Silica gel foam sealing material capable of preventing termite gnawing and preparation method of silica gel foam sealing material

Abstract

The invention provides a silica gel foam sealing material capable of preventing termite gnawing and a preparation method of the silica gel foam sealing material, and belongs to the technical field of polymer sealing materials. The raw material formula of the silica gel foam sealing material is as follows: vinyl silicone oil, a reinforcing filler, a flame-retardant filler, a contact insecticide, a bait, an odorant, a structure control agent, an inhibitor, a platinum catalyst, a foaming agent, hydroxyl silicone oil and hydrogen-containing silicone oil. Wherein the contact insecticide is one or more of pyrethroids, neonicotinoids, phenyl pyrazoles, boric acid, glycine, erythritol and fipronil; the bait agent is one or more of diatomite, talcum powder, capsaicin, dihydrocapsaicin and denatonium benzoate; the odorant is one or more of camphor oil, peppermint oil, limonin, limonene, citral, capraldehyde, octanal and nonanal. The silica gel foam sealing material disclosed by the invention has excellent flame retardant property, mechanical property and ant gnawing resistance, and the integrity of the sealing material can be well protected.

Description

Technical Field

[0001] The invention belongs to the technical field of polymer sealing materials, and in particular relates to a silicone foam sealing material that is ant-proof and a preparation method thereof. Background Art

[0002] Silicone foam sealing material is a porous material with a silicone matrix at its core, endowed with unique elastic and cushioning properties through a foaming process. Its backbone is composed of silicon-oxygen bonds, giving the material excellent temperature resistance, chemical inertness, and aging resistance. It is widely used in sealing, shock absorption, and thermal insulation. With the increasing demand for lightweight and safe materials in new energy vehicles, aerospace, and electronic equipment, silicone foam is becoming a key material for battery pack encapsulation, precision instrument protection, and building sealing. The advantages of silicone foam sealing materials include low density, high resilience, low compression set, and the ability to withstand mechanical stress and thermal cycling in complex environments. However, traditional silicone foam still has limitations in flame retardancy, buffer gradient control, and bio-resistance, making it difficult to fully meet the high safety and long life requirements of power batteries. In new energy vehicle battery packs, in particular, the material must simultaneously meet multiple functions such as lightweighting, thermal protection, and bio-resistance, placing even higher demands on the performance of silicone foam.

[0003] At present, the preparation of silicone foam mainly relies on two processes: physical foaming and chemical foaming. Physical foaming forms a bubble structure in silicone rubber by introducing inert gas or low-boiling point liquid. Its advantage is good uniformity of the bubbles, but the process is complicated and the cost is high. Chemical foaming produces gas by decomposing the foaming agent (such as AC, OBSH). Although it is easy to operate, it can easily lead to uneven distribution of bubbles, limited foaming ratio, and stress concentration in the material at high temperatures. In addition, in order to improve the flame retardant properties, the existing technology often adds inorganic flame retardants (such as aluminum hydroxide, magnesium hydroxide) or liquid flame retardants, but the high filler ratio will reduce the elasticity and cushioning properties of the material, and even cause bubble collapse or a decrease in mechanical strength. At the same time, although the closed-cell structure of traditional silicone foam can isolate moisture, it cannot effectively deal with biological erosion problems such as ants. Its surface hardness and chemical inertness may attract insects and ants to eat it. These problems limit the long-term reliability of silicone foam in scenarios with high safety requirements (such as power battery sealing), and there is an urgent need to improve and upgrade the material design and preparation process.

[0004] To optimize the overall performance of silicone foam, some researchers have introduced ceramicization reactions to enhance its high-temperature resistance and thermal insulation capabilities, or adjusted the foaming system to smooth the stress-strain curve. For example, adopting an open-pore structure design can enhance cushioning performance, but open-pore materials are prone to reduced mechanical strength due to weak pore walls. Adding functional fillers (such as nanosilica) can improve mechanical properties but at the expense of foaming uniformity. Furthermore, none of these improvements address the core issue of the material's susceptibility to bioerosion. In the actual application of new energy vehicle battery packs, insects such as ants may destroy the airtightness of the battery casing by gnawing on the sealing material, leading to electrolyte leakage or short circuit risks, and thus thermal runaway. Although existing silicone foam is chemically inert, its soft texture and pore structure still provide a breakthrough point for biological invasion. Therefore, there is an urgent need to develop a silicone foam sealing material that is both flame-retardant and ant-resistant, while maintaining its original performance advantages, to achieve active protection against bioerosion, thereby comprehensively improving the safety and service life of new energy vehicle batteries. Summary of the Invention

[0005] The purpose of the present invention is to provide a silicone foam sealing material that is resistant to ant gnawing and a preparation method thereof. By introducing a contact agent combined with a bait agent and an odorant, material components that are disgusting or toxic to rats, insects and ants are added to the sealing material, thereby achieving the effect of repelling rats, insects and ants and protecting the integrity of the sealing material.

[0006] To achieve the above objectives, the present invention can be implemented through the following technical solutions:

[0007] The present invention provides a silicone foam sealing material for preventing ants from gnawing and a preparation method thereof, which comprises the following raw materials in parts by weight:

[0008] 30-50 parts of vinyl silicone oil, 10-30 parts of reinforcing filler, 40-80 parts of flame retardant filler, 0.02-0.2 parts of contact agent, 2-20 parts of bait, 0.2-2 parts of odorant, 2-8 parts of structure control agent, 0.1-0.3 parts of inhibitor, 0.3-0.7 parts of platinum catalyst, 1-5 parts of foaming agent, 2-6 parts of hydroxy silicone oil, and 5-15 parts of hydrogenated silicone oil.

[0009] Preferably, a silicone foam sealing material for preventing ants from gnawing comprises the following raw materials in parts by weight:

[0010] 40-50 parts of vinyl silicone oil, 19-30 parts of reinforcing filler, 50-60 parts of flame retardant filler, 0.12-0.16 parts of contact agent, 4-8 parts of bait, 1-1.2 parts of odorant, 2-8 parts of structure control agent, 0.2-0.25 parts of inhibitor, 0.6-0.7 parts of platinum catalyst, 2-3.5 parts of foaming agent, 3-5 parts of hydroxy silicone oil, and 11-13 parts of hydrogenated silicone oil.

[0011] Preferably, the viscosity of the vinyl silicone oil is 1000-3000 mPa·s (25° C.), and the vinyl content is 0.1-0.4 wt %.

[0012] Preferably, the reinforcing filler is composed of carbon black and white carbon black, and the specific surface area of ​​the white carbon black is 200-400m 2 / g, including but not limited to 200, 300, 400m 2 / g one or more.

[0013] Preferably, the weight ratio of the carbon black to the white carbon black is 1-2:8-15.

[0014] Preferably, the flame retardant filler is one or more of aluminum hydroxide, zinc oxide, zinc borate, and magnesium hydroxide.

[0015] Preferably, in some embodiments, the flame retardant filler is composed of aluminum hydroxide and magnesium hydroxide in a weight ratio of 15-20:10-20.

[0016] Preferably, in some embodiments, the flame retardant filler is composed of aluminum hydroxide, magnesium hydroxide, and zinc borate in a weight ratio of 15-20:10-20:5-10.

[0017] Preferably, in some embodiments, the flame retardant filler is composed of magnesium hydroxide and zinc oxide in a weight ratio of 10-20:5-10.

[0018] Preferably, the contact killer is one or more of pyrethroids, neonicotinoids, phenylpyrazoles, boric acid, glycine, erythritol, and fipronil.

[0019] Preferably, in some embodiments, the contact killer is composed of glycine and erythritol in a weight ratio of 0.02-0.04:0.06-0.08.

[0020] Preferably, the bait is one or more of diatomaceous earth, talc, capsaicin, dihydrocapsaicin, and denatonium benzoate.

[0021] Preferably, the odorant is one or more of camphor oil, peppermint oil, limonin, limonene, citral, decanal, octanal, and nonanal.

[0022] Preferably, the structure control agent is one or more of diphenylsilanediol, α,ω-dihydroxypolydimethylsiloxane, and dialkyldialkoxysilane.

[0023] Preferably, the inhibitor is one or more of 2-methyl-3-butyn-2-ol, 1-ethynylcyclohexanol, tetramethyltetravinylcyclotetrasiloxane, and diallyl maleate.

[0024] Preferably, in some embodiments, the inhibitor is composed of tetramethyltetravinylcyclotetrasiloxane and diallyl maleate in a weight ratio of 0.1-0.2:0.1-0.2.

[0025] Preferably, the platinum catalyst includes at least one platinum compound, including but not limited to platinum water, chloroplatinic acid or a platinum complex.

[0026] Preferably, the foaming agent is one or more of water, ethanol, n-propanol, n-butanol, and pentanol.

[0027] Preferably, the viscosity of the hydroxy silicone oil is 10-40 mm 2 / s (25 ° C), the hydroxyl content is 6-12wt%.

[0028] Preferably, the viscosity of the hydrogenated silicone oil is 100-300 mm 2 / s (25℃), hydrogen content is 1.0-1.6wt%.

[0029] Preferably, the raw material formula of the anti-ant gnawing silicone foam sealing material also includes a synergistic filler; preferably, the added amount of the synergistic filler is 4-8 parts by weight.

[0030] In the preparation process of synergistic fillers, chitosan is first protonated in acetic acid and then cross-linked with the phosphate groups of phytic acid through electrostatic interaction. 2+ It chelates with phytic acid to form a three-dimensional network skeleton. Heating promotes the thermal motion of the chitosan molecular chain and enhances the bridging effect of phytic acid. After drying, a micron-nanoscale through-hole porous structure is formed. This carrier has both the rigid support of hydroxyapatite and the toughness of the chitosan-phytic acid network, laying the foundation for subsequent drug loading and mechanical enhancement. Secondly, capsaicin and matrine penetrate the porous carrier. Vacuum impregnation forces the drug solution into the deep pores, where the drug molecules are anchored to the pore walls through hydrogen bonds and van der Waals forces. Polymethylsilsesquioxane and epoxy-terminated silicone oil undergo an epoxy ring-opening reaction catalyzed by triethylamine, forming a dense cross-linked network on the carrier surface, achieving a sustained drug release effect. Capsaicin release stimulates insect chemoreceptors, while matrine simultaneously leaks out and interferes with nerve conduction, creating a dual effect that repels ants. The inorganic (Si-O-Si) backbone of polymethylsilsesquioxane provides rigid support, while the flexible long chains of epoxy-terminated silicone oil impart elasticity. When the sealing material is compressed, the siloxane layer absorbs energy through reversible deformation, while the epoxy crosslinks restrict molecular chain slip, reducing permanent deformation. Furthermore, the nanohydroxyapatite in the porous carrier acts as a "hard point" to resist compression, while the chitosan-phytic acid network dissipates stress through hydrogen bonding. The surface siloxane coating elastically recovers its shape after stress is released, synergistically achieving high rebound rate and low compression set.

[0031] In summary, the synergistic filler of the present invention provides drug storage and primary mechanical skeleton through the inner core porous carrier, and the surface silicone coating layer realizes the controlled release and interface strengthening of the anti-ant synergistic component. The nano-hydroxyapatite reinforcement, chitosan-phytic acid network toughening, and silicone cross-linked network elastic recovery work synergistically, so that the sealing material has excellent mechanical stability while preventing ant invasion.

[0032] Preferably, the anti-ant-eating silicone foam sealing material comprises the following raw materials in parts by weight:

[0033] 40-50 parts of vinyl silicone oil, 19-30 parts of reinforcing filler, 50-60 parts of flame retardant filler, 0.12-0.16 parts of contact agent, 4-8 parts of bait, 1-1.2 parts of odorant, 2-8 parts of structure control agent, 0.2-0.25 parts of inhibitor, 0.6-0.7 parts of platinum catalyst, 2-3.5 parts of foaming agent, 3-5 parts of hydroxy silicone oil, 11-13 parts of hydrogenated silicone oil, and 4-8 parts of synergistic filler.

[0034] Preferably, the preparation method of the synergistic filler is as follows:

[0035] Nano-hydroxyapatite is added to water and ultrasonically dispersed to obtain a hydroxyapatite suspension; chitosan is dissolved in an acetic acid solution, phytic acid is added and stirred; the hydroxyapatite suspension is then added, heated and stirred, centrifuged, and dried to obtain a porous carrier;

[0036] Dissolving capsaicin and matrine in methanol to obtain a synergistic solution; immersing a porous carrier in the synergistic solution, performing vacuum impregnation adsorption, rotary evaporation, and drying to obtain a drug-loaded porous carrier;

[0037] The polymethylsilsesquioxane and the epoxy-terminated silicone oil are dissolved in isopropyl alcohol, triethylamine and a drug-loaded porous carrier are added, the mixture is heated and stirred, filtered, and dried to obtain a synergistic filler.

[0038] Preferably, the weight ratio of the nano-hydroxyapatite, chitosan and phytic acid is 3-8:2-4:0.5-1.5.

[0039] Preferably, the weight ratio of capsaicin, matrine and porous carrier is 0.5-0.7:0.3-0.5:5-10.

[0040] Preferably, the weight ratio of the polymethylsilsesquioxane, epoxy-terminated silicone oil, triethylamine, and drug-loaded porous carrier is 1-3:0.5-2:0.04-0.06:5-10.

[0041] Preferably, the preparation method of the synergistic filler is as follows:

[0042] By weight, 3-8 parts of nano-hydroxyapatite are added to 70-150 parts of water and ultrasonically dispersed for 20-40 minutes to obtain a hydroxyapatite suspension; 2-4 parts of chitosan are dissolved in 100-200 parts of a 1-3 wt% acetic acid solution, 0.5-1.5 parts of phytic acid are added, and the mixture is stirred at 20-30°C and 100-300 rpm for 20-40 minutes; the hydroxyapatite suspension is then added, the mixture is heated to 55-70°C, stirred for 1-3 hours, centrifuged, and freeze-dried to obtain a porous carrier;

[0043] Dissolve 0.5-0.7 parts of capsaicin and 0.3-0.5 parts of matrine in 20-40 parts of methanol to obtain a synergistic solution; immerse 5-10 parts of a porous carrier in the synergistic solution, vacuum immerse and adsorb for 1-2 hours, remove the solvent by rotary evaporation, and vacuum dry to obtain a drug-loaded porous carrier;

[0044] Dissolve 1-3 parts of polymethylsilsesquioxane and 0.5-2 parts of epoxy-terminated silicone oil in 40-60 parts of isopropyl alcohol, add 0.04-0.06 parts of triethylamine and 5-10 parts of drug-loaded porous carrier, stir at 40-50° C. and 100-300 rpm for 2-4 hours, filter, and vacuum dry to obtain a synergistic filler.

[0045] Preferably, the average particle size of the nano-hydroxyapatite is 10-100 nm.

[0046] Preferably, the average molecular weight of the chitosan is 10,000-30,000, and the degree of deacetylation is ≥95%.

[0047] Preferably, the CAS number of the polymethylsilsesquioxane is 68554-70-1.

[0048] Preferably, the viscosity of the epoxy-terminated silicone oil is 200-300 cs (25° C.), and the epoxy value is 0.01-0.03 mol / 100 g.

[0049] Preferably, the ultrasound has a frequency of 20-40 kHz and a power of 200-300 W.

[0050] Preferably, the vacuum impregnation adsorption conditions are -0.1 to -0.05 MPa and 34-50°C.

[0051] Preferably, the temperature of the rotary evaporation is 40-50°C.

[0052] The present invention also provides a method for preparing an ant-resistant silicone foam sealing material, comprising the following steps:

[0053] Step S1: adding a portion (1 / 2 of the formula) of vinyl silicone oil, reinforcing filler, flame retardant filler, contact agent, bait, odorant, structure control agent and inhibitor, and platinum catalyst to a planetary mixer and mixing uniformly to prepare component A;

[0054] Step S2: adding the remaining (1 / 2 of the formula amount) vinyl silicone oil, reinforcing filler, flame retardant filler, contact agent, bait, odorant, structure control agent and foaming agent, hydroxy silicone oil, and hydrogen silicone oil to a planetary mixer and mixing uniformly to prepare component B;

[0055] Step S3: pouring component A and component B into a constant temperature tank, stirring, extruding on a calendering line, and curing and shaping to obtain a silicone foam sealing material that is ant-proof.

[0056] Preferably, in steps S1 and S2, the rotation speed of the planetary mixer is 50-60 rpm.

[0057] Preferably, in step S3, the components A and B are poured into the thermostatic tank at a weight ratio of 1-2:1-2.

[0058] Preferably, in step S3, the temperature of the thermostatic tank is set to 20-25° C., and the mixture is stirred at 1000-3000 rpm for 40-60 seconds.

[0059] Preferably, in step S3, the curing temperature is 90-110° C. and the curing time is 3-5 minutes.

[0060] Preferably, in step S2, the synergistic filler is uniformly mixed with other raw materials to form component B, and the other steps are the same.

[0061] Preferably, a method for preparing a silicone foam sealing material that is ant-resistant comprises the following steps:

[0062] Step S1: adding a portion (1 / 2 of the formula) of vinyl silicone oil, reinforcing filler, flame retardant filler, contact agent, bait, odorant, structure control agent and inhibitor, and platinum catalyst to a planetary mixer and mixing uniformly to prepare component A;

[0063] Step S2: The remaining (1 / 2 of the formula) vinyl silicone oil, reinforcing filler, flame retardant filler, contact agent, bait, odorant, structure control agent and foaming agent, hydroxy silicone oil, hydrogen silicone oil, and synergistic filler are mixed and added to a planetary mixer and mixed evenly to prepare component B;

[0064] Step S3: pouring component A and component B into a constant temperature tank, stirring, extruding on a calendering line, and curing and shaping to obtain a silicone foam sealing material that is ant-proof.

[0065] Compared with the prior art, the advantages and beneficial effects of the present invention are:

[0066] The present invention provides a silicone foam sealing material that is resistant to ant gnawing and a preparation method thereof. By introducing contact killers, attractants and odorants, ants and insects are driven away from the sealing material upon smelling a strong or sensitive odor, or the odor and toxicity of the ants and insects are released after they have bitten the sealing material. By transmitting information between groups, other ants and rodents are effectively prevented from continuing to gnaw. The added contact killers, attractants and odorants have good compatibility with silicone rubber, have little effect on the sealing performance of the sealing material, and meet environmental protection requirements. DETAILED DESCRIPTION

[0067] The following is a clear and complete description of the technical solutions in the embodiments of the present invention. Obviously, the embodiments described are only some embodiments of the present invention, not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making any creative efforts are within the scope of protection of the present invention.

[0068] The raw materials used in the examples and comparative examples of the present invention were all self-made or commercially available, but are not limited to the following materials:

[0069] Vinyl silicone oil: viscosity of 1500 mPa·s (25° C.), vinyl content of 0.23 wt %, purchased from Jiangsu Kexing New Materials Co., Ltd.

[0070] Fumed silica: Specific surface area is 200g / m 2 , purchased from Zhejiang Fujite Group Co., Ltd.

[0071] Fumed silica: Specific surface area is 400g / m 2 , purchased from Zhejiang Fujite Group Co., Ltd.

[0072] Hydroxyl silicone oil: hydroxyl content 6wt%, viscosity 40mm 2 / s (25°C), purchased from Jiangxi Guibo Chemical Co., Ltd.

[0073] Hydroxyl silicone oil: hydroxyl content 8wt%, viscosity 40mm 2 / s (25°C), purchased from Jiangxi Guibo Chemical Co., Ltd.

[0074] Hydroxyl silicone oil: hydroxyl content 12wt%, viscosity 40mm 2 / s (25°C), purchased from Jiangxi Guibo Chemical Co., Ltd.

[0075] Hydrogenated silicone oil: hydrogen content 1.4wt%, viscosity 150mm 2 / s (25 °C), purchased from Shandong Longhui Chemical Co., Ltd.

[0076] Hydrogenated silicone oil: hydrogen content 1.6wt%, viscosity 150mm 2 / s (25 °C), purchased from Shandong Longhui Chemical Co., Ltd.

[0077] Nanohydroxyapatite: with an average particle size of 20 nm, purchased from Suzhou Yongqinquan Intelligent Equipment Co., Ltd.

[0078] Chitosan: average molecular weight of 20,000, deacetylation degree ≥ 95%, purchased from Shenzhen Lijing Biochemical Technology Co., Ltd.

[0079] Polymethylsilsesquioxane: CAS number 68554-70-1, purchased from Zhongshan Dixin Chemical Co., Ltd.

[0080] Epoxy-terminated silicone oil: viscosity 250 cs (25° C.), epoxy value 0.02 mol / 100 g, purchased from Jiaxing United Chemical Co., Ltd.

[0081] Anti-mildew paint: Model 9512-Y, purchased from Beijing Kalide Technology Development Co., Ltd.

[0082] Example 1

[0083] This embodiment provides a silicone foam sealing material that is ant-resistant, comprising the following raw materials in parts by weight:

[0084] 40 parts of vinyl silicone oil, 22 parts of reinforcing filler, 60 parts of flame retardant filler, 0.12 parts of contact agent, 8 parts of bait, 1.2 parts of odorant, 2 parts of structure control agent, 0.2 parts of inhibitor, 0.6 parts of platinum catalyst, 3 parts of foaming agent, hydroxyl silicone oil (hydroxyl content 6wt%, viscosity 40mm 2 / s) 5 parts, hydrogenated silicone oil (hydrogen content 1.4wt%, viscosity 150mm 2 / s)12 copies.

[0085] The reinforcing filler is composed of carbon black and fumed silica (specific surface area of ​​200g / m 2 ) are composed in a weight ratio of 1:10.

[0086] The flame retardant filler consists of aluminum hydroxide, magnesium hydroxide and zinc borate in a weight ratio of 15:10:5.

[0087] The contact killer is pyrethroid (beta-cypermethrin).

[0088] The bait is diatomaceous earth.

[0089] The odorant is camphor oil.

[0090] The foaming agent is water.

[0091] The structure control agent is α,ω-dihydroxypolydimethylsiloxane.

[0092] The inhibitor is tetramethyltetravinylcyclotetrasiloxane.

[0093] The platinum catalyst is chloroplatinic acid.

[0094] A method for preparing an ant-resistant silicone foam sealing material comprises the following steps:

[0095] Step S1: 20 parts of vinyl silicone oil, 11 parts of reinforcing filler, 30 parts of flame retardant filler, 0.06 parts of contact agent, 4 parts of bait, 0.6 parts of odorant, 1 part of structure control agent, 0.2 parts of inhibitor, and 0.6 parts of platinum catalyst were mixed and added into a planetary mixer, and mixed at a speed of 50 rpm to obtain component A;

[0096] Step S2: Add another portion of 20 parts of vinyl silicone oil, 11 parts of reinforcing filler, 30 parts of flame retardant filler, 0.06 parts of contact agent, 4 parts of bait, 0.6 parts of odorant, 1 part of structure control agent, 3 parts of foaming agent, 5 parts of hydroxy silicone oil, and 12 parts of hydrogen silicone oil to a planetary mixer, mix well at 50 rpm, and prepare component B;

[0097] Step S3: Pour component A and component B into a thermostatic tank in a weight ratio of 1:1, set the temperature to 20°C, stir at 1000 rpm for 60 seconds, extrude on a calendering line, and cure at 100°C for 4 minutes to obtain an ant-proof silicone foam sealing material.

[0098] Example 2

[0099] This embodiment provides a silicone foam sealing material that is ant-resistant, comprising the following raw materials in parts by weight:

[0100] 44 parts of vinyl silicone oil, 19 parts of reinforcing filler, 60 parts of flame retardant filler, 0.14 parts of contact agent, 4 parts of bait, 1 part of odorant, 3 parts of structure control agent, 0.25 parts of inhibitor, 0.7 parts of platinum catalyst, 3.5 parts of foaming agent, hydroxyl silicone oil (hydroxyl content 8wt%, viscosity 40mm 2 / s) 3 parts, hydrogenated silicone oil (hydrogen content 1.6wt%, viscosity 150mm 2 / s)11 copies.

[0101] The reinforcing filler is composed of carbon black and fumed silica (specific surface area of ​​400g / m 2 ) is composed of 1.5:8 by weight.

[0102] The flame retardant filler consists of aluminum hydroxide and magnesium hydroxide in a weight ratio of 20:10.

[0103] The contact killer is a phenylpyrazole (fipronil).

[0104] The bait is denatonium benzoate.

[0105] The odorant is limonin.

[0106] The foaming agent is n-propanol.

[0107] The structure control agent is dihydrocarbyldialkoxysilane.

[0108] The inhibitor is tetramethyltetravinylcyclotetrasiloxane.

[0109] The platinum catalyst is a platinum complex.

[0110] A method for preparing an ant-resistant silicone foam sealing material comprises the following steps:

[0111] Step S1: 22 parts of vinyl silicone oil, 9.5 parts of reinforcing filler, 30 parts of flame retardant filler, 0.07 parts of contact agent, 2 parts of bait, 0.5 parts of odorant, 1.5 parts of structure control agent, 0.25 parts of inhibitor, and 0.7 parts of platinum catalyst were mixed and added into a planetary mixer, and mixed at a speed of 50 rpm to obtain component A;

[0112] Step S2: Add another portion of 22 parts of vinyl silicone oil, 9.5 parts of reinforcing filler, 30 parts of flame retardant filler, 0.07 parts of contact agent, 2 parts of bait, 0.5 parts of odorant, 1.5 parts of structure control agent, 3.5 parts of foaming agent, 3 parts of hydroxy silicone oil, and 11 parts of hydrogen silicone oil to a planetary mixer, mix well at 50 rpm, and prepare component B;

[0113] Step S3: Pour component A and component B into a thermostatic tank in a weight ratio of 1:1, set the temperature to 20°C, stir at 1500 rpm for 60 seconds, extrude on a calendering line, and cure at 100°C for 4 minutes to obtain an ant-proof silicone foam sealing material.

[0114] Example 3

[0115] This embodiment provides a silicone foam sealing material that is ant-resistant, comprising the following raw materials in parts by weight:

[0116] 50 parts of vinyl silicone oil, 30 parts of reinforcing filler, 50 parts of flame retardant filler, 0.16 parts of contact agent, 6 parts of bait, 1.2 parts of odorant, 8 parts of structure control agent, 0.2 parts of inhibitor, 0.6 parts of platinum catalyst, 2 parts of foaming agent, hydroxyl silicone oil (hydroxyl content 12wt%, viscosity 40mm 2 / s) 3 parts, hydrogenated silicone oil (hydrogen content 1.4wt%, viscosity 150mm 2 / s)13 copies.

[0117] The reinforcing filler is composed of carbon black, fumed silica (specific surface area of ​​200g / m 2 ), fumed silica (specific surface area of ​​400g / m 2 ) is composed of 1:10:4 by weight.

[0118] The flame retardant filler is composed of magnesium hydroxide and zinc oxide in a weight ratio of 20:5.

[0119] The contact killer consists of glycine and erythritol in a weight ratio of 0.02:0.06.

[0120] The bait is talcum powder.

[0121] The odorant is decanal.

[0122] The foaming agent is ethanol.

[0123] The structure control agent is diphenylsilanediol.

[0124] The inhibitor is composed of tetramethyltetravinylcyclotetrasiloxane and diallyl maleate in a weight ratio of 0.1:0.1.

[0125] The platinum catalyst is platinum water.

[0126] A method for preparing an ant-resistant silicone foam sealing material comprises the following steps:

[0127] Step S1: 25 parts of vinyl silicone oil, 15 parts of reinforcing filler, 25 parts of flame retardant filler, 0.08 parts of contact agent, 3 parts of bait, 0.6 parts of odorant, 4 parts of structure control agent, 0.2 parts of inhibitor, and 0.6 parts of platinum catalyst were mixed and added into a planetary mixer, and mixed at a speed of 50 rpm to obtain component A;

[0128] Step S2: Add another portion of 25 parts of vinyl silicone oil, 15 parts of reinforcing filler, 25 parts of flame retardant filler, 0.08 parts of contact agent, 3 parts of bait, 0.6 parts of odorant, 4 parts of structure control agent, 2 parts of foaming agent, 3 parts of hydroxy silicone oil, and 13 parts of hydrogen silicone oil to a planetary mixer, mix well at 50 rpm, and prepare component B;

[0129] Step S3: Pour component A and component B into a thermostatic tank in a weight ratio of 1:1, set the temperature to 20°C, stir at 1800 rpm for 60 seconds, extrude on a calendering line, and cure at 110°C for 3 minutes to obtain an ant-proof silicone foam sealing material.

[0130] Example 4

[0131] Compared with Example 1, this embodiment differs in that: 4 parts by weight of synergistic filler is added to the raw material formula of the anti-ant gnawing silicone foam sealing material; accordingly, in step S2, 4 parts by weight of synergistic filler is evenly mixed with other raw materials to form component B, and the other steps are the same.

[0132] The preparation method of the synergistic filler is as follows:

[0133] 5 parts by weight of nano-hydroxyapatite (average particle size of 20 nm) were added to 100 parts of water and ultrasonically dispersed at an ultrasonic frequency of 40 kHz and a power of 300 W for 30 minutes to obtain a hydroxyapatite suspension; 3 parts of chitosan (average molecular weight of 20,000, degree of deacetylation ≥ 95%) were dissolved in 100 parts of a 2 wt% acetic acid solution, 1 part of phytic acid was added, and the mixture was stirred at 25° C. and 200 rpm for 30 minutes; the hydroxyapatite suspension was then added, the mixture was heated to 60° C. and stirred for 2 hours, centrifuged, and freeze-dried to obtain a porous carrier;

[0134] Dissolve 0.6 parts of capsaicin and 0.4 parts of matrine in 30 parts of methanol to obtain a synergistic solution; immerse 8 parts of a porous carrier in the synergistic solution, vacuum immerse and adsorb at -0.09 MPa and 40°C for 1 hour, remove the solvent by rotary evaporation at 45°C, and vacuum dry to obtain a drug-loaded porous carrier;

[0135] 2 parts of polymethylsilsesquioxane and 1 part of epoxy-terminated silicone oil (viscosity of 250 cs, epoxy value of 0.02 mol / 100 g) were dissolved in 50 parts of isopropanol, 0.05 parts of triethylamine and 8 parts of drug-loaded porous carrier were added, and the mixture was stirred at 45°C and 200 rpm for 3 hours, filtered, and vacuum dried to obtain a synergistic filler.

[0136] Example 5

[0137] Compared with Example 2, this embodiment differs in that: 5 parts by weight of synergistic filler is added to the raw material formula of the anti-ant gnawing silicone foam sealing material; accordingly, in step S2, 5 parts by weight of synergistic filler is evenly mixed with other raw materials to form component B, and the other steps are the same.

[0138] The preparation method of the synergistic filler is as follows:

[0139] 5 parts by weight of nano-hydroxyapatite (average particle size of 20 nm) were added to 100 parts of water and ultrasonically dispersed at an ultrasonic frequency of 40 kHz and a power of 300 W for 30 minutes to obtain a hydroxyapatite suspension; 3 parts of chitosan (average molecular weight of 20,000, degree of deacetylation ≥ 95%) were dissolved in 100 parts of a 2 wt% acetic acid solution, 1 part of phytic acid was added, and the mixture was stirred at 25° C. and 200 rpm for 30 minutes; the hydroxyapatite suspension was then added, the mixture was heated to 60° C. and stirred for 2 hours, centrifuged, and freeze-dried to obtain a porous carrier;

[0140] Dissolve 0.6 parts of capsaicin and 0.4 parts of matrine in 30 parts of methanol to obtain a synergistic solution; immerse 8 parts of a porous carrier in the synergistic solution, vacuum immerse and adsorb at -0.09 MPa and 40°C for 1 hour, remove the solvent by rotary evaporation at 45°C, and vacuum dry to obtain a drug-loaded porous carrier;

[0141] 2 parts of polymethylsilsesquioxane and 1 part of epoxy-terminated silicone oil (viscosity of 250 cs, epoxy value of 0.02 mol / 100 g) were dissolved in 50 parts of isopropanol, 0.05 parts of triethylamine and 8 parts of drug-loaded porous carrier were added, and the mixture was stirred at 45°C and 200 rpm for 3 hours, filtered, and vacuum dried to obtain a synergistic filler.

[0142] Example 6

[0143] Compared with Example 3, this embodiment differs in that: 8 parts by weight of synergistic filler is added to the raw material formula of the anti-ant gnawing silicone foam sealing material; accordingly, in step S2, 8 parts by weight of synergistic filler is evenly mixed with other raw materials to form component B, and the other steps are the same.

[0144] The preparation method of the synergistic filler is as follows:

[0145] 5 parts by weight of nano-hydroxyapatite (average particle size of 20 nm) were added to 100 parts of water and ultrasonically dispersed at an ultrasonic frequency of 40 kHz and a power of 300 W for 30 minutes to obtain a hydroxyapatite suspension; 3 parts of chitosan (average molecular weight of 20,000, degree of deacetylation ≥ 95%) were dissolved in 100 parts of a 2 wt% acetic acid solution, 1 part of phytic acid was added, and the mixture was stirred at 25° C. and 200 rpm for 30 minutes; the hydroxyapatite suspension was then added, the mixture was heated to 60° C. and stirred for 2 hours, centrifuged, and freeze-dried to obtain a porous carrier;

[0146] Dissolve 0.6 parts of capsaicin and 0.4 parts of matrine in 30 parts of methanol to obtain a synergistic solution; immerse 8 parts of a porous carrier in the synergistic solution, vacuum immerse and adsorb at -0.09 MPa and 40°C for 1 hour, remove the solvent by rotary evaporation at 45°C, and vacuum dry to obtain a drug-loaded porous carrier;

[0147] 2 parts of polymethylsilsesquioxane and 1 part of epoxy-terminated silicone oil (viscosity of 250 cs, epoxy value of 0.02 mol / 100 g) were dissolved in 50 parts of isopropanol, 0.05 parts of triethylamine and 8 parts of drug-loaded porous carrier were added, and the mixture was stirred at 45°C and 200 rpm for 3 hours, filtered, and vacuum dried to obtain a synergistic filler.

[0148] Comparative Example 1

[0149] This comparative example is a blank example. Compared with Example 1, the difference is that the contact agent, bait and odorant in Example 1 are not added, and the other steps are the same.

[0150] Comparative Example 2

[0151] Compared with Example 1, this comparative example differs in that: the contact agent, bait and odorant in Example 1 are not added, a commercially available mildew-proof coating is coated on the surface of the sealing material, and the other steps are the same.

[0152] Comparative Example 3

[0153] This comparative example is a blank example. Compared with Example 4, the difference is that the preparation method of the synergistic filler is different, as follows: The preparation method of the synergistic filler is as follows:

[0154] 5 parts by weight of nano-hydroxyapatite (average particle size of 20 nm) were added to 100 parts of water and ultrasonically dispersed at an ultrasonic frequency of 40 kHz and a power of 300 W for 30 minutes to obtain a hydroxyapatite suspension; 3 parts of chitosan (average molecular weight of 20,000, degree of deacetylation ≥ 95%) were dissolved in 100 parts of a 2 wt% acetic acid solution, 1 part of phytic acid was added, and the mixture was stirred at 25° C. and 200 rpm for 30 minutes; the hydroxyapatite suspension was then added, the mixture was heated to 60° C. and stirred for 2 hours, centrifuged, and freeze-dried to obtain a porous carrier;

[0155] 0.6 parts of capsaicin and 0.4 parts of matrine were dissolved in 30 parts of methanol to obtain a synergistic liquid; 8 parts of a porous carrier were immersed in the above-mentioned synergistic liquid, vacuum impregnation and adsorption were carried out at -0.09 MPa and 40°C for 1 hour, the solvent was removed by rotary evaporation at 45°C, and vacuum drying was carried out to obtain a synergistic filler.

[0156] Performance Testing

[0157] The silicone foam sealing materials prepared in Examples 1-6 and Comparative Examples 1-3 were respectively prepared into 100 mm × 100 mm × 3 mm samples and tested for compression rebound stress and compression set according to ASTM D1056. The silicone foam sealing materials were also prepared into 100 mm × 100 mm × 3 mm samples and tested for vertical burning rating according to UL-94. Furthermore, the silicone foam sealing materials were prepared into 20 mm × 20 mm × 3 mm samples and placed in a rat, insect, and ant test chamber for five days to evaluate the degree of bite damage. The test results are shown in Table 1.

[0158] Table 1: Performance test results of silicone foam sealing materials

[0159]

[0160] From the above test results, it can be seen that when comparing Examples 1-6 with Comparative Examples 1-3, compared with Comparative Example 1 in which no contact agent, bait agent, or odorant is added, Comparative Example 2 does not add contact agent, bait agent, or odorant but applies a commercially available mildew-proof coating (its flame retardant properties are reduced, and its effect in repelling or poisoning rats, insects, and ants is limited), Examples 1-3 directly add contact agent, bait agent, and odorant to the sealing material, which can effectively improve the sealing material's anti-ant gnawing performance, but its compression rebound performance and compression deformation resistance are slightly reduced; for this reason, based on the raw material formula of Examples 1-3, Examples 4-6 add a synergistic filler by a specific method (in comparison, Comparative Example 3 cannot achieve the same effect due to the different synergistic fillers), which can synergize with other components in the raw material formula to further improve the sealing material's anti-ant gnawing performance, and make it have excellent flame retardant properties, compression rebound performance, and compression deformation resistance, which is more conducive to protecting the integrity of the sealing material. Through the above comparison, the importance of the technical solution defined in the present invention for its technical effect is demonstrated.

[0161] The above is a preferred embodiment of the present invention. It should be pointed out that for ordinary technicians in this technical field, several improvements and modifications can be made without departing from the principles of the present invention. These improvements and modifications should also be regarded as within the scope of protection of the present invention.

Claims

1. A silicone foam sealing material that is resistant to ant gnawing, characterized in that: Calculated by weight, it includes the following raw materials: 30-50 parts of vinyl silicone oil, 10-30 parts of reinforcing filler, 40-80 parts of flame retardant filler, 0.02-0.2 parts of contact agent, 2-20 parts of bait, 0.2-2 parts of odorant, 2-8 parts of structure control agent, 0.1-0.3 parts of inhibitor, 0.3-0.7 parts of platinum catalyst, 1-5 parts of foaming agent, 2-6 parts of hydroxy silicone oil, and 5-15 parts of hydrogenated silicone oil.

2. The ant-proof silicone foam sealing material according to claim 1, characterized in that: The contact killer is one or more of pyrethroids, neonicotinoids, phenylpyrazoles, boric acid, glycine, erythritol, and fipronil; the bait is one or more of diatomaceous earth, talc, capsaicin, dihydrocapsaicin, and denatonium benzoate; the odorant is one or more of camphor oil, peppermint oil, limonin, limonene, citral, decanal, octanal, and nonanal.

3. The ant-proof silicone foam sealing material according to claim 1, characterized in that: The reinforcing filler is composed of carbon black and white carbon black; the flame retardant filler is one or more of aluminum hydroxide, zinc oxide, zinc borate, and magnesium hydroxide.

4. The ant-proof silicone foam sealing material according to claim 1, characterized in that: The structure control agent is one or more of diphenylsilanediol, α,ω-dihydroxypolydimethylsiloxane, and dialkyldialkoxysilane; the inhibitor is one or more of 2-methyl-3-butyn-2-ol, 1-ethynylcyclohexanol, tetramethyltetravinylcyclotetrasiloxane, and diallyl maleate.

5. The ant-proof silicone foam sealing material according to claim 1, characterized in that: The platinum catalyst includes at least one platinum compound, and the platinum compound includes platinum water, chloroplatinic acid or a platinum complex; the foaming agent is one or more of water, ethanol, n-propanol, n-butanol and pentanol.

6. The ant-proof silicone foam sealing material according to claim 1, characterized in that: The viscosity of the vinyl silicone oil is 1000-3000 mPa·s, and the vinyl content is 0.1-0.4 wt%; the viscosity of the hydroxy silicone oil is 10-40 mm 2 / s, hydroxyl content is 6-12wt%; the viscosity of the hydrogen silicone oil is 100-300mm 2 / s, and the hydrogen content is 1.0-1.6wt%.

7. The ant-proof silicone foam sealing material according to claim 1, characterized in that: The raw material formula of the anti-ant gnawing silicone foam sealing material also includes a synergistic filler; the added amount of the synergistic filler is 4-8 parts by weight.

8. The ant-proof silicone foam sealing material according to claim 7, characterized in that: The preparation method of the synergistic filler is as follows: Nano-hydroxyapatite is added to water and ultrasonically dispersed to obtain a hydroxyapatite suspension; chitosan is dissolved in an acetic acid solution, phytic acid is added and stirred; the hydroxyapatite suspension is then added, heated and stirred, centrifuged, and dried to obtain a porous carrier; Dissolving capsaicin and matrine in methanol to obtain a synergistic solution; immersing a porous carrier in the synergistic solution, performing vacuum impregnation adsorption, rotary evaporation, and drying to obtain a drug-loaded porous carrier; The polymethylsilsesquioxane and the epoxy-terminated silicone oil are dissolved in isopropyl alcohol, triethylamine and a drug-loaded porous carrier are added, the mixture is heated and stirred, filtered, and dried to obtain a synergistic filler.

9. The ant-proof silicone foam sealing material according to claim 8, characterized in that: The weight ratio of the nano-hydroxyapatite, chitosan and phytic acid is 3-8:2-4:0.5-1.5; the weight ratio of capsaicin, matrine and porous carrier is 0.5-0.7:0.3-0.5:5-10; the weight ratio of polymethylsilsesquioxane, epoxy-terminated silicone oil, triethylamine and drug-loaded porous carrier is 1-3:0.5-2:0.04-0.06:5-10.

10. The method for preparing the ant-proof silicone foam sealing material according to any one of claims 1 to 9, characterized in that: The steps include: Step S1: adding a portion of vinyl silicone oil, reinforcing filler, flame retardant filler, contact agent, bait, odorant, structure control agent and inhibitor, and platinum catalyst to a planetary mixer and mixing uniformly to prepare component A; Step S2: Mix the remaining vinyl silicone oil, reinforcing filler, flame retardant filler, contact agent, bait, odorant, structure control agent and foaming agent, hydroxy silicone oil, hydrogen silicone oil or synergistic filler and add them to a planetary mixer, mix them evenly as component B; Step S3: pouring component A and component B into a constant temperature tank, stirring, extruding on a calendering line, and curing and shaping to obtain a silicone foam sealing material that is ant-proof.

Images