Karstedt catalyst, and hydrogen-containing MQ silicone resin is 104-105:1:100; the isopropanol solution of hydrogen-containing MQ silicone resin is prepared by mixing hydrogen-containing MQ silicone resin and isopropanol in a mass ratio of 1:

3.

5. The method for preparing a weather-resistant high-viscosity adhesive formulation according to claim 1, characterized in that, In step (1), when preparing the epoxy-modified hydrogen-containing MQ silicone resin: The stirring and heat preservation conditions are as follows: stirring and heat preservation at 55-65℃ for 10-20 min in a nitrogen atmosphere; the dropping conditions are as follows: dropping at 55-65℃ for 1 h in a nitrogen atmosphere; the reaction conditions are as follows: heating to 80-85℃ at a heating rate of 10℃ / h in a nitrogen atmosphere, and reacting for 6-7 h.

6. The method for preparing a weather-resistant high-viscosity adhesive formulation according to claim 1, characterized in that, In step (1), when preparing the antioxidant-modified hydrogen-containing MQ silicone resin, the mass ratio of epoxy-modified hydrogen-containing MQ silicone resin, p-aminodiphenylamine, and hexafluoroisopropanol is 1:1.8-2:2-3; the reaction conditions are: stirring and reacting at 120-140℃ for 8-24 hours.

7. The method for preparing a weather-resistant high-viscosity adhesive formulation according to claim 1, characterized in that, In step (2), the antioxidant-modified silica is prepared by the following steps: S1. Mix antioxidant GM, KH590 and toluene evenly, add triethylamine catalyst dropwise, react, and after the reaction is complete, rotary evaporate to obtain antioxidant-modified silane coupling agent. S2. Mix nano-silica and 25 vol% ethanol aqueous solution, disperse by ultrasonication, adjust the pH value, add antioxidant-modified silane coupling agent, continue the reaction, filter, wash, and dry to obtain antioxidant-modified silica.

8. The method for preparing a weather-resistant high-viscosity adhesive formulation according to claim 7, characterized in that, In step (2), when preparing antioxidant-modified silica: In S1: the molar ratio of antioxidant GM to KH590 is 1-1.2:1; the added mass of toluene is 2-5 times the sum of the masses of antioxidant GM and KH590; the added mass of catalyst triethylamine is 8-12% of the sum of the masses of antioxidant GM and KH590; the reaction conditions are: reaction in a nitrogen atmosphere at 40-50℃ for 4-5 hours. In S2, the mass ratio of nano-silica, 25 vol% ethanol aqueous solution, and antioxidant-modified silane coupling agent is 10:60-80:3-4; the reaction conditions are as follows: in a nitrogen atmosphere, at a pH of 4, and at a temperature of 50-60°C, the reaction continues for 3-4 hours.

9. A weather-resistant high-viscosity adhesive preparation obtained by the preparation method of the weather-resistant high-viscosity adhesive preparation as described in any one of claims 1-8.

Images