An organosilicon adhesive material with antibacterial effect and its preparation method

Abstract

The present invention relates to the technical field of silicone adhesive materials, and more specifically, to a silicone adhesive material with antibacterial effects and a preparation method thereof. The raw materials of the silicone adhesive material include 20 to 40 parts of modified antibacterial silicone resin, 0.62 to 2.8 parts of crosslinking agent, 0.4 to 2.3 parts of accelerator, 0.2 to 1.5 parts of dispersant, 0.5 to 2 parts of reinforcing agent, 45 to 70 parts of filler, 0.1 to 0.7 parts of catalyst, and 1 to 3 parts of inhibitor. The adhesive material provided by the present invention has a moderate viscosity, strong antibacterial property, long storage period, can be quickly cured at high temperature, can be constructed by processes such as scraping and dispensing, and the prepared adhesive layer has strong adhesiveness, good sealing property, shear strength greater than 2 MPa, long service life, and is not easy to mildew and discolor. This material is particularly suitable for environments such as the ocean where mildew and other bacterial hazards are likely to occur in hot and humid conditions, and is an antibacterial silicone adhesive material with broad application prospects.

Description

Technical Field

[0001] The present invention relates to the technical field of silicone adhesives, and more specifically, to a silicone adhesive material with antibacterial effect and a preparation method thereof. Background Art

[0002] Silicone adhesives can achieve curing through addition reaction at high temperature. After curing, they have good sealing and bonding properties and can be widely used in shell gaps to achieve bonding and sealing functions. However, during long-term service in a humid and hot environment, their surfaces are vulnerable to microbial erosion, and various forms of molds are formed on their surfaces. Eventually, as the colonies expand, the adhesives become moldy, discolored, and the bonding falls off on a large area, losing their sealing and waterproof properties and affecting the service life of the adhesives. This poses a requirement for the antibacterial property of the adhesives. Summary of the Invention

[0003] The present invention aims to solve at least one of the technical problems existing in the prior art. To this end, an object of one aspect of the present invention is to provide a silicone adhesive material with antibacterial effect. The raw materials of the silicone adhesive material include 20-40 parts of modified antibacterial silicone resin, 0.62-2.8 parts of cross-linking agent, 0.4-2.3 parts of accelerator, 0.2-1.5 parts of dispersant, 0.5-2 parts of reinforcing agent, 45-70 parts of filler, 0.1-0.7 parts of catalyst, and 1-3 parts of inhibitor.

[0004] Another object of the present invention is to provide a preparation method of a silicone adhesive material with antibacterial effect. The specific steps are as follows

[0005] S1. Preparation of antibacterial agent: Add 2,4,6-trichloro-1,3,5-triazine to 2-cyanoisonicotinohydrazide, dropwise add NaOH at 0-4°C and stir well, then pour the reaction mixture onto crushed ice, continue stirring, and neutralize with dilute hydrochloric acid. Filter, wash, dry, recrystallize, and purify the reactants to obtain the antibacterial agent;

[0006] S2. Preparation of modified silicone resin: Add silicone resin and tetrahydrofuran (THF) to the reaction kettle in sequence, introduce nitrogen to bubble and discharge air, add α,α-dimethoxy-α-phenylacetophenone (DMPA), mercaptoethylamine hydrochloride, and methanol under a nitrogen atmosphere, mix evenly, irradiate with a mercury lamp at room temperature, neutralize with saturated sodium bicarbonate solution, and then pour into deionized water for sedimentation, wash with water, and vacuum dry to obtain a modified silicone resin containing amino groups in the molecular chain;

[0007] S3. Preparation of modified antibacterial silicone resin: Add the antibacterial agent prepared in S1 to the amino-group-containing modified silicone resin prepared in S2, dropwise add NaOH at a temperature of 0 - 4°C and stir thoroughly, then pour the mixture onto crushed ice, continue stirring, neutralize with dilute hydrochloric acid, and then filter, wash with water, and vacuum dry the mixture to obtain the modified antibacterial silicone resin;

[0008] S4. Preparation of component A of antibacterial silicone adhesive: Vacuum disperse the modified antibacterial silicone resin, crosslinking agent, accelerator, filler, and dispersant prepared in S3 in a double planetary mixer, stir thoroughly, and then add a reinforcing agent and continue stirring to obtain a mixture as component A;

[0009] S5. Preparation of component B of antibacterial silicone adhesive: Vacuum disperse the modified antibacterial silicone resin, catalyst, filler, dispersant, and inhibitor prepared in S3 in a double planetary mixer, stir thoroughly, and then add a reinforcing agent and continue stirring to obtain a mixture as component B;

[0010] S6. Preparation of antibacterial silicone adhesive: Mix the component A prepared in S4 with the component B prepared in S5, and vacuum disperse in a double planetary mixer for 10 - 20 minutes to obtain an antibacterial silicone adhesive.

[0011] Preferably, in S1, the molar ratio of 2,4,6-trichloro-1,3,5-triazine to 2-cyanoisonicotinohydrazide is 1:1, the concentration of NaOH is 3%, the dropping amount is the same as the molar amount of 2,4,6-trichloro-1,3,5-triazine, stir thoroughly for 2 hours, neutralize with 3% dilute hydrochloric acid to a pH of 6.5 - 7.5, wash with water, the drying temperature is 50°C - 70°C, the drying time is 4 - 8 hours, perform recrystallization with acetone, and use hexane-ethyl acetate with a volume ratio of 4:1 as the eluent to purify the reactants by column chromatography. The chemical formula is as follows

[0012]

[0013] Preferably, in S2, the molar ratio of silicone resin, tetrahydrofuran, α,α-dimethoxy-α-phenylacetophenone, mercaptoethylamine hydrochloride, and methanol is 2:125:0.05:4:60, irradiate with a mercury lamp for 30 minutes, neutralize with saturated sodium bicarbonate solution to a pH of 6.5 - 7.5, repeat washing with water 3 times, the vacuum degree for vacuum drying is -0.1 MPa - -0.5 MPa, the temperature is 50°C - 70°C, and the time is 4 - 8 hours. The silicone resin is one or a mixture of two of methyl vinyl silicone resin and phenyl vinyl silicone resin. The viscosity of the silicone resin is between 1500 mPa·S and 80000 mPa·S, and the vinyl content is 0.1% - 15%. The chemical formula is as follows

[0014]

[0015] Preferably, the molar ratio of the amino-group-containing modified silicone resin to the antibacterial agent in S3 is 1:1, the concentration of NaOH is 3%, the dropping amount is the same as the molar amount of the modified silicone resin, and it is stirred thoroughly for 2 hours, neutralized with dilute hydrochloric acid with a concentration of 3% to a pH of 6.5 - 7.5, rinsed repeatedly with deionized water 3 times, and vacuum dried at a vacuum degree of -0.1 MPa to -0.5 MPa, a temperature of 50°C to 70°C, and a time of 4 to 8 hours. The chemical formula is as follows

[0016]

[0017] Preferably, the mass ratio of the modified antibacterial silicone resin, crosslinking agent, accelerator, filler, and dispersant in S4 is 20 - 40:0.62 - 2.8:0.4 - 2.3:45 - 70:0.2 - 1.5. The vacuum dispersion of the double planetary mixer has a vacuum degree of -0.065 MPa to -0.08 MPa, the stirring time is 10 min to 30 min, and the stirring time for adding the reinforcing agent is 15 min to 40 min.

[0018] Preferably, the crosslinking agent in S4 is hydrogen-containing silicone oil, and the Si-H bond content of the hydrogen-containing silicone oil is 1% - 15%; the accelerator is an adhesion promoter, and one or a combination of more than two of vinyltriethoxysilane (A-151), vinyltrimethoxysilane (A-171), γ-aminopropyltriethoxysilane (KH-550), and γ-(2,3-epoxypropane)propyltrimethoxysilane is selected; the filler is one or a combination of more than two of light calcium carbonate, montmorillonite, mica powder, and zinc oxide; the dispersant is one or a combination of more than two of BYK-161, BYK-163, and BYK-110; the reinforcing agent is one or a combination of two of fumed silica and precipitated silica.

[0019] Preferably, the mass ratio of the modified antibacterial silicone resin, catalyst, filler, dispersant, and inhibitor in S5 is 20 - 40:0.1 - 0.7:45 - 70:0.2 - 1.5:1 - 3. The vacuum dispersion of the double planetary mixer has a vacuum degree of -0.065 MPa to -0.08 MPa, the stirring time is 10 min to 30 min, and the stirring time for adding the reinforcing agent is 15 min to 40 min.

[0020] Preferably, the catalyst in S5 is a metal catalyst which is one or a combination of ruthenium, palladium, and platinum; the filler is one or a combination of two or more of light calcium carbonate, montmorillonite, mica powder, and zinc oxide; the dispersant is one or a combination of two or more of BYK-161, BYK-163, and BYK-110; the inhibitor is an alkynol, and one or a combination of two or more of methyl butynol, 3,5-dimethyl-1-hexyn-3-ol, and 1-hexynyl-1-cyclohexanol is selected; the reinforcing agent is one or a combination of two of fumed silica and precipitated silica.

[0021] Preferably, in S6, the mass ratio of component A to component B is 1:1, the vacuum degree of vacuum dispersion of the double planetary mixer is -0.065 MPa to -0.08 MPa, and the stirring time is 10 min to 20 min.

[0022] The beneficial effects of the present invention are as follows:

[0023] The 2,4,6-trichloro-1,3,5-triazine selected in the present invention has high efficiency, broad-spectrum antibacterial property, good compatibility, and can maintain long-term stable activity within a wide pH value range. By introducing 2-cyanoisonicotinohydrazide with antibacterial specificity on the molecular framework of 2,4,6-trichloro-1,3,5-triazine, the antibacterial specificity of 2-cyanoisonicotinohydrazide is increased on the basis of antibacterial property, the antibacterial property is effectively enhanced while delaying the generation of drug resistance, and the antibacterial synergistic effect between the two is realized. At the same time, the drug resistance when used alone is increased. This antibacterial agent is combined with vinyl siloxane through an ammonolysis reaction, effectively avoiding the problems of internal delamination and decreased mechanical properties in the organosilicon adhesive during physical blending, and improving the antibacterial activity of the organosilicon adhesive. This modification method effectively improves the problem that the organosilicon adhesive is vulnerable to microbial invasion by bacteria, fungi, etc. when used in a humid and hot environment, forms various forms of mildew on its surface, and finally causes large-area mildew, discoloration, and bonding failure of the adhesive with the expansion of the colony, losing the sealing and waterproof performance and affecting the service life of the adhesive.

[0024] The present invention is a two-component addition-curing adhesive, effectively avoiding the problem of harsh environmental requirements during the single-component encapsulation process. Components A and B are separately encapsulated and have a longer storage time. After components A and B are mixed during use, they can be quickly cured when the temperature is increased. Compared with the condensation-type single-component organosilicon adhesive, it has a higher curing efficiency, and the curing is addition-curing without the release of small molecule substances during the curing process, and the size is more stable after curing.

[0025] The adhesive material provided by the present invention has a moderate viscosity, strong antibacterial property, long storage period, can be quickly cured at high temperature, and can be constructed by processes such as scraping and dispensing. The prepared adhesive layer has stable dimensions, strong adhesion, good sealing performance, shear strength greater than 2 MPa, long service life, and is not easy to mildew and discolor. This material has excellent sealing performance and is especially suitable for humid and hot environments prone to bacterial damage such as the ocean. It is an antibacterial organosilicon adhesive material with broad application prospects.

[0026] The additional aspects and advantages of the present invention will become apparent in the following description or be learned through the practice of the present invention. Embodiments

[0027] In order to more clearly understand the above objects, features and advantages of the present invention, the present invention will be further described in detail below with reference to specific embodiments. It should be noted that, without conflict, the embodiments of the present application and the features in the embodiments can be combined with each other.

[0028] Many specific details are set forth in the following description in order to fully understand the present invention. However, the present invention can also be implemented in other ways different from those described herein. Therefore, the protection scope of the present invention is not limited by the specific embodiments disclosed below. Examples

[0029] S1. Preparation of antibacterial agent: Add 0.01 mol of 2,4,6-trichloro-1,3,5-triazine to 0.01 mol of 2-cyanoisonicotinohydrazide, dropwise add 0.01 mol of 3% NaOH at a temperature of 0 - 4 °C and stir well for 2 hours. Then pour the reaction mixture onto crushed ice, continue stirring, and neutralize it with 3% dilute hydrochloric acid to a pH of 7. Filter the reactants, wash them with water, and then dry them. The drying temperature is 60 °C and the drying time is 7 hours. The dried reactants are recrystallized with acetone, and finally, the reactants are purified by column chromatography using hexane-ethyl acetate (4:1) as the eluent to obtain the antibacterial agent;

[0030] S2. Preparation of modified silicone resin: 0.02 mol of methyl vinyl siloxane (vinyl content 2%, 10000 mPa·S) and 1.25 mol of tetrahydrofuran (THF) were successively added into the reaction kettle. Nitrogen was introduced for bubbling to expel air. Under a nitrogen atmosphere, 0.5 mmol of α,α-dimethoxy-α-phenylacetophenone (DMPA), 0.04 mol of mercaptoethylamine hydrochloride, and 0.6 mol of methanol were added and mixed evenly. After irradiating with a mercury lamp at room temperature for 30 min, it was neutralized to pH 7 with saturated sodium bicarbonate solution, and then poured into deionized water for sedimentation. After washing with water 3 times repeatedly, it was vacuum dried with a vacuum degree of -0.3 MPa, a temperature of 60 °C, and a time of 7 hours to obtain methyl vinyl siloxane containing amino groups in the molecular chain;

[0031] S3. Preparation of modified antibacterial silicone resin: 0.01 mol of antibacterial agent prepared in S1 was added to 0.01 mol of methyl vinyl siloxane containing amino groups prepared in S2. 0.01 mol of 3% NaOH was added dropwise at a temperature of 0 - 4 °C and stirred thoroughly for 2 hours. Then the mixture was poured onto crushed ice, continuously stirred, and neutralized to pH 7 with 3% dilute hydrochloric acid. The mixture was filtered, washed with deionized water 3 times repeatedly, and then vacuum dried with a vacuum degree of -0.3 MPa, a temperature of 60 °C, and a time of 7 hours to obtain modified antibacterial silicone resin;

[0032] S4. Preparation of component A of antibacterial silicone adhesive: 35.4 parts by weight of modified antibacterial silicone resin prepared in S3, 1.67 parts by weight of hydrogen-containing silicone oil (Si-H bond content 1.5%), 0.91 parts by weight of A-171, 60.73 parts by weight of light calcium carbonate, and 0.53 parts by weight of BYK-110 were vacuum dispersed in a double planetary mixer with a vacuum degree of -0.07 MPa, and the stirring time was 10 min - 30 min. 0.76 parts by weight of fumed silica was added and stirred for another 15 min - 40 min to obtain a mixture as component A;

[0033] S5. Preparation of component B of antibacterial silicone adhesive: 35.4 parts by weight of modified antibacterial silicone resin prepared in S3, 0.26 parts by weight of platinum catalyst, 61.32 parts by weight of light calcium carbonate, 0.53 parts by weight of BYK-110, and 1.73 parts by weight of methyl butynol were vacuum dispersed in a double planetary mixer with a vacuum degree of -0.07 MPa, stirred for 10 min - 30 min, 0.76 parts by weight of fumed silica was added and stirred for another 15 min - 40 min to obtain a mixture as component B;

[0034] S6. Preparation of antibacterial silicone adhesive: Mix the component A prepared in S4 with the component B prepared in S5, and conduct vacuum dispersion in a double planetary mixer for 10 min to 20 min with a vacuum degree of -0.07 MPa to obtain an antibacterial silicone adhesive. Example

[0035] S1. Preparation of antibacterial agent: Add 0.01 mol of 2,4,6-trichloro-1,3,5-triazine to 0.01 mol of 2-cyanoisonicotinohydrazide, dropwise add 0.01 mol of 3% NaOH at a temperature of 0 to 4 °C and stir well for 2 hours. Then pour the reaction mixture onto crushed ice, continue stirring, and neutralize it to pH 7 with 3% dilute hydrochloric acid. Filter the reactants, wash them with water, and then dry them. The drying temperature is 60 °C, the drying time is 7 hours. The dried reactants are recrystallized with acetone, and finally purified by column chromatography using hexane-ethyl acetate (4:1) as the eluent to obtain the antibacterial agent.

[0036] S2. Preparation of modified silicone resin: Add 0.02 mol of methylvinylsiloxane (vinyl content 5%, 10000 mPa·S) and 1.25 mol of tetrahydrofuran (THF) to the reaction kettle in sequence, introduce nitrogen to bubble out the air, add 0.5 mmol of α,α-dimethoxy-α-phenylacetophenone (DMPA), 0.04 mol of mercaptoethylamine hydrochloride, and 0.6 mol of methanol under a nitrogen atmosphere, and mix evenly. After irradiating with a mercury lamp at room temperature for 30 min, neutralize it to pH 7 with saturated sodium bicarbonate solution, then pour it into deionized water for sedimentation. Repeat washing with water 3 times, and then conduct vacuum drying with a vacuum degree of -0.3 MPa, a temperature of 60 °C, and a time of 7 hours to obtain methylvinylsiloxane containing amino groups in the molecular chain.

[0037] S3. Preparation of modified antibacterial silicone resin: Add 0.01 mol of the antibacterial agent prepared in S1 to 0.01 mol of the amino-group-containing methylvinylsiloxane prepared in S2, dropwise add 0.01 mol of 3% NaOH at a temperature of 0 to 4 °C and stir well for 2 hours. Then pour the mixture onto crushed ice, continue stirring, and neutralize it to pH 7 with 3% dilute hydrochloric acid. Filter the mixture, repeat washing with deionized water 3 times, and then conduct vacuum drying with a vacuum degree of -0.3 MPa, a temperature of 60 °C, and a time of 7 hours to obtain the modified antibacterial silicone resin.

[0038] S4. Preparation of Component A of the Antibacterial Organosilicone Adhesive: Add 35.4 parts by weight of the modified antibacterial organosilicone resin prepared in S3, 1.67 parts by weight of the hydrogen-containing silicone oil (Si-H bond content 1.5%), 0.91 parts by weight of A-171, 60.73 parts by weight of light calcium carbonate, and 0.53 parts by weight of BYK-110 into a double planetary mixer for vacuum dispersion. The vacuum degree is -0.07 MPa, and the stirring time is 10 min to 30 min. Then add 0.76 parts by weight of fumed silica and continue stirring for 15 min to 40 min to obtain a mixture as Component A;

[0039] S5. Preparation of Component B of the Antibacterial Organosilicone Adhesive: Add 35.4 parts by weight of the modified antibacterial organosilicone resin prepared in S3, 0.26 parts by weight of the platinum catalyst, 61.32 parts by weight of light calcium carbonate, 0.53 parts by weight of BYK-110, and 1.73 parts by weight of methylbutynol into a double planetary mixer for vacuum dispersion. The vacuum degree is -0.07 MPa, stir for 10 min to 30 min, add 0.76 parts by weight of fumed silica and continue stirring for 15 min to 40 min to obtain a mixture as Component B;

[0040] S6. Preparation of the Antibacterial Organosilicone Adhesive: Mix the Component A prepared in S4 with the Component B prepared in S5, and conduct vacuum dispersion in a double planetary mixer for 10 min to 20 min. The vacuum degree is -0.07 MPa to obtain an organosilicone adhesive with antibacterial effect. Example

[0041] S1. Preparation of the Antibacterial Agent: Add 0.01 mol of 2,4,6-trichloro-1,3,5-triazine to 0.01 mol of 2-cyanoisonicotinohydrazide, dropwise add 0.01 mol of 3% NaOH at a temperature of 0 - 4 °C and stir thoroughly for 2 hours. Then pour the reaction mixture onto crushed ice, continue stirring, and neutralize it with 3% dilute hydrochloric acid to a pH of 7. Filter the reactant, wash it with water, and then dry it. The drying temperature is 60 °C, and the drying time is 7 hours. The dried reactant is recrystallized with acetone, and finally, the reactant is purified by column chromatography using hexane-ethyl acetate (4:1) as the eluent to obtain the antibacterial agent;

[0042] S2. Preparation of modified silicone resin: 0.02 mol of methyl vinyl siloxane (vinyl content 2%, 20000 mPa·S) and 1.25 mol of tetrahydrofuran (THF) were successively added into the reaction kettle. Nitrogen was introduced for bubbling to expel air. Under a nitrogen atmosphere, 0.5 mmol of α,α-dimethoxy-α-phenylacetophenone (DMPA), 0.04 mol of mercaptoethylamine hydrochloride, and 0.6 mol of methanol were added and mixed evenly. After irradiating with a mercury lamp at room temperature for 30 min, it was neutralized with saturated sodium bicarbonate solution to a pH of 7, and then poured into deionized water for sedimentation. After repeating the water washing 3 times, vacuum drying was carried out at a vacuum degree of -0.3 MPa, a temperature of 60 °C, and a time of 7 hours to obtain methyl vinyl siloxane containing amino groups in the molecular chain;

[0043] S3. Preparation of modified antibacterial silicone resin: 0.01 mol of antibacterial agent prepared in S1 was added to 0.01 mol of methyl vinyl siloxane containing amino groups prepared in S2. Deionized water was added dropwise at a temperature of 0 - 4 °C. After repeating the water washing 3 times, vacuum drying was carried out at a vacuum degree of -0.3 MPa, a temperature of 60 °C, and a time of 7 hours to obtain modified antibacterial silicone resin;

[0044] S4. Preparation of component A of antibacterial silicone adhesive: 35.4 parts by weight of modified antibacterial silicone resin prepared in S3, 1.67 parts by weight of hydrogen-containing silicone oil (Si-H bond content 1.5%), 0.91 parts by weight of A-171, 60.73 parts by weight of light calcium carbonate, and 0.53 parts by weight of BYK-110 were vacuum-dispersed in a double planetary mixer at a vacuum degree of -0.07 MPa, and the stirring time was 10 min - 30 min. 0.76 parts by weight of fumed silica was added and stirring continued for 15 min - 40 min to obtain a mixture as component A;

[0045] S5. Preparation of component B of antibacterial silicone adhesive: 35.4 parts by weight of modified antibacterial silicone resin prepared in S3, 0.26 parts by weight of platinum catalyst, 61.32 parts by weight of light calcium carbonate, 0.53 parts by weight of BYK-110, and 1.73 parts by weight of methyl butynol were vacuum-dispersed in a double planetary mixer at a vacuum degree of -0.07 MPa and stirred for 10 min - 30 min. 0.76 parts by weight of fumed silica was added and stirring continued for 15 min - 40 min to obtain a mixture as component B;

[0046] S6. Preparation of antibacterial silicone adhesive: Component A prepared in S4 and component B prepared in S5 were mixed and vacuum-dispersed in a double planetary mixer for 10 min - 20 min at a vacuum degree of -0.07 MPa to obtain an antibacterial silicone adhesive.

[0047] Comparative Example 1

[0048] S1. Preparation of antibacterial agent: Add 0.01 mol of 2,4,6-trichloro-1,3,5-triazine to 0.01 mol of 2-cyanoisonicotinohydrazide, dropwise add 0.01 mol of 3% NaOH at 0 - 4 °C and stir well for 2 hours. Then pour the reaction mixture onto crushed ice, continue stirring, and neutralize it to pH 7 with 3% dilute hydrochloric acid. Filter the reactants, wash them with water, and then dry them. The drying temperature is 60 °C, and the drying time is 7 hours. The dried reactants are recrystallized with acetone, and finally, column chromatography is used to purify the reactants with hexane-ethyl acetate (4:1) as the eluent to obtain the antibacterial agent;

[0049] S2. Preparation of antibacterial silicone resin: Add 0.01 mol of the antibacterial agent prepared in S1 to 0.01 mol of methyl vinyl silicone resin, dropwise add 0.01 mol of 3% NaOH at 0 - 4 °C and stir well for 2 hours. Then pour the mixture onto crushed ice, continuously stir, and neutralize it to pH 7 with 3% dilute hydrochloric acid. Filter the mixture, wash it with deionized water repeatedly 3 times, and then vacuum dry it. The vacuum degree is -0.3 MPa, the temperature is 60 °C, and the time is 7 hours to obtain the modified antibacterial silicone resin;

[0050] S3. Preparation of component A of antibacterial silicone adhesive: Add 35.4 parts by weight of the antibacterial silicone resin prepared in S2, 1.67 parts by weight of hydrogen-containing silicone oil (Si-H bond content 1.5%), 0.91 parts by weight of A-171, 60.73 parts by weight of light calcium carbonate, and 0.53 parts by weight of BYK-110 into a double planetary mixer for vacuum dispersion. The vacuum degree is -0.07 MPa, and the stirring time is 10 min - 30 min. Then add 0.76 parts by weight of fumed silica and continue stirring for 15 min - 40 min to obtain a mixture as component A;

[0051] S4. Preparation of component B of antibacterial silicone adhesive: Add 35.4 parts by weight of the antibacterial silicone resin prepared in S2, 0.26 parts by weight of platinum catalyst, 61.32 parts by weight of light calcium carbonate, 0.53 parts by weight of BYK-110, and 1.73 parts by weight of methyl butynol into a double planetary mixer for vacuum dispersion. The vacuum degree is -0.07 MPa, stir for 10 min - 30 min, then add 0.76 parts by weight of fumed silica and continue stirring for 15 min - 40 min to obtain a mixture as component B;

[0052] S5. Preparation of antibacterial silicone adhesive: Mix the component A prepared in S3 and the component B prepared in S4, and conduct vacuum dispersion in a double planetary mixer for 10 min - 20 min. The vacuum degree is -0.07 MPa to obtain an antibacterial silicone adhesive.

[0053] Comparative Example 2

[0054] S1. Preparation of modified silicone resin: 0.02 mol of methyl vinyl siloxane (vinyl content 2%, 10,000 mPa·S) and 1.25 mol of tetrahydrofuran (THF) were successively added to a reaction kettle. Nitrogen was introduced for bubbling to expel air. Under a nitrogen atmosphere, 0.5 mmol of α,α-dimethoxy-α-phenylacetophenone (DMPA), 0.04 mol of mercaptoethylamine hydrochloride, and 0.6 mol of methanol were added and mixed evenly. After irradiating with a mercury lamp at room temperature for 30 min, it was neutralized with saturated sodium bicarbonate solution to a pH of 7. Subsequently, it was poured into deionized water for sedimentation. After repeating the water washing 3 times, vacuum drying was carried out with a vacuum degree of -0.3 MPa, a temperature of 60 °C, and a time of 7 hours to obtain methyl vinyl siloxane containing amino groups in the molecular chain;

[0055] S2. Preparation of modified antibacterial silicone resin: 0.01 mol of 2,4,6-trichloro-1,3,5-triazine was added to 0.01 mol of the amino-containing methyl vinyl siloxane prepared in S1. 0.01 mol of 3% NaOH was added dropwise at a temperature of 0 - 4 °C and stirred well for 2 hours. Then the mixture was poured onto crushed ice, continuously stirred, and neutralized with 3% dilute hydrochloric acid to a pH of 7. The mixture was filtered, and after repeating the water washing with deionized water 3 times, vacuum drying was carried out with a vacuum degree of -0.3 MPa, a temperature of 60 °C, and a time of 7 hours to obtain the modified antibacterial silicone resin;

[0056] S3. Preparation of component A of antibacterial silicone adhesive: 35.4 parts by weight of the modified antibacterial silicone resin prepared in S2, 1.67 parts by weight of hydrogen-containing silicone oil (Si-H bond content 1.5%), 0.91 parts by weight of A-171, 60.73 parts by weight of light calcium carbonate, and 0.53 parts by weight of BYK-110 were subjected to vacuum dispersion in a double planetary mixer with a vacuum degree of -0.07 MPa, and the stirring time was 10 min - 30 min. 0.76 parts by weight of fumed silica was added and stirring continued for 15 min - 40 min to obtain a mixture as component A;

[0057] S4. Preparation of component B of antibacterial silicone adhesive: 35.4 parts by weight of the modified antibacterial silicone resin prepared in S2, 0.26 parts by weight of platinum catalyst, 61.32 parts by weight of light calcium carbonate, 0.53 parts by weight of BYK-110, and 1.73 parts by weight of methyl butynol were subjected to vacuum dispersion in a double planetary mixer with a vacuum degree of -0.07 MPa, stirred for 10 min - 30 min, 0.76 parts by weight of fumed silica was added and stirring continued for 15 min - 40 min to obtain a mixture as component B;

[0058] S5. Preparation of antibacterial silicone adhesive: Mix the A component prepared in S3 with the B component prepared in S4, and conduct vacuum dispersion in a double planetary mixer for 10 min to 20 min with a vacuum degree of -0.07 MPa to obtain an antibacterial silicone adhesive.

[0059] Comparative Example 3

[0060] S1. Preparation of antibacterial agent: Add 0.01 mol of 2,4,6-trichloro-1,3,5-triazine to 0.01 mol of 2-cyanoisonicotinohydrazide, dropwise add 0.01 mol of 3% NaOH at a temperature of 0 - 4 °C and stir well for 2 hours. Then pour the reaction mixture onto crushed ice, continue to stir, and neutralize it to pH 7 with 3% dilute hydrochloric acid. Filter the reactants, wash them with water, and then dry them. The drying temperature is 60 °C and the drying time is 7 hours. The dried reactants are recrystallized with acetone, and finally purified by column chromatography using hexane-ethyl acetate (4:1) as the eluent to obtain the antibacterial agent;

[0061] S2. Preparation of component A of silicone adhesive: Disperse 35.4 parts by weight of silicone resin, 1.67 parts by weight of hydrogen-containing silicone oil (Si-H bond content 1.5%), 0.91 parts by weight of A-171, 60.73 parts by weight of light calcium carbonate, and 0.53 parts by weight of BYK-110 in a double planetary mixer under a vacuum degree of -0.07 MPa for 10 min to 30 min. Then add 0.76 parts by weight of fumed silica and continue to stir for 15 min to 40 min to obtain a mixture as component A;

[0062] S3. Preparation of component B of antibacterial silicone adhesive: Disperse 35.4 parts by weight of modified silicone resin, 0.26 parts by weight of platinum catalyst, 56.55 parts by weight of light calcium carbonate, 0.53 parts by weight of BYK-110, 1.73 parts by weight of methylbutynol, and 4.77 parts by weight of the antibacterial agent prepared in S1 in a double planetary mixer under a vacuum degree of -0.07 MPa for 10 min to 30 min. Then add 0.76 parts by weight of fumed silica and continue to stir for 15 min to 40 min to obtain a mixture as component B;

[0063] S4. Preparation of antibacterial silicone adhesive: Mix the A component prepared in S2 with the B component prepared in S3, and conduct vacuum dispersion in a double planetary mixer for 10 min to 20 min with a vacuum degree of -0.07 MPa to obtain an antibacterial silicone adhesive.

[0064] Comparative experiment:

[0065] The bonding performance of the adhesive was compared by shear strength. The adhesives prepared in the above Examples 1 to 3 and Comparative Examples 1 to 3 were used to bond the aluminum substrates together, and then the peel strength was tested.

[0066] The antibacterial performance of the adhesive was compared by a mildew resistance test. The adhesives prepared in the above Examples 1 to 3 and Comparative Examples 1 to 3 were sterilized and then tested. The two strains of bacteria used were Aspergillus niger and Scopulariopsis brevicaulis, and the changes in the products during the cultivation process were recorded.

[0067] The shear strength of the sample was determined according to GB / T 7124-2008; the mildew test was determined according to GJB150.10A-2009, and the test results are shown in Table 1.

[0068] Table 1: Test data of the functional indicators of the samples obtained in the examples and comparative examples

[0069]

[0070] The above are only the preferred embodiments of the present invention and are not intended to limit the present invention. For those skilled in the art, various modifications and changes can be made to the present invention. Any modifications, equivalent replacements, improvements, etc. made within the spirit and principle of the present invention shall be included in the protection scope of the present invention.

Claims

1. A preparation method of an organosilicon adhesive material with antibacterial effect, characterized in that: The raw materials of the silicone adhesive material include 20-40 parts of modified antibacterial silicone resin, 0.62-2.8 parts of crosslinking agent, 0.4-2.3 parts of accelerator, 0.2-1.5 parts of dispersant, 0.5-2 parts of reinforcing agent, 45-70 parts of filler, 0.1-0.7 parts of catalyst and 1-3 parts of inhibitor; The specific steps are as follows S1. Preparation of antibacterial agent: Add 2,4,6-trichloro-1,3,5-triazine to 2-cyanoisonicotinohydrazide, dropwise add NaOH at 0-4 °C and stir well, then pour the reaction mixture onto crushed ice, continue stirring, and neutralize with dilute hydrochloric acid. After filtering, washing, drying, recrystallizing and purifying the reactants, the antibacterial agent is obtained; S2. Preparation of modified silicone resin: Add silicone resin and tetrahydrofuran to the reaction kettle in turn, pass nitrogen gas to bubble out air, add α,α-dimethoxy-α-phenylacetophenone, mercaptoethylamine hydrochloride and methanol under nitrogen atmosphere, mix evenly, irradiate with a mercury lamp at room temperature, neutralize with saturated sodium bicarbonate solution, and then pour it into deionized water for sedimentation, wash with water, and vacuum dry to obtain a modified silicone resin containing amino groups in the molecular chain; S3. Preparation of modified antibacterial silicone resin: Add the antibacterial agent prepared in S1 to the modified silicone resin containing amino groups prepared in S2, dropwise add NaOH at 0-4 °C and stir well, then pour the mixture onto crushed ice, continue stirring, and neutralize with dilute hydrochloric acid. Then filter, wash with water and vacuum dry the mixture to obtain the modified antibacterial silicone resin; S4. Preparation of component A of antibacterial silicone adhesive: Vacuum disperse the modified antibacterial silicone resin, crosslinking agent, accelerator, filler and dispersant prepared in S3 in a double planetary mixer, stir well, and then add the reinforcing agent and continue stirring to obtain a mixture as component A; S5. Preparation of component B of antibacterial silicone adhesive: Vacuum disperse the modified antibacterial silicone resin, catalyst, filler, dispersant, inhibitor prepared in S3 in a double planetary mixer, stir well, and then add the reinforcing agent and continue stirring to obtain a mixture as component B; S6. Preparation of antibacterial silicone adhesive: Mix component A prepared in S4 with component B prepared in S5, and vacuum disperse in a double planetary mixer for 10 min - 20 min to obtain an antibacterial silicone adhesive.

2. The preparation method of an organosilicon adhesive material with antibacterial effect according to claim 1, characterized in that: In S1, the molar ratio of 2,4,6-trichloro-1,3,5-triazine to 2-cyanoisonicotinohydrazide is 1:1, the concentration of NaOH is 3%, the dropping amount is the same as the molar amount of 2,4,6-trichloro-1,3,5-triazine, stir well for 2 hours, neutralize with 3% dilute hydrochloric acid to pH 6.5 - 7.5, wash with water, the drying temperature is 50 °C - 70 °C, the drying time is 4 - 8 hours, recrystallize with acetone, and use hexane-ethyl acetate with a volume ratio of 4:1 as the eluent to purify the reactants by column chromatography.

3. The preparation method of an organosilicon adhesive material with antibacterial effect according to claim 1, characterized in that: In S2, the molar ratio of silicone resin, tetrahydrofuran, α,α-dimethoxy-α-phenylacetophenone, mercaptoethylamine hydrochloride, and methanol is 2:125:0.05:4:

60. Irradiate with a mercury lamp for 30 min, neutralize with saturated sodium bicarbonate solution to a pH of 6.5 - 7.5, wash repeatedly with water 3 times, and vacuum dry at a vacuum degree of -0.1 MPa to -0.5 MPa, a temperature of 50 °C to 70 °C, and a time of 4 to 8 hours. The silicone resin is one or a mixture of two of methyl vinyl silicone resin and phenyl vinyl silicone resin. The viscosity of the silicone resin is between 1500 mPa·S and 80000 mPa·S, and the vinyl content is 0.1% to 15%.

4. The preparation method of an organosilicon adhesive material with antibacterial effect according to claim 1, characterized in that: In S3, the molar ratio of amino-modified silicone resin and antibacterial agent is 1:1, the concentration of NaOH is 3%, the dropping amount is the same as the molar amount of the modified silicone resin, stir well for 2 hours, neutralize with 3% dilute hydrochloric acid to a pH of 6.5 - 7.5, rinse repeatedly with deionized water 3 times, and vacuum dry at a vacuum degree of -0.1 MPa to -0.5 MPa, a temperature of 50 °C to 70 °C, and a time of 4 to 8 hours.

5. The preparation method of an organosilicon adhesive material with antibacterial effect according to claim 1, characterized in that: In S4, the mass ratio of modified antibacterial silicone resin, crosslinking agent, accelerator, filler, and dispersant is 20 - 40:0.62 - 2.8:0.4 - 2.3:45 - 70:0.2 - 1.

5. The double planetary mixer is vacuum dispersed at a vacuum degree of -0.065 MPa to -0.08 MPa, the stirring time is 10 min to 30 min, and the stirring time for adding the reinforcing agent is 15 min to 40 min.

6. The preparation method of an organosilicon adhesive material with antibacterial effect according to claim 1, characterized in that: In S4, the crosslinking agent is hydrogen-containing silicone oil, and the Si-H bond content of the hydrogen-containing silicone oil is 1% to 15%; the accelerator is an adhesion promoter, and one or a combination of more than two of vinyltriethoxysilane, vinyltrimethoxysilane, γ-aminopropyltriethoxysilane, and γ-(2,3-epoxypropane)propyltrimethoxysilane is selected; the filler is one or a combination of more than two of light calcium carbonate, montmorillonite, mica powder, and zinc oxide; the dispersant is one or a combination of more than two of BYK-161, BYK-163, and BYK-110; the reinforcing agent is one or a combination of two of fumed silica and precipitated silica.

7. The preparation method of an organosilicon adhesive material with antibacterial effect according to claim 1, characterized in that: In S5, the mass ratio of modified antibacterial silicone resin, catalyst, filler, dispersant, and inhibitor is 20 - 40:0.1 - 0.7:45 - 70:0.2 - 1.5:1 - 3. The double planetary mixer is vacuum dispersed at a vacuum degree of -0.065 MPa to -0.08 MPa, the stirring time is 10 min to 30 min, and the stirring time for adding the reinforcing agent is 15 min to 40 min.

8. The preparation method of an organosilicon adhesive material with antibacterial effect according to claim 1, characterized in that: The catalyst in S5 is a metal catalyst composed of one or more combinations of ruthenium, palladium, and platinum; the filler is one or a combination of two or more of light calcium carbonate, montmorillonite, mica powder, and zinc oxide; the dispersant is one or a combination of two or more of BYK-161, BYK-163, and BYK-110; the inhibitor is an acetylenic alcohol, and one or a combination of two or more of methyl butynol, 3,5-dimethyl-1-hexyn-3-ol, and 1-hexynyl-1-cyclohexanol is selected; the reinforcing agent is one or a combination of two of fumed silica and precipitated silica.

9. The preparation method of an organosilicon adhesive material with antibacterial effect according to claim 1, characterized in that: In S6, the mass ratio of component A to component B is 1:1, the vacuum degree of vacuum dispersion by the double planetary mixer is -0.065 MPa to -0.08 MPa, and the stirring time is 10 min to 20 min.

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