Antibacterial and deodorant silica gel sealing material and preparation method thereof

Abstract

The application relates to the technical field of silica gel sealing materials, and discloses an antibacterial and odor-resistant silica gel sealing material and a preparation method thereof. The antibacterial and odor-resistant silica gel sealing material comprises methyl vinyl silicone rubber, fumed silica, hydroxyl silicone oil, hydrogen-containing silicone oil, a platinum catalyst, an inhibitor, silane coupling modified composite functional fillers and an organic silicon quaternary ammonium salt. The silane coupling modified composite functional fillers are obtained by jointly carrying out silane coupling modification on zinc antibacterial agents and odor-removing fillers. The zinc antibacterial agents and the odor-removing fillers are jointly subjected to silane coupling modification, and the silane coupling modified composite functional fillers are formed and then added to a silica gel system, so that the antibacterial components and the odor-adsorbing components are jointly distributed in the silica gel matrix. The zinc antibacterial agents and the odor-removing fillers can jointly participate in subsequent mixing and vulcanization by jointly carrying out silane coupling modification on the zinc antibacterial agents and the odor-removing fillers, so that the difference in the dispersion state of the functional components is reduced.

Description

Technical Field

[0001] This invention relates to the field of silicone sealing materials technology, specifically to an antibacterial and odor-resistant silicone sealing material and its preparation method. Background Technology

[0002] Silicone sealing materials are widely used in household appliances, food containers, medical aids, bathroom fixtures, and building sealants due to their weather resistance, temperature resistance, chemical stability, and elastic recovery properties. With the diversification of usage environments, some silicone sealing materials need to simultaneously possess antibacterial and deodorizing functions to meet the needs of use in humid, enclosed, or odor-prone environments. Therefore, introducing antibacterial and deodorizing components into silicone materials has become an important development direction for functionalized silicone sealing materials.

[0003] Existing antibacterial and deodorizing silicone materials are typically prepared by directly adding zinc-based antibacterial agents, deodorizing fillers, or other functional additives to a silicone system. Some technical solutions involve surface-treating the antibacterial agents or deodorizing fillers separately before adding them to the silicone system, and then dispersing them in the silicone matrix through processes such as mixing and vulcanization to obtain the corresponding antibacterial and deodorizing properties.

[0004] However, the inventors of this application discovered in the process of realizing the technical solution of this application that in the prior art, zinc-based antibacterial agents and deodorizing fillers are usually treated by direct addition or by adding them to the silica gel system after separate modification. This causes zinc-based antibacterial agents and deodorizing fillers to easily form different dispersion states in the subsequent mixing and vulcanization process, resulting in a problem of large differences in the dispersion state of functional components. Summary of the Invention

[0005] To address the shortcomings of existing technologies, this invention provides an antibacterial and deodorizing silicone sealing material and its preparation method, which solves the problem that zinc-based antibacterial agents and deodorizing fillers easily form different dispersion states during subsequent mixing and vulcanization processes in existing technologies.

[0006] To achieve the above objectives, the present invention is implemented through the following technical solution: an antibacterial and odor-resistant silicone sealing material, comprising the following components by weight: 100 parts of methyl vinyl silicone rubber; 15-35 parts of fumed silica; and 2-8 parts of hydroxyl silicone oil;

[0007] 1-5 parts of hydrogen-containing silicone oil; 0.05-0.5 parts of platinum catalyst; 0.01-0.2 parts of inhibitor; 3-14 parts of silane coupling modified composite functional filler; 0.5-3 parts of organosilicon quaternary ammonium salt;

[0008] The silane coupling modified composite functional filler is obtained by silane coupling modification of a zinc-based antibacterial agent and an odor-removing filler, wherein the mass ratio of the zinc-based antibacterial agent to the odor-removing filler is 1:(0.3-2.5).

[0009] The preparation process of the silane coupling modified composite functional filler includes: adding zinc-based antibacterial agent and deodorizing filler together into a silane coupling treatment solution for modification treatment. The silane coupling treatment solution is composed of silane coupling agent, ethanol and deionized water. The mass ratio of silane coupling agent, ethanol and deionized water is 1:(5~20):(0.5~5). The modification temperature is 30~60℃ and the modification time is 1~4h.

[0010] Preferably, the vinyl content of the methyl vinyl silicone rubber is 0.05% to 1.5%; the specific surface area of ​​the fumed silica is 150 to 300 m² / g; the viscosity of the hydroxyl silicone oil is 20 to 1000 mPa·s; and the hydrogen content of the hydrogen-containing silicone oil is 0.1% to 1.6%.

[0011] Preferably, the zinc-based antibacterial agent is one or more of zinc oxide, basic zinc carbonate, and zinc silicate; the deodorizing filler is one or more of zeolite powder, diatomaceous earth, porous silicate, and activated silica.

[0012] Preferably, the silane coupling agent is one or more of vinyltriethoxysilane, vinyltrimethoxysilane, aminopropyltriethoxysilane, and glycidyl etheroxypropyltrimethoxysilane; the amount of the silane coupling agent is 1% to 8% of the total mass of the zinc-based antibacterial agent and the deodorizing filler; and the pH value of the silane coupling treatment solution is 4 to 6.

[0013] Preferably, the organosilicon quaternary ammonium salt is 3-(trimethoxysilyl)propyldimethyloctadecylammonium chloride or a derivative thereof; the particle size of the silane coupling modified composite functional filler is 1-30 μm.

[0014] Preferably, a method for preparing an antibacterial and odor-resistant silicone sealing material includes the following steps:

[0015] S1. Dry the zinc-based antibacterial agent and the deodorizing filler at 80-120℃ for 1-4 hours respectively;

[0016] S2. Mix silane coupling agent, ethanol and deionized water at a mass ratio of 1:(5~20):(0.5~5) and hydrolyze at 20~40℃ for 20~60min to obtain silane coupling treatment solution;

[0017] S3. Add the zinc-based antibacterial agent and deodorizing filler obtained in step S1 to the silane coupling treatment solution obtained in step S2, and stir at 30-60℃ for 1-4 hours to obtain the modified slurry.

[0018] S4. The modified slurry is dried to obtain a silane coupling modified composite functional filler.

[0019] S5. Methyl vinyl silicone rubber, fumed silica, hydroxyl silicone oil, silane coupling modified composite functional filler and organosilicon quaternary ammonium salt are mixed to obtain the base rubber compound.

[0020] S6. Add hydrogen-containing silicone oil, platinum catalyst and inhibitor to the base rubber compound, mix and then perform vacuum degassing;

[0021] S7. The degassed rubber material is molded and vulcanized to obtain antibacterial and odor-proof silicone sealant.

[0022] Preferably, in step S3, the pH value of the silane coupling treatment solution is 4-6; the stirring speed is 300-1000 r / min; the amount of silane coupling agent added is 1%-8% of the total mass of the zinc-based antibacterial agent and the deodorizing filler; and the mass ratio of the zinc-based antibacterial agent to the deodorizing filler is 1:(0.3-2.5).

[0023] Preferably, in step S4, the drying temperature is 80–120°C; the drying time is 2–6 h; after drying, the material is crushed and sieved to make the particle size of the obtained silane coupling modified composite functional filler 1–30 μm.

[0024] Preferably, in step S5, the mixing temperature is 40-100℃; the mixing time is 30-100 min; and the base rubber compound is heat-treated at 80-150℃ for 0.5-3 h.

[0025] Preferably, in step S6, the mixing temperature is 15–40°C; the vacuum degree of the vacuum degassing is -0.08–-0.10 MPa; and the vacuum degassing time is 5–30 min.

[0026] In step S7, molding is performed using compression molding. The mold temperature is 120–180°C, the molding pressure is 5–20 MPa, and the vulcanization time is 5–30 min. After the first vulcanization is completed, a second vulcanization process is performed. The second vulcanization temperature is 150–200°C, and the second vulcanization time is 1–4 h.

[0027] This invention provides an antibacterial and odor-resistant silicone sealing material and its preparation method. It has the following beneficial effects:

[0028] 1. This invention modifies zinc-based antibacterial agents and deodorizing fillers by silane coupling, and then adds the silane-coupled modified composite functional filler to the silica gel system, so that the zinc-based antibacterial agents and deodorizing fillers can participate in the subsequent mixing and vulcanization process, thereby reducing the difference in the dispersion state of functional components.

[0029] 2. This invention simultaneously sets zinc-based antibacterial agents, deodorizing fillers, and organosilicon quaternary ammonium salts in a silicone system, and utilizes hydrogen-containing silicone oil and methyl vinyl silicone rubber to form a cross-linked network, so that the antibacterial components and odor-absorbing components are distributed together in the silicone matrix.

[0030] 3. This invention modifies zinc-based antibacterial agents and deodorizing fillers by silane coupling, thereby introducing organosilicon groups onto the surface of the silane coupling modified composite functional filler, which improves the compatibility distribution between the silane coupling modified composite functional filler and the silica matrix. Attached Figure Description

[0031] Figure 1 This is a flowchart illustrating the preparation process of the silane coupling modified composite functional filler of the present invention.

[0032] Figure 2 This is a flowchart illustrating the preparation process of the antibacterial and deodorizing silicone sealing material of the present invention.

[0033] Figure 3 This is a comparison chart of the antibacterial rate and ammonia removal rate test results between the embodiments and the comparative examples of the present invention;

[0034] Figure 4 This is a comparison chart of the tensile strength, elongation at break, and Shore A hardness test results of the embodiments and comparative examples of the present invention. Detailed Implementation

[0035] The technical solution of the present invention will now be clearly and completely described with reference to the accompanying drawings. Obviously, the described embodiments are only a part of the embodiments of the present invention, and not all of them. All other embodiments obtained by those skilled in the art based on the embodiments of the present invention without creative effort are within the scope of protection of the present invention.

[0036] The present application will be further described in detail below with reference to the embodiments.

[0037] Please refer to the attached document. Figure 1 Preparation Example 1: Preparation of silane coupling modified composite functional fillers

[0038] Weigh out 100g of zinc oxide and 80g of zeolite powder for later use.

[0039] Add 15g of vinyltriethoxysilane to a three-necked flask containing 150g of ethanol and 20g of deionized water. Stir at 400r / min for 30min at 25℃. Adjust the pH of the system to 5 with glacial acetic acid to complete the pre-hydrolysis of the silane coupling agent and obtain the silane coupling treatment solution.

[0040] Subsequently, 100g of zinc oxide and 80g of zeolite powder were added to the above silane coupling treatment solution, and stirred continuously at 600r / min for 2h at 50℃, so that the zinc oxide particles and zeolite powder particles could simultaneously come into contact with the silane coupling treatment solution and undergo surface modification.

[0041] After mixing, the resulting slurry was transferred to a forced-air drying oven and dried at 100°C for 4 hours.

[0042] After drying, the material was pulverized using a pulverizer and sieved through a 100-mesh sieve to obtain the silane coupling modified composite functional filler. Particle size analysis showed that the D50 particle size of the obtained silane coupling modified composite functional filler was 8.7 μm. The mass of the silane coupling modified composite functional filler obtained after this modification treatment was calculated to be 140.6 g.

[0043] Preparation Example 2: Preparation of Silane Coupling Modified Composite Functional Filler

[0044] Weigh out 120g of zinc silicate and 60g of diatomaceous earth for later use.

[0045] 18g of aminopropyltriethoxysilane was added to a reaction vessel containing 180g of ethanol and 25g of deionized water. The mixture was stirred at 500 rpm for 40 min at 30°C, and the pH of the system was adjusted to 4.5 using glacial acetic acid to obtain the silane coupling treatment solution. Subsequently, 120g of zinc silicate and 60g of diatomaceous earth were added to the silane coupling treatment solution, and the mixture was stirred at 700 rpm for 3 h at 55°C.

[0046] After modification, the resulting slurry was dried in a 105℃ forced-air drying oven for 5 hours.

[0047] After drying, the material was mechanically pulverized and sieved through a 120-mesh sieve to obtain the silane coupling modified composite functional filler. Particle size analysis showed that the D50 particle size of the obtained silane coupling modified composite functional filler was 6.4 μm. The mass of the silane coupling modified composite functional filler obtained after this modification treatment was calculated to be 192.3 g.

[0048] Please refer to the attached document. Figure 2 Example 1: This example provides an antibacterial and odor-resistant silicone sealing material and its preparation method.

[0049] The methyl vinyl silicone rubber used in this embodiment has a vinyl content of 0.05%; the fumed silica has a specific surface area of ​​150 m² / g; the hydroxyl silicone oil has a viscosity of 20 mPa·s; the hydrogen-containing silicone oil has a hydrogen content of 0.1%; and the organosilicon quaternary ammonium salt used is 3-(trimethoxysilyl)propyldimethyloctadecylammonium chloride.

[0050] The prepared antibacterial and deodorizing silicone sealing material comprises, by weight: 100 parts methyl vinyl silicone rubber; 15 parts fumed silica; 2 parts hydroxyl silicone oil; 1 part hydrogen-containing silicone oil; and 0.05 parts platinum catalyst.

[0051] 0.01 parts of inhibitor; 3 parts of silane coupling modified composite functional filler; 0.5 parts of organosilicon quaternary ammonium salt.

[0052] Among them, the silane coupling modified composite functional filler is obtained by joint modification of zinc oxide and zeolite powder, with a mass ratio of zinc oxide to zeolite powder of 1:0.3.

[0053] Antibacterial and odor-resistant silicone sealant is prepared according to the following steps:

[0054] S1. Place 100g of zinc oxide and 30g of zeolite powder in a forced-air drying oven and dry at 80℃ for 1 hour.

[0055] S2. Add 3g of vinyltriethoxysilane to a mixture of 15g of ethanol and 1.5g of deionized water, stir at 20°C for 20min, and adjust the pH of the system to 6 to obtain the silane coupling treatment solution.

[0056] S3. Add the zinc oxide and zeolite powder obtained in step S1 to the silane coupling treatment solution obtained in step S2, and stir at 300 r / min for 1 h at 30°C to obtain the modified slurry.

[0057] S4. The modified slurry is dried at 80℃ for 2 hours, pulverized and passed through a 100-mesh sieve to obtain silane coupling modified composite functional filler.

[0058] S5. Add 100g of methyl vinyl silicone rubber to a two-roll mill and plasticize for 5 minutes. Then add 15g of fumed silica, 2g of hydroxyl silicone oil, 3g of silane coupling modified composite functional filler and 0.5g of organosilicon quaternary ammonium salt. Mix at 40°C for 30 minutes to obtain the base rubber compound.

[0059] S6. Add 1g of hydrogen-containing silicone oil, 0.05g of platinum catalyst and 0.01g of inhibitor to the base rubber compound, mix at 15℃ for 5min, and degas at a vacuum of -0.08MPa for 5min.

[0060] S7. Place the degassed rubber material in a mold for compression molding. The mold temperature is 120℃, the molding pressure is 5MPa, and the vulcanization time is 5min. Then, perform a second-stage vulcanization at 150℃ for 1h to obtain an antibacterial and odor-resistant silicone sealant.

[0061] Example 2: This example provides an antibacterial and odor-resistant silicone sealing material and its preparation method.

[0062] The methyl vinyl silicone rubber used in this embodiment has a vinyl content of 0.80%; the fumed silica has a specific surface area of ​​220 m² / g; the hydroxyl silicone oil has a viscosity of 500 mPa·s; the hydrogen-containing silicone oil has a hydrogen content of 0.8%; and the organosilicon quaternary ammonium salt used is 3-(trimethoxysilyl)propyldimethyloctadecylammonium chloride.

[0063] The prepared antibacterial and deodorizing silicone sealing material comprises, by weight: 100 parts methyl vinyl silicone rubber; 25 parts fumed silica; 5 parts hydroxyl silicone oil; 3 parts hydrogen-containing silicone oil; 0.25 parts platinum catalyst; 0.10 parts inhibitor; 8 parts silane coupling modified composite functional filler; and 1.5 parts organosilicon quaternary ammonium salt.

[0064] Among them, the silane coupling modified composite functional filler is obtained by modifying zinc oxide and zeolite powder together, with the mass ratio of zinc oxide to zeolite powder being 1:1.

[0065] Antibacterial and odor-resistant silicone sealant is prepared according to the following steps:

[0066] S1. Place 100g of zinc oxide and 100g of zeolite powder in a forced-air drying oven and dry at 100℃ for 2 hours.

[0067] S2. Add 10g of vinyltriethoxysilane to a mixture of 100g of ethanol and 10g of deionized water, stir at 30°C for 40min, and adjust the pH of the system to 5 to obtain the silane coupling treatment solution.

[0068] S3. Add the zinc oxide and zeolite powder obtained in step S1 to the silane coupling treatment solution obtained in step S2, and stir at 600 r / min for 2 h at 50°C to obtain the modified slurry.

[0069] S4. The modified slurry is dried at 100℃ for 4 hours, pulverized and passed through a 120-mesh sieve to obtain silane coupling modified composite functional filler.

[0070] S5. Add 100g of methyl vinyl silicone rubber to a two-roll mill and plasticize for 8 minutes. Then add 25g of fumed silica, 5g of hydroxyl silicone oil, 8g of silane coupling modified composite functional filler and 1.5g of organosilicon quaternary ammonium salt. Mix at 70°C for 60 minutes to obtain the base rubber compound.

[0071] S6. Heat-treat the base rubber compound at 120℃ for 1.5h; then add 3g of hydrogen-containing silicone oil, 0.25g of platinum catalyst and 0.10g of inhibitor, mix at 25℃ for 15min, and degas at a vacuum of -0.09MPa for 15min.

[0072] S7. The degassed rubber compound is molded at a mold temperature of 150℃, a molding pressure of 10MPa, and a vulcanization time of 15min. Then, a second-stage vulcanization is carried out at 180℃ for 2h to obtain an antibacterial and odor-proof silicone sealant.

[0073] Example 3: This example provides an antibacterial and odor-resistant silicone sealing material and its preparation method.

[0074] The methyl vinyl silicone rubber used in this embodiment has a vinyl content of 1.5%; the fumed silica used has a specific surface area of ​​300 m² / g; the hydroxyl silicone oil used has a viscosity of 1000 mPa·s; the hydrogen-containing silicone oil used has a hydrogen content of 1.6%; and the organosilicon quaternary ammonium salt used is 3-(trimethoxysilyl)propyldimethyloctadecylammonium chloride.

[0075] The prepared antibacterial and deodorizing silicone sealing material comprises, by weight: 100 parts methyl vinyl silicone rubber; 35 parts fumed silica; 8 parts hydroxyl silicone oil; 5 parts hydrogen-containing silicone oil; 0.50 parts platinum catalyst; 0.20 parts inhibitor; 14 parts silane coupling modified composite functional filler; and 3 parts organosilicon quaternary ammonium salt.

[0076] Among them, the silane coupling modified composite functional filler is obtained by joint modification of zinc silicate and diatomite, with a mass ratio of zinc silicate to diatomite of 1:2.5.

[0077] Antibacterial and odor-resistant silicone sealant is prepared according to the following steps:

[0078] S1. Place 100g of zinc silicate and 250g of diatomaceous earth in a forced-air drying oven and dry at 120℃ for 4 hours.

[0079] S2. Add 28g of aminopropyltriethoxysilane to a mixture of 560g of ethanol and 140g of deionized water, stir at 40℃ for 60min, and adjust the pH of the system to 4 to obtain the silane coupling treatment solution.

[0080] S3. Add the zinc silicate and diatomaceous earth obtained in step S1 to the silane coupling treatment solution obtained in step S2, and stir at 1000 r / min for 4 h at 60°C to obtain the modified slurry.

[0081] S4. The modified slurry was dried at 120℃ for 6 hours, pulverized and passed through a 150-mesh sieve to obtain the silane coupling modified composite functional filler.

[0082] S5. Add 100g of methyl vinyl silicone rubber to a two-roll mill and plasticize for 10 minutes. Then add 35g of fumed silica, 8g of hydroxyl silicone oil, 14g of silane coupling modified composite functional filler and 3g of organosilicon quaternary ammonium salt. Mix at 100°C for 100 minutes to obtain the base rubber compound.

[0083] S6. Heat-treat the base rubber compound at 150℃ for 3 hours; then add 5g of hydrogen-containing silicone oil, 0.50g of platinum catalyst and 0.20g of inhibitor, mix at 40℃ for 30 minutes, and degas at a vacuum of -0.10MPa for 30 minutes.

[0084] S7. The degassed rubber compound is molded at a mold temperature of 180℃, a molding pressure of 20MPa, and a vulcanization time of 30min. Then, a second-stage vulcanization is carried out at 200℃ for 4h to obtain an antibacterial and odor-resistant silicone sealant.

[0085] Comparative Example 1: Compared with Example 2, the difference is that in step S3, the co-silane coupling modification treatment of zinc-based antibacterial agent and deodorizing filler is not performed. Specifically, zinc oxide and zeolite powder are directly added to the mixing system in step S5 after drying, and the other raw material types, addition amounts, and preparation process parameters are the same as in Example 2.

[0086] Comparative Example 2: Compared with Example 2, the difference is that in step S3, zinc oxide and zeolite powder are respectively subjected to silane coupling modification treatment. Specifically, zinc oxide is added separately to the silane coupling treatment solution for modification, and zeolite powder is added separately to another silane coupling treatment solution with the same formulation for modification; after drying treatment, they are added together to the mixing system in step S5. The other raw material types, addition amounts, and preparation process parameters are the same as in Example 2.

[0087] Comparative Example 3: Compared with Example 2, the difference is that in step S5, the silane coupling modified component prepared by zeolite powder is not added. Specifically, the silane coupling modified composite functional filler is obtained only by silane coupling modification of zinc oxide, and its addition amount is consistent with the amount of zinc-based antibacterial agent in Example 2. The other raw material types, addition amounts, and preparation process parameters are the same as in Example 2.

[0088] Comparative Example 4: Compared with Example 2, the difference is that no organosilicon quaternary ammonium salt is added in step S5. The other raw material types, addition amounts, and preparation process parameters are the same as in Example 2.

[0089] Comparative Example 5: Compared with Example 2, the difference is that in step S3, the mass ratio of zinc oxide to zeolite powder is adjusted to 1:3.5. This mass ratio exceeds the 1:(0.3~2.5) range defined in this invention. The other raw material types, addition amounts, and preparation process parameters are the same as in Example 2.

[0090] Performance testing

[0091] Test method: The antibacterial and odor-resistant silicone sealing materials prepared in Examples 1-3 and Comparative Examples 1-5 were used as test samples.

[0092] (1) Antibacterial performance test: The antibacterial performance test is conducted in accordance with the test principle of GB / T 20944.3-2008 "Evaluation of antibacterial properties of textiles - Part 3: Vibration method".

[0093] The 50mm×50mm sample was placed in an Erlenmeyer flask containing a Staphylococcus aureus suspension and incubated with shaking at 37°C for 24 hours.

[0094] After the culture is completed, the number of colonies is measured and the antibacterial rate is calculated according to the following formula: Antibacterial rate (%) = (A-B) / A×100; where: A is the number of colonies in the control group; B is the number of colonies in the sample group.

[0095] (2) Odor removal performance test: Ammonia was used as a simulated odor gas. The sample was placed in a 5L sealed test container, and ammonia gas with an initial concentration of 100mg / m³ was introduced into the container.

[0096] The ammonia concentration inside the container was measured after standing at 25℃ for 24 hours.

[0097] The ammonia removal rate is calculated using the following formula: Ammonia removal rate (%) = (C0 - C1) / C0 × 100;

[0098] Where: C0 is the initial ammonia concentration; C1 is the ammonia concentration after the test.

[0099] (3) Tensile property test: The tensile property test shall be conducted in accordance with GB / T 528-2009 "Determination of tensile stress-strain properties of vulcanized rubber or thermoplastic rubber". The test items include: tensile strength (MPa); elongation at break (%).

[0100] (4) Hardness test: The hardness test shall be conducted in accordance with GB / T 531.1-2008 "Test method for indentation hardness of vulcanized rubber or thermoplastic rubber". The test results shall be expressed as Shore A hardness.

[0101] Example 1 93.2 71.5 Example 2 98.1 89.4 Example 3 98.7 91.8 Comparative Example 1 82.6 63.7 Comparative Example 2 89.5 75.8 Comparative Example 3 97.6 38.4 Comparative Example 4 91.8 88.2 Comparative Example 5 94.7 78.3

[0102] Table 1. Test results of antibacterial and deodorizing properties

[0103] Example 1 7.5 350 48 Example 2 8.9 420 55 Example 3 9.2 405 58 Comparative Example 1 6.8 310 47 Comparative Example 2 7.4 340 50 Comparative Example 3 8.5 395 54 Comparative Example 4 8.3 385 54 Comparative Example 5 7.8 360 53

[0104] Table 2 Mechanical property test results

[0105] In conjunction with Example 2 and Comparative Examples 1-3, and in conjunction with Table 1 and Figure 3 It can be seen that the silane coupling modification of the composite functional filler affects both antibacterial and deodorizing properties. Comparative Example 1 did not undergo silane coupling modification, Comparative Example 2 used separate modification methods, and Comparative Example 3 did not introduce deodorizing filler components; all three showed differences in antibacterial rate and ammonia removal rate compared to Example 2. This indicates that when zinc-based antibacterial agents and deodorizing fillers are jointly modified by silane coupling to form a silane coupling modified composite functional filler, and then introduced into the silica gel system, both antibacterial and odor-adsorbing components can be formed simultaneously.

[0106] Based on Examples 1-3 and Comparative Example 5, and referring to Table 1, it can be seen that the ratio of zinc-based antibacterial agent to deodorizing filler affects the antibacterial and deodorizing properties. When the mass ratio of zinc-based antibacterial agent to deodorizing filler is within the range defined by this invention, the samples exhibit corresponding antibacterial rates and ammonia removal rates; when this ratio exceeds the defined range, the test results change.

[0107] Combined with Examples 1-3 and Table 2 and Figure 4 It can be seen that the antibacterial and deodorizing silicone sealing materials prepared by this invention all have tensile strength, elongation at break and Shore A hardness, indicating that the prepared materials can maintain the basic physical properties of silicone sealing materials.

[0108] Based on Examples 2 and 4, and referring to Table 1, it can be seen that the introduction of organosilicon quaternary ammonium salts affects antibacterial properties. With all other conditions remaining constant, the antibacterial rates differed between Examples 2 and 4, indicating that organosilicon quaternary ammonium salts participate in the formation of the antibacterial component.

[0109] In other embodiments, the zinc-based antibacterial agent may be basic zinc carbonate in addition to zinc oxide and zinc silicate; the deodorizing filler may be porous silicate or activated silica in addition to zeolite powder and diatomaceous earth; and the silane coupling agent may be vinyltriethoxysilane or glycidoxypropyltrimethoxysilane in addition to vinyltrimethoxysilane and aminopropyltriethoxysilane. Under the above-mentioned substitution conditions, the preparation can be carried out according to the methods described in Examples 1 to 3.

[0110] Although embodiments of the invention have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and alterations can be made to these embodiments without departing from the principles and spirit of the invention, the scope of which is defined by the appended claims and their equivalents.

Claims

1. An antibacterial and odor-resistant silicone sealing material, characterized in that, By weight, it comprises the following components: 100 parts methyl vinyl silicone rubber; 15-35 parts fumed silica; 2-8 parts hydroxyl silicone oil; 1-5 parts of hydrogen-containing silicone oil; 0.05-0.5 parts of platinum catalyst; 0.01-0.2 parts of inhibitor; 3-14 parts of silane coupling modified composite functional filler; 0.5-3 parts of organosilicon quaternary ammonium salt; The silane coupling modified composite functional filler is obtained by silane coupling modification of a zinc-based antibacterial agent and an odor-removing filler, wherein the mass ratio of the zinc-based antibacterial agent to the odor-removing filler is 1:(0.3-2.5). The preparation process of the silane coupling modified composite functional filler includes: adding zinc-based antibacterial agent and deodorizing filler together into a silane coupling treatment solution for modification treatment. The silane coupling treatment solution is composed of silane coupling agent, ethanol and deionized water. The mass ratio of silane coupling agent, ethanol and deionized water is 1:(5~20):(0.5~5). The modification temperature is 30~60℃ and the modification time is 1~4h.

2. The antibacterial and odor-resistant silicone sealing material according to claim 1, characterized in that, The methyl vinyl silicone rubber has a vinyl content of 0.05% to 1.5%; the fumed silica has a specific surface area of ​​150 to 300 m² / g; the hydroxyl silicone oil has a viscosity of 20 to 1000 mPa·s; and the hydrogen-containing silicone oil has a hydrogen content of 0.1% to 1.6%.

3. The antibacterial and odor-resistant silicone sealing material according to claim 1, characterized in that, The zinc-based antibacterial agent is one or more of zinc oxide, basic zinc carbonate, and zinc silicate; the deodorizing filler is one or more of zeolite powder, diatomaceous earth, porous silicate, and activated silica.

4. The antibacterial and odor-resistant silicone sealing material according to claim 1, characterized in that, The silane coupling agent is one or more of vinyltriethoxysilane, vinyltrimethoxysilane, aminopropyltriethoxysilane, and glycidoxypropyltrimethoxysilane; the amount of the silane coupling agent is 1% to 8% of the total mass of the zinc-based antibacterial agent and the deodorizing filler; the pH value of the silane coupling treatment solution is 4 to 6.

5. The antibacterial and odor-resistant silicone sealing material according to claim 1, characterized in that, The organosilicon quaternary ammonium salt is 3-(trimethoxysilyl)propyldimethyloctadecylammonium chloride or its derivative; the particle size of the silane coupling modified composite functional filler is 1-30 μm.

6. A method for preparing an antibacterial and odor-resistant silicone sealing material, characterized in that, The application of an antibacterial and odor-resistant silicone sealing material according to any one of claims 1-5 includes the following steps: S1. Dry the zinc-based antibacterial agent and the deodorizing filler at 80-120℃ for 1-4 hours respectively; S2. Mix silane coupling agent, ethanol and deionized water at a mass ratio of 1:(5~20):(0.5~5) and hydrolyze at 20~40℃ for 20~60min to obtain silane coupling treatment solution; S3. Add the zinc-based antibacterial agent and deodorizing filler obtained in step S1 to the silane coupling treatment solution obtained in step S2, and stir at 30-60℃ for 1-4 hours to obtain the modified slurry. S4. The modified slurry is dried to obtain a silane coupling modified composite functional filler. S5. Methyl vinyl silicone rubber, fumed silica, hydroxyl silicone oil, silane coupling modified composite functional filler and organosilicon quaternary ammonium salt are mixed to obtain the base rubber compound. S6. Add hydrogen-containing silicone oil, platinum catalyst and inhibitor to the base rubber compound, mix and then perform vacuum degassing; S7. The degassed rubber material is molded and vulcanized to obtain antibacterial and odor-proof silicone sealant.

7. The method for preparing an antibacterial and deodorizing silicone sealing material according to claim 6, characterized in that, In step S3, the pH value of the silane coupling treatment solution is 4 to 6; the stirring speed is 300 to 1000 r / min; the amount of silane coupling agent added is 1% to 8% of the total mass of zinc-based antibacterial agent and deodorizing filler; the mass ratio of zinc-based antibacterial agent to deodorizing filler is 1:(0.3 to 2.5).

8. The method for preparing an antibacterial and odor-resistant silicone sealing material according to claim 6, characterized in that, In step S4, the drying temperature is 80–120°C; the drying time is 2–6 h; after drying, the material is crushed and sieved to make the particle size of the obtained silane coupling modified composite functional filler 1–30 μm.

9. The method for preparing an antibacterial and deodorizing silicone sealing material according to claim 6, characterized in that, In step S5, the mixing temperature is 40–100°C; the mixing time is 30–100 min; and the base rubber compound is heat-treated at 80–150°C for 0.5–3 h.

10. The method for preparing an antibacterial and odor-resistant silicone sealing material according to claim 6, characterized in that, In step S6, the mixing temperature is 15–40°C; the vacuum degree of the vacuum degassing is -0.08–-0.10 MPa; and the vacuum degassing time is 5–30 min. In step S7, molding is performed using compression molding. The mold temperature is 120–180°C, the molding pressure is 5–20 MPa, and the vulcanization time is 5–30 min. After the first vulcanization is completed, a second vulcanization process is performed. The second vulcanization temperature is 150–200°C, and the second vulcanization time is 1–4 h.

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