Biosafety type silane modified MS sealant for container

Abstract

The invention relates to the technical field of MS (Murashige-Skoog) sealants, in particular to a container biosafety type silane modified MS sealant and a preparation method thereof. The container biosafety type silane modified MS sealant is prepared from the following raw materials in percentage by mass: 15 to 30 weight percent of base glue, 40 to 60 weight percent of filler composition, 12 to 20 weight percent of plasticizer, 0.5 to 5 weight percent of silane coupling agent, 0.5 to 1.5 weight percent of organic tin catalyst, 0.5 to 3.0 weight percent of anti-aging additive and 0.5 to 2.5 weight percent of water removal agent, the filler composition comprises a basic filler, a thixotropic filler, an antibacterial and mildew-proof filler and a pest-proof filler, and the thixotropic filler is a spherical inorganic filler. The MS sealant has good antibacterial and mildew-proof performance and insect and disease prevention effects, and meets the requirements of the MS sealant for biological safety.

Description

Technical Field

[0001] The present invention relates to the technical field of MS sealants, and in particular to a container bio-safe silane-modified MS sealant. Background Art

[0002] MS glue, also known as silane-modified polyether, is mainly used for bonding, caulking, jointing, sealing, waterproofing, strengthening, etc. of building substrates. MS glue has good adhesiveness, storage stability, high elasticity, flexibility, paintability, environmental friendliness and weather resistance, making it suitable for connecting inorganic materials, metals and plastics, and is widely used in industrial fields such as refrigerated trucks, containers, elevators, furniture, curtain walls, etc.

[0003] The curing mechanism of silane-modified polyether sealant belongs to moisture curing. The organosiloxane organic active functional groups at both ends of the macromolecular polyether chain react with water in the air to generate silanol groups (Si-OH) through hydrolysis. Condensation occurs between Si-OH groups or between Si-OH and Si-OR to release water or methanol and ethanol, forming Si-O-Si bonds. After room temperature vulcanization, a network structure elastomer with a flexible polyether chain as the backbone and Si-O-Si bonds as cross-linking points is formed.

[0004] Existing silane-modified polyether MS glue, such as a mildew-proof one-component silane-modified polyether sealant disclosed in publication number CN111635726A, contains 12-80% of organosilicon-modified polyether base material, 0-45% of plasticizer, 2-5% of titanium dioxide, 0-70% of calcium carbonate, 0-10% of white carbon black, 0.5-2% of water remover, 1-5% of coupling agent, 0.5-1.5% of light stabilizer, 0.5-1.5% of ultraviolet absorber, and 0.05-0.5% of antibacterial and mildew-proof agent; the antibacterial and mildew-proof agent is any one or a combination of 2-methyl-4-isothiazolin-3-one, 5-chloro-2-methyl-4-isothiazolin-3-one, N-octyl-4-isothiazolin-3-one, (4,5-dichloro-N-octyl-4-isothiazolin-3-one) isothiazolinone, 2-butyl-1,2-benzisothiazolin-3-one and 1,2-benzisothiazolin-3-one. This MS glue has the characteristics of 0-level double mildew prevention, universal indoor and outdoor use, environmental friendliness, solvent-free, non-toxic, extremely low VOC, no odor, stain-resistant and easy to scrub, excellent anti-ultraviolet and wind and weather resistance, and is suitable for a variety of substrates.

[0005] Another example is a kind of MS sealant with insect repellent and anti-ultraviolet aging properties, which is disclosed in Publication No. CN111978906B. By weight, it at least includes the following components: 5-25 parts of silane oligomer, 5-20 parts of fluorine-containing terminal hydroxyl polyether, 0.1-0.5 parts of catalyst, 1-5 parts of dehydrating agent, 5-20 parts of plasticizer, 15-30 parts of filler, and 0.1-0.5 parts of multifunctional POSS-based microcapsule. Compared with traditional MS sealants, this MS sealant has excellent performance in terms of insect repellent, erosion resistance, anti-ultraviolet aging, and anti-wetting.

[0006] In the field of waterproof sealing of containers, it shows excellent waterproof sealing and shockproof performance. As a commonly used transportation tool in international trade, containers have become the main route for the spread of exotic pests, posing significant risks in terms of biosecurity. The reason is that during transportation, the internal environment of the container is airtight, humid, and high-temperature, providing good conditions for the breeding of harmful organisms. In addition, the outer surface of the container may also be attached with eggs and animals, and the spread of various harmful organisms poses a serious threat to the biosecurity of each country. The MS sealants in the prior art can be given good antibacterial and antifungal properties by adding antibacterial and antifungal agents, reducing the breeding of harmful organisms and enhancing the biosecurity of containers. Or adding multifunctional POSS-based microcapsules containing insect repellent essential oils can give it better insect repellent effects and reduce the damage of harmful insects to the sealed joints of containers.

[0007] In the containers for the import and export shipping of logs, there are higher requirements for the antibacterial and antifungal properties of MS sealants, and they also need to have the effects of insect repellent and pest elimination. The MS sealants with insect repellent effects in the prior art cannot cope with the damage of termites to the sealed joints of containers. After termites damage the sealed joints of containers and enter the interior to gnaw the stored wood, it also brings ecological threats caused by organisms. The existing MS sealants can no longer meet the performance requirements of MS sealants in the containers for the import and export shipping of logs. There is an urgent need for a container biosecurity type silane-modified MS sealant with good antibacterial and antifungal properties and termite prevention. Summary of the Invention

[0008] In order to meet the performance requirements of MS sealants in the containers for the import and export shipping of logs that the existing MS sealants can no longer meet, the present invention provides a container biosecurity type silane-modified MS sealant.

[0009] The container biosecurity type silane-modified MS sealant provided by the present invention is achieved through the following technical solutions:

[0010] A container bio-safe silane-modified MS sealant is made from raw materials in the following mass percentages: 15-30 wt% of base glue, 40-60 wt% of filler composition, 12-20 wt% of plasticizer, 0.5-5 wt% of silane coupling agent, 0.5-1.5 wt% of organotin catalyst, 0.5-3.0 wt% of anti-aging agent, and 0.5-2.5 wt% of water remover; the filler composition includes base filler, thixotropic filler, antibacterial and mildew-proof filler, and pest-proof filler, and the thixotropic filler is spherical inorganic filler; the antibacterial and mildew-proof filler is a flaky inorganic filler with antibacterial and mildew-proof particles grafted on the surface, and the antibacterial and mildew-proof filler accounts for 1-6 wt% of the total mass of the filler composition; the pest-proof filler is a porous medium loaded with pest control agents, and the pest-proof filler accounts for 5-15 wt% of the total mass of the filler composition.

[0011] The MS sealant in the present invention has good adhesion, high elasticity, flexibility, environmental friendliness, resistance to damp heat aging performance and salt spray resistance, and at the same time has good antibacterial and mildew-proof performance and the effect of preventing pests and diseases, meeting the requirements of MS sealant for biosecurity.

[0012] Preferably, the thixotropic filler is at least one of spherical alumina, spherical alumina, spherical silica, and white carbon black; the thixotropic filler accounts for 5-25 wt% of the total mass of the filler composition.

[0013] In the present invention, using spherical inorganic filler as a thixotropic agent can, on the one hand, enhance the thixotropy and leveling property of the MS glue, making it easier to operate during construction, and can prevent the MS glue from sagging during construction, ensuring the smooth progress of construction. On the other hand, it can prevent the MS glue from stratifying or phase-separating during storage, maintaining its good fluidity, and can also prevent the MS glue from precipitating during storage, giving it good storage stability. In addition, the spherical inorganic thixotropic agent can adjust the viscosity of the MS glue, making it maintain ideal fluidity and viscosity during use and obtaining a better caulking and bonding effect.

[0014] Preferably, the flaky inorganic filler with antibacterial and mildew-proof particles grafted on the surface includes a flaky inorganic filler carrier and antibacterial and mildew-proof particles grafted on the surface of the flaky inorganic filler carrier through sol-gel method + hydrogen reduction reaction, and the antibacterial and mildew-proof particles are one or a combination of nano-scale silver clusters, copper clusters, zinc clusters, manganese clusters, iron clusters, and titanium clusters.

[0015] Preferably, the flaky inorganic filler is one or a combination of mica powder with an average particle size of 0.050-5.0 microns, molybdenum disulfide, flaky silicon nitride, and MXene two-dimensional material.

[0016] The sheet-like inorganic filler of the surface-grafted antibacterial and mildew-proof particles in the present invention can not only endow the MS sealant with good antibacterial and mildew-proof properties, but also its sheet-like structure can effectively improve the salt spray resistance of the MS sealant, better meeting the weather resistance requirements of the MS sealant for containers.

[0017] Preferably, the preparation method of the sheet-like inorganic filler of the surface-grafted antibacterial and mildew-proof particles is as follows: Dissolve the metal salt in deionized water to form a metal ion solution. After adding the sheet-like inorganic filler to the metal particle solution, perform ultrasonic dispersion treatment for 0.5 - 1 h. Add ammonia water or hydroxide to form a hydroxide colloid with -OH of the metal ions and load it on the sheet-like inorganic to form a hydroxide @ sheet-like inorganic composite colloid. After pressure filtration and vacuum drying, obtain a metal hydroxide @ sheet-like inorganic composite powder. Place it in an air atmosphere and calcine it at 400 - 700 °C for 1 - 4 h to form a nano metal oxide @ sheet-like inorganic composite powder. Finally, transfer it to a hydrogen atmosphere and perform calcination reduction at 400 - 700 °C for 1 - 4 h. The obtained solid powder is ball-milled and pulverized to obtain the sheet-like inorganic filler of the surface-grafted antibacterial and mildew-proof particles.

[0018] The preparation method of the antibacterial and mildew-proof filler in the present invention is relatively simple, facilitating large-scale production, reducing the production cost of the antibacterial and mildew-proof filler, and further reducing the total production cost of the MS sealant.

[0019] Preferably, the porous medium loaded with the insect repellent includes a porous medium carrier and an insect repellent loaded in the internal voids of the porous medium carrier. The porous medium carrier is any one or a combination of mesoporous silica, zeolite powder, porous ceramic powder, halloysite powder, and porous polylactic acid microspheres.

[0020] Preferably, the insect repellent is one or a combination of malathion, imidacloprid, nitenpyram, acetamiprid, thiacloprid, thiamethoxam, clothianidin, dinotefuran, spirotetramat, cyantraniliprole, sulfoxaflor, spinetoram, bifenazate, flupyradifurone, cyfluthrin, tetramethrin, deltamethrin, bifenthrin, ethofenprox, pyrethrum, benzyl benzoate, and imidacloprid powder.

[0021] Further preferably, the porous medium carrier is mesoporous silica, and the insect repellent is composed of imidacloprid in combination with at least one of deltamethrin and bifenthrin.

[0022] In the present invention, the pest control filler can conduct contact killing and prevention on insects with chewing mouthparts. The mesoporous silica loaded with the insect repellent can, on the one hand, effectively drive away pests, and on the other hand, improve the thixotropy, leveling property, and storage stability of the MS sealant. The advantage of using mesoporous silica as a spherical filler is that it can improve the fluidity of the MS sealant. The addition amount of the pest control filler has little influence on the viscosity and fluidity of the MS sealant, and the thixotropy, leveling property, and storage stability of the MS sealant can be ensured even under a high filler content. The amount of plasticizer can be reduced at the same viscosity, which can not only ensure the excellent caulking and bonding performance of the MS sealant, but also improve the mechanical tensile strength of the MS sealant.

[0023] Preferably, the preparation method of the porous medium loaded with the insect repellent: Put 5 - 10 parts by weight of the porous medium into reaction kettle A, and put 0.5 - 2 parts by weight of the insect repellent into reaction kettle B. Input 5 - 20 parts by weight of supercritical carbon dioxide into reaction kettle B. The pressure of the supercritical carbon dioxide is 30 - 40 MPa, and the temperature is 40 - 45 °C. The insect repellent is fully dissolved in the supercritical carbon dioxide to obtain an insect repellent solution. Input the obtained supercritical carbon dioxide-based insect repellent solution into reaction kettle A, stir and mix for 0.5 - 2 h, and remove the supercritical carbon dioxide under reduced pressure to obtain the porous medium loaded with the insect repellent.

[0024] The preparation method of the porous medium loaded with the insect repellent in the present invention is relatively simple, facilitating large-scale production, reducing the production cost of the antibacterial and mildew-proof filler, and thus reducing the total production cost of the MS sealant.

[0025] Preferably, the base filler consists of nano-calcium carbonate and heavy calcium carbonate in a mass ratio of 1:(0.1 - 0.3). The average particle size of the nano-calcium carbonate is 20 - 100 nm, and the average particle size of the heavy calcium carbonate is 5 - 50 microns.

[0026] The nano-calcium carbonate plays a role in toughening and strengthening the MS sealant. Its compounding with the heavy calcium carbonate to form the base filler can improve the mechanical strength, reduce the cost, processing performance, and storage stability of the MS sealant.

[0027] In summary, the present invention has the following advantages:

[0028] 1. The MS sealant in the present invention has good adhesion, high elasticity, flexibility, environmental friendliness, resistance to damp and heat aging, and salt spray resistance. At the same time, it also has good antibacterial and mildew-proof performance and the effect of preventing insect pests and diseases, meeting the requirements of the MS sealant for biosafety.

[0029] 2. In the present invention, the pest control filler is composed of a porous polylactic acid microsphere loaded with an insecticidal agent and a mesoporous silica loaded with a repellent agent, which endows the MS sealant with good biosafety performance. Moreover, the addition amount of the pest control filler has little influence on the viscosity and fluidity of the MS sealant, which can ensure the thixotropy, leveling property, and storage stability of the MS sealant, and endow the MS sealant with excellent caulking and bonding properties and painting and construction performance.

[0030] 3. In the present invention, the preparation methods of the antibacterial and antifungal filler and the pest control filler are relatively simple, which is convenient for large-scale production, reduces the production cost of the filler composition, and further reduces the total production cost of the MS sealant. Detailed Embodiments

[0031] In order to further understand the creativity and technological progress of the present invention, the preferred implementation schemes of the present invention will be described in detail below in combination with examples and comparative examples.

[0032] Example: A container biosafety type silane-modified MS sealant is made from the following raw materials in mass percentages: 15 - 30 wt% of a base rubber, 40 - 60 wt% of a filler composition, 12 - 20 wt% of a plasticizer, 0.5 - 5 wt% of a silane coupling agent, 0.5 - 1.5 wt% of an organotin catalyst, 0.5 - 3.0 wt% of an anti-aging aid, and 0.5 - 2.5 wt% of a water scavenger. The base rubber is an MS resin represented by Kaneka, such as silane-terminated polyether KANEKA MS POLYMER S303H, KANEKA MS POLYMER S203H. Or a GENIOSIL STP-E resin represented by Wacker, such as STP-E10. The plasticizer is any one of DOP, DCP, DBP, DINP, DPHP, DIDP, DINCH, polyether diol, and polyether triol. The silane coupling agent is any one of KH540, KH550, KH560, KH561, KH792, and KH602. The organotin catalyst is any one of dibutyltin dilaurate, stannous octoate, and dibutyltin diacetate. The water scavenger is any one of vinyltriethoxysilane KH151, vinyltrimethoxysilane KH171, and vinyltris(2-methoxyethoxy)silane KH172. The anti-aging aid is composed of an antioxidant and an ultraviolet light absorber, and the mass ratio of the antioxidant to the ultraviolet light absorber is 1:(0.6 - 1.2). The antioxidant is selected as a compound of antioxidant 1010 and antioxidant 168. The ultraviolet light absorber is a compound of UV-326 and UV-622.

[0033] The filler composition includes a base filler, a thixotropic filler, an antibacterial and antifungal filler, and a pest control filler.

[0034] The base filler consists of nano calcium carbonate and heavy calcium carbonate with a mass ratio of 1:(0.1 - 0.3). The average particle size of the nano calcium carbonate is 20 - 100 nm, and the average particle size of the heavy calcium carbonate is 5 - 50 microns.

[0035] The thixotropic filler is a spherical inorganic filler, and the thixotropic filler accounts for 5 - 25 wt% of the total mass of the filler composition. The thixotropic filler is at least one of spherical alumina, spherical silica powder, and spherical fumed silica.

[0036] The antibacterial and mildew-proof filler is a flaky inorganic filler grafted with antibacterial and mildew-proof particles on the surface. The antibacterial and mildew-proof filler accounts for 1 - 6 wt% of the total mass of the filler composition. The flaky inorganic filler grafted with antibacterial and mildew-proof particles on the surface includes a flaky inorganic filler carrier and antibacterial and mildew-proof particles grafted onto the surface of the flaky inorganic filler carrier through a sol-gel method + hydrogen reduction reaction. The flaky inorganic filler is one or a combination of muscovite powder, molybdenum disulfide, flaky silicon nitride, and MXene two-dimensional materials with an average particle size of 0.050 - 5.0 microns. The antibacterial and mildew-proof particles are one or a combination of nano silver clusters, nano copper clusters, nano zinc clusters, nano manganese clusters, nano iron clusters, and nano titanium clusters at the nanoscale.

[0037] The preparation method of the flaky inorganic filler grafted with antibacterial and mildew-proof particles on the surface is as follows: Dissolve the metal salt in deionized water to form a metal ion solution. After adding the flaky inorganic filler to the metal particle solution, perform ultrasonic dispersion treatment for 0.5 - 1 h. Add ammonia water or hydroxide to make the metal ions form a hydroxide colloid with -OH and load it on the flaky inorganic composite to form a hydroxide@flaky inorganic composite colloid. After vacuum filtration and vacuum drying, obtain a metal hydroxide@flaky inorganic composite powder. Place it in an air atmosphere and calcine it at 400 - 700 °C for 1 - 4 h to form a nano metal oxide@flaky inorganic composite powder. Finally, transfer it to a hydrogen atmosphere and calcine and reduce it at 400 - 700 °C for 1 - 4 h. The obtained solid powder is ball-milled and pulverized to obtain the flaky inorganic filler grafted with antibacterial and mildew-proof particles on the surface.

[0038] The pest control filler is a porous medium loaded with pest control agents. The pest control filler accounts for 5 - 15 wt% of the total mass of the filler composition. The porous medium loaded with pest control agents includes porous polylactic acid microspheres loaded with insecticidal agents and mesoporous silica loaded with insect repellent agents. The mass ratio of the porous polylactic acid microspheres loaded with insecticidal agents to the mesoporous silica loaded with insect repellent agents is 1:(0.5 - 2).

[0039] The insecticide in the porous polylactic acid microspheres loaded with insecticide is one or a combination of malathion, imidacloprid, nitenpyram, acetamiprid, thiacloprid, thiamethoxam, clothianidin, dinotefuran, spirotetramat, cyantraniliprole, sulfoxaflor, spinetoram, bifenazate, flupyradifurone, cyfluthrin, tetramethrin, deltamethrin, bifenthrin, etofenprox, silafluofen, benzyl benzoate, and imidacloprid powder.

[0040] The insect repellent in the mesoporous silica loaded with insect repellent is one or a combination of citronella extract, camphor leaf extract, wormwood extract, neem extract, and ginger extract.

[0041] Preparation method of porous polylactic acid microspheres loaded with insecticide: Place the porous polylactic acid microspheres on a wire mesh tray, load the wire mesh tray containing the porous polylactic acid microspheres in the middle of the reaction kettle, after purging the air with nitrogen, evacuate to a vacuum until the kettle pressure is 0.005 - 0.02 MPa, heat the insecticide to form an insecticide vapor and input it from the bottom of the reaction kettle, the flow rate of the insecticide vapor flowing in is 10 - 40 sccm, continuously input the insecticide vapor until the kettle pressure returns to normal pressure, and the porous polylactic acid microspheres loaded with insecticide can be obtained.

[0042] Preparation Example 1: The preparation method of nano - copper clusters @ muscovite powder is as follows:

[0043] Step 1. Add 100 mL of distilled water into a 250 mL beaker, add 2.5 g of anhydrous copper sulfate to the beaker and mix evenly, add 10 g of muscovite powder (2000 mesh, Wanshu Mineral Products Co., Ltd., Lingshou County), add a 0.1 mol / L sodium hydroxide solution at a rotation speed of 100 rpm until Cu is completely precipitated, adjust the rotation speed to 240 rpm and stir for 90 min, and let it stand for aging for 24 h to obtain a muscovite composite colloid.

[0044] Step 2. Wash the muscovite composite colloid three times with distilled water and then filter it to obtain a white solid powder. Place the obtained solid powder in a vacuum drying oven and dry it at 120 °C and a vacuum degree of 500 Pa for 6 h. Transfer the obtained solid powder to an atmosphere tube furnace for calcination treatment. Heat it to 650 °C at a rate of 20 °C / min in an air atmosphere and calcine for 3 h. Then, introduce a hydrogen - argon mixed gas into the atmosphere tube furnace, the volume ratio of hydrogen to argon in the hydrogen - argon mixed gas is 1:3, maintain the temperature at 650 °C for a calcination reduction reaction for 4 h, open the furnace and let it cool naturally to room temperature. Place the obtained white powder in a planetary ball mill, use zirconia as the grinding beads, first ball - mill at 300 rpm for 5 min, then ball - mill at 60 rpm for 25 min, and screen the discharged material with a 2500 - mesh sieve. The material screened out by the 2500 - mesh sieve is the nano - copper clusters @ muscovite powder.

[0045] Preparation Example 2: The preparation method of silver nanocluster@muscovite powder is as follows: Step 1. Add 100 mL of distilled water into a 250 mL beaker, add 1.7 g of silver nitrate into the beaker and mix evenly, add 10 g of 2000-mesh muscovite powder, add ammonia water with a concentration of 4 wt% at a rotation speed of 100 rpm until Ag is completely precipitated, adjust the rotation speed to 240 rpm and stir for 90 min, and let it stand for aging for 24 h to obtain a muscovite composite colloid;

[0046] Step 2. Wash the muscovite composite colloid three times with distilled water and then perform suction filtration to obtain a white solid powder. The obtained solid powder is placed in a vacuum drying oven and dried at 120 °C and a vacuum degree of 500 Pa for 6 h. The obtained solid powder is transferred to an atmosphere tube furnace for calcination treatment. It is heated to 450 °C at a rate of 20 °C / min in an air atmosphere and calcined for 3 h. Then, a hydrogen-argon mixed gas is introduced into the atmosphere tube furnace. The volume ratio of hydrogen to argon in the hydrogen-argon mixed gas is 1:3. The calcination reduction reaction is carried out at a temperature of 450 °C for 4 h. The furnace is opened and naturally cooled to room temperature. The obtained white powder is placed in a planetary ball mill, with zirconia as the grinding beads. First, ball mill at 300 rpm for 5 min, and then ball mill at 60 rpm for 25 min. The discharged material is screened with a 2500-mesh sieve, and the sifted material of the 2500-mesh sieve is the obtained silver nanocluster@muscovite powder.

[0047] The difference between Preparation Example 3 and Preparation Example 2 is that: the preparation method of silver nanocluster@silicon nitride powder is as follows: Step 1. Add 100 mL of distilled water into a 250 mL beaker, add 1.7 g of silver nitrate into the beaker and mix evenly, add 10 g of silicon nitride nanosheets (average thickness: <100 nm, sheet diameter: 1 - 3 μm, specific surface area: 30 m2 / g, particle morphology: sheet-like, appearance: white, Wuhan Kemike Biopharmaceutical Technology Co., Ltd.), add ammonia water with a concentration of 4 wt% at a rotation speed of 100 rpm until Ag is completely precipitated, adjust the rotation speed to 240 rpm and stir for 90 min, and let it stand for aging for 24 h to obtain a silicon nitride composite colloid.

[0048] The difference between Preparation Example 4 and Preparation Example 2 is that: the preparation method of silver nanocluster@molybdenum disulfide powder is as follows: Step 1. Add 100 mL of distilled water into a 250 mL beaker, add 1.7 g of silver nitrate into the beaker and mix evenly, add 10 g of ultrafine molybdenum disulfide (black, particle size 3 - 5 microns, CAS No. 1317 - 33 - 5, Ningbo Luofei Nano Technology Co., Ltd.), add ammonia water with a concentration of 4 wt% at a rotation speed of 100 rpm until Ag is completely precipitated, adjust the rotation speed to 240 rpm and stir for 90 min, and let it stand for aging for 24 h to obtain a molybdenum disulfide composite colloid.

[0049] Preparation Example 5: The preparation method of the mesoporous silica loaded with insecticidal agents is as follows: Put 500 g parts by weight of mesoporous silica (mesoporous spherical silica from Wuhu Xinda New Material Technology Co., Ltd., model XD-S200J, particle size 5 - 9 μm, pore diameter ≥ 200 nm, alcohol-modified, amphiphilic) into reactor A, and put 80 g parts by weight of the insect-proof agent - imidacloprid into reactor B. Input 1 kg of supercritical carbon dioxide into reactor B, with the pressure of the supercritical carbon dioxide being 40 MPa and the temperature being 40 °C. The insect-proof agent is fully dissolved in the supercritical carbon dioxide to obtain an insect-proof liquid medicine. Input the obtained insect-proof liquid medicine of supercritical carbon dioxide into reactor A, stir and mix for 12 h, and remove the supercritical carbon dioxide under reduced pressure to obtain the mesoporous silica loaded with imidacloprid.

[0050] Preparation Example 6: The preparation method of the mesoporous silica loaded with insect repellent agents is as follows: Put 500 g parts by weight of mesoporous silica XD-S200J into reactor A, and put 50 g parts by weight of the insect-proof agent - imidacloprid and 30 g of deltamethrin into reactor B. Input 1 kg of supercritical carbon dioxide into reactor B, with the pressure of the supercritical carbon dioxide being 40 MPa and the temperature being 40 °C. The insect-proof agent is fully dissolved in the supercritical carbon dioxide to obtain an insect-proof liquid medicine. Input the obtained insect-proof liquid medicine of supercritical carbon dioxide into reactor A, stir and mix for 12 h, and remove the supercritical carbon dioxide under reduced pressure to obtain the mesoporous silica loaded with imidacloprid + deltamethrin.

[0051] Preparation Example 7: The preparation method of the mesoporous silica loaded with insect repellent agents is as follows: Put 500 g parts by weight of mesoporous silica XD-S200J into reactor A, and put 50 g parts by weight of the insect-proof agent - imidacloprid and 30 g of bifenthrin into reactor B. Input 1 kg of supercritical carbon dioxide into reactor B, with the pressure of the supercritical carbon dioxide being 40 MPa and the temperature being 40 °C. The insect-proof agent is fully dissolved in the supercritical carbon dioxide to obtain an insect-proof liquid medicine. Input the obtained insect-proof liquid medicine of supercritical carbon dioxide into reactor A, stir and mix for 12 h, and remove the supercritical carbon dioxide under reduced pressure to obtain the mesoporous silica loaded with imidacloprid + bifenthrin.

[0052] Specific preferred implementation solutions

[0053] Example 1: A container biosecurity type silane-modified MS sealant is made from raw materials in the following mass percentages: 26.5 wt% of base rubber - silane-capped polyether KANEKA MS POLYMER S303H, 28.5 wt% of nano calcium carbonate, 12.25 wt% of heavy calcium carbonate, 4.75 wt% of spherical silica, 0.5 wt% of antibacterial and mildew-proof filler (nano copper cluster@muscovite powder in Preparation Example 1), 4 wt% of mesoporous silica loaded with imidacloprid in Preparation Example 5, 16 wt% of dipropylheptyl phthalate (DPHP), 4.45 wt% of silane coupling agent KH550 (γ-aminopropyltriethoxysilane), 0.55 wt% of organotin catalyst - dibutyltin dilaurate, 0.45 wt% of antioxidant 1010, 0.05 wt% of antioxidant 168, 0.3 wt% of UV-326, 0.2 wt% of UV-622, 1.5 wt% of water scavenger - vinyltriethoxysilane KH151.

[0054] Sources of raw materials: Silane-capped polyether KANEKA MS POLYMER S303H, supplied by Shanghai Huanyang Chemical Technology Co., Ltd. Nano calcium carbonate is Hakuenka Shirakaba DD of Shiraishi Kogyo Co., Ltd., and the precipitated calcium carbonate is surface-treated with rosin acid and has uniform ultrafine particles of 50 nm as primary particles. Heavy calcium carbonate is 2000 mesh, supplied by Shijiazhuang Weijia Mineral Products Co., Ltd. Spherical silica, with an average particle size of 100 nm, supplied by Shanghai Xiangtian Nano Materials Co., Ltd. Dipropylheptyl phthalate, CAS: 53306-54-0, supplied by Zhongshan Yuanda New Materials Co., Ltd. γ-aminopropyltriethoxysilane KH550 and vinyltriethoxysilane KH151, supplied by Hangzhou Jessica Chemical Co., Ltd. Dibutyltin dilaurate T12, supplied by Shandong Yunxin New Materials Technology Co., Ltd. Antioxidant 1010, antioxidant 168, UV-326, UV-622, supplied by Nanjing Milan Chemical Co., Ltd.

[0055] The preparation method of a container biosecurity type silane-modified MS sealant is as follows: Add 265 parts of base glue - silane-capped polyether KANEKA MS POLYMER S303H, 285 parts of nano calcium carbonate, 122.5 parts of heavy calcium carbonate, 475 parts of spherical silica, 5 parts of nano copper cluster @ muscovite powder in Preparation Example 1, 40 parts of imidacloprid-loaded mesoporous silica, 160 parts of dipropylheptyl phthalate, 44.5 parts of silane coupling agent KH550, 4.5 parts of antioxidant 1010, 0.5 part of antioxidant 168, 3 parts of UV-326, and 2 parts of UV-622 into a double planetary stirring kettle, stir and disperse at 120 °C and a vacuum degree of ≤ -0.095 MPa for 2 h. When the mixture cools to below 40 °C, add 15 parts of vinyltriethoxysilane KH151 and continue stirring for 15 min; finally, add 5.5 parts of dibutyltin dilaurate and stir for 30 min under a vacuum condition of ≤ -0.095 MPa, discharge, and fill to obtain the finished container biosecurity type silane-modified MS sealant.

[0056] The difference between Example 2 and Example 1 is that the container biosecurity type silane-modified MS sealant is made from the following raw materials by mass percentage: 26.5 wt% of base glue - silane-capped polyether KANEKA MS POLYMER S303H, 28.5 wt% of nano calcium carbonate, 11.75 wt% of heavy calcium carbonate, 4.75 wt% of spherical silica, 1 wt% of antibacterial and mildew-proof filler (nano copper cluster @ muscovite powder in Preparation Example 1), 4 wt% of imidacloprid-loaded mesoporous silica, 16 wt% of dipropylheptyl phthalate, 4.45 wt% of silane coupling agent KH550, 0.55 wt% of organotin catalyst - dibutyltin dilaurate, 0.45 wt% of antioxidant 1010, 0.05 wt% of antioxidant 168, 0.3 wt% of UV-326, 0.2 wt% of UV-622, and 1.5 wt% of water remover - vinyltriethoxysilane KH151.

[0057] Example 3 is different from Example 1 in that the container bio-safe silane-modified MS sealant is made of raw materials with the following mass percentages: 26.5 wt% of the base rubber - silane-capped polyether KANEKA MS POLYMER S303H, 28.5 wt% of nano calcium carbonate, 11.25 wt% of heavy calcium carbonate, 4.75 wt% of spherical silica, 1.5 wt% of antibacterial and mildew-proof filler (nano copper cluster @ mica powder in Preparation Example 1), 4 wt% of imidacloprid-loaded mesoporous silica in Preparation Example 5, 16 wt% of dipropylheptyl phthalate, 4.45 wt% of silane coupling agent KH550, 0.55 wt% of organotin catalyst - dibutyltin dilaurate, 0.45 wt% of antioxidant 1010, 0.05 wt% of antioxidant 168, 0.3 wt% of UV-326, 0.2 wt% of UV-622, 1.5 wt% of water scavenger - vinyltriethoxysilane KH151.

[0058] Example 4 is different from Example 1 in that the container bio-safe silane-modified MS sealant is made of raw materials with the following mass percentages: 26.5 wt% of the base rubber - silane-capped polyether KANEKA MS POLYMER S303H, 28.5 wt% of nano calcium carbonate, 10.75 wt% of heavy calcium carbonate, 4.75 wt% of spherical silica, 2 wt% of antibacterial and mildew-proof filler (nano copper cluster @ mica powder in Preparation Example 1), 4 wt% of imidacloprid-loaded mesoporous silica in Preparation Example 5, 16 wt% of dipropylheptyl phthalate, 4.45 wt% of silane coupling agent KH550, 0.55 wt% of organotin catalyst - dibutyltin dilaurate, 0.45 wt% of antioxidant 1010, 0.05 wt% of antioxidant 168, 0.3 wt% of UV-326, 0.2 wt% of UV-622, 1.5 wt% of water scavenger - vinyltriethoxysilane KH151.

[0059] Example 5 is different from Example 1 in that the container bio-safe silane-modified MS sealant is made from raw materials in the following mass percentages: 26.5 wt% of base rubber - silane-capped polyether KANEKA MS POLYMER S303H, 28.5 wt% of nano calcium carbonate, 9.75 wt% of heavy calcium carbonate, 4.75 wt% of spherical silica, 3 wt% of antibacterial and mildew-proof filler (nano copper cluster @ muscovite powder in Preparation Example 1), 4 wt% of mesoporous silica loaded with imidacloprid in Preparation Example 5, 16 wt% of dipropylheptyl phthalate, 4.45 wt% of silane coupling agent KH550, 0.55 wt% of organic tin catalyst - dibutyltin dilaurate, 0.45 wt% of antioxidant 1010, 0.05 wt% of antioxidant 168, 0.3 wt% of UV-326, 0.2 wt% of UV-622, 1.5 wt% of water scavenger - vinyltriethoxysilane KH151.

[0060] Example 6 is different from Example 1 in that the container bio-safe silane-modified MS sealant is made from raw materials in the following mass percentages: 26.5 wt% of base rubber - silane-capped polyether KANEKA MS POLYMER S303H, 28.5 wt% of nano calcium carbonate, 11.75 wt% of heavy calcium carbonate, 4.75 wt% of spherical silica, 0.5 wt% of nano copper cluster @ muscovite powder in Preparation Example 1, 0.5 wt% of nano silver cluster @ muscovite powder in Preparation Example 2, 4 wt% of mesoporous silica loaded with imidacloprid in Preparation Example 5, 16 wt% of dipropylheptyl phthalate, 4.45 wt% of silane coupling agent KH550, 0.55 wt% of organic tin catalyst - dibutyltin dilaurate, 0.45 wt% of antioxidant 1010, 0.05 wt% of antioxidant 168, 0.3 wt% of UV-326, 0.2 wt% of UV-622, 1.5 wt% of water scavenger - vinyltriethoxysilane KH151.

[0061] Example 7 is different from Example 6 in that the container bio-safe silane-modified MS sealant is made from the following raw materials by mass percentage: 26.5 wt% of base rubber - silane-capped polyether KANEKA MS POLYMER S303H, 28.5 wt% of nano calcium carbonate, 11.75 wt% of heavy calcium carbonate, 4.75 wt% of spherical silica, 0.5 wt% of nano copper cluster@muscovite powder in Preparation Example 1, 0.5 wt% of nano silver cluster@silicon nitride powder in Preparation Example 3, 4 wt% of imidacloprid-loaded mesoporous silica in Preparation Example 5, 16 wt% of dipropylheptyl phthalate, 4.45 wt% of silane coupling agent KH550, 0.55 wt% of organotin catalyst - dibutyltin dilaurate, 0.45 wt% of antioxidant 1010, 0.05 wt% of antioxidant 168, 0.3 wt% of UV-326, 0.2 wt% of UV-622, 1.5 wt% of water scavenger - vinyltriethoxysilane KH151.

[0062] Example 8 is different from Example 6 in that the container bio-safe silane-modified MS sealant is made from the following raw materials by mass percentage: 26.5 wt% of base rubber - silane-capped polyether KANEKA MS POLYMER S303H, 28.5 wt% of nano calcium carbonate, 11.75 wt% of heavy calcium carbonate, 4.75 wt% of spherical silica, 0.5 wt% of nano copper cluster@muscovite powder in Preparation Example 1, 0.5 wt% of nano silver cluster@molybdenum disulfide powder in Preparation Example 4, 4 wt% of imidacloprid-loaded mesoporous silica in Preparation Example 5, 16 wt% of dipropylheptyl phthalate, 4.45 wt% of silane coupling agent KH550, 0.55 wt% of organotin catalyst - dibutyltin dilaurate, 0.45 wt% of antioxidant 1010, 0.05 wt% of antioxidant 168, 0.3 wt% of UV-326, 0.2 wt% of UV-622, 1.5 wt% of water scavenger - vinyltriethoxysilane KH151.

[0063] Example 9 is different from Example 7 in that the container bio-safe silane-modified MS sealant is made of raw materials in the following mass percentages: 26.5 wt% of base rubber - silane-capped polyether KANEKA MS POLYMER S303H, 28.5 wt% of nano calcium carbonate, 11.75 wt% of heavy calcium carbonate, 4 wt% of spherical silica, 0.75 wt% of spherical alumina, 0.5 wt% of the nano copper cluster @ muscovite powder in Preparation Example 1, 0.5 wt% of the nano silver cluster @ silicon nitride powder in Preparation Example 3, 4 wt% of the imidacloprid-loaded mesoporous silica in Preparation Example 5, 16 wt% of dipropylheptyl phthalate, 4.45 wt% of silane coupling agent KH550, 0.55 wt% of organic tin catalyst - dibutyltin dilaurate, 0.45 wt% of antioxidant 1010, 0.05 wt% of antioxidant 168, 0.3 wt% of UV-326, 0.2 wt% of UV-622, 1.5 wt% of water scavenger - vinyltriethoxysilane KH151.

[0064] Example 10 is different from Example 7 in that the container bio-safe silane-modified MS sealant is made of raw materials in the following mass percentages: 26.5 wt% of base rubber - silane-capped polyether KANEKA MS POLYMER S303H, 28.5 wt% of nano calcium carbonate, 12.5 wt% of heavy calcium carbonate, 5.5 wt% of spherical silica, 0.5 wt% of the nano copper cluster @ muscovite powder in Preparation Example 1, 0.5 wt% of the nano silver cluster @ silicon nitride powder in Preparation Example 3, 2.5 wt% of the imidacloprid-loaded mesoporous silica in Preparation Example 5, 16 wt% of dipropylheptyl phthalate, 4.45 wt% of silane coupling agent KH550, 0.55 wt% of organic tin catalyst - dibutyltin dilaurate, 0.45 wt% of antioxidant 1010, 0.05 wt% of antioxidant 168, 0.3 wt% of UV-326, 0.2 wt% of UV-622, 1.5 wt% of water scavenger - vinyltriethoxysilane KH151.

[0065] Example 11 is different from Example 7 in that the container bio-safe silane-modified MS sealant is made of the following raw materials by mass percentage: 26.5 wt% of base rubber - silane-capped polyether KANEKA MS POLYMER S303H, 28.5 wt% of nano calcium carbonate, 11 wt% of heavy calcium carbonate, 4.5 wt% of spherical silica, 0.5 wt% of nano copper cluster@muscovite powder in Preparation Example 1, 0.5 wt% of nano silver cluster@silicon nitride powder in Preparation Example 3, 5 wt% of imidacloprid-loaded mesoporous silica in Preparation Example 5, 16 wt% of dipropylheptyl phthalate, 4.45 wt% of silane coupling agent KH550, 0.55 wt% of organotin catalyst - dibutyltin dilaurate, 0.45 wt% of antioxidant 1010, 0.05 wt% of antioxidant 168, 0.3 wt% of UV-326, 0.2 wt% of UV-622, 1.5 wt% of water scavenger - vinyltriethoxysilane KH151.

[0066] Example 12 is different from Example 7 in that the container bio-safe silane-modified MS sealant is made of the following raw materials by mass percentage: 26.5 wt% of base rubber - silane-capped polyether KANEKA MS POLYMER S303H, 28.5 wt% of nano calcium carbonate, 9.5 wt% of heavy calcium carbonate, 3.5 wt% of spherical silica, 0.5 wt% of nano copper cluster@muscovite powder in Preparation Example 1, 0.5 wt% of nano silver cluster@silicon nitride powder in Preparation Example 3, 7.5 wt% of imidacloprid-loaded mesoporous silica in Preparation Example 5, 16 wt% of dipropylheptyl phthalate, 4.45 wt% of silane coupling agent KH550, 0.55 wt% of organotin catalyst - dibutyltin dilaurate, 0.45 wt% of antioxidant 1010, 0.05 wt% of antioxidant 168, 0.3 wt% of UV-326, 0.2 wt% of UV-622, 1.5 wt% of water scavenger - vinyltriethoxysilane KH151.

[0067] Example 13 is different from Example 10 in that the imidacloprid-loaded mesoporous silica in Preparation Example 5 is replaced by the imidacloprid + deltamethrin-loaded mesoporous silica in Preparation Example 6.

[0068] Example 14 is different from Example 10 in that the imidacloprid-loaded mesoporous silica in Preparation Example 5 is replaced by the imidacloprid + bifenthrin-loaded mesoporous silica in Preparation Example 6.

[0069] Example 15 is different from Example 11 in that the container bio-safe silane-modified MS sealant is made of the following raw materials in mass percentages: 26.5 wt% of silane-terminated polyether KANEKA MS POLYMER S303H, 28.5 wt% of nano calcium carbonate, 11 wt% of heavy calcium carbonate, 4.5 wt% of spherical silica, 0.5 wt% of nano copper cluster@muscovite powder in Preparation Example 1, 0.5 wt% of nano silver cluster@silicon nitride powder in Preparation Example 3, 5 wt% of mesoporous silica loaded with insect repellent in Preparation Example 5, 6 wt% of dipropylheptyl phthalate, 10 wt% of polypropylene glycol EP-330NG with a molecular weight of 5000, 4.45 wt% of silane coupling agent KH550, 0.55 wt% of organic tin catalyst - dibutyltin dilaurate, 0.45 wt% of antioxidant 1010, 0.05 wt% of antioxidant 168, 0.3 wt% of UV-326, 0.2 wt% of UV-622, 1.5 wt% of vinyltriethoxysilane KH151

[0070] Example 16 is different from Example 11 in that the container bio-safe silane-modified MS sealant is made of the following raw materials in mass percentages: 26.5 wt% of silane-terminated polyether KANEKA MS POLYMER S303H, 28.5 wt% of nano calcium carbonate, 11 wt% of heavy calcium carbonate, 4.5 wt% of spherical silica, 0.5 wt% of nano copper cluster@muscovite powder in Preparation Example 1, 0.5 wt% of nano silver cluster@silicon nitride powder in Preparation Example 3, 5 wt% of mesoporous silica loaded with insect repellent in Preparation Example 5, 16 wt% of polypropylene glycol EP-330NG with a molecular weight of 5000, 4.45 wt% of silane coupling agent KH550, 0.55 wt% of organic tin catalyst - dibutyltin dilaurate, 0.45 wt% of antioxidant 1010, 0.05 wt% of antioxidant 168, 0.3 wt% of UV-326, 0.2 wt% of UV-622, 1.5 wt% of water scavenger - vinyltriethoxysilane KH151.

[0071] Example 17 is different from Example 1 in that the nano calcium carbonate is replaced with nano calcium carbonate from Zhejiang Manli Nano Technology Co., Ltd., model ML-CaCO3-N50, particle size 50 nm, quasi-spherical, white.

[0072] The difference between Comparative Example 1 and Example 1 is that the container biosecurity type silane-modified MS sealant is made of raw materials in the following mass percentages: 26.5 wt% of base rubber - silane-capped polyether KANEKA MS POLYMER S303H, 29.15 wt% of nano calcium carbonate, 12.85 wt% of heavy calcium carbonate, 4.75 wt% of spherical silica, 16 wt% of dipropylheptyl phthalate (DPHP), 4.45 wt% of silane coupling agent KH550 (γ-aminopropyltriethoxysilane), 0.55 wt% of organotin catalyst - dibutyltin dilaurate, 0.45 wt% of antioxidant 1010, 0.05 wt% of antioxidant 168, 0.3 wt% of UV-326, 0.2 wt% of UV-622, 1.5 wt% of water scavenger - vinyltriethoxysilane KH151.

[0073] The difference between Comparative Example 2 and Example 1 is that the container biosecurity type silane-modified MS sealant is made of raw materials in the following mass percentages: 26.5 wt% of silane-capped polyether KANEKA MS POLYMER S303H, 28.5 wt% of nano calcium carbonate, 12.25 wt% of heavy calcium carbonate, 4.75 wt% of spherical silica, 0.5 wt% of muscovite powder, 4 wt% of mesoporous silica loaded with insecticidal agents in Preparation Example 5, 16 wt% of dipropylheptyl phthalate, 4.45 wt% of silane coupling agent KH550, 0.55 wt% of organotin catalyst - dibutyltin dilaurate, 0.45 wt% of antioxidant 1010, 0.05 wt% of antioxidant 168, 0.3 wt% of UV-326, 0.2 wt% of UV-622, 1.5 wt% of water scavenger KH151.

[0074] The difference between Comparative Example 3 and Example 1 is that the container biosecurity type silane-modified MS sealant is made of raw materials in the following mass percentages: 26.5 wt% of base rubber - silane-capped polyether KANEKA MS POLYMER S303H, 28.5 wt% of nano calcium carbonate, 12.5 wt% of heavy calcium carbonate, 4.75 wt% of spherical silica, 0.25 wt% of nano copper cluster@muscovite powder in Preparation Example 1, 4 wt% of mesoporous silica loaded with insecticidal agents in Preparation Example 5, 16 wt% of dipropylheptyl phthalate, 4.45 wt% of silane coupling agent KH550, 0.55 wt% of organotin catalyst - dibutyltin dilaurate, 0.45 wt% of antioxidant 1010, 0.05 wt% of antioxidant 168, 0.3 wt% of UV-326, 0.2 wt% of UV-622, 1.5 wt% of vinyltriethoxysilane KH151.

[0075] The difference between Comparative Example 4 and Example 1 lies in that the container bio-safe silane-modified MS sealant is made of the following raw materials by mass percentage: 26.5 wt% of base rubber - silane-capped polyether KANEKA MS POLYMER S303H, 28.5 wt% of nano calcium carbonate, 12.25 wt% of heavy calcium carbonate, 4.75 wt% of spherical silica, 0.5 wt% of the nano copper cluster @ mica powder in Preparation Example 1, 4 wt% of mesoporous silica XD-S200J, 16 wt% of dipropylheptyl phthalate, 4.45 wt% of silane coupling agent KH550, 0.55 wt% of organotin catalyst - dibutyltin dilaurate, 0.45 wt% of antioxidant 1010, 0.05 wt% of antioxidant 168, 0.3 wt% of UV-326, 0.2 wt% of UV-622, 1.5 wt% of water scavenger - vinyltriethoxysilane KH151.

[0076] The difference between Comparative Example 5 and Example 1 lies in that the container bio-safe silane-modified MS sealant is made of the following raw materials by mass percentage: 26.5 wt% of silane-capped polyether KANEKA MS POLYMER S303H, 28.5 wt% of nano calcium carbonate, 12.5 wt% of heavy calcium carbonate, 7.5 wt% of spherical silica, 0.5 wt% of the nano copper cluster @ mica powder in Preparation Example 1, 1 wt% of mesoporous silica loaded with insect repellent in Preparation Example 5, 16 wt% of dipropylheptyl phthalate, 4.45 wt% of silane coupling agent KH550, 0.55 wt% of organotin catalyst - dibutyltin dilaurate, 0.45 wt% of antioxidant 1010, 0.05 wt% of antioxidant 168, 0.3 wt% of UV-326, 0.2 wt% of UV-622, 1.5 wt% of vinyltriethoxysilane KH151.

[0077] Performance detection test 1. The mildew-proof performance was determined according to "GB / T 13477.25-2024 Test methods for building sealants - Part 25: Determination of mildew resistance".

[0078] Performance detection test 2. The antibacterial performance was determined according to QB / T 2591-2023 (Test methods for antibacterial properties and antibacterial effects of antibacterial plastics). For the test bacteria, Escherichia coli (ATCC25922) and Staphylococcus aureus (ATCC 6538) were selected as representatives of Gram-negative and Gram-positive bacteria. The quantitative test was carried out by the film sticking method. After the antibacterial rubber was in contact with the culture medium containing the bacterial solution for a certain time (such as 24 h), the antibacterial rate was calculated by the plate counting method. If the antibacterial rate > 90%, it can be determined that the sealant has Class II antibacterial performance. If the antibacterial rate > 99%, it can be determined that the sealant has Class I antibacterial performance.

[0079] Performance Detection Test 3. Biosafety Test: The MS sealant is frozen with liquid nitrogen and then crushed to obtain test powder sifted through a 500-mesh sieve. 1 part of the test powder is mixed evenly with 99 parts of pine sawdust as termite food. An MGSS test barrel is made of MGSS stainless steel, with a wall thickness of 0.8 mm, an inner diameter of 50 cm, and a height of 30 cm. The inner bottom of the MGSS test barrel is divided into a concentric food placement area with a diameter of 10 cm. On the concentric food placement area, 2 mm of termite food is evenly spread, and 100 termites are placed. After 48 h, the survival situation of the termites is observed. If the termite survival rate ≤ 20%, the MS sealant has Class II biosafety; if the termite survival rate ≤ 10%, the MS sealant has Class I biosafety.

[0080] Table 1: Biosafety Test Parameter Table of MS Sealant in Examples 1-17 and Comparative Examples 1-5

[0081]

[0082] Combined with Examples 1-5 and Comparative Examples 1-3 and Table 1, it can be seen that when the addition amount of the antibacterial and mildew-proof filler ≥ 0.5 wt%, the MS sealant can be given a good bactericidal effect of Class II (>90%). When the addition amount of the antibacterial and mildew-proof filler ≥ 1.0 wt%, the MS sealant can be given a good bactericidal effect of Class I (>99%).

[0083] Combined with Examples 1-5 and Examples 6-8 and Table 1, it can be seen that when the addition amount of the antibacterial and mildew-proof filler is 0.5 wt%, the MS sealant prepared by using any one of nano copper clusters@muscovite powder, nano copper clusters@silicon nitride, and nano copper clusters@molybdenum disulfide in combination with nano copper clusters@muscovite powder has a good bactericidal effect of Class I (>99%). The antibacterial and mildew-proof property of the sheet-like inorganic filler loaded with nano silver clusters is better.

[0084] Combined with Example 7, Examples 8-14 and Comparative Examples 4-5 and Table 1, it can be seen that when the addition amount of the pest control filler ≥ 2.5 wt%, the MS sealant can be given Class II biosafety. When the addition amount of the pest control filler ≥ 4.0 wt%, the MS sealant can be given Class I biosafety. And when the addition amount of the pest control filler is 2.5 wt%, the MS sealant prepared by using the pest control fillers in Preparation Examples 6 and 7 has Class I biosafety, that is, the pest control fillers in Preparation Examples 6 and 7 have better pest control effects.

[0085] Performance Detection Test 4. Skin Drying Time: The test is carried out in accordance with Method 8.2B specified in GB / T 13477.5-2024 - Test Methods for Building Sealant Materials - Part 5: Determination of Skin Drying Time.

[0086] Performance detection test 5.1. Tensile strength was determined in accordance with GB / T 528-2009.

[0087] Performance detection test 5.2. Bond strength was tested in accordance with GB / T 7124-2008 Determination of tensile shear strength of adhesives (rigid material to rigid material).

[0088] Performance detection test 6. Damp heat resistance test. The tensile strength and bond strength of the sealant were determined in accordance with GB / T 28-2009 after being placed at 90 °C / 85% humidity for 300 h.

[0089] Performance detection test 7. Salt spray resistance test. The sealant was immersed in artificial seawater (pH of artificial seawater = 8, temperature = 40 °C, sodium chloride concentration = 3.50%) for 168 h, and the tensile strength and bond strength of the sealant were determined in accordance with GB / T 28-2009.

[0090] Table 2: Mechanical property test parameters of MS sealants in Examples 1-17 and Comparative Examples 1-5

[0091]

[0092]

[0093] Combined with Examples 1-5 and Comparative Examples 1-3 and combined with Tables 1-2, it can be seen that the addition of mica powder or antibacterial and mildew-proof filler can improve the damp heat aging resistance and salt spray resistance of MS sealants. Compared with mica powder, the addition of antibacterial and mildew-proof filler not only improves the damp heat aging resistance and salt spray resistance of MS sealants, but also endows MS sealants with good biosafety performance (antibacterial and mildew-proof performance).

[0094] Combined with Examples 1, 10-14 and Comparative Examples 3-4 and combined with Tables 1-2, it can be seen that the addition of insect-proof filler has basically no adverse effect on the damp heat aging resistance and salt spray resistance of MS sealants, and can improve the good biosafety performance (insect-proof performance) of MS sealants.

[0095] Combined with Example 1 and Example 17 and combined with Tables 1-2, it can be seen that the MS sealant prepared by using Hakuenka white cloud flower DD of Shiraishi Kogyo Co., Ltd. and rosin acid surface-modified precipitated calcium carbonate has relatively good mechanical properties and bond strength, and also has relatively better damp heat aging resistance and salt spray resistance.

[0096] Combined with Example 10 and Examples 15-16 and in combination with Tables 1-2, it can be seen that using polypropylene glycol EP-330NG with a molecular weight of 5000 as a plasticizer or using a compound of polypropylene glycol EP-330NG with a molecular weight of 5000 and dipropylheptyl phthalate as a plasticizer can improve the mechanical properties and bonding strength of the prepared MS sealant relatively well, and the resistance to damp heat aging and salt spray properties are also relatively better. However, it should be noted that the MS sealant prepared with polypropylene glycol EP-330NG with a molecular weight of 5000 as a plasticizer has a relatively higher viscosity, and its extrusion fluidity is slightly worse than that of the MS sealant prepared with dipropylheptyl phthalate as a plasticizer, that is, the caulking and bonding performance decreases slightly. Using a compound of polypropylene glycol EP-330NG with a molecular weight of 5000 and dipropylheptyl phthalate as a plasticizer, the prepared MS sealant has relatively good mechanical properties, bonding strength, resistance to damp heat aging and salt spray properties, and the extrusion fluidity can also be adjusted by controlling the content of dipropylheptyl phthalate, and the caulking and bonding performance is better than that of the MS sealant prepared with polypropylene glycol EP-330NG with a molecular weight of 5000 as a plasticizer. According to the requirements of the application scenario, select MS sealant products with different caulking and bonding properties and physical and chemical properties.

[0097] In summary, the MS sealant in the present invention has good adhesiveness, high elasticity, flexibility, environmental friendliness, resistance to damp heat aging and salt spray properties, and at the same time has good antibacterial and antifungal properties and the effect of preventing pests and diseases, meeting the requirements of MS sealant for biosafety.

[0098] It should be noted that: This specific embodiment is only an explanatory illustration of the technical solution of the present invention, and it is not a limitation of the present invention. Those skilled in the art can make modifications without creative contributions to this embodiment according to needs after reading this specification, but as long as it is within the scope of the claims of the present invention, it is protected by the patent law.

Claims

1. A biosafety silane-modified MS sealant for containers, characterized by: The invention is made of the following raw materials in percentage by weight: 15-30 wt% of a base glue, 40-60 wt% of a filler composition, 12-20 wt% of a plasticizer, 0.5-5 wt% of a silane coupling agent, 0.5-1.5 wt% of an organic tin catalyst, 0.5-3.0 wt% of an anti-aging aid, and 0.5-2.5 wt% of a dewatering agent; the filler composition comprises a basic filler, a thixotropic filler, an antibacterial and mildew-proof filler, and an insect-proof filler, wherein the thixotropic filler is a spherical inorganic filler; the antibacterial and mildew-proof filler is a flaky inorganic filler with antibacterial and mildew-proof particles grafted on the surface, and the antibacterial and mildew-proof filler accounts for 1-6 wt% of the total mass of the filler composition; the insect-proof filler is a porous medium loaded with an insect repellent, and the insect-proof filler accounts for 5-15 wt% of the total mass of the filler composition.

2. The biosafety silane-modified MS sealant for containers according to claim 1, characterized in that: The thixotropic filler is at least one of spherical alumina, spherical alumina, spherical silica, and white carbon black; the thixotropic filler accounts for 5-25wt% of the total mass of the filler composition.

3. The biosafety silane-modified MS sealant for containers according to claim 1, characterized in that: The flaky inorganic filler with surface-grafted antibacterial and mildew-proof particles comprises a flaky inorganic filler carrier and antibacterial and mildew-proof particles grafted on the surface of the flaky inorganic filler carrier by a sol-gel method + hydrogen reduction reaction, wherein the antibacterial and mildew-proof particles are one or a combination of nano-scale nanosilver clusters, nano-copper clusters, nano-zinc clusters, nano-manganese clusters, nano-iron clusters, and nano-titanium clusters.

4. The biosafety silane-modified MS sealant for containers according to claim 3, characterized in that: The flaky inorganic filler is one or a combination of muscovite powder with an average particle size of 0.050-5.0 microns, molybdenum disulfide, flaky silicon nitride, and MXene two-dimensional materials.

5. The biosafety silane-modified MS sealant for containers according to claim 4, characterized in that: The preparation method of the flaky inorganic filler with surface grafted antibacterial and mildew-proof particles is as follows: a metal salt solvent is dissolved in deionized water to form a metal ion solution, the flaky inorganic filler is added to the metal particle solution and then ultrasonically dispersed for 0.5-1h, ammonia water or hydroxide is added to allow the metal ions to react with -OH to form a hydroxide colloid loaded on the flaky inorganic composite to form a hydroxide@flaky inorganic composite colloid, and metal hydroxide@flaky inorganic composite powder is obtained through reduced pressure filtration and vacuum drying, which is placed in an air atmosphere and calcined at 400-700°C for 1-4h to form nano-metal oxide@flaky inorganic composite powder, and finally the flaky inorganic filler is transferred to a hydrogen atmosphere and calcined and reduced at 400-700°C for 1-4h, and the obtained solid powder is ball-milled to obtain the flaky inorganic filler with surface grafted antibacterial and mildew-proof particles.

6. The biosafety silane-modified MS sealant for containers according to claim 1, characterized in that: The porous medium loaded with insect repellent comprises a porous medium carrier and the insect repellent loaded in the internal voids of the porous medium carrier. The porous medium carrier is any one or more combinations of mesoporous silica, zeolite powder, porous ceramic powder, halloysite powder, and porous polylactic acid microspheres.

7. The biosafety silane-modified MS sealant for containers according to claim 6, characterized in that: The insect repellent is one or a combination of malathion, imidacloprid, nitenpyram, acetamiprid, thiacloprid, thiamethoxam, clothianidin, dinotefuran, spirotetramat, cyanamide, sulfoxaflor, spinetoram, bifenazate, flupyrazone, cyfluthrin, tetrathrin, deltamethrin, bifenthrin, ethathrin, pseudocyanurate, benzyl borate benzoate, and imidacloprid powder.

8. The biosafety silane-modified MS sealant for containers according to claim 7, characterized in that: The porous medium carrier is mesoporous silica, and the insect repellent is a compound of imidacloprid and at least one of deltamethrin and bifenthrin.

9. The biosafety silane-modified MS sealant for containers according to claim 7, characterized in that: The preparation method of the porous medium loaded with insect repellent comprises the following steps: putting 5-10 parts by weight of the porous medium into a reactor A, putting 0.5-2 parts by weight of the insect repellent into a reactor B, inputting 5-20 parts by weight of supercritical carbon dioxide into the reactor B, wherein the pressure of the supercritical carbon dioxide is 30-40 MPa and the temperature is 40-45° C., the insect repellent is fully dissolved in the supercritical carbon dioxide to obtain an insect repellent liquid, inputting the obtained insect repellent liquid obtained by supercritical carbon dioxide into the reactor A, stirring and mixing for 0.5-2 hours, and removing the supercritical carbon dioxide under reduced pressure to obtain the porous medium loaded with the insect repellent.

10. The biosafety silane-modified MS sealant for containers according to claim 1, characterized in that: The basic filler is composed of nano calcium carbonate and heavy calcium carbonate in a mass ratio of 1:(0.1-0.3), the average particle size of the nano calcium carbonate is 20-100 nm, and the average particle size of the heavy calcium carbonate is 5-50 microns.

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