Anti-termite silane modified MS sealant

Abstract

The invention relates to the technical field of MS sealant preparation, in particular to an anti-termite silane modified MS sealant. The anti-termite silane modified MS sealant is prepared from the following raw materials in parts by weight: 100 parts of a silane modified polyether resin composition, 5-20 parts of aliphatic epoxy resin, 50-100 parts of a plasticizer, 50-200 parts of a filler composition, 5-10 parts of an anti-termite additive, 0.5-2 parts of an aromatic imine latent curing agent, 0.05-2 parts of an organic tin catalyst, 5-15 parts of a coupling agent, 1-10 parts of a water removal agent and 5-25 parts of a thixotropic agent. And 2-10 parts of an anti-aging auxiliary agent. The termite repellent material has the effect of repelling termites, has good ultraviolet aging resistance and mechanical property, can improve the disease and pest erosion resistance of the container, and can improve the freight safety performance.

Description

Technical Field

[0001] The present application relates to the technical field of MS sealant preparation, and particularly relates to a termite-proof silane-modified MS sealant. Background Art

[0002] Silane-modified polyether sealant is a high-performance environmentally friendly sealant based on a polyether resin terminated with an alkoxysilane. Due to its main-chain polyether structural unit and terminal silane structure, the silane-modified polyether sealant combines the advantages of silicone sealant and polyurethane sealant, showing high anti-deformation displacement ability, good adhesiveness, paintability, environmental friendliness, and easy operability, etc., and is thus widely used in the fields of construction, industry, rail transit, interior decoration, etc.

[0003] In recent years, public health and safety incidents and alien species invasion incidents caused by imported containers have been reported from time to time. The pest problems encountered in container transportation have become increasingly prominent. The hardest-hit areas with frequent pest occurrences mainly focus on refrigerated goods, food goods, or other containers that may inadvertently transport harmful organisms.

[0004] However, the existing silane-modified polyether sealant has a poor termite-proof effect. Termites can damage the sealant structure and escape from the container gap, causing serious termite invasion hazards, resulting in its inability to meet the pest control performance requirements of container sealants. For this reason, the invention provides a termite-proof silane-modified MS sealant. Summary of the Invention

[0005] In order to solve the problem of the poor termite-proof effect of the existing silane-modified polyether sealant, the present invention provides a termite-proof silane-modified MS sealant.

[0006] The termite-proof silane-modified MS sealant provided by the present invention is achieved through the following scheme:

[0007] A termite-proof silane-modified MS sealant is made from the following raw materials in parts by weight: 100 parts of silane-modified polyether resin composition, 5 - 20 parts of aliphatic epoxy resin, 50 - 100 parts of plasticizer, 50 - 200 parts of filler composition, 5 - 10 parts of termite-proof auxiliary, 0.5 - 2 parts of aromatic imine type latent curing agent, 0.05 - 0.5 parts of organotin catalyst, 5 - 15 parts of coupling agent, 1 - 10 parts of water remover, 5 - 25 parts of thixotropic agent, 2 - 6 parts of anti-ultraviolet aging auxiliary, 2 - 6 parts of antioxidant auxiliary.

[0008] In the present invention, a special slow-release termite-proofing auxiliary agent is adopted to disperse harmful organisms such as termites by slowly releasing termite-proofing agents, preventing harmful organisms such as termites from aggregating at the sealed gaps of containers and damaging the sealing structure. Even if invasive harmful organisms are mixed in the shipped goods, they can be restricted inside the container, and there is still time for remedies and preventive measures during the unloading stage of the goods, endowing the present invention with a good effect of driving away termites and meeting the pest control performance requirements of container sealants. The termite-proofing auxiliary agent has good compatibility with MS resin and can be evenly dispersed inside the matrix resin, ensuring the termite-proofing effect. At the same time, it can improve the overall ultraviolet aging resistance and mechanical properties, enhance the anti-pest erosion performance of the container, and also has good waterproof durability and bonding stability, which can better protect the safety of shipped goods.

[0009] Preferably, the preparation method of the termite-proofing auxiliary agent is as follows:

[0010] S1. First, perform acidification treatment on halloysite nanotubes. After acidification treatment, wash them with deionized water until neutral and dry to obtain finished halloysite nanotubes. The acidification treatment expands the inner cavity volume of the halloysite nanotubes;

[0011] At the same time, prepare an epoxy silane hydrolysis solution by dissolving 0.5 - 2 parts of epoxy silane in 100 parts of deionized water, adding dilute hydrochloric acid with a concentration of 0.05 - 0.2 mol / L, adjusting the pH value to 3 - 4, and hydrolyzing for 20 - 40 min;

[0012] S2. Mix the finished halloysite nanotubes and the epoxy silane hydrolysis solution evenly according to a mass ratio of 1:(14 - 39), place them in an ultrasonic dispersion mixer at room temperature for 2 - 12 hours of ultrasonic dispersion treatment, then filter, wash with water, dry, and pulverize to obtain modified halloysite nanotubes, that is, epoxy-modified halloysite nanotubes;

[0013] S3. Mix the epoxy-modified halloysite nanotubes, ginger carbon dioxide supercritical extraction solution, and ethanol evenly according to a mass ratio of 1:(1 - 2):20, place them in an ultrasonic dispersion mixer at room temperature for 2 - 4 hours of ultrasonic dispersion treatment, perform magnetic stirring for 6 - 24 h after ultrasonic dispersion treatment, then filter, wash with alcohol, dry, and pulverize to obtain the finished termite-proofing auxiliary agent.

[0014] In the present invention, the slow-release termite-proofing auxiliary agent formed by loading the ginger carbon dioxide supercritical extraction solution on halloysite nanotubes can achieve a good effect of driving away termites. At the same time, the surface of the halloysite nanotubes with a high aspect ratio at the nanoscale can improve the overall bonding strength, weather resistance, and mechanical properties, enhance the anti-pest erosion performance of the container, and also has good waterproof durability and bonding stability, which can better protect the safety of shipped goods. In addition, the preparation method of the termite-proofing auxiliary agent is relatively simple and convenient for mass production.

[0015] Preferably, the preparation method of the ginger carbon dioxide critical extract is as follows:

[0016] S1. After slicing the ginger, it is dried at low temperature until the moisture content is lower than 6.0 wt% to obtain the ginger raw material. The obtained ginger raw material is crushed by liquid nitrogen to obtain ginger powder with a particle size of 200 - 325 mesh;

[0017] S2. The ginger powder obtained in S1 is placed in a supercritical CO 2 extraction equipment for three - stage extraction:

[0018] In the pre - pressure stage extraction, the pressure of supercritical CO 2 is 15 - 20 MPa, the temperature of supercritical CO 2 is 40 - 45 °C, the flow rate of supercritical CO 2 is 20 - 40 kg / h, and the extraction time is 30 - 60 min;

[0019] In the middle - pressure stage extraction, the pressure of supercritical CO 2 is 20 - 25 MPa, the temperature of supercritical CO 2 is 40 - 45 °C, the flow rate of supercritical CO 2 is 20 - 40 kg / h, and the extraction time is 30 - 60 min;

[0020] In the post - pressure stage extraction, the pressure of supercritical CO 2 is 25 - 35 MPa, the temperature of supercritical CO 2 is 40 - 45 °C, the flow rate of supercritical CO 2 is 20 - 40 kg / h, and the extraction time is 30 - 60 min;

[0021] The pressure of the first - stage separation kettle is 10 ± 0.5 MPa, and the temperature is 40 - 45 °C;

[0022] The pressure of the second - stage separation kettle is 5 ± 0.5 MPa, and the temperature is 40 - 45 °C. The liquid in the second - stage separation kettle is collected to obtain the ginger carbon dioxide critical extract.

[0023] Through the carbon dioxide critical extraction technology, the components in ginger that can effectively disperse termites can be effectively extracted. The contents of gingerol, ginger oil, and gingerone in the ginger carbon dioxide critical extract are relatively high. Compared with the ginger extract obtained by conventional alcohol extraction, the ginger carbon dioxide critical extract has a better effect on dispersing termites, and thus can improve the overall termite - proof effect of the present invention.

[0024] Preferably, the silane - modified polyether resin composition is made of amino - silane, allyl glycidyl ether, polyether diol, organic solvent, chain extender, and catalyst;

[0025] Preparation method of the silane-modified polyether resin composition: Dissolve polyether diol in an organic solvent, add a chain extender and a catalyst to obtain a polyether diol intermediate, add allyl glycidyl ether for end-capping. After the reaction, distill off the unreacted allyl glycidyl ether, and dehydrate under vacuum to obtain allyl glycidyl ether-capped polyether diol. Mix the allyl glycidyl ether-capped polyether diol, amino silane, and catalyst evenly for hydrosilylation reaction to obtain the silane-modified polyether resin composition.

[0026] The preparation method of the silane-modified polyether resin composition is relatively simple, which is convenient for entrusting manufacturers to produce the silane-modified polyether resin, reducing the production cost and use cost of the silane-modified polyether resin composition.

[0027] Preferably, the catalyst is at least one of sodium methoxide, potassium methoxide, tetrabutyl titanate, DMP-30, BDMA, boron trifluoride-ether complex, and boron trifluoride-ethylamine complex.

[0028] Preferably, the organic solvent is any one of toluene, xylene, and cyclohexanone.

[0029] Preferably, the amino silane is at least one of trimethoxysilane, triethoxysilane, methyldiethoxysilane, and methyldimethoxysilane.

[0030] Preferably, the polyether diol is any one of polyoxypropylene diol, polyoxyethylene diol, polytetrahydrofuran diol, polytetrahydrofuran-oxyethylene diol, and polytetrahydrofuran-oxypropylene diol with a molecular weight of 500-3000.

[0031] Preferably, the chain extender is any one of diglycidyl ether, hexanediol diglycidyl ether, ethylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, and 1,4-butanediol diglycidyl ether.

[0032] Preferably, the fluorosilicon-modified aliphatic epoxy resin is mainly made of allyl 1,1,2,3,3,3-hexafluoropropyl ether, γ-methacryloxypropylmethyldimethoxysilane, azobisisobutyronitrile, xylene, aliphatic epoxy resin, and DMP-30.

[0033] The fluorosilicon-modified aliphatic epoxy resin in the present invention can improve the overall salt spray resistance and anti-ultraviolet aging performance, and is suitable for use in high-salt spray scenarios of ocean freight, expanding the application range of MS sealant.

[0034] Preferably, the aliphatic epoxy resin is a fluorosilicon-modified aliphatic epoxy resin, and the specific preparation method is as follows:

[0035] S1. γ-Methacryloxypropylmethyldimethoxysilane is hydrolyzed at a pH value of 3 - 4 and a temperature of 25 - 40 °C for 20 - 40 min. The hydrolysis product is dissolved in xylene, and an equimolar amount of allyl 1,1,2,3,3,3-hexafluoropropyl ether and an appropriate amount of azobisisobutyronitrile are added. A double-bond polymerization reaction is carried out at 80 - 100 °C for 100 - 150 min to obtain a fluorosilicon intermediate.

[0036] S2. Aliphatic epoxy resin is dissolved in a xylene solvent and heated to 100 - 120 °C. An appropriate amount of DMP-30 is added dropwise. After mixing evenly, the fluorosilicon intermediate is added dropwise at a rate of 1 - 2 mL / min under nitrogen protection. After the addition is completed, the reaction is maintained at 100 - 120 °C for 100 - 150 min to obtain a colorless transparent or light yellow liquid. After cooling, the fluorosilicon-modified aliphatic epoxy resin is taken out.

[0037] The preparation method of the fluorosilicon-modified aliphatic epoxy resin in the present invention is relatively mature, facilitating batch production, reducing the production cost of the fluorosilicon-modified aliphatic epoxy resin, and thus the overall production cost can be preferably optimized.

[0038] Preferably, the plasticizer is any one of polyethylene glycol with a molecular weight of 3000 - 5000, polypropylene glycol with a molecular weight of 3000 - 5000, dioctyl phthalate, diisononyl 1,2-cyclohexanedicarboxylate, trioctyl phosphate, and citrate.

[0039] Preferably, the filler composition is any one or a combination of calcium carbonate, titanium dioxide, talc powder, kaolin, diatomaceous earth, montmorillonite, white carbon black, aluminum hydroxide, magnesium hydroxide, and zinc oxide.

[0040] Preferably, the organotin catalyst is any one or a combination of dibutyltin dilaurate, stannous octoate, and dibutyltin diacetate.

[0041] Preferably, the coupling agent is any one or a combination of aminosilane, methacryloxy silane, and epoxy silane; the water remover is vinyl silane.

[0042] Preferably, the thixotropic agent is any one or a combination of organic bentonite, fumed silica, silica powder, and hydrogenated castor oil.

[0043] Preferably, the anti-aging aid is composed of an anti-ultraviolet aging aid, an antioxidant aid, and a harmful light shielding agent.

[0044] Preferably, the anti-ultraviolet aging aid is any one or a combination of more than one of UV-531, UV-9, UV-284, UV-213, UV-234, UV-320, UV-326, UV-328, UV-329, UV-P, UV-T, UV-622, UV-770, UV-571, UV-991, UV-783, UV-1130.

[0045] Preferably, the antioxidant aid is any one or a combination of more than one of antioxidant 1010, antioxidant 1076, antioxidant 245, antioxidant 168, antioxidant 1098, antioxidant 1024.

[0046] Preferably, the harmful light shielding reagent is any one or a combination of more than one of nanoscale zinc oxide, silicon dioxide, silicon nitride, titanium nitride.

[0047] Preferably, the mass ratio of the anti-ultraviolet aging aid, antioxidant aid, and harmful light shielding reagent in the anti-aging aid is (40 - 60):(40 - 60):(5 - 20).

[0048] Preferably, the preparation method of the termite-proof silane-modified MS sealant is as follows: At room temperature, 100 parts of silane-modified polyether resin composition, 5 - 20 parts of fluorosilane-modified aliphatic epoxy resin, 50 - 100 parts of plasticizer, 50 - 200 parts of filler composition, 5 - 10 parts of termite-proof aid, 0.5 - 2 parts of aromatic imine-type latent curing agent, 5 - 15 parts of coupling agent, 1 - 10 parts of water remover, 5 - 25 parts of thixotropic agent, 2 - 6 parts of anti-ultraviolet aging aid, and 2 - 6 parts of antioxidant aid are added to the reaction kettle, stirred under nitrogen protection for 0.5 - 1 h, then vacuum dehydrated at 100 - 120 °C for 1 - 2 h, and then cooled to below 50 °C, and 0.05 - 0.5 parts of organotin catalyst is added, and vacuum defoaming treatment is carried out to obtain the finished product of silane-modified polyether sealant.

[0049] The preparation method of the present invention is relatively simple, with low operation difficulty and is convenient for realizing batch production and manufacturing.

[0050] In summary, the present application has the following advantages:

[0051] 1. The present invention has the effect of repelling termites and has good ultraviolet aging resistance and mechanical properties itself, which can improve the anti-pest erosion performance of containers and further improve the freight safety performance.

[0052] 2. The slow-release termite-proofing aid formed by the loading of ginger carbon dioxide critical extraction solution on halloysite nanotubes in the present invention can achieve a good effect of repelling termites. At the same time, it can improve the overall bonding strength, weather resistance and mechanical properties, and enhance the anti-pest erosion performance, waterproof durability and bonding stability of the container.

[0053] 3. In the present invention, the contents of gingerol, ginger oil and gingerone in the ginger extract obtained by the supercritical carbon dioxide extraction technology are relatively high. Compared with the ginger extract obtained by conventional alcohol extraction, the supercritical carbon dioxide extraction solution of ginger has a better effect of dispersing termites, which can endow the present invention with a better termite-dispersing effect.

[0054] 4. The preparation method involved in the present invention is relatively simple, which is convenient for industrial production, reduces the overall production cost of the termite-proofing silane-modified MS sealant, and is convenient for enhancing the market competitiveness of the product. Detailed Embodiments

[0055] In order to further understand the creativity and technological progress of the present invention, the preferred embodiments of the present invention will be discussed in detail below with reference to examples and comparative examples.

[0056] Examples

[0057] A termite-proofing silane-modified MS sealant is made from the following raw materials in parts by weight:

[0058] 100 parts of silane-modified polyether resin composition, 5 - 20 parts of aliphatic epoxy resin, 50 - 100 parts of plasticizer, 50 - 200 parts of filler composition, 5 - 10 parts of termite-proofing aid, 0.5 - 2 parts of aromatic imine-type latent curing agent, 0.05 - 2 parts of organotin catalyst, 5 - 15 parts of coupling agent, 1 - 10 parts of water remover, 5 - 25 parts of thixotropic agent, 2 - 10 parts of anti-outer aging aid.

[0059] The preparation method of the termite-proofing silane-modified MS sealant is as follows: At room temperature, 100 parts of silane-modified polyether resin composition, 5 - 20 parts of fluorosilane-modified aliphatic epoxy resin, 50 - 100 parts of plasticizer, 50 - 200 parts of filler composition, 5 - 10 parts of termite-proofing aid, 0.5 - 2 parts of aromatic imine-type latent curing agent, 5 - 15 parts of coupling agent, 1 - 10 parts of water remover, 5 - 25 parts of thixotropic agent, 2 - 6 parts of anti-ultraviolet aging aid, and 2 - 6 parts of antioxidant aid are added to the reaction kettle, stirred for 0.5 - 1 h under nitrogen protection, then vacuum dehydrated at 100 - 120 °C for 1 - 2 h, and then cooled to below 50 °C, 0.05 - 0.5 parts of organotin catalyst is added, and vacuum defoaming treatment is carried out to obtain the finished product of the silane-modified polyether sealant.

[0060] In the formulation of the termite-proof silane-modified MS sealant, the filler composition is any one or more combinations of calcium carbonate, titanium dioxide, talc powder, kaolin, diatomaceous earth, montmorillonite, fumed silica, aluminum hydroxide, magnesium hydroxide, zinc oxide. Generally, the filler composition is mainly calcium carbonate filler, and the calcium carbonate is mainly added with heavy calcium carbonate with a mesh size of 325 - 2000. To improve the mechanical properties of the termite-proof silane-modified MS sealant, the calcium carbonate filler is composed of heavy calcium carbonate with a mesh size of 325 - 2000 and nano calcium carbonate with a particle size of less than 1 micron, and the mass ratio of nano calcium carbonate to heavy calcium carbonate is 1:(9 - 20).

[0061] The silane-modified MS sealant has flame retardancy requirements. The filler contains aluminum hydroxide and magnesium hydroxide. The content of aluminum hydroxide and / or magnesium hydroxide in the silane-modified MS sealant is greater than 20 wt%, and good flame retardant effects can be achieved.

[0062] The fumed silica has a nanoscale particle size, which can play a role in adjusting the viscosity and preventing sedimentation. Under the nano effect, it can also improve the overall mechanical strength and anti-ultraviolet aging performance of the silane-modified MS sealant.

[0063] Zinc oxide can be used as an activator and accelerator. By reacting with the accelerator to generate a zinc salt complex, it promotes the cross-linking reaction process, thereby improving the curing speed and mechanical properties of the sealant. Moreover, zinc oxide also has excellent thermal conductivity and heat capacity, which can improve the thermal stability and aging resistance of the sealant.

[0064] Preferably, the zinc oxide is selected as nano zinc oxide and / or zinc oxide whiskers.

[0065] Preferably, the filler composition is mainly composed of heavy calcium carbonate with a mesh size of 325 - 2000, nano calcium carbonate with a particle size of less than 1 micron, fumed silica, and zinc oxide, and is compounded with at least one combination of aluminum hydroxide and magnesium hydroxide, which can endow the silane-modified MS sealant with good overall flame retardant performance, mechanical properties, and anti-ultraviolet aging performance.

[0066] The plasticizer is any one of polyethylene glycol with a molecular weight of 3000 - 5000, polypropylene glycol with a molecular weight of 3000 - 5000, dioctyl phthalate, diisononyl 1,2-cyclohexanedicarboxylate, trioctyl phosphate, and citrate. The polyethylene glycol with a molecular weight of 3000 - 5000 and the polypropylene glycol with a molecular weight of 3000 - 5000 in the plasticizer have better compatibility with the matrix resin - silane-modified polyether resin. The side chain of the polypropylene glycol with a molecular weight of 3000 - 5000 has a methyl group, and its flexibility is relatively better. Therefore, the plasticizer is preferably polypropylene glycol with a molecular weight of 3000 - 5000. The plasticizer is specifically selected as polypropylene glycol with a molecular weight of 5000.

[0067] The organotin catalyst is any one or a combination of dibutyltin dilaurate, stannous octoate, and dibutyltin diacetate. Preferably, the organotin catalyst is dibutyltin dilaurate.

[0068] The coupling agent is any one or a combination of aminosilane, methacryloxy silane, and epoxy silane. The coupling agent is epoxy silane, specifically 3-glycidoxypropyltrimethoxysilane.

[0069] The water scavenger is vinyl silane, specifically vinyltriethoxysilane KH151.

[0070] The thixotropic agent is any one or a combination of organobentonite, fumed silica, silica powder, and hydrogenated castor oil. The thixotropic agent improves the anti-settling performance of the sealant and the construction performance. Preferably, it is spherical fumed silica, which fixes the solid particles in the system by constructing a three-dimensional network structure to prevent them from settling due to gravity, achieving good anti-settling performance. Moreover, the spherical fumed silica can improve the fluidity of the sealant and avoid excessive filler content, which may affect the extrusion flow effect of the silane-modified MS sealant.

[0071] The addition of anti-aging additives can improve the anti-ultraviolet aging performance of the silane-modified MS sealant.

[0072] The anti-aging additives are composed of anti-ultraviolet aging additives, antioxidant additives, and harmful light shielding agents.

[0073] The anti-ultraviolet aging additives are any one or a combination of UV-531, UV-9, UV-284, UV-213, UV-234, UV-320, UV-326, UV-328, UV-329, UV-P, UV-T, UV-622, UV-770, UV-571, UV-991, UV-783, and UV-1130.

[0074] Preferably, the anti-ultraviolet aging additives are composed of a mixture of UV-326 and UV-622.

[0075] The antioxidant additives are any one or a combination of antioxidant 1010, antioxidant 1076, antioxidant 245, antioxidant 168, antioxidant 1098, and antioxidant 1024.

[0076] Preferably, the antioxidant additives are composed of a mixture of antioxidant 1010 and antioxidant 168.

[0077] The harmful light shielding agent can effectively reflect infrared and ultraviolet rays, and play a good role in assisting to improve the overall anti-ultraviolet aging performance. The harmful light shielding agent is any one or a combination of nano-scale zinc oxide, silicon dioxide, silicon nitride, and titanium nitride. Preferably, the harmful light shielding agent is silicon nitride.

[0078] Preferably, the mass ratio of the anti-ultraviolet aging agent, antioxidant agent, and harmful light shielding agent in the anti-aging aid is (40-60):(40-60):(5-20).

[0079] The termite-proofing aid uses inorganic porous minerals as carriers, and the termite-proofing agent is loaded into the internal cavity of the inorganic porous mineral carrier, which can achieve the effect of slow-release of the termite-proofing agent, and thus can achieve a good termite-dispersing effect.

[0080] The inorganic porous minerals can be selected from zeolite powder, kaolin, diatomaceous earth, intercalated montmorillonite, halloysite, etc. Among them, the termite-proofing aid prepared with halloysite nanotubes as the carrier has the best comprehensive improvement effect on the silane-modified MS sealant. The termite-proofing aid synthesized from halloysite nanotubes with a high aspect ratio not only has a good slow-release insecticidal effect, but also can improve the mechanical strength and weather resistance of the silane-modified MS sealant.

[0081] The preparation method of the termite-proofing aid is as follows:

[0082] S1. First, acidify the halloysite nanotubes. After acidification, wash them with deionized water until neutral and dry to obtain the finished halloysite nanotubes. The acidification treatment expands the inner cavity volume of the halloysite nanotubes;

[0083] At the same time, prepare the epoxy silane hydrolysis solution by dissolving 0.5-2 parts of epoxy silane in 100 parts of deionized water, adding 0.05-0.2 mol of dilute hydrochloric acid, adjusting the pH value to 3-4, and hydrolyzing for 20-40 minutes;

[0084] S2. Mix the finished halloysite nanotubes and the epoxy silane hydrolysis solution evenly according to a mass ratio of 1:(14-39), place them in an ultrasonic dispersion mixer at room temperature for 2-12 hours of ultrasonic dispersion treatment, and then filter, wash with water, dry, and crush to obtain the modified halloysite nanotubes, that is, epoxy-modified halloysite nanotubes;

[0085] S3. Mix the epoxy-modified halloysite nanotubes, ginger carbon dioxide supercritical extraction solution, and ethanol evenly according to a mass ratio of 1:(1-2):20, place them in an ultrasonic dispersion mixer at room temperature for 2-4 hours of ultrasonic dispersion treatment, and after ultrasonic dispersion treatment, stir magnetically for 6-24 hours, and then filter, wash with alcohol, dry, and crush to obtain the finished termite-proofing aid.

[0086] The epoxy matrix in the epoxy-modified halloysite nanotubes can react with the active hydrogen atoms of the effective anti-insect components in the ginger carbon dioxide critical extract, and the epoxy groups will produce the following addition reaction, which improves the compatibility between the epoxy-modified halloysite nanotubes and the effective anti-insect components in the ginger carbon dioxide critical extract. The effective anti-insect components in the ginger carbon dioxide critical extract can be adsorbed in the pores of the epoxy-modified halloysite nanotubes. The released small molecules of the effective anti-insect components in the ginger carbon dioxide critical extract can penetrate the polymer molecular chains, achieving a long-lasting slow-release anti-insect effect, effectively driving away termites, and effectively controlling the invasion and harm of termites.

[0087] The components in the ginger carbon dioxide critical extract that have a strong stimulating effect on termites are mainly gingerol, ginger oil, and gingerone. In the prior art, the components in the ginger extract obtained by alcohol extraction or steam extraction are relatively complex, resulting in relatively low relative contents of gingerol, ginger oil, and gingerone, and the anti-insect effect of the existing ginger extract is generally average.

[0088] In the present invention, the components in ginger that can effectively disperse termites can be effectively extracted by technology carbon dioxide critical extraction. The contents of gingerol, ginger oil, and gingerone in the ginger carbon dioxide critical extract are relatively high, endowing the silane-modified MS sealant with the effect of dispersing termites.

[0089] Ginger carbon dioxide critical extraction relies on a supercritical CO 2 extraction device, and the specific extraction method is as follows:

[0090] The preparation method of the ginger carbon dioxide critical extract includes the following steps,

[0091] S1. Wash and slice ginger, with the thickness of the ginger slices being 1 mm. Dry the ginger slices at a low temperature of 20 °C until the water content is lower than 6.0 wt% to obtain the ginger raw material. Place the obtained ginger raw material in a liquid nitrogen crusher for liquid nitrogen crushing treatment, and use 200- and 325-mesh sieves to screen out the ginger powder with a particle size of 200-325 meshes;

[0092] S2. Place the ginger powder obtained in S1 in a supercritical CO 2 extraction device for three-stage extraction treatment:

[0093] In the front-pressure stage extraction, the pressure of supercritical CO 2 is 15-20 MPa, the temperature of supercritical CO 2 is 40-45 °C, the flow rate of supercritical CO 2 is 20-40 kg / h, and the extraction time is 30-60 min;

[0094] In the middle-pressure stage extraction, the pressure of supercritical CO 2 is 20-25 MPa, the temperature of supercritical CO 2 is 40-45 °C, the flow rate of supercritical CO 2The flow rate is 20 - 40 kg / h, and the extraction time is 30 - 60 min;

[0095] In the post - compression stage extraction, the supercritical CO 2 has a pressure of 25 - 35 MPa, and the supercritical CO 2 has a temperature of 40 - 45 °C, and the supercritical CO 2 has a flow rate of 20 - 40 kg / h, and the extraction time is 30 - 60 min;

[0096] The pressure of the first - stage separation kettle is 10 ± 0.5 MPa, and the temperature is 40 - 45 °C;

[0097] The pressure of the second - stage separation kettle is 5 ± 0.5 MPa, and the temperature is 40 - 45 °C. Collect the liquid in the second - stage separation kettle to obtain the ginger carbon dioxide critical extract.

[0098] The silane - modified polyether in the silane - modified polyether resin composition can be selected from commercially available conventional silane - modified polyethers such as S3630E, S3430E, S2420E, S3410E, etc.

[0099] The silane - modified polyether resin composition can also be designed and synthesized independently. The silane - modified polyether resin composition is made from amino - silane, allyl glycidyl ether, polyether diol, organic solvent, chain extender, and catalyst. The organic solvent is any one of toluene, xylene, and cyclohexanone.

[0100] The amino - silane is at least one of trimethoxysilane, triethoxysilane, methyldiethoxysilane, and methyldimethoxysilane. Preferably, the amino - silane is trimethoxysilane.

[0101] The catalyst is at least one of sodium methoxide, potassium methoxide, tetrabutyl titanate, DMP - 30, BDMA, boron trifluoride - ether complex, and boron trifluoride - ethylamine complex. Preferably, the catalyst is a compound of DMP - 30 and boron trifluoride - ether complex.

[0102] The chain extender is any one of diglycidyl ether, hexanediol diglycidyl ether, ethylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, and 1,4 - butanediol diglycidyl ether. Preferably, the chain extender is neopentyl glycol diglycidyl ether, which has a branched - chain methyl structure and can improve the overall flexibility.

[0103] The polyether diol has a direct relationship with the main - chain structure of the silane - modified polyether resin, which has a direct impact on the overall mechanical strength, bonding strength, bonding stability, low - temperature flexibility, and weather resistance.

[0104] The polyether diol is any one of polyoxypropylene diols, polyoxyethylene diols, polytetrahydrofuran diols, polytetrahydrofuran-oxyethylene diols, and polytetrahydrofuran-oxypropylene diols with a molecular weight of 500-3000. Conventional polyether diols are selected as polyoxypropylene diols and polyoxyethylene diols with a molecular weight of 500-3000. Among them, the polyoxypropylene diol has side-chain methyl groups in the main chain, low crystallinity, and better flexibility, and is the main polymer repeating unit structure in currently commercially available silane-modified polyether resins.

[0105] In the present invention, it is preferably to use any one of polytetrahydrofuran diols, polytetrahydrofuran-oxyethylene diols, and polytetrahydrofuran-oxypropylene diols as the polyether diol. The tetrahydrofuran structure can improve the overall excellent hydrolysis resistance, wear resistance, oil resistance, and low-temperature flexibility. The silane-modified MS sealant prepared therefrom has better comprehensive performance and is suitable for the sealing requirements of ocean containers, expanding its application range.

[0106] The preparation of the silane-modified polyether resin composition is relatively conventional. To facilitate the reader's understanding of the synthesis raw materials of the silane-modified polyether resin, the synthesis method of the silane-modified polyether resin is briefly explained as follows: First, dissolve the polyether diol in an organic solvent, add a chain extender and a catalyst, and react for a period of time to obtain a polyether diol intermediate with a molecular weight of 6000-15000. Control the molecular weight by controlling the reaction time. After the polyether diol intermediate reacts to a molecular weight of 6000-15000, detect the hydroxyl content of the polyether diol intermediate, add an excessive amount of allyl glycidyl ether for end-capping. After the end-capping reaction is completed, distill out the unreacted allyl glycidyl ether, and dehydrate under vacuum to obtain allyl glycidyl ether-capped polyether diol; Finally, mix the allyl glycidyl ether-capped polyether diol, amino silane, and catalyst evenly, and carry out a hydrosilylation reaction at 60-65°C for 0.5-2 h to obtain the silane-modified polyether resin composition.

[0107] The aliphatic epoxy resin is specifically selected as polybutadiene epoxy resin (2000# epoxy resin) to ensure the flexibility of the silane-modified MS sealant, and at the same time improve the overall bonding strength and mechanical strength of the sealant.

[0108] In the high-salt-spray ocean shipping environment, higher requirements are put forward for the salt spray resistance and weather resistance of the silane-modified MS sealant. Therefore, the aliphatic epoxy resin is subjected to fluorosilicon modification treatment. The obtained fluorosilicon-modified aliphatic epoxy resin has excellent weather resistance and heat stability. The prepared silane-modified MS sealant can be used for the sealing of containers for ocean shipping.

[0109] Preparation Example 1: The fluorosilicon-modified aliphatic epoxy resin is mainly composed of allyl 1,1,2,3,3,3-hexafluoropropyl ether (CAS No. 59158-81-5), γ-methacryloxypropylmethyldimethoxysilane KH570 (CAS No. 3978-58-3), azobisisobutyronitrile (CAS No. 78-67-1), xylene (CAS No. 1330-20-7), polybutadiene epoxy resin (CAS: 129288-65-9, epoxy equivalent: 220, softening point: 18 °C), and DMP-30 (CAS No. 90-72-2).

[0110] The preparation method of the fluorosilicon-modified aliphatic epoxy resin is as follows:

[0111] S1. 0.1 mol (23.2 g) of γ-methacryloxypropylmethyldimethoxysilane and 50 g of deionized water are mixed evenly, and then the pH value of the system is adjusted to 3.5 with 0.1 mol / L dilute hydrochloric acid. The mixture is heated in a water bath to 40 °C and maintained at 40 °C for a half-hour hydrolysis reaction. After dehydration treatment, the obtained hydrolysis product is dissolved in xylene. 0.1 mol (20.8 g) of allyl 1,1,2,3,3,3-hexafluoropropyl ether and 0.24 g of azobisisobutyronitrile are added. The temperature is raised to 85 °C, and a double-bond polymerization reaction is carried out at 85 °C and a rotation speed of 80 rpm for 90 min. After 30 min of the reaction, 0.04 g of the 0.24 g of azobisisobutyronitrile is added to the system, and 0.24 g is added to the system every 30 min. After 90 min of the reaction, the temperature is raised to 95 °C, and a double-bond polymerization reaction is carried out at 95 °C and a rotation speed of 80 rpm for 15 min to obtain a fluorosilicon intermediate;

[0112] S2. 132.4 g of polybutadiene epoxy resin aliphatic epoxy resin is dissolved in 250 mL of xylene solvent, stirred and mixed evenly, and then heated to 110 °C. 0.36 g of DMP-30 is added dropwise to the system. After mixing evenly, the fluorosilicon intermediate prepared in S1 is added dropwise at a rate of 2.0 mL / min under nitrogen protection. After the addition is completed, the reaction is maintained at 110 °C for 120 min to obtain a colorless transparent or light yellow liquid. After cooling, the fluorosilicon-modified aliphatic epoxy resin is taken out.

[0113] Preparation Example 2: The preparation method of ginger carbon dioxide critical extraction liquid includes the following steps

[0114] S1. Ginger is washed and sliced into pieces with a thickness of 1 mm. The ginger slices are dried at a low temperature of 20 °C until the water content is lower than 6.0 wt% to obtain ginger raw materials. The obtained ginger raw materials are placed in a liquid nitrogen crusher for liquid nitrogen crushing treatment, and 200 and 325-mesh sieves are used to screen out ginger powder with a particle size of 200-325 mesh;

[0115] S2. The ginger powder in S1 is placed in supercritical CO2 Three-stage extraction treatment is carried out in the extraction equipment:

[0116] In the pre-pressure stage extraction, the pressure of supercritical CO 2 is 16.5 MPa, the temperature of supercritical CO 2 is 40 °C, the flow rate of supercritical CO 2 is 35 kg / h, and the extraction time is 60 min;

[0117] In the medium-pressure stage extraction, the pressure of supercritical CO 2 is 22 MPa, the temperature of supercritical CO 2 is 40 - 45 °C, the flow rate of supercritical CO 2 is 40 kg / h, and the extraction time is 60 min;

[0118] In the post-pressure stage extraction, the pressure of supercritical CO 2 is 26.5 MPa, the temperature of supercritical CO 2 is 40 - 45 °C, the flow rate of supercritical CO 2 is 40 kg / h, and the extraction time is 60 min;

[0119] The pressure of the first-stage separation kettle is 10 MPa and the temperature is 40 °C;

[0120] The pressure of the second-stage separation kettle is 5 MPa and the temperature is 40 °C. The liquid in the second-stage separation kettle is collected to obtain the ginger carbon dioxide critical extract.

[0121] Preparation Example 3: The silane-modified polyether resin composition is made of trimethoxysilane (CAS No. 2487-90-3), allyl glycidyl ether (CAS No. 106-92-3), polyoxypropylene glycol with a molecular weight of 400 (PPG-400, Jiangsu Haian Petrochemical Factory), cyclohexanone (CAS No. 108-94-1), neopentyl glycol diglycidyl ether (CAS No. 17557-23-2), DMP-30 (CAS No. 90-72-2), boron trifluoride-ether (CAS: 109-63-7), and tetrabutyl titanate.

[0122] The preparation method of the silane-modified polyether resin composition is as follows:

[0123] First, dissolve 400 g of polypropylene glycol PPG-400 with a molecular weight of 400 in 400 g of cyclohexanone organic solvent. After mixing evenly, raise the temperature to 120 °C. While maintaining at 120 °C and 0.25 MPa, dropwise add neopentyl glycol diglycidyl ether containing 0.05 wt% DMP-30 (that is, 0.5 g of DMP-30 is contained in 100 g of neopentyl glycol diglycidyl ether) into the system at a dropping rate of 5 mL / min. After reacting for 90 min, detect the hydroxyl value of the system. When the detected hydroxyl value is between 16 - 18 mgKOH / g, then cool down to 60 °C to obtain a polyether diol intermediate;

[0124] Then, the measured hydroxyl value of the polyether diol intermediate is 17.26 mgKOH / g. Take 650 g of the above-prepared polyether diol intermediate, add 12.4 g of excessive allyl glycidyl ether and 0.5 g of boron trifluoride-ether complex, adjust the temperature to 60 °C and carry out a capping reaction for 45 min. After the capping reaction ends, distill out the unreacted allyl glycidyl ether, and carry out vacuum dehydration to obtain allyl glycidyl ether-capped polyether diol;

[0125] Finally, add 13.2 g of trimethoxysilane and 0.4 g of tetrabutyl titanate to the allyl glycidyl ether-capped polyether diol and mix evenly. While maintaining at 60 °C, carry out a hydrosilylation reaction for 1 h. After the reaction ends, distill out the unreacted trimethoxysilane monomer, and carry out vacuum dehydration to obtain a silane-modified polyether resin composition.

[0126] The difference between Preparation Example 4 and Preparation Example 3 is that the silane-modified polyether resin composition is made from trimethoxysilane, allyl glycidyl ether, polypropylene glycol PPG-400 with a molecular weight of 400, cyclohexanone, 1,4-butanediol diglycidyl ether (CAS No.: 2425-79-8), DMP-30, and boron trifluoride-ether complex.

[0127] The preparation method of the silane-modified polyether resin composition is as follows:

[0128] First, dissolve 400 g of polypropylene glycol PPG-400 with a molecular weight of 400 in 400 g of cyclohexanone organic solvent. After mixing evenly, raise the temperature to 120 °C. While maintaining at 120 °C and 0.25 MPa, dropwise add 1,4-butanediol diglycidyl ether containing 0.05 wt% DMP-30 (that is, 0.5 g of DMP-30 is contained in 100 g of 1,4-butanediol diglycidyl ether) into the system at a dropping rate of 5 mL / min. After reacting for 90 min, detect the hydroxyl value of the system. When the detected hydroxyl value is between 16 - 18 mgKOH / g, then cool down to 60 °C to obtain a polyether diol intermediate;

[0129] Then, the measured hydroxyl value of the polyether diol intermediate was 18.1 mg KOH / g. 620 g of the above-prepared polyether diol intermediate was taken, 12.4 g of excessive allyl glycidyl ether and 0.5 g of boron trifluoride-ether were added, the temperature was adjusted to 60 °C for end-capping reaction for 45 min. After the end-capping reaction, the unreacted allyl glycidyl ether was distilled off, and allyl glycidyl ether-capped polyether diol was obtained by vacuum dehydration;

[0130] Finally, 13.2 g of trimethoxysilane and 0.4 g of tetrabutyl titanate were added to the allyl glycidyl ether-capped polyether diol and mixed evenly. The hydrosilylation reaction was carried out at 60 °C for 1 h. After the reaction, the unreacted trimethoxysilane monomer was distilled off, and the silane-modified polyether resin composition was obtained by vacuum dehydration.

[0131] The difference between Preparation Example 5 and Preparation Example 3 is that the silane-modified polyether resin composition is made of trimethoxysilane, allyl glycidyl ether, polytetrahydrofuran diol with a molecular weight of 650 (BASF PolyTHF 650), cyclohexanone, neopentyl glycol diglycidyl ether, DMP-30, and boron trifluoride-ether complex.

[0132] The preparation method of the silane-modified polyether resin composition is as follows:

[0133] First, 650 g of polytetrahydrofuran diol with a molecular weight of 650 (BASF PolyTHF 650) was dissolved in 800 g of cyclohexanone organic solvent. After mixing evenly, the temperature was raised to 120 °C, and at 120 °C and 0.25 MPa, neopentyl glycol diglycidyl ether containing 0.05 wt% DMP-30 (i.e., 0.5 g of DMP-30 in 100 g of neopentyl glycol diglycidyl ether) was added dropwise to the system at a dropping rate of 5 mL / min. After reacting for 90 min, the hydroxyl value of the system was detected. When the detected hydroxyl value was between 12 - 15 mg KOH / g, the temperature was lowered to 60 °C to obtain the polyether diol intermediate;

[0134] Then, the measured hydroxyl value of the polyether diol intermediate was 14.03 mg KOH / g. 800 g of the above-prepared polyether diol intermediate was taken, 12.4 g of excessive allyl glycidyl ether and 0.5 g of boron trifluoride-ether were added, the temperature was adjusted to 60 °C for end-capping reaction for 45 min. After the end-capping reaction, the unreacted allyl glycidyl ether was distilled off, and allyl glycidyl ether-capped polyether diol was obtained by vacuum dehydration;

[0135] Finally, 13.2 g of trimethoxysilane and 0.4 g of tetrabutyl titanate were added to the allyl glycidyl ether-capped polyether diol and mixed evenly. The hydrosilylation reaction was carried out at 60 °C for 1 h. After the reaction, the unreacted trimethoxysilane monomer was distilled off, and the silane-modified polyether resin composition was obtained by vacuum dehydration.

[0136] The difference between Preparation Example 6 and Preparation Example 3 is that the silane-modified polyether resin composition is made of trimethoxysilane, allyl glycidyl ether, polytetrahydrofuran-ethylene glycol with a molecular weight of 1000 (Nippon Oil Corporation Polycerin DC-1100), cyclohexanone, neopentyl glycol diglycidyl ether, DMP-30, and boron trifluoride-ether complex.

[0137] The preparation method of the silane-modified polyether resin composition is as follows:

[0138] First, dissolve 1000 g of polytetrahydrofuran-ethylene glycol with a molecular weight of 1000 (Nippon Oil Corporation Polycerin DC-1100) in 1000 g of cyclohexanone organic solvent. After mixing evenly, heat up to 120 °C, and maintain at 120 °C and 0.25 MPa to dropwise add neopentyl glycol diglycidyl ether containing 0.05 wt% DMP-30 (that is, 0.5 g of DMP-30 in 100 g of neopentyl glycol diglycidyl ether) into the system at a dropping rate of 5 mL / min. After reacting for 90 min, detect the hydroxyl value of the system. When the detected hydroxyl value is between 12 - 15 mgKOH / g, cool down to 60 °C to obtain a polyether diol intermediate;

[0139] Then, the measured hydroxyl value of the polyether diol intermediate is 13.20 mgKOH / g. Take 850 g of the above-prepared polyether diol intermediate, add 12.4 g of excessive allyl glycidyl ether and 0.5 g of boron trifluoride-ether, adjust the temperature to 60 °C for end-capping reaction for 45 min. After the end-capping reaction, distill out the unreacted allyl glycidyl ether, and dehydrate under vacuum to obtain allyl glycidyl ether-capped polyether diol;

[0140] Finally, add 13.2 g of trimethoxysilane and 0.4 g of tetrabutyl titanate to the allyl glycidyl ether-capped polyether diol, mix evenly, maintain at 60 °C for hydrosilylation reaction for 1 h. After the reaction, distill out the unreacted trimethoxysilane monomer, and dehydrate under vacuum to obtain the silane-modified polyether resin composition.

[0141] The difference between Preparation Example 7 and Preparation Example 3 is that the silane-modified polyether resin composition is made of trimethoxysilane, allyl glycidyl ether, polytetrahydrofuran-propylene glycol with a molecular weight of 1000 (Nippon Oil Corporation Polycerin DCB-1000), cyclohexanone, neopentyl glycol diglycidyl ether, DMP-30, and boron trifluoride-ether complex.

[0142] The preparation method of the silane-modified polyether resin composition is as follows:

[0143] First, dissolve 1000 g of polytetrahydrofuran - propylene oxide diol with a molecular weight of 1000 (Polycerin DCB - 1000, manufactured by Nippon Oil Corporation) in 1000 g of cyclohexanone organic solvent. After mixing evenly, raise the temperature to 120 °C, and maintain at 120 °C and 0.25 MPa to dropwise add neopentyl glycol diglycidyl ether containing 0.05 wt% DMP - 30 (that is, 0.5 g of DMP - 30 in 100 g of neopentyl glycol diglycidyl ether) into the system at a dropping rate of 5 mL / min. After reacting for 90 min, detect the hydroxyl value of the system. When the detected hydroxyl value is between 12 - 15 mgKOH / g, then cool down to 60 °C to obtain a polyether diol intermediate;

[0144] Then, the measured hydroxyl value of the polyether diol intermediate is 12.75 mgKOH / g. Take 880 g of the above - prepared polyether diol intermediate, add 12.4 g of excessive allyl glycidyl ether and 0.5 g of boron trifluoride - diethyl ether, adjust the temperature to 60 °C for end - capping reaction for 45 min. After the end - capping reaction, distill out the unreacted allyl glycidyl ether, and dehydrate under vacuum to obtain allyl glycidyl ether - capped polyether diol;

[0145] Finally, add 13.2 g of trimethoxysilane and 0.4 g of tetrabutyl titanate to the allyl glycidyl ether - capped polyether diol and mix evenly. Maintain at 60 °C for hydrosilylation reaction for 1 h. After the reaction, distill out the unreacted trimethoxysilane monomer, and dehydrate under vacuum to obtain a silane - modified polyether resin composition.

[0146] Preparation Example 8: The preparation method of the termite - proofing agent is as follows:

[0147] S1. First, perform acidification treatment on halloysite nanotubes (Lingshou County Nanyu Mineral Products Processing Factory, scientific research grade). Take 10 g of halloysite nanotubes and mix evenly with 20 mL of dilute sulfuric acid with a concentration of 0.05 mol / L. Place it in an ultrasonic dispersion stirrer at room temperature for 4 - hour ultrasonic dispersion treatment. The ultrasonic frequency is 40 kHz, and the power is 600 W. After acidification treatment, wash with deionized water until neutral, and place it in a vacuum drying oven. Vacuum - dry at 125 °C for 8 hours to obtain the finished halloysite nanotubes. After acidification treatment, the inner cavity volume of the halloysite nanotubes is enlarged, and the loading amount of the insect - repellent agent is increased;

[0148] Meanwhile, prepare an epoxy - silane hydrolysis solution. Dissolve 0.5 part of epoxy - silane KH - 560 in 100 parts of deionized water. Under magnetic stirring at 120 rpm, add dilute hydrochloric acid with a concentration of 0.05 mol / L, adjust the pH value to 3.5, hydrolyze for 30 min, and dehydrate to obtain the epoxy - silane hydrolysis solution;

[0149] S2. The finished halloysite nanotubes are mixed evenly with the hydrolyzed solution of epoxy silane according to a mass ratio of 1:19, placed in an ultrasonic dispersion mixer at room temperature for 4 hours of ultrasonic dispersion treatment, with an ultrasonic frequency of 40 kHz and a power of 600 W, then filtered, washed with water, vacuum dried, and pulverized to obtain epoxy-modified halloysite nanotubes;

[0150] S3. The epoxy-modified halloysite nanotubes, ginger carbon dioxide critical extraction solution, and ethanol are mixed evenly according to a mass ratio of 1:2:20 to obtain a mixture. 0.1 part of boron trifluoride-ether is added to 100 parts of the obtained mixture, placed in an ultrasonic dispersion mixer at room temperature for 2 hours of ultrasonic dispersion treatment, with an ultrasonic frequency of 40 kHz and a power of 600 W. After the ultrasonic dispersion treatment, it is magnetically stirred at 60 °C at 120 rpm for 1 hour and magnetically stirred at 120 rpm at room temperature for 11 hours, then filtered, washed with alcohol, vacuum dried, and pulverized to prepare the finished termite-proofing agent.

[0151] The difference between Preparation Example 9 and Preparation Example 8 is that: the halloysite nanotubes are replaced with 4A zeolite powder of 2000 mesh, and a slow-release termite-proofing agent with zeolite as the carrier is prepared.

[0152] The difference between Preparation Example 10 and Preparation Example 8 is that: the preparation method of the termite-proofing agent is as follows:

[0153] S1. First, the halloysite nanotubes (from Lingshou County Nanyu Mineral Products Processing Factory, scientific research grade) are acidified. Take 10 g of halloysite nanotubes and 20 mL of deionized water, place them in an ultrasonic dispersion mixer at room temperature for 4 hours of ultrasonic dispersion treatment, with an ultrasonic frequency of 40 kHz and a power of 600 W, place them in a vacuum drying oven, and vacuum dry at 125 °C for 8 hours to obtain the finished halloysite nanotubes;

[0154] At the same time, prepare the hydrolyzed solution of epoxy silane. Dissolve 0.5 part of epoxy silane KH-560 in 100 parts of deionized water, add dilute hydrochloric acid with a concentration of 0.05 mol / L under magnetic stirring at 120 rpm, adjust the pH value to 3.5, hydrolyze for 30 min, and dehydrate to obtain the hydrolyzed solution of epoxy silane;

[0155] At the same time, prepare the ginger extract: Mix 10 parts of commercially available ginger powder (provided by Hebei Jiuyu Biotechnology Co., Ltd.) evenly with 5 parts of deionized water and 5 parts of absolute alcohol to obtain the ginger extract;

[0156] S2. The finished halloysite nanotubes are mixed evenly with the hydrolyzed solution of epoxy silane according to a mass ratio of 1:19, placed in an ultrasonic dispersion mixer at room temperature for 4 hours of ultrasonic dispersion treatment, with an ultrasonic frequency of 40 kHz and a power of 600 W, then filtered, washed with water, vacuum dried, and pulverized to obtain epoxy-modified halloysite nanotubes;

[0157] S3. Mix the epoxy-modified halloysite nanotubes, ginger extract, and ethanol evenly at a mass ratio of 1:4:20 to obtain a mixture. Add 0.1 part of boron trifluoride-etherate to 100 parts of the obtained mixture, place it in an ultrasonic dispersion mixer at room temperature for 2 hours of ultrasonic dispersion treatment, with an ultrasonic frequency of 40 kHz and a power of 600 W. After ultrasonic dispersion treatment, stir magnetically at 60 °C at 120 rpm for 1 hour, and stir magnetically at 120 rpm at room temperature for 11 hours. Then filter, wash with alcohol, vacuum dry, and pulverize to obtain the finished termite-proofing additive.

[0158] Specific preferred implementation examples

[0159] Example 1: The formulation of the termite-proofing silane-modified MS sealant is as follows: 100 parts of silane-modified polyether resin S3430E, 60 parts of polypropylene glycol EP-330NG with a molecular weight of 5000, 120 parts of heavy calcium carbonate with a mesh size of 2000, 20 parts of nano calcium carbonate, 15 parts of fumed silica, 5 parts of tetrapod zinc oxide whiskers, 5 parts of the termite-proofing additive in Preparation Example 8, 0.7 part of aromatic imine-type latent curing agent XY 401, 0.3 part of dibutyltin dilaurate, 6 parts of 3-glycidoxypropyltrimethoxysilane KH560, 3 parts of N-β-(aminoethyl)-γ-aminopropyltrimethoxysilane KH792, 4 parts of vinyltriethoxysilane KH151, 5 parts of thixotropic agent - spherical silica, 6 parts of polybutadiene epoxy resin (CAS: 129288-65-9), 2 parts of UV-326, 2 parts of UV-622, 3.6 parts of antioxidant 1010, 0.4 part of antioxidant 168, 2 parts of nano silicon nitride.

[0160] The heavy calcium carbonate with a mesh size of 2000 is provided by Shijiazhuang Weijia Mineral Products Co., Ltd. The nano calcium carbonate YDHT-03 with a particle size distribution range of 20-50 nm is provided by Tianjin Yandong Haotian Mineral Products Co., Ltd. The fumed silica is Cabot CAB-O-SIL M5, a hydrophilic fumed nano-silica. The tetrapod zinc oxide whiskers, with a diameter of 0.5-5 microns and a length of 10-50 microns, are from Hubei Xinyuhong Biomedical Technology Co., Ltd. The high-purity spherical silica powder, with an average particle size of 100 nm, is from Qinghe Ruijiang Metal Materials Co., Ltd. The polybutadiene epoxy resin is from Wuhan Huaxiang Kejie Biotechnology Co., Ltd., with an epoxy equivalent of 220 and a softening point of 18 °C.

[0161] The preparation method of the termite-proof silane-modified MS sealant is as follows: At room temperature, accurately metered silane-modified polyether resin composition, aliphatic epoxy resin, plasticizer, filler composition, termite-proofing agent, aromatic imine-type latent curing agent, coupling agent, water remover, thixotropic agent, and anti-aging agent are added to a reaction kettle. Stir for 0.5 h under nitrogen protection, then dehydrate under vacuum at 120 °C for 2 h, and then cool down to below 50 °C. Add an organotin catalyst and perform vacuum defoaming treatment to obtain the finished product of the silane-modified polyether sealant.

[0162] The difference between Example 2 and Example 1 is that the formulation of the termite-proof silane-modified MS sealant is as follows: 100 parts of silane-modified polyether resin S3430E, 60 parts of polypropylene glycol EP-330NG with a molecular weight of 5000, 117 parts of heavy calcium carbonate with a mesh size of 2000, 20 parts of nano calcium carbonate, 15 parts of fumed silica, 5 parts of tetrapod zinc oxide whiskers, 8 parts of the termite-proofing agent in Preparation Example 8, 0.7 part of aromatic imine-type latent curing agent XY 401, 0.3 part of dibutyltin dilaurate, 6 parts of 3-glycidoxypropyltrimethoxysilane KH560, 3 parts of N-β-(aminoethyl)-γ-aminopropyltrimethoxysilane KH792, 4 parts of vinyltriethoxysilane KH151, 5 parts of thixotropic agent - spherical silica, 6 parts of polybutadiene epoxy resin, 2 parts of UV-326, 2 parts of UV-622, 3.6 parts of antioxidant 1010, 0.4 part of antioxidant 168, 2 parts of nano silicon nitride.

[0163] The difference between Example 3 and Example 1 is that the formulation of the termite-proof silane-modified MS sealant is as follows: 100 parts of silane-modified polyether resin S3430E, 60 parts of polypropylene glycol EP-330NG with a molecular weight of 5000, 115 parts of heavy calcium carbonate with a mesh size of 2000, 20 parts of nano calcium carbonate, 15 parts of fumed silica, 5 parts of tetrapod zinc oxide whiskers, 10 parts of the termite-proofing agent in Preparation Example 8, 0.7 part of aromatic imine-type latent curing agent XY 401, 0.3 part of dibutyltin dilaurate, 9 parts of 3-glycidoxypropyltrimethoxysilane KH560, 4 parts of vinyltriethoxysilane KH151, 5 parts of thixotropic agent - spherical silica, 6 parts of polybutadiene epoxy resin, 2 parts of UV-326, 2 parts of UV-622, 3.6 parts of antioxidant 1010, 0.4 part of antioxidant 168, 2 parts of nano silicon nitride.

[0164] The difference between Example 4 and Example 1 is that the termite-proofing agent in Preparation Example 8 is replaced with the termite-proofing agent in Preparation Example 9, and the other components remain unchanged.

[0165] Example 5 is different from Example 1 in that the termite-proofing auxiliary in Preparation Example 8 is replaced with the termite-proofing auxiliary in Preparation Example 10, and the other components remain unchanged.

[0166] Example 6 is different from Example 1 in that the silane-modified polyether resin S3430E is replaced with the silane-modified polyether composition in Preparation Example 3, and the other components remain unchanged.

[0167] Example 7 is different from Example 1 in that the silane-modified polyether resin S3430E is replaced with the silane-modified polyether composition in Preparation Example 4, and the other components remain unchanged.

[0168] Example 8 is different from Example 1 in that the silane-modified polyether resin S3430E is replaced with the silane-modified polyether composition in Preparation Example 5, and the other components remain unchanged.

[0169] Example 9 is different from Example 1 in that the silane-modified polyether resin S3430E is replaced with the silane-modified polyether composition in Preparation Example 6, and the other components remain unchanged.

[0170] Example 10 is different from Example 1 in that the silane-modified polyether resin S3430E is replaced with the silane-modified polyether composition in Preparation Example 7, and the other components remain unchanged.

[0171] Example 11 is different from Example 9 in that the formulation of the termite-proofing silane-modified MS sealant is as follows: 100 parts of the silane-modified polyether in Preparation Example 6, 60 parts of polypropylene glycol EP-330NG with a molecular weight of 5000, 125 parts of heavy calcium carbonate with a mesh size of 2000, 20 parts of nano calcium carbonate, 15 parts of fumed silica, 5 parts of the termite-proofing auxiliary in Preparation Example 8, 0.7 part of the aromatic imine-type latent curing agent XY 401, 0.3 part of dibutyltin dilaurate, 6 parts of 3-glycidoxypropyltrimethoxysilane KH560, 3 parts of N-β-(aminoethyl)-γ-aminopropyltrimethoxysilane KH792, 4 parts of vinyltriethoxysilane KH151, 5 parts of thixotropic agent - spherical silica, 6 parts of polybutadiene epoxy resin, 2 parts of UV-326, 2 parts of UV-622, 3.6 parts of antioxidant 1010, 0.4 part of antioxidant 168, and 2 parts of nano silicon nitride.

[0172] Example 12 is different from Example 9 in that the formulation of the termite-proof silane-modified MS sealant is as follows: 100 parts of the silane-modified polyether in Preparation Example 6, 60 parts of polypropylene glycol EP-330NG with a molecular weight of 5000, 135 parts of heavy calcium carbonate with a mesh size of 2000, 25 parts of nano calcium carbonate, 5 parts of the termite-proofing agent in Preparation Example 8, 0.7 part of the aromatic imine-type latent curing agent XY 401, 0.3 part of dibutyltin dilaurate, 6 parts of 3-glycidoxypropyltrimethoxysilane KH560, 3 parts of N-β-(aminoethyl)-γ-aminopropyltrimethoxysilane KH792, 4 parts of vinyltriethoxysilane KH151, 5 parts of thixotropic agent - spherical silica, 6 parts of polybutadiene epoxy resin, 2 parts of UV-326, 2 parts of UV-622, 3.6 parts of antioxidant 1010, 0.4 part of antioxidant 168, 2 parts of nano silicon nitride.

[0173] Example 13 is different from Example 9 in that the formulation of the termite-proof silane-modified MS sealant is as follows: 100 parts of the silane-modified polyether in Preparation Example 6, 60 parts of polypropylene glycol EP-330NG with a molecular weight of 5000, 160 parts of heavy calcium carbonate with a mesh size of 2000, 8 parts of the termite-proofing agent in Preparation Example 8, 0.7 part of the aromatic imine-type latent curing agent XY 401, 0.3 part of dibutyltin dilaurate, 6 parts of 3-glycidoxypropyltrimethoxysilane KH560, 3 parts of N-β-(aminoethyl)-γ-aminopropyltrimethoxysilane KH792, 4 parts of vinyltriethoxysilane KH151, 5 parts of thixotropic agent - spherical silica, 6 parts of polybutadiene epoxy resin, 2 parts of UV-326, 2 parts of UV-622, 3.6 parts of antioxidant 1010, 0.4 part of antioxidant 168, 2 parts of nano silicon nitride.

[0174] Example 14 is different from Example 9 in that the polybutadiene epoxy resin is replaced with the fluorosilane-modified polybutadiene epoxy resin in Preparation Example 2, and the other components remain unchanged.

[0175] The difference between Example 15 and Example 9 is as follows: The formulation of the termite-proof silane-modified MS sealant is as follows: 100 parts of the silane-modified polyether in Preparation Example 6, 60 parts of polypropylene glycol EP-330NG with a molecular weight of 5000, 120 parts of heavy calcium carbonate with a mesh size of 2000, 20 parts of nano calcium carbonate, 15 parts of fumed silica, 5 parts of tetrapod zinc oxide whiskers, 5 parts of the termite-proofing agent in Preparation Example 8, 0.85 part of the aromatic imine-type latent curing agent XY 401, 0.3 part of dibutyltin dilaurate, 6 parts of 3-glycidoxypropyltrimethoxysilane KH560, 3 parts of N-β-(aminoethyl)-γ-aminopropyltrimethoxysilane KH792, 4 parts of vinyltriethoxysilane KH151, 5 parts of the thixotropic agent - spherical silica, 12 parts of the fluorosilane-modified polybutadiene epoxy resin in Preparation Example 2, 2 parts of UV-326, 2 parts of UV-622, 3.6 parts of antioxidant 1010, 0.4 part of antioxidant 168, 2 parts of nano silicon nitride.

[0176] The difference between Example 16 and Example 9 is as follows: The formulation of the termite-proof silane-modified MS sealant is as follows: 100 parts of the silane-modified polyether in Preparation Example 6, 60 parts of polypropylene glycol EP-330NG with a molecular weight of 5000, 120 parts of heavy calcium carbonate with a mesh size of 2000, 20 parts of nano calcium carbonate, 15 parts of fumed silica, 5 parts of tetrapod zinc oxide whiskers, 5 parts of the termite-proofing agent in Preparation Example 8, 1.1 parts of the aromatic imine-type latent curing agent XY 401, 0.3 part of dibutyltin dilaurate, 6 parts of 3-glycidoxypropyltrimethoxysilane KH560, 3 parts of N-β-(aminoethyl)-γ-aminopropyltrimethoxysilane KH792, 4 parts of vinyltriethoxysilane KH151, 5 parts of the thixotropic agent - spherical silica, 20 parts of the fluorosilane-modified polybutadiene epoxy resin in Preparation Example 2, 2 parts of UV-326, 2 parts of UV-622, 3.6 parts of antioxidant 1010, 0.4 part of antioxidant 168, 2 parts of nano silicon nitride.

[0177] The difference between Comparative Example 1 and Example 1 is as follows: The termite-proofing agent in Preparation Example 8 is replaced with (Lingshou County Nanyu Mineral Products Processing Factory, scientific research grade), and the other components remain unchanged.

[0178] The difference between Comparative Example 2 and Example 1 is as follows: The formulation of the termite-proof silane-modified MS sealant is as follows: 100 parts of silane-modified polyether resin S3430E, 60 parts of polypropylene glycol EP-330NG with a molecular weight of 5000, 125 parts of heavy calcium carbonate with a mesh size of 2000, 20 parts of nano calcium carbonate, 15 parts of fumed silica, 5 parts of tetrapod zinc oxide whiskers, 0.7 part of aromatic imine-type latent curing agent XY 401, 0.3 part of dibutyltin dilaurate, 6 parts of 3-glycidoxypropyltrimethoxysilane KH560, 3 parts of N-β-(aminoethyl)-γ-aminopropyltrimethoxysilane KH792, 4 parts of vinyltriethoxysilane KH151, 5 parts of thixotropic agent - spherical silica, 6 parts of polybutadiene epoxy resin, 2 parts of UV-326, 2 parts of UV-622, 3.6 parts of antioxidant 1010, 0.4 part of antioxidant 168, 2 parts of nano silicon nitride.

[0179] The difference between Comparative Example 3 and Example 1 is as follows: The formulation of the termite-proof silane-modified MS sealant is as follows: 100 parts of silane-modified polyether resin S3430E, 60 parts of polypropylene glycol EP-330NG with a molecular weight of 5000, 123 parts of heavy calcium carbonate with a mesh size of 2000, 20 parts of nano calcium carbonate, 15 parts of fumed silica, 5 parts of tetrapod zinc oxide whiskers, 2 parts of the termite-proofing aid in Preparation Example 8, 0.7 part of aromatic imine-type latent curing agent XY 401, 0.3 part of dibutyltin dilaurate, 6 parts of 3-glycidoxypropyltrimethoxysilane KH560, 3 parts of N-β-(aminoethyl)-γ-aminopropyltrimethoxysilane KH792, 4 parts of vinyltriethoxysilane KH151, 5 parts of thixotropic agent - spherical silica, 6 parts of polybutadiene epoxy resin, 2 parts of UV-326, 2 parts of UV-622, 3.6 parts of antioxidant 1010, 0.4 part of antioxidant 168, 2 parts of nano silicon nitride.

[0180] The difference between Comparative Example 4 and Example 9 lies in that the formulation of the termite-proof silane-modified MS sealant is as follows: 106 parts of the silane-modified polyether in Preparation Example 6, 60 parts of polypropylene glycol EP-330NG with a molecular weight of 5000, 120 parts of heavy calcium carbonate with a mesh size of 2000, 20 parts of nano calcium carbonate, 15 parts of fumed silica, 5 parts of tetrapod zinc oxide whiskers, 5 parts of the termite-proofing agent in Preparation Example 8, 1.1 parts of aromatic imine-type latent curing agent XY 401, 0.3 parts of dibutyltin dilaurate, 6 parts of 3-glycidoxypropyltrimethoxysilane KH560, 3 parts of N-β-(aminoethyl)-γ-aminopropyltrimethoxysilane KH792, 4 parts of vinyltriethoxysilane KH151, 5 parts of thixotropic agent - spherical silica, 2 parts of UV-326, 2 parts of UV-622, 3.6 parts of antioxidant 1010, 0.4 parts of antioxidant 168, 2 parts of nano silicon nitride.

[0181] The difference between Comparative Example 5 and Example 9 lies in that the formulation of the termite-proof silane-modified MS sealant is as follows: 100 parts of the silane-modified polyether in Preparation Example 6, 60 parts of polypropylene glycol EP-330NG with a molecular weight of 5000, 120 parts of heavy calcium carbonate with a mesh size of 2000, 20 parts of nano calcium carbonate, 15 parts of fumed silica, 5 parts of tetrapod zinc oxide whiskers, 5 parts of the termite-proofing agent in Preparation Example 8, 0.85 parts of aromatic imine-type latent curing agent XY 401, 0.3 parts of dibutyltin dilaurate, 6 parts of 3-glycidoxypropyltrimethoxysilane KH560, 3 parts of N-β-(aminoethyl)-γ-aminopropyltrimethoxysilane KH792, 4 parts of vinyltriethoxysilane KH151, 5 parts of thixotropic agent - spherical silica, 6 parts of the fluorosilane-modified polybutadiene epoxy resin in Preparation Example 2, 2.5 parts of UV-326, 2.5 parts of UV-622, 4.5 parts of antioxidant 1010, 0.5 parts of antioxidant 168.

[0182] Performance detection test:

[0183] 1. Surface drying time: The test is carried out in accordance with Method 8.2B specified in GB / T 13477.5-2002 - Test Methods for Building Sealant Materials - Part 5: Determination of Surface Drying Time.

[0184] 2. Tensile strength and elongation at break tests are carried out in accordance with GB / T528-2009 - Determination of Tensile Stress-Strain Properties of Vulcanized Rubber or Thermoplastic Rubber.

[0185] 3. Tear strength is tested in accordance with the provisions of GB / T 529—1991 Determination of Tear Strength of Vulcanized Rubber.

[0186] 4 Tensile strength and its change rate: Place it at 90 °C for 300 h, at 120 °C for 3 h, place it in an anhydrous ultraviolet box for 300 h, and soak it in artificial seawater (pH of artificial seawater = 8, temperature is 40 °C, sodium chloride concentration is 3.50%) for 168 h. Determine the tensile strength of the sealant according to GB / T 28 - 2009.

[0187] Calculate the tensile strength change rate = 100 - (F 测 / F 初始 ) * 100, where F 初始 : Initial tensile strength; F 测 is the tested tensile strength after aging.

[0188] Table 1: Test parameter table of silane - modified MS sealants in Examples 1 - 16 and Comparative Examples 1 - 5

[0189]

[0190] Table 2: Test parameter table of silane - modified MS sealants in Examples 1 - 16 and Comparative Examples 1 - 5

[0191]

[0192] Combined with Example 1 and Comparative Examples 1 - 2 and combined with Tables 1 - 2, it can be seen that the addition of the termite - proofing agent or halloysite nanotubes in Preparation Example 8 can improve the mechanical properties, tear strength, and weather resistance of the prepared silane - modified MS sealant.

[0193] Combined with Example 1 and Examples 2 - 3 and combined with Tables 1 - 2, it can be seen that when the termite - proofing agent uses halloysite nanotubes as a carrier, the mechanical properties, tear strength, and weather resistance of the prepared silane - modified MS sealant are relatively better.

[0194] Combined with Example 1, Examples 4 - 5 and Comparative Examples 2 - 3 and combined with Tables 1 - 2, it can be seen that the more the addition amount of the termite - proofing agent in Preparation Example 8, the relatively better the mechanical properties, tear strength, and weather resistance of the prepared silane - modified MS sealant. When the addition amount of the termite - proofing agent in Preparation Example 8 is greater than 8 parts, the improvement amplitude of the mechanical properties, tear strength, and weather resistance of the prepared silane - modified MS sealant slows down. Therefore, it is relatively better to control the addition amount of the termite - proofing agent in Preparation Example 8 to be 5 - 8 parts.

[0195] Combined with Example 1 and Examples 6 - 10 and in combination with Tables 1 - 2, it can be seen that for the silicon - modified allyl polyether compositions in Preparation Examples 3 - 7, the mechanical properties, tear strength, and weather resistance of the prepared silane - modified MS sealant are superior to those of the silane - modified MS sealant prepared from the silane - modified polyether resin S3430E. By comparing Examples 6 - 10, it is found that for the silane - modified MS sealant prepared from the silicon - modified allyl polyether compositions in Preparation Examples 5 - 6, the mechanical properties, tear strength, and weather resistance are more excellent.

[0196] Combined with Example 9 and Examples 11 - 13 and in combination with Tables 1 - 2, it can be seen that the filler composition consists of 2000 - mesh heavy calcium carbonate, nano - calcium carbonate, fumed silica, and zinc oxide whiskers, which can improve the mechanical properties, tear strength, and weather resistance of the prepared silane - modified MS sealant.

[0197] Combined with Example 9, Examples 14 - 16 and Comparative Example 4 and in combination with Tables 1 - 2, it can be seen that the fluorosilicon - modified polybutadiene epoxy resin in Preparation Example 2 can improve the mechanical properties, tear strength, and weather resistance of the prepared silane - modified MS sealant. When the addition amount of the fluorosilicon - modified polybutadiene epoxy resin is ≥12, it can shorten the surface - drying time of the silane - modified MS sealant, and thus can promote the rapid curing of the silane - modified MS sealant.

[0198] Combined with Example 9 and Comparative Example 5 and in combination with Tables 1 - 2, it can be seen that the anti - ultraviolet - aging additive, antioxidant additive, and harmful - light - shielding reagent in the anti - external - aging additive with a mass ratio of 4:4:2 can slightly improve the weather resistance of the prepared silane - modified MS sealant.

[0199] Termite prevention test: Apply an appropriate amount of sealant on a polytetrafluoroethylene plate with a diameter of 100 cm, with a thickness of about 2 mm. After curing for half an hour, a termite-proof silane-modified MS sealant layer is formed on the upper surface of the polytetrafluoroethylene plate. An insect-proof area C with a diameter of 20 cm is formed on the polytetrafluoroethylene plate, which is divided into area A and area B. Area B is a ring with an inner diameter of 20 cm and an outer diameter of 50 cm, and area A is a ring with an inner diameter of 50 cm and an outer diameter of 100 cm. Further divide area A into area A1 (a ring with an inner diameter of 20 cm and an outer diameter of 30 cm), area A2 (a ring with an inner diameter of 30 cm and an outer diameter of 40 cm), and area A3 (a ring with an inner diameter of 40 cm and an outer diameter of 50 cm); divide area B into area B1 (a ring with an inner diameter of 50 cm and an outer diameter of 60 cm), area B2 (a ring with an inner diameter of 60 cm and an outer diameter of 70 cm), area B3 (a ring with an inner diameter of 70 cm and an outer diameter of 80 cm), area B4 (a ring with an inner diameter of 80 cm and an outer diameter of 90 cm), and area B5 (a ring with an inner diameter of 90 cm and an outer diameter of 100 cm). Test: Release 50 termites into area B3 of the polytetrafluoroethylene plate. Area B3 is divided into five termite release points with a diameter of 10 cm, and 10 termites are placed in each termite release point. A food release area with a diameter of 5 cm is demarcated in the insect-proof area C, and pine sawdust is placed in the food release area. After 8 hours, observe the number of termites in areas A, B, and C, and count and draw them into a table.

[0200] Table 3: Termite dispersal test parameter table of silane-modified MS sealant in Examples 1-10 and Comparative Examples 1-3

[0201]

[0202] Table 4: Termite dispersal test parameter table of silane-modified MS sealant after 300 h of ultraviolet aging in an anhydrous ultraviolet box in Examples 1-10 and Comparative Examples 1-3

[0203]

[0204] Combined with Examples 1-5 and Comparative Example 1 and combined with Tables 3-4, it can be seen that the silane-modified MS sealant prepared with the termite-proofing agent in Preparation Examples 8-10 of the present invention has a good termite dispersal effect.

[0205] Combined with Example 1 and Examples 2-3 and combined with Tables 3-4, it can be seen that the silane-modified MS sealant prepared with the termite-proofing agent in Preparation Example 8 of the present invention has a better termite dispersal effect.

[0206] Combined with Examples 1-10 and Comparative Examples 2-3 and combined with Tables 3-4, it can be seen that it is appropriate to control the addition amount of the termite-proofing agent in the formula of the present invention to be 5-10 parts, which can ensure the overall termite dispersal effect of the silane-modified MS sealant. Excessive addition of the termite-proofing agent has a small increase in the termite dispersal effect and will increase the cost.

[0207] In summary, the present invention has the effect of repelling termites and has good mechanical properties and weather resistance, which can improve the anti-pest erosion performance of containers and further improve the freight safety performance.

[0208] 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. After reading this specification, those skilled in the art can make modifications to this embodiment without creative contributions as needed, 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 silane-modified MS sealant for preventing termites, characterized in that: The anti-termite silane-modified MS sealant comprises the following raw materials in parts by weight: 100 parts of a silane-modified polyether resin composition, 5-20 parts of an aliphatic epoxy resin, 50-100 parts of a plasticizer, 50-200 parts of a filler composition, 5-10 parts of an anti-termite auxiliary agent, 0.5-2 parts of an aromatic imine-type latent curing agent, 0.05-2 parts of an organic tin catalyst, 5-15 parts of a coupling agent, 1-10 parts of a dehydrating agent, 5-25 parts of a thixotropic agent, and 2-10 parts of an anti-aging auxiliary agent.

2. The anti-termite silane modified MS sealant according to claim 1, characterized in that: The silane-modified polyether resin composition comprises hydrosilane, allyl glycidyl ether, polyether diol, organic solvent, chain extender and catalyst; The catalyst is at least one of sodium methoxide, potassium methoxide, tetrabutyl titanate, DMP-30, N,N-dimethylbenzylamine BDMA, boron trifluoride-ether complex, and boron trifluoride-ethylamine complex; the organic solvent is any one of toluene, xylene, and cyclohexanone; and the hydrosilane is at least one of trimethoxysilane, triethoxysilane, methyldiethoxysilane, and methyldimethoxyhydrogensilane.

3. The anti-termite silane modified MS sealant according to claim 2, characterized in that: The polyether diol is any one of polyoxypropylene diol, polyoxyethylene diol, polytetrahydrofuran diol, polytetrahydrofuran-oxyethylene diol, and polytetrahydrofuran-oxypropylene diol with a molecular weight of 500-3000; the chain extender is any one of diglycidyl ether, hexanediol diglycidyl ether, ethylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, and 1,4-butanediol diglycidyl ether.

4. The anti-termite silane modified MS sealant according to claim 2, characterized in that: The preparation method of the silane-modified polyether resin composition is as follows: dissolving polyether diol in an organic solvent, adding a chain extender and a catalyst to obtain a polyether diol intermediate, adding allyl glycidyl ether for end-capping, distilling off unreacted allyl glycidyl ether after the reaction, vacuum dehydrating to obtain allyl glycidyl ether-end-capped polyether diol, and uniformly mixing allyl glycidyl ether-end-capped polyether diol, hydrogen silane, and a catalyst to perform a hydrosilylation reaction to obtain a silane-modified polyether resin composition.

5. The anti-termite silane modified MS sealant according to claim 1, characterized in that: The fluorine-silicon modified aliphatic epoxy resin is mainly prepared from allyl 1,1,2,3,3,3-hexafluoropropyl ether, gamma-methacryloxypropylmethyldimethoxysilane, azobisisobutyronitrile, xylene, aliphatic epoxy resin and DMP-30.

6. The anti-termite silane modified MS sealant according to claim 5, characterized in that: The aliphatic epoxy resin is a fluorine-silicon modified aliphatic epoxy resin, and the specific preparation method is as follows: S1.γ-methacryloxypropylmethyldimethoxysilane is hydrolyzed at a pH of 3-4 and 25-40°C for 20-40 minutes, the hydrolysis product is dissolved in xylene, an equimolar amount of allyl 1,1,2,3,3,3-hexafluoropropyl ether and an appropriate amount of azobisisobutyronitrile are added, and double bond polymerization reaction is carried out at 80-100°C for 100-150 minutes to obtain a fluorosilicon intermediate; S2. Dissolve the aliphatic epoxy resin in xylene solvent, heat to 100-120°C, add appropriate amount of DMP-30, mix well, and then add fluorosilicone intermediate at 1-2mL / min under nitrogen protection. After the addition is completed, maintain the reaction at 100-120°C for 100-150min to obtain a colorless transparent or light yellow liquid. After cooling, take out and obtain fluorosilicone modified aliphatic epoxy resin.

7. The anti-termite silane modified MS sealant according to claim 1, characterized in that: The preparation method of the anti-termite auxiliary agent is as follows: S1. The halloysite nanotubes are first subjected to acid treatment, and after acid treatment, they are washed with deionized water until neutral and dried to obtain finished halloysite nanotubes, and the acid treatment expands the inner cavity volume of the halloysite nanotubes; Meanwhile, epoxy silane hydrolyzate is prepared, 0.5-2 parts of epoxy silane is dissolved in 100 parts of deionized water, dilute hydrochloric acid with a concentration of 0.05-0.2 mol / L is added, the pH value is adjusted to 3-4, and hydrolyzed for 20-40 minutes to obtain; S2. The finished halloysite nanotubes and epoxy silane hydrolyzate are mixed uniformly in a mass ratio of 1: (14-39), placed in an ultrasonic dispersing mixer at room temperature for 2-12 hours of ultrasonic dispersion treatment, and then filtered, washed, dried, and crushed to obtain modified halloysite nanotubes, namely epoxy-modified halloysite nanotubes; S3. Mix epoxy-modified halloysite nanoparticles, ginger carbon dioxide critical extract and ethanol in a mass ratio of 1: (1-2): 20, place in an ultrasonic disperser for 2-4 hours of ultrasonic dispersion treatment at room temperature, stir magnetically for 6-24 hours after ultrasonic dispersion treatment, and then filter, wash with alcohol, dry and crush to obtain a finished anti-termite additive.

8. The anti-termite silane modified MS sealant according to claim 1, characterized in that: The anti-aging agent is composed of an anti-ultraviolet aging agent, an antioxidant agent, and a harmful light shielding agent in a mass ratio of (40-60): (40-60): (5-20); the harmful light shielding agent is any one or more combinations of nano-scale zinc oxide, silicon dioxide, silicon nitride, and titanium nitride.

9. The anti-termite silane modified MS sealant according to claim 8, characterized in that: The anti-ultraviolet aging aid is any one or more combinations of UV-531, UV-9, UV-284, UV-213, UV-234, UV-320, UV-326, UV-328, UV-329, UV-P, UV-T, UV-622, UV-770, UV-571, UV-991, UV-783, and UV-1130; the antioxidant aid is any one or more combinations of antioxidant 1010, antioxidant 1076, antioxidant 245, antioxidant 168, antioxidant 1098, and antioxidant 1024.

10. The anti-termite silane modified MS sealant according to claim 1, characterized in that: The preparation method of the anti-termite silane modified MS sealant is as follows: at room temperature, 100 parts of a silane modified polyether resin composition, 5-20 parts of a fluorosilicone modified aliphatic epoxy resin, 50-100 parts of a plasticizer, 50-200 parts of a filler composition, 5-10 parts of an anti-termite auxiliary agent, 0.5-2 parts of an aromatic imine type latent curing agent, 5-15 parts of a coupling agent, 1-10 parts of a dehydrating agent, 5-25 parts of a thixotropic agent, 2-6 parts of an anti-ultraviolet aging auxiliary agent, and 2-6 parts of an antioxidant auxiliary agent are added into a reaction kettle, stirred for 0.5-1h under nitrogen protection, then vacuum dehydrated at 100-120°C for 1-2h, finally cooled to below 50°C, added with 0.05-0.5 parts of an organic tin catalyst, and subjected to vacuum degassing treatment to obtain a finished silane modified polyether sealant.

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