Composite high-temperature insulating material as well as preparation method and application thereof

Abstract

The invention provides a composite high-temperature insulating material as well as a preparation method and application thereof. The composite high-temperature insulating material comprises a silica gel composite material and a mica paper composite material; wherein the raw materials of the silica gel composite material comprise the following components in parts by weight: 100 parts of raw silicone rubber; 1-50 parts by weight of silicone resin; 0-15 parts by weight of a structured control agent; 1-60 parts by weight of a reinforcing system; 10-150 parts by weight of a main flame retardant system; 5-100 parts by weight of a synergistic flame retardant system; 5-150 parts by weight of an inorganic filling system; 0-300 parts by weight of an organic solvent; the synergistic auxiliary agent comprises 1-200ppm of a platinum compound or a complex based on the platinum content; 1-10 parts by weight of a curing agent system; 0-1 part by weight of a curing inhibitor system; and 0.1-10 parts by weight of a color matching system. In a special system, the silica gel composite material is compounded with the mica paper composite material by adopting a set process through the formula design of the silica gel composite material, so that the flame retardant property is excellent, and meanwhile, the requirements that the high-temperature sintering non-cracking shape is kept well and the crusting property is complete are met, so that the flame-retardant, fireproof and fire-resistant requirements are met.

Description

Technical Field

[0001] The invention relates to the field of modification and processing of polymer insulating composite materials, and in particular to a composite high-temperature insulating material and a preparation method and application thereof. Background Art

[0002] The fields of new energy and energy storage are developing rapidly, and safety protection is essential behind the prosperity. Thermal runaway has always been the focus of attention in the fields of new energy power batteries and energy storage. When thermal runaway occurs, if there is a material that can effectively insulate under high temperature conditions, it can provide valuable time for disposal or escape. At the same time, sometimes due to space constraints, the thickness of the material used is limited, so thin products that meet high-temperature insulation and dimensional stability under high temperature have great application value. Summary of the invention

[0003] In view of the above-mentioned shortcomings of the prior art, the purpose of the present invention is to provide a composite high-temperature insulation material and a preparation method and application thereof, which can simultaneously meet the requirements of high-temperature insulation and dimensional retention, so as to solve the problems in the prior art.

[0004] The technical solution of the present invention is:

[0005] The present invention provides a composite high-temperature insulating material, which comprises a silica gel composite material and a mica paper composite material; wherein the raw materials of the silica gel composite material comprise the following components in parts by weight:

[0006] 100 parts by weight of silicone rubber;

[0007] Silicone resin 1-50 parts by weight;

[0008] 0-15 parts by weight of a structural control agent;

[0009] Reinforcement system 1-60 parts by weight;

[0010] Main flame retardant system 10-150 parts by weight;

[0011] Synergistic flame retardant system 5-100 parts by weight;

[0012] Inorganic filler system 5-150 parts by weight;

[0013] 0-300 parts by weight of organic solvent;

[0014] The synergist is calculated based on the platinum content, and the platinum compound or complex is 1-200ppm;

[0015] 1-10 parts by weight of curing agent system;

[0016] Curing inhibitor system, 0-1 parts by weight;

[0017] Coloring system 0.1-10 parts by weight.

[0018] The present invention also provides a method for preparing a composite high-temperature insulating material, the method comprising:

[0019] 1) Solid silica gel kneading and mixing process: kneading and mixing silicone rubber raw rubber, silicone resin, reinforcement system, structural control agent, main flame retardant system, synergistic flame retardant system, inorganic filler system, platinum compound or complex, and color matching system, and then adding curing agent system through an open mill to obtain solid silicone rubber compound; wherein the silicone rubber raw rubber is silicone rubber solid raw rubber;

[0020] 2) Liquid silicone rubber mixing process: kneading and mixing silicone rubber raw rubber, silicone resin, reinforcement system, structural control agent, main flame retardant system, synergistic flame retardant system, inorganic filler system, platinum compound or complex, color matching system, curing inhibitor system, and curing agent system to obtain liquid silicone rubber mixed rubber; wherein the silicone rubber raw rubber system is a silicone rubber liquid raw rubber system;

[0021] 3) Compounding the solid silicone rubber compound and the mica paper composite material component described in step 1) by calendering using a calender to form a composite high-temperature insulating material;

[0022] Or, the solid silicone rubber compound described in step 1) is dissolved in an organic solvent, and compounded with the mica paper composite material component by a scraping machine to form a composite high-temperature insulating material;

[0023] Or, the liquid silicone rubber compound described in step 2) is compounded with the mica paper composite material component by a scraping machine to form a composite high-temperature insulating material;

[0024] Alternatively, the liquid silicone rubber compound described in step 2) is compounded with the mica paper composite material component by dipping in a dipping machine to form a composite high-temperature insulating material.

[0025] The present invention also provides applications of the composite high-temperature insulating material as described above in the present invention and / or the composite high-temperature insulating material prepared by the preparation method as described above in the present invention in the field of new energy and energy storage.

[0026] By adopting the above technical solution, the beneficial effects of the present invention are:

[0027] In the special system of the present invention, excellent flame retardant performance is guaranteed, while meeting the requirements of high temperature sintering without cracking, maintaining good shape and complete crusting, so as to achieve the requirements of flame retardancy, fire prevention and fire resistance. BRIEF DESCRIPTION OF THE DRAWINGS

[0028] Figure 1 Shown is a physical picture of the silica gel composite material layer of Example 3 of the present invention.

[0029] Figure 2 Shown is a physical picture of the mica paper composite material layer of Example 3 of the present invention.

[0030] Figure 3 This shows the state of Example 3 after being treated in a muffle furnace at 800°C. DETAILED DESCRIPTION

[0031] Hereinafter, the composite high temperature insulation material, preparation method and application implementation manner provided by the present invention will be described in detail.

[0032] The "range" disclosed in the present application is defined in the form of a lower limit and an upper limit, and a given range is defined by selecting a lower limit and an upper limit, and the selected lower limit and upper limit define the boundaries of the particular range. The range defined in this way can be inclusive or exclusive of the end values, and can be arbitrarily combined, that is, any lower limit can be combined with any upper limit to form a range. For example, if a range of 60 to 120 and 80 to 110 is listed for a particular parameter, it is understood that a range of 60 to 110 and 80 to 120 is also expected. In addition, if the minimum range values ​​1 and 2 are listed, and if the maximum range values ​​3, 4 and 5 are listed, the following ranges can all be expected: 1 to 3, 1 to 4, 1 to 5, 2 to 3, 2 to 4 and 2 to 5. In the present application, unless otherwise specified, the numerical range "a to b" represents an abbreviation of any real number combination between a and b, where a and b are both real numbers. For example, the numerical range "0-5" means that all real numbers between "0-5" are listed in this document, and "0-5" is just an abbreviation of these numerical combinations. In addition, when a parameter is expressed as an integer ≥ 2, it is equivalent to disclosing that the parameter is, for example, an integer of 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, etc.

[0033] After extensive research and exploration, the inventor of the present invention designed a specific formula, especially in combination with a mica paper composite material, and further optimized the design and process route for processing to ensure excellent flame retardant performance, while meeting the requirements of high-temperature sintering without cracking, maintaining a good shape, and complete crusting, so as to achieve the requirements of flame retardancy, fire prevention, and fire resistance. On this basis, this application was completed.

[0034]

Composite high temperature insulation material

[0035] The present invention provides a composite high-temperature insulating material, which comprises a silica composite material and a mica paper composite material. The silica composite material comprises silicone rubber raw rubber, silicone resin, a structural control agent, a reinforcement system, a main flame retardant system, a synergistic flame retardant system, an inorganic filler system, an organic solvent, a synergistic auxiliary agent, a curing inhibitor system, a curing agent system, and a coloring system.

[0036] In the composite high-temperature insulating material provided by the present invention, the raw materials of the silica gel composite material include 100 parts by weight of silicone rubber raw rubber.

[0037] Further, the molecular weight of the silicone rubber raw rubber is 0.1-1.1 million molecular weight, and the vinyl content is 0%-5%. Optionally, the molecular weight of the silicone rubber raw rubber can be, for example, 0.1-20,000 molecular weight, 20,000-150,000 molecular weight, 20,000-250,000 molecular weight, 150,000-250,000 molecular weight, 150,000-450,000 molecular weight, 450,000-600,000 molecular weight, 600,000-700,000 molecular weight, 500,000-700,000 molecular weight, 500,000-100,000 molecular weight, 100,000-450,000 molecular weight, 500,000-600,000 molecular weight, 100,000-600,000 molecular weight, 450,000-700,000 molecular weight, 700,000-1.1 million molecular weight, etc. Optionally, the vinyl content is 0%-0.5%, 0.5-2%, 2-5%, 0.1-4.5%, 4.5-5%, 1-1.3%, 1-2%, 1-2.4%, etc.

[0038] Furthermore, the silicone rubber raw rubber is methyl vinyl silicone rubber raw rubber.

[0039] Furthermore, the silicone rubber raw rubber is silicone rubber liquid raw rubber and / or silicone rubber solid raw rubber.

[0040] In the composite high-temperature insulating material provided by the present invention, the raw materials of the silica gel composite material include 1-50 parts by weight of silicone resin. Optionally, the silicone resin is 1-25 parts by weight, 5-25 parts by weight, 25-50 parts by weight, 3-35 parts by weight, 15-35 parts by weight, 35-50 parts by weight, etc.

[0041] Furthermore, the silicone resin is selected from one or more of dry environmentally friendly silicone resin, mica bonding silicone resin, environmentally friendly silicone resin, methyl MQ silicone resin, and vinyl MQ silicone resin.

[0042] In the composite high-temperature insulating material provided by the present invention, the raw materials of the silica composite material include 0-15 parts by weight of a structural control agent. Optionally, the structural control agent may be, for example, 0.1-1 parts by weight, 2-12 parts by weight, 12-15 parts by weight, 0.3-10 parts by weight, 10-15 parts by weight, etc.

[0043] Furthermore, the structuring control agent is selected from one or more of hydroxy silicone oil and silane coupling agent.

[0044] In the composite high-temperature insulating material provided by the present invention, the raw materials of the silica gel composite material include 1-60 parts by weight of a reinforcement system. Optionally, the reinforcement system is 1-35 parts by weight, 35-60 parts by weight, 1-5 parts by weight, 5-35 parts by weight, 35-60 parts by weight, 1-10 parts by weight, 10-15 parts by weight, 15-25 parts by weight, 25-35 parts by weight or 10-35 parts by weight.

[0045] Furthermore, the reinforcement system is selected from one or more of fumed silica or precipitated silica, for example, silica 813, silica 520, modified silica HL150A, and the like.

[0046] In the composite high-temperature insulating material provided by the present invention, the raw materials of the silica gel composite material include 10-150 parts by weight of the main flame retardant system. Optionally, the main flame retardant system is 10-60 parts by weight, 60-150 parts by weight, 15-70 parts by weight, 70-150 parts by weight, 10-40 parts by weight, 40-80 parts by weight, 80-120 parts by weight, 80-150 parts by weight, 25-60 parts by weight, etc.

[0047] Furthermore, the main flame retardant system is selected from one or more of aluminum hydroxide and magnesium hydroxide.

[0048] In the composite high-temperature insulating material provided by the present invention, the raw materials of the silica gel composite material include 5-100 parts by weight of the synergistic flame retardant system. Optionally, the synergistic flame retardant system is 5-30 parts by weight, 30-80 parts by weight, 80-100 parts by weight, 10-50 parts by weight, 15-60 parts by weight, etc.

[0049] Furthermore, the synergistic flame retardant system is selected from one or more of zinc borate, magnesium carbonate, hydrotalcite, boehmite, hydrotalcite-like powder, hydromagnesite powder, zinc oxide, etc. For example, it can be a compound of zinc borate and zinc oxide; a compound of magnesium carbonate, boehmite, and zinc oxide; a compound of zinc borate and magnesium carbonate; a compound of zinc oxide, boehmite, and magnesium carbonate, etc.

[0050] In the composite high-temperature insulating material provided by the present invention, the raw materials of the silica gel composite material include 5-150 parts by weight of an inorganic filler system. Optionally, the inorganic filler system may be, for example, 5-35 parts by weight, 35-100 parts by weight, 5-30 parts by weight, 30-90 parts by weight, 30-100 parts by weight, 50-120 parts by weight, 60-150 parts by weight, etc.

[0051] Furthermore, the inorganic filling system is selected from one or more of montmorillonite, kaolin, diatomite, silica powder, wollastonite powder, mica powder, sodium silicate, basalt chopped fibers, etc. Optionally, the inorganic filling system is a compound of mica powder, low-melting glass powder, and basalt chopped fibers; a compound of wollastonite, silica powder, low-melting glass powder, and basalt chopped fibers; a compound of low-melting glass powder, basalt chopped fibers, mica powder, and kaolin; a compound of low-melting glass powder, wollastonite, basalt chopped fibers, and mica powder, etc.

[0052] In the composite high temperature insulating material provided by the present invention, the raw materials of the silica composite material include 0-300 parts by weight of organic solvent. Optionally, the weight of the organic solvent can be, for example, 0-100 parts by weight, 100-200 parts by weight, 200-300 parts by weight, etc.

[0053] Furthermore, the organic solvent is selected from one or more of toluene, xylene, acetone, mineral oil and the like.

[0054] In the composite high temperature insulating material provided by the present invention, the raw materials of the silica composite material include a synergist, and the synergist is calculated based on the platinum content, and the platinum compound or complex is 1-200ppm. It can be selected from 4-50ppm, 50-200ppm, 10-60ppm, 60-200ppm, and 10-15ppm.

[0055] In the composite high-temperature insulating material provided by the present invention, the raw materials of the silica gel composite material include 1-10 parts by weight of the curing agent system, which can be 1-5 parts by weight or 5-10 parts by weight.

[0056] Furthermore, the curing agent system is selected from one or more of bis(2,4-dichlorobenzoyl) peroxide, hydrogen-containing silicone oil, and the like.

[0057] Optionally, the weight parts of hydrogen-containing silicone oil are 0-10 weight parts, 0.1-10 weight parts, 0.5-8 weight parts, 1-5 weight parts, 5-10 weight parts, 0-4 weight parts, 1-4 weight parts, 4-10 weight parts, etc.

[0058] In the composite high-temperature insulating material provided by the present invention, the raw materials of the silicone composite material include 0-1 parts by weight of a curing inhibitor system. Optionally, the weight of the curing inhibitor system can be, for example, 0-0.1 parts by weight, 0.1-1 parts by weight, 0.1-0.5 parts by weight or 0.5-1 parts by weight.

[0059] Furthermore, the curing inhibitor system is selected from one or more of the acetylenic alcohol compounds 2-methyl-3-butyn-2-ol, 3,5-dimethyl-1-hexyn-3-ol, and ethynyl cyclohexanol.

[0060] In the composite high-temperature insulating material provided by the present invention, the raw materials of the silica composite material include 0.1-10 parts by weight of the coloring system. Optionally, the weight of the coloring system is 0.5-10 parts by weight, 0.1-10 parts by weight, 1.5-6 parts by weight, or 6-10 parts by weight.

[0061] Furthermore, the color matching system is selected from one or more of titanium dioxide, black iron oxide, red iron oxide, yellow iron oxide, and carbon black, such as black iron oxide; a combination of carbon black and black iron oxide.

[0062] In the composite high-temperature insulating material provided by the present invention, the composite high-temperature insulating material includes a mica paper composite material. The mica paper composite material is a composite material of mica paper and glass fiber cloth. Further, the mica paper is mica paper of different thicknesses made from one or more of muscovite or phlogopite or synthetic mica or calcined mica, and then composited with glass fiber cloth of different thicknesses and warp and weft densities to form a mica paper composite material. Further, the mica paper composite material is selected from one or more of a single-layer mica paper plus a single-layer glass fiber, a single-layer mica paper plus a double-layer glass fiber, a double-layer mica paper plus a single-layer glass fiber, and a multi-layer mica paper plus a multi-layer glass fiber.

[0063] In the composite high-temperature insulating material provided by the present invention, the weight proportion of the silica gel composite material is 25%-75%, and the weight proportion of the corresponding mica paper composite material is 75%-25%.

[0064] In a specific embodiment of the present invention, the composite high-temperature insulating material comprises a silica composite material and a mica paper composite material; wherein the raw materials of the silica composite material include the following components in parts by weight:

[0065] 100 parts by weight of silicone rubber;

[0066] Silicone resin 1-50 parts by weight;

[0067] 0-15 parts by weight of a structural control agent;

[0068] Reinforcement system 1-60 parts by weight;

[0069] Main flame retardant system 10-150 parts by weight;

[0070] Synergistic flame retardant system 5-100 parts by weight;

[0071] Inorganic filler system 5-150 parts by weight;

[0072] 0-300 parts by weight of organic solvent;

[0073] The synergist is calculated based on the platinum content, and the platinum compound or complex is 1-200ppm;

[0074] 1-10 parts by weight of curing agent system;

[0075] Curing inhibitor system, 0-1 parts by weight;

[0076] Coloring system 0.1-10 parts by weight.

[0077]

Preparation method of composite high temperature insulation material

[0078] The present invention also provides a method for preparing a composite high-temperature insulating material, the method comprising: compounding a silica gel composite material and a mica paper composite material together through a preset calendering, coating or dipping process, and forming the composite material through a high-temperature drying oven. Specifically:

[0079] 1) Solid silica gel kneading and mixing process: kneading and mixing silicone rubber raw rubber, silicone resin, reinforcement system, structural control agent, main flame retardant system, synergistic flame retardant system, inorganic filler system, platinum compound or complex, and color matching system, and then adding curing agent system through an open mill to obtain solid silicone rubber compound; wherein, the silicone rubber raw rubber is silicone rubber solid raw rubber.

[0080] 2) Liquid silicone rubber mixing process: kneading and mixing silicone rubber raw rubber, silicone resin, reinforcement system, structural control agent, main flame retardant system, synergistic flame retardant system, inorganic filler system, platinum compound or complex, color matching system, curing inhibitor system, and curing agent system to prepare liquid silicone rubber mixed rubber; wherein the silicone rubber raw rubber system is a silicone rubber liquid raw rubber system.

[0081] 3) Compounding the solid silicone rubber compound and the mica paper composite material component described in step 1) by calendering using a calender (e.g., a three-roll calender, a four-roll calender, or a five-roll calender) to form a composite high-temperature insulating material;

[0082] Or, the solid silicone rubber compound described in step 1) is dissolved in an organic solvent, and compounded with the mica paper composite material component by a scraping machine to form a composite high-temperature insulating material;

[0083] Or, the liquid silicone rubber compound described in step 2) is compounded with the mica paper composite material component by a scraping machine to form a composite high-temperature insulating material;

[0084] Alternatively, the liquid silicone rubber compound described in step 2) is compounded with the mica paper composite material component by dipping in a dipping machine to form a composite high-temperature insulating material.

[0085] In step 1), kneading and mixing are carried out in a kneading machine with an initial temperature of 10-60°C and a rotation speed of 25-55r / min, the mixing time is 60-240 minutes, heat treatment is started at 110°C for 45-120 minutes, the temperature is lowered to below 100°C for debinding, and after being left at room temperature for 12 hours, filtering is carried out to obtain a solid silicone rubber compound.

[0086] In step 2), kneading and mixing are carried out in a double planetary agitator with a controlled temperature range of 5-20°C, a stirring speed of 5-150r / min, and a dispersion speed of 100-2000r / min. The mixing time is 20-120 minutes, and the vacuum treatment is performed for 10-60 minutes to obtain a liquid silicone rubber compound.

[0087] In step 3), the thickness of the composite high temperature insulation material may be, for example, 0.15-0.35 mm.

[0088] A composite high-temperature insulating material and a preparation method of the present invention can specifically adopt the following scheme:

[0089] Solution 1: includes the following steps:

[0090] Silica gel kneading and mixing process: 100 parts by weight of methyl vinyl silicone rubber, 600,000-700,000 molecular weight, 0.5-2% vinyl content; 5-25 parts by weight of vinyl MQ silicone resin; 5-35 parts by weight of reinforcing system; 2-12 parts by weight of structural control agent; 40-80 parts by weight of main flame retardant system; 30-80 parts by weight of synergistic flame retardant system; 5-35 parts by weight of inorganic filling system; calculated by platinum content, platinum compound or complex 10-60ppm; 0.5-10 parts by weight of toning system; kneading and mixing in a kneading machine with an initial temperature of 25°C and a rotation speed of 35-45r / min, the mixing time is 120-200 minutes, heat treatment is started at 110°C for 45-60 minutes, the vacuum degree is -0.055±0.015MPa, the temperature is lowered to below 90-110°C for debinding, and after standing at room temperature for 12 hours, filtering is performed to obtain mixed silicone rubber;

[0091] The obtained mixed silicone rubber is added with 0.8-1.6% of di-2-4 as a curing agent, and then the silicone composite material and the mica tape composite material are compounded together through a calendering process using a five-roll calender, wherein the thickness of the silicone layer is 0.05-0.15mm, the thickness of the mica tape layer is 0.1-0.2mm, and then the composite material is cured at high temperature at 180°C-240°C in a drying oven, and the thickness of the final composite high-temperature insulating material is 0.15-0.35mm.

[0092] Solution 2: includes the following steps:

[0093] Silica gel kneading and mixing process: 100 parts by weight of methyl vinyl silicone rubber raw rubber, 450,000-600,000 molecular weight, vinyl content 0.5-2%; 3-35 parts by weight of vinyl MQ silicone resin; 5-35 parts by weight of reinforcing system; 2-12 parts by weight of structural control agent; 40-80 parts by weight of main flame retardant system; 30-80 parts by weight of synergistic flame retardant system; 30-100 parts by weight of inorganic filling system; calculated by platinum content, platinum compound 10-60ppm of a substance or complex; 0.5-15 parts by weight of a toning system; kneading and mixing in a kneader at an initial temperature of 25°C and a rotation speed of 35-45r / min, the mixing time is 120-200 minutes, heat treatment is started at 110°C for 45-60 minutes, the vacuum degree is -0.055±0.015MPa, the temperature is lowered to below 90-110°C for degumming, and after standing at room temperature for 12 hours, filtering is performed to obtain a mixed silicone rubber;

[0094] The obtained mixed silicone rubber is added with 0.8-1.6% of di-2-tetrafluoroethylene as a curing agent by weight of the mixed silicone rubber, and then 50-200 parts by weight of an organic solvent is added through a double planetary stirrer for stirring and dissolving. Subsequently, the mixed solution is scraped onto a mica composite material through a scraper, wherein the thickness of the silicone layer is 0.05-0.15 mm, the thickness of the mica tape layer is 0.1-0.2 mm, and then the mixed solution is cured at high temperature at 180°C-240°C in a drying oven, and the thickness of the obtained composite high-temperature insulating material is finally 0.15-0.35 mm.

[0095] Solution 3: includes the following steps:

[0096] Silicone mixing process: 100 parts by weight of methyl vinyl silicone rubber raw rubber, 20,000-150,000 molecular weight, vinyl content 0.1-4.5%; 0-25 parts by weight of vinyl MQ silicone resin; 1-35 parts by weight of reinforcement system; 10-60 parts by weight of main flame retardant system; 10-50 parts by weight of synergistic flame retardant system; 50-110 parts by weight of inorganic filling system; 0.1-1 parts by weight of curing inhibitor system; 1-5 parts by weight of curing system; platinum-containing 4-50ppm of platinum compound or complex; 0.1-10 parts by weight of coloring system; mixing in a planetary agitator with an initial temperature of 25°C, a cooling system control temperature of 10°C-18°C, a stirring speed of 5-145r / min, and a dispersion speed of 0-2500r / min, the mixing time is 30-120 minutes, the vacuum degree is -0.09±0.01MPa, and the vacuum time is 20-60 minutes to obtain mixed silicone rubber;

[0097] The obtained mixed silicone rubber is passed through a liquid glue coating production line to compound the silicone composite material and the mica tape composite material together through a coating and scraping process, wherein the thickness of the silicone layer is 0.05-0.15mm, and the thickness of the mica tape layer is 0.1-0.2mm. Then it is passed through a drying oven at 100℃-240℃ and high-temperature cured. The final composite high-temperature insulating material has a thickness of 0.15-0.35mm.

[0098] Solution 4: includes the following steps:

[0099] Silicone mixing process: 100 parts by weight of methyl vinyl silicone rubber raw rubber, 20,000-250,000 molecular weight, vinyl content 0.1-4.5%; 0-25 parts by weight of vinyl MQ silicone resin; 1-35 parts by weight of reinforcement system; 15-70 parts by weight of main flame retardant system; 15-60 parts by weight of synergistic flame retardant system; 60-120 parts by weight of inorganic filling system; 0.1-1 parts by weight of curing inhibitor system; 0.5-8 parts by weight of curing system; Platinum content calculation, platinum compound or complex 4-50ppm; 0.1-10 parts by weight of coloring system; mixing in a planetary agitator with an initial temperature of 25°C, a cooling system control temperature of 10°C-18°C, a stirring speed of 5-145r / min, a dispersion speed of 0-2500r / min, a mixing time of 30-120 minutes, a vacuum degree of -0.09±0.01MPa, and a vacuum time of 20-60 minutes to obtain mixed silicone rubber;

[0100] Add 50-300 parts by weight of the organic solvent system into a planetary agitator to dilute the obtained mixed silicone rubber, control the temperature of the cooling system to 10°C-18°C, the stirring speed to 5-145r / min, and the dispersion speed to 0-2500r / min in the planetary agitator for dilution and stirring for 10-60min;

[0101] The obtained diluted mixed silica gel is used to impregnate the mica tape composite material into the silica gel solution through the impregnation liquid glue production line, and then compounded together through a dip-coating process, wherein the thickness of the silica gel layer is 0.05-0.15mm, the thickness of the mica tape layer is 0.1-0.2mm, and then passed through a drying oven at 100℃-240℃ and high-temperature curing, and the final composite high-temperature insulating material has a thickness of 0.15-0.35mm.

[0102]

use

[0103] The present invention also provides applications of the composite high-temperature insulating material of the first aspect of the present invention and / or the composite high-temperature insulating material prepared according to the aforementioned preparation method of the present invention in the field of new energy and energy storage.

[0104] The beneficial effects of the present invention are further illustrated below in conjunction with embodiments.

[0105] In order to make the invention purpose, technical scheme and beneficial technical effect of the present invention clearer, the present invention is further described in detail below in conjunction with examples. However, it should be understood that the examples of the present invention are only for explaining the present invention, not for limiting the present invention, and the examples of the present invention are not limited to the examples given in the specification. The specific experimental conditions or operating conditions not specified in the examples are made under conventional conditions, or are made under the conditions recommended by the material supplier.

[0106] In addition, it should be understood that one or more method steps mentioned in the present invention do not exclude the existence of other method steps before or after the combination step or the insertion of other method steps between these explicitly mentioned steps, unless otherwise specified; it should also be understood that the combination connection relationship between one or more devices / apparatuses mentioned in the present invention does not exclude the existence of other devices / apparatuses before or after the combination device / apparatus or the insertion of other devices / apparatuses between these explicitly mentioned two devices / apparatuses, unless otherwise specified. Moreover, unless otherwise specified, the numbering of each method step is only a convenient tool for identifying each method step, and is not intended to limit the order of arrangement of each method step or the scope of the present invention. Changes or adjustments in their relative relationships should also be regarded as the scope of the present invention without substantially changing the technical content.

[0107] In the following examples, unless otherwise specified, various raw materials of the present invention can be purchased from the market or prepared according to conventional methods in the art.

[0108] Example 1

[0109] Silica gel kneading and mixing process: 100 parts by weight of solid methyl vinyl silicone rubber raw rubber, 600,000 molecular weight, vinyl content 1% (Hesheng Silicon Industry, 112-5); 15 parts by weight of vinyl MQ silicone resin (Jiangxi Haiduo Silicone Materials, AX02); 25 parts by weight of white carbon black 813 as a reinforcement system; 10 parts by weight of hydroxy silicone oil (Jiangsu Quanli Chemical Co., Ltd.) as a structuring control agent; 60 parts by weight of aluminum hydroxide and magnesium hydroxide as the main flame retardant system; 30 parts by weight of zinc borate and zinc oxide synergistic flame retardant system (the weight ratio of zinc borate to zinc oxide is 1:1); 30 parts by weight of mica powder, low melting point glass powder, and basalt chopped fiber compound powder The inorganic filler system is composed of mica powder, low melting point glass powder and basalt chopped fibers in a weight ratio of 2:2:1. The platinum complex is 10 ppm (platinum (0)-1,3-diethene-1,1,3,3-tetramethyldisiloxane, Guangdong Siye New Materials) based on the platinum content. 6 parts by weight of black iron oxide is used as the coloring system. The kneading and mixing are carried out in a kneading machine with an initial temperature of 25°C and a rotation speed of 40 r / min. The mixing time is 120 minutes. The heat treatment is started at 110°C for 450 minutes. The vacuum degree is -0.055±0.005MPa. The temperature is lowered to below 100°C for debinding. After being left at room temperature for 12 hours, the mixed silicone rubber is filtered to obtain the mixed silicone rubber.

[0110] The obtained mixed silicone rubber is added with double 24 as a curing agent at a ratio of 0.8% by weight of the mixed silicone rubber, and then the silicone composite material and the mica tape composite material are compounded together through a calendering process using a five-roll calender, wherein the thickness of the silicone layer is 0.08mm, the thickness of the mica tape layer is 0.12mm, and then passed through a drying oven at 200°C for high-temperature curing, and the final composite high-temperature insulating material has a thickness of 0.2mm.

[0111] Example 2

[0112] Silica gel kneading and mixing process: 100 parts by weight of solid methyl vinyl silicone rubber raw rubber, 450,000 molecular weight, vinyl content 2% (Hesheng Silicon Industry, 112-6); 35 parts by weight of vinyl MQ silicone resin (Jiangxi Haiduo Silicone Materials, AX02); 35 parts by weight of white carbon black 520 as a reinforcement system; 12 parts by weight of hydroxy silicone oil and silane coupling agent 172 (Jiangsu Quanli Chemical Co., Ltd.) compounded as a structuring control agent (the weight ratio of hydroxy silicone oil to 172 is 5:1); 40 parts by weight of aluminum hydroxide as the main flame retardant system; 50 parts by weight of magnesium carbonate, boehmite, zinc oxide compound powder as a synergistic flame retardant system (the weight ratio of magnesium carbonate, boehmite, zinc oxide is 2:2:1); 60 parts by weight of wollastonite, silica powder, low melting point glass powder, Basalt chopped fiber composite powder is used as the inorganic filling system (wollastonite, silica powder, low melting point glass powder, basalt chopped fiber weight ratio is 4:2:3:1); calculated by platinum content, platinum complex 12ppm (platinum (0)-1,3-diethene-1,1,3,3-tetramethyldisiloxane, Guangdong Siye New Materials); 2 parts by weight of carbon black and iron oxide black composite powder is used as the coloring system (the weight ratio of carbon black and iron oxide black is 1:9); kneading and mixing are carried out in a kneading machine with an initial temperature of 25°C and a rotation speed of 40r / min, the mixing time is 150 minutes, heat treatment is started at 110°C for 60 minutes, the vacuum degree is -0.06±0.01MPa, the temperature is lowered to below 90°C for debinding, and filtered after being left at room temperature for 12 hours to obtain the mixed silicone rubber;

[0113] The obtained mixed silicone rubber is added with di-2,4 as a curing agent at a ratio of 1.5% by weight of the mixed silicone rubber, and then 200 parts by weight of xylene are added as an organic solvent through a double planetary agitator for stirring and dissolving. Subsequently, the mixed solution is scraped onto the mica composite material through a scraper, wherein the thickness of the silicone layer is 0.1 mm, the thickness of the mica tape layer is 0.1 mm, and then it is passed through a drying oven at 180°C for high-temperature curing, and the final composite high-temperature insulating material has a thickness of 0.2 mm.

[0114] Example 3

[0115] Silicone mixing process: 100 parts by weight of methyl vinyl silicone rubber raw rubber, 50,000 molecular weight, vinyl content 2.4% (Runhe silicone, RH-Vi5000HP); 15 parts by weight of vinyl MQ silicone resin (Jiangxi Haiduo silicone material, AX02); 15 parts by weight of modified white carbon black HL150A as the reinforcement system; 25 parts by weight of aluminum hydroxide as the main flame retardant system; 30 parts by weight of zinc borate and magnesium carbonate compound as the synergistic flame retardant system (the weight ratio of zinc borate and magnesium carbonate is 1:2); 75 parts by weight of low-melting point glass powder, basalt chopped fiber, mica powder, kaolin compound powder as the inorganic filling system (low-melting point glass powder, basalt chopped fiber, mica powder, kaolin The weight ratio of soil is 4:2:4:5); 0.3 parts by weight of curing inhibitor system (ethynyl cyclohexanol); 4 parts by weight of hydrogenated silicone oil as a synergistic curing system; calculated by platinum content, platinum complex 11ppm (platinum (0)-1,3-diethene-1,1,3,3-tetramethyldisiloxane, Guangdong Siye New Materials); 1.5 parts by weight of black iron oxide as a color matching system; mixing in a planetary agitator with an initial temperature of 25°C, a cooling system control temperature of 10°C-18°C, a stirring speed of 5-145r / min, and a dispersion speed of 0-2500r / min, the mixing time is 45 minutes, the vacuum degree is -0.09±0.01MPa, and the vacuum time is 30 minutes;

[0116] The obtained mixed silicone is passed through a liquid glue coating production line to compound the silicone composite material and the mica tape composite material together through a coating and scraping process, wherein the silicone layer has a thickness of 0.15mm and the mica tape layer has a thickness of 0.15mm. Then it is passed through a drying oven at 100℃-240℃ and high-temperature cured. The final composite high-temperature insulating material has a thickness of 0.3mm.

[0117] Example 4

[0118] Silica gel mixing process: 100 parts by weight of methyl vinyl silicone rubber raw rubber, 100,000 molecular weight, vinyl content 1.3% (Runhe silicone, RH-Vi50000); 15 parts by weight of vinyl MQ silicone resin (Jiangxi Haiduo silicone material, AX02); 10 parts by weight of modified white carbon black HL150A as a reinforcement system; 30 parts by weight of aluminum hydroxide main flame retardant system; 40 parts by weight of zinc oxide, boehmite, magnesium carbonate compound powder as a synergistic flame retardant system (the weight ratio of zinc oxide, boehmite, and magnesium carbonate is 1:1:2); 90 parts by weight of low-melting point glass powder, wollastonite, basalt chopped fiber, and mica powder compound powder as an inorganic filling system (low-melting point glass powder, wollastonite, basalt chopped fiber, mica The weight ratio of the powder is 2:4:1:2); 0.4 parts by weight of the inhibitor system; 5 parts by weight of hydrogenated silicone oil as a synergistic curing system; calculated based on the platinum content, the platinum complex is 15ppm (platinum (0)-1,3-diethene-1,1,3,3-tetramethyldisiloxane, Guangdong Guiye New Materials); 3 parts by weight of carbon black and iron oxide black compound powder as a coloring system (the weight ratio of carbon black and iron oxide black is 1:9); the mixing is carried out in a planetary agitator with an initial temperature of 25°C, a cooling system control temperature of 10°C-18°C, a stirring speed of 5-145r / min, and a dispersion speed of 0-2500r / min. The mixing time is 70 minutes, the vacuum degree is -0.09±0.01MPa, and the vacuum time is 30 minutes;

[0119] 200 parts by weight of xylene as an organic solvent system is added into a planetary agitator to dilute the obtained mixed silica gel. The cooling system is controlled at a temperature of 10°C-18°C, a stirring speed of 5-145r / min, and a dispersion speed of 5-2500r / min. The dilution and stirring are performed in the planetary agitator for 40 minutes.

[0120] The obtained diluted mixed silica gel is used to impregnate the mica tape composite material into the silica gel solution through the impregnation liquid glue production line, and then compounded together through a dip-coating process, wherein the thickness of the silica gel layer is 0.08mm, the thickness of the mica tape layer is 0.1mm, and then it is passed through a drying oven at 220℃ and high-temperature cured. The final composite high-temperature insulating material has a thickness of 0.18mm.

[0121] Table 1 Performance comparison table

[0122]

[0123] Description: The flame retardant performance is characterized by comparing the UL94 flame retardant and oxygen index; the high-temperature insulation effect of the material is evaluated by high-temperature sintering integrity and high-temperature insulation resistance; the operability of the rubber is characterized by processability;

[0124] Test standards: Flame retardant: tested according to UL94-V0 (2mm thickness sample); Oxygen index: tested according to GB / T 10707; Sintering integrity: sample preparation (production sample, cut sample length and width 100mm*100mm), put into muffle furnace, sinter at 800℃ for 2 hours, and compare the appearance of samples before and after sintering; Processability: feedback from actual production phenomena; High temperature insulation: insulation resistance at high temperature (800℃), refer to GB / T10581-2006, >0.3MΩ.

[0125] In summary, the present invention effectively overcomes various shortcomings of the prior art and has high industrial utilization value.

[0126] The above is only a preferred embodiment of the present invention, and is not any formal or substantial limitation of the present invention. It should be pointed out that ordinary technicians in this technical field can make several improvements and supplements without departing from the method of the present invention, and these improvements and supplements should also be regarded as the protection scope of the present invention. Any technician familiar with this profession, without departing from the spirit and scope of the present invention, can make some changes, modifications and evolutions of the technical content disclosed above, which are equivalent embodiments of the present invention; at the same time, any changes, modifications and evolutions of any equivalent changes made to the above embodiments based on the essential technology of the present invention are still within the scope of the technical solution of the present invention.

Claims

1. A composite high temperature insulating material, characterized in that: The composite high-temperature insulating material comprises a silica gel composite material and a mica paper composite material; wherein the raw materials of the silica gel composite material comprise the following components by weight: 100 parts by weight of silicone rubber; Silicone resin 1-50 parts by weight; 0-15 parts by weight of a structural control agent; Reinforcement system 1-60 parts by weight; Main flame retardant system 10-150 parts by weight; Synergistic flame retardant system 5-100 parts by weight; Inorganic filler system 5-150 parts by weight; 0-300 parts by weight of organic solvent; The synergist is calculated based on the platinum content, and the platinum compound or complex is 1-200ppm; 1-10 parts by weight of curing agent system; 0-1 parts by weight of curing inhibitor system; Coloring system 0.1-10 parts by weight.

2. The composite high temperature insulating material according to claim 1, characterized in that: The molecular weight of the silicone rubber is 0.1-1.1 million molecular weight, and the vinyl content is 0%-5%; And / or, the silicone rubber raw rubber is methyl vinyl silicone rubber raw rubber; And / or, the silicone rubber raw rubber is silicone rubber liquid raw rubber and / or silicone rubber solid raw rubber.

3. The composite high temperature insulating material according to claim 1, characterized in that: The silicone resin is selected from one or more of dry environmentally friendly silicone resin, mica bonding silicone resin, environmentally friendly silicone resin, methyl MQ silicone resin, and vinyl MQ silicone resin.

4. The composite high temperature insulating material according to claim 1, characterized in that: The structural control agent is selected from one or more of hydroxy silicone oil and silane coupling agent; And / or, the reinforcement system is selected from one or more of fumed silica or precipitated silica.

5. The composite high temperature insulating material according to claim 1, characterized in that: The main flame retardant system is selected from one or more of aluminum hydroxide and magnesium hydroxide; And / or, the synergistic flame retardant system is selected from one or more of zinc borate, magnesium carbonate, hydrotalcite, boehmite, hydrotalcite-like powder, hydromagnesite powder, and zinc oxide; And / or, the inorganic filler system is selected from one or more of montmorillonite, kaolin, diatomaceous earth, silica powder, wollastonite powder, mica powder, sodium silicate, and basalt chopped fibers; And / or, the color matching system is selected from one or more of titanium dioxide, black iron oxide, red iron oxide, yellow iron oxide, and carbon black; And / or, the curing agent system is selected from one or more of bis(2,4-dichlorobenzoyl peroxide), hydrogen-containing silicone oil and / or, the curing inhibitor system is selected from one or more of the acetylenic alcohol compounds 2-methyl-3-butyn-2-ol, 3,5-dimethyl-1-hexyn-3-ol, and ethynyl cyclohexanol; And / or, the organic solvent is selected from one or more of toluene, xylene, acetone and mineral oil.

6. The composite high temperature insulating material according to claim 1, characterized in that: The mica paper composite material is a composite material of mica paper and glass fiber; And / or, in the composite high-temperature insulating material, the weight proportion of the silica gel composite material is 25%-75%, and the weight proportion of the corresponding mica paper composite material is 75%-25%.

7. The composite high temperature insulating material according to claim 6, characterized in that: The mica paper is one or more of muscovite, phlogopite, synthetic mica or calcined mica mica paper; And / or, the mica paper composite material is selected from one or more of single-layer mica paper plus single-layer glass fiber, single-layer mica paper plus double-layer glass fiber, double-layer mica paper plus single-layer glass fiber, and multi-layer mica paper plus multi-layer glass fiber.

8. The method for preparing a composite high-temperature insulating material according to any one of claims 1 to 7, characterized in that: The preparation method comprises: 1) Solid silica gel kneading and mixing process: kneading and mixing silicone rubber raw rubber, silicone resin, reinforcement system, structural control agent, main flame retardant system, synergistic flame retardant system, inorganic filler system, platinum compound or complex, and color matching system, and then adding curing agent system through an open mill to obtain solid silicone rubber compound; wherein the silicone rubber raw rubber is silicone rubber solid raw rubber; 2) Liquid silicone rubber mixing process: kneading and mixing silicone rubber raw rubber, silicone resin, reinforcement system, structural control agent, main flame retardant system, synergistic flame retardant system, inorganic filler system, platinum compound or complex, color matching system, curing inhibitor system, and curing agent system to obtain liquid silicone rubber mixed rubber; wherein the silicone rubber raw rubber system is a silicone rubber liquid raw rubber system; 3) Compounding the solid silicone rubber compound and the mica paper composite material component described in step 1) by calendering using a calender to form a composite high-temperature insulating material; Or, the solid silicone rubber compound described in step 1) is dissolved in an organic solvent, and compounded with the mica paper composite material component by a scraping machine to form a composite high-temperature insulating material; Or, the liquid silicone rubber compound described in step 2) is compounded with the mica paper composite material component by a scraping machine to form a composite high-temperature insulating material; Alternatively, the liquid silicone rubber compound described in step 2) is compounded with the mica paper composite material component by dipping in a dipping machine to form a composite high-temperature insulating material.

9. The method for preparing a composite high-temperature insulating material according to claim 8, characterized in that: In step 1), the initial temperature of kneading and mixing is 10-60°C, and the rotation speed is 25-55r / min; and / or, the mixing time is 60-240 minutes; And / or, in step 2), kneading and mixing are carried out in a double planetary agitator with a temperature range of 5-20°C, a stirring speed of 5-150r / min, and a dispersion speed of 100-2000r / min; And / or, in step 2), the mixing time is 20-120 minutes and the vacuum treatment is 10-60 minutes; And / or, in step 3), the thickness of the composite high temperature insulation material is 0.15-0.35 mm.

10. Application of the composite high-temperature insulating material according to any one of claims 1 to 7 and / or the composite high-temperature insulating material prepared according to the preparation method according to any one of claims 8 to 9 in the field of new energy and energy storage.

Images