Temperature-regulating and heat-insulating material as well as preparation method and application thereof

Abstract

The invention discloses a temperature-regulating and heat-insulating material as well as a preparation method and application thereof. The temperature-regulating and heat-insulating material comprises polyimide aerogel fibers, the polyimide aerogel fibers contain microcapsules, and the microcapsules contain a phase-change material. Therefore, the temperature-regulating and heat-insulating material disclosed by the invention not only has the characteristics of light weight, high strength, weather resistance and low heat conductivity of a polyimide material, but also realizes dual functions of temperature regulation and heat insulation by introducing the phase-change material.

Description

Technical Field

[0001] The present application relates to the technical field of polymer materials, and in particular to a temperature regulating and heat insulating material and a preparation method and application thereof. Background Art

[0002] With the advancement of automobile technology, improving cabin thermal comfort has become a focus of the industry. At present, the thermal insulation performance of automobile roofs is poor, resulting in large temperature fluctuations in the cabin, especially in extreme climates, which not only affects the comfort of passengers, but also leads to increased air conditioning energy consumption. Although traditional automobile roof insulation materials, such as fiber felt, polyurethane and polyethylene foam, have certain sound insulation, heat insulation and noise reduction effects, their flame retardant properties and thermal insulation efficiency still need to be improved.

[0003] As a lightweight solid material with a nanoscale three-dimensional porous network structure, aerogel has shown great application potential in many fields due to its low density, high porosity, large specific surface area and low thermal conductivity, including flame retardant insulation, filtration adsorption, energy storage equipment, and dual-use military and civilian fields such as aerospace. Although traditional polyimide aerogel fibers have the advantages of light weight and high strength, their functions are relatively single and they lack the ability to automatically adjust the temperature according to environmental changes, which limits their potential in improving thermal comfort.

[0004] Therefore, there is an urgent need to develop a material that can be used for automobile roofs and has temperature regulating and heat insulating effects. Summary of the invention

[0005] The present application aims to solve one of the technical problems in the related art at least to some extent.

[0006] In the first aspect of the present application, the present application proposes a temperature regulating and heat insulating material. According to an embodiment of the present application, the temperature regulating and heat insulating material comprises: polyimide aerogel fibers, the polyimide aerogel fibers contain microcapsules, and the microcapsules contain phase change materials. Therefore, the temperature regulating and heat insulating material of the present application not only has the light weight, high strength, weather resistance and low thermal conductivity characteristics of polyimide materials, but also realizes the dual functions of temperature regulating and heat insulating through the introduction of phase change materials (PCM).

[0007] According to an embodiment of the present application, the phase change material includes at least one of higher aliphatic hydrocarbons, fatty acids and their esters, polyols, and crystalline hydrated salts.

[0008] According to an embodiment of the present application, the wall material of the microcapsule is melamine-formaldehyde resin.

[0009] According to an embodiment of the present application, the higher aliphatic hydrocarbons include at least one of n-hexadecane, n-octadecane, and paraffin.

[0010] According to an embodiment of the present application, the fatty acid and its esters include at least one of stearic acid and palmitic acid.

[0011] According to an embodiment of the present application, the polyols include at least one of pentaerythritol, neopentyl glycol, and trimethylolethane.

[0012] According to an embodiment of the present application, the crystalline hydrated salt includes at least one of Na2SO4·10H2O and Mn(NO3)2·6H2O.

[0013] In the second aspect of the present application, the present application proposes a method for preparing the temperature regulating and heat insulating material described in the first aspect. According to an embodiment of the present application, the method comprises: polymerizing a dibasic anhydride and a diamine in a first solvent to obtain a spinning solution; mixing the spinning solution with microcapsules to obtain the temperature regulating and heat insulating material; wherein the microcapsules contain a phase change material. Therefore, by adding microcapsules containing a phase change material during the preparation of polyimide aerogel fibers, the temperature regulating and heat insulating properties of the final product can be improved.

[0014] According to an embodiment of the present application, the mass concentration of the microcapsules in the spinning solution is 10%-50%.

[0015] According to an embodiment of the present application, the molar ratio of the diamine to the dibasic anhydride is 1:(1.0-1.2).

[0016] According to an embodiment of the present application, the total mass of the diamine and the dibasic anhydride accounts for 5%-25% of the total mass of the diamine, the dibasic anhydride and the first solvent;

[0017] According to an embodiment of the present application, the dibasic anhydride includes at least one of bisphenol A diether dianhydride (BPADA) and hexafluorodianhydride (6FDA).

[0018] According to an embodiment of the present application, the diamine includes at least one of 2,2'-bis(trifluoromethyl)-4,4'-diaminophenyl ether (6FODA), 2,2'-bis[4-(4-aminophenoxy)phenyl]propane (BAPP), 2,2'-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane (HFBAPP), 4,4'-diaminobiphenyl-2,2'-dicarboxylic acid, 4,4'-bis(3-aminophenoxy)biphenyl (BAPB-M), and bis(4-aminophenyl)terephthalate (BAPT).

[0019] According to an embodiment of the present application, the phase change material includes at least one of higher aliphatic hydrocarbons, fatty acids and their esters, polyols, and crystalline hydrated salts.

[0020] According to an embodiment of the present application, the wall material of the microcapsule is melamine-formaldehyde resin.

[0021] According to an embodiment of the present application, the particle size of the microcapsule is 20 μm-80 μm.

[0022] According to an embodiment of the present application, the first solvent includes at least one of N-methylpyrrolidone (NMP), m-cresol, and dimethylacetamide (DMAc).

[0023] According to an embodiment of the present application, the polymerization reaction is carried out under a protective atmosphere.

[0024] According to an embodiment of the present application, the polymerization reaction is carried out at 150° C.-200° C. for 4 h-12 h.

[0025] According to an embodiment of the present application, the mixing process is performed under stirring conditions.

[0026] According to an embodiment of the present application, the mixing treatment is carried out at 130° C.-180° C. for 1 h-4 h.

[0027] According to an embodiment of the present application, after the mixing process, the method further comprises: subjecting the mixed product to spinning and drying to obtain the temperature regulating and heat insulating material.

[0028] In the third aspect of the present application, the present application proposes the use of the temperature-regulating and heat-insulating material described in the first aspect or the temperature-regulating and heat-insulating material prepared by the method described in the second aspect in the preparation of automotive parts, textiles, spacecraft parts and / or rocket parts. As mentioned above, the temperature-regulating and heat-insulating material of the present application has excellent temperature-regulating and heat-insulating properties. By using the material of the present application to prepare other products, the same characteristics can be given to them, so that they have better temperature-regulating and heat-insulating properties.

[0029] In the fourth aspect of the present application, the present application proposes a car roof. According to an embodiment of the present application, the car roof includes the temperature-regulating and heat-insulating material described in the first aspect or the temperature-regulating and heat-insulating material prepared by the method described in the second aspect. As mentioned above, the temperature-regulating and heat-insulating material of the present application has excellent temperature-regulating and heat-insulating properties. When it is applied to the car roof, it can effectively isolate the influence of the external temperature on the interior of the cabin, improve thermal comfort, reduce air-conditioning energy consumption, and thus extend the battery life of new energy vehicles.

[0030] According to an embodiment of the present application, the automobile roof further includes an outer decorative layer and a polypropylene skeleton layer.

[0031] Additional aspects and advantages of the present application will be given in part in the description below, and in part will become apparent from the description below, or will be learned through the practice of the present application. BRIEF DESCRIPTION OF THE DRAWINGS

[0032] The above and / or additional aspects and advantages of the present application will become apparent and easily understood from the description of the embodiments in conjunction with the following drawings, in which:

[0033] Figure 1 A structural diagram of a polyimide aerogel fiber according to an embodiment of the present application is shown;

[0034] Figure 2 The experimental process of preparing a temperature regulating and heat insulating material according to an embodiment of the present application is shown. Figure 1 ;

[0035] Figure 3 The experimental process of preparing a temperature regulating and heat insulating material according to an embodiment of the present application is shown. Figure 2 ;

[0036] Figure 4 A structural diagram of a polyimide aerogel fiber cloth according to an embodiment of the present application is shown;

[0037] Figure 5 A structural diagram of a car roof according to an embodiment of the present application is shown;

[0038] Reference numerals: 01: outer decorative layer; 02: polyimide aerogel fiber cloth; 03: polypropylene skeleton layer. DETAILED DESCRIPTION

[0039] The embodiments of the present application are described in detail below. The embodiments described below are exemplary and are only used to explain the present application, and cannot be understood as limiting the present application.

[0040] Unless otherwise defined, all technical and scientific terms used in this application have the same meanings as those commonly understood by technicians in the technical field to which this application belongs; the terms used in this application are only for the purpose of describing specific embodiments and are not intended to limit this application; unless otherwise specified, the numerical values ​​of the parameters mentioned in this application can be measured using various measurement methods commonly used in the art (for example, they can be tested according to the methods given in the embodiments of this application).

[0041] The endpoints and any values ​​of the ranges disclosed in this application are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of each range, the endpoint values ​​of each range and the individual point values, and the individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be regarded as specifically disclosed in this application.

[0042] The terms "including" and "having" in the specification and claims of the present application and any modifications thereof are open expressions, that is, including the contents specified in the present application but not excluding other contents.

[0043] In the description of this application, the terms "first" and "second" are used for descriptive purposes only and should not be understood as indicating or implying relative importance or implicitly indicating the number of the indicated technical features. "First feature" and "second feature" may include one or more of the features.

[0044] In the description of the present application, “plurality” means two or more.

[0045] In the description of the present application, "A and / or B" may include the case of A alone, the case of B alone, or any of the cases of A and B, where A and B are only used for examples and may be any technical feature connected by "and / or" in the present application.

[0046] Unless otherwise specified, all embodiments and optional embodiments of the present application can be combined with each other to form a new technical solution.

[0047] Temperature control insulation materials

[0048] In a first aspect of the present application, the present application proposes a temperature regulating and heat insulating material. According to an embodiment of the present application, the temperature regulating and heat insulating material comprises: polyimide aerogel fibers, the polyimide aerogel fibers contain microcapsules, and the microcapsules contain phase change materials. Figure 1 As can be seen from the cross-sectional view of the polyimide aerogel fiber, the porous cross-section of the polyimide aerogel contains microcapsules. Therefore, the temperature regulating and heat insulating material of the present application not only has the light weight, high strength, weather resistance and low thermal conductivity characteristics of the polyimide material, but also realizes the dual functions of temperature regulating and heat insulation through the introduction of phase change material (PCM). Among them, the phase change material can absorb and release heat within a certain temperature range, thereby regulating the temperature of the surrounding environment. When the ambient temperature rises, the PCM absorbs heat and changes from a solid state to a liquid state. In this process, the heat is absorbed, which helps to reduce the temperature of the environment surrounding the material. On the contrary, when the ambient temperature decreases, the PCM changes from a liquid state to a solid state, releasing heat, which helps to increase the temperature of the environment surrounding the material. Therefore, the phase change latent heat of the PCM can enhance the thermal insulation capacity of the material, and at the same time play an automatic regulating role when the temperature changes.

[0049] In some embodiments of the present application, the phase change material includes at least one of higher aliphatic hydrocarbons, fatty acids and their esters, polyols, and crystalline hydrated salts. Therefore, the above-mentioned types of phase change materials can not only improve the thermal insulation performance of the material, but also absorb and release heat within a certain temperature range, thereby playing a role in temperature regulation.

[0050] Illustratively, the higher aliphatic hydrocarbons include, but are not limited to, one or more of n-hexadecane, n-octadecane, and paraffin.

[0051] Illustratively, the fatty acids and their esters include, but are not limited to, one or more of stearic acid and palmitic acid.

[0052] Illustratively, the polyols include, but are not limited to, one or more of pentaerythritol, neopentyl glycol, and trimethylolethane.

[0053] Illustratively, the crystalline hydrated salts include, but are not limited to, one or more of Na2SO4·10H2O, Mn(NO3)2·6H2O.

[0054] In some embodiments of the present application, the wall material of the microcapsule is melamine-formaldehyde resin. Thus, melamine-formaldehyde resin can bind to a large number of hydrogen bond acceptors in the polyimide structure through surface hydrogen bond donors, such as Figure 1 As shown, the microcapsules containing phase change materials are evenly and stably distributed in the polyimide aerogel fibers, ensuring that the polyimide aerogel fibers can effectively absorb and release heat under different temperature conditions, which not only achieves the temperature regulation effect but also enhances the thermal insulation performance.

[0055] It should be noted that, in the microcapsule of the present application, the phase change material is used as the core material, and the wall material is coated on the surface of the phase change material.

[0056] In some embodiments of the present application, the diameter of the polyimide aerogel fiber is 100 μm-200 μm, for example, 100 μm, 120 μm, 140 μm, 160 μm, 200 μm, etc., or a range consisting of any of the above values.

[0057] In some embodiments of the present application, the particle size of the microcapsule is 20 μm-80 μm, for example, 20 μm, 30 μm, 40 μm, 50 μm, 60 μm, 70 μm, 80 μm, etc., or a range consisting of any of the above values.

[0058] Method for preparing temperature regulating and heat insulating material

[0059] In the second aspect of the present application, the present application proposes a method for preparing the temperature regulating and heat insulating material described in the first aspect. According to an embodiment of the present application, referring to Figure 2 , the method comprising:

[0060] S100: Polymerization

[0061] In this step, a polyimide spinning solution is obtained by polymerizing a dibasic anhydride and a diamine in a first solvent.

[0062] In some embodiments of the present application, the molar ratio of the diamine to the dibasic anhydride is 1:(1-1.2). For example, it can be 1:1, 1:1.05, 1:1.1, 1:1.15, 1:1.2, etc., or can be a range of any of the above values. Thus, by making the molar ratio of the diamine to the dibasic anhydride within the above range, it is possible to promote the full polymerization of the dibasic anhydride and the diamine, thereby improving the reaction efficiency and the polymer molecular weight.

[0063] In some embodiments of the present application, the total mass of the diamine and the dibasic anhydride accounts for 5%-25% of the total mass of the diamine, the dibasic anhydride and the first solvent. For example, it can be 5%, 10%, 15%, 20%, 25%, etc., or can be a range of any of the above values. In this way, the molecular weight of the polymer solution can be guaranteed.

[0064] In some embodiments of the present application, the dibasic anhydride includes but is not limited to at least one of bisphenol A diether dianhydride (BPADA) and hexafluorodianhydride (6FDA). The structures of BPADA and 6FDA are as follows:

[0065]

[0066] In some embodiments of the present application, the diamine includes but is not limited to at least one of 2,2'-bis(trifluoromethyl)-4,4'-diaminophenyl ether (6FODA), 2,2'-bis[4-(4-aminophenoxy)phenyl]propane (BAPP), 2,2'-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane (HFBAPP), 4,4'-diaminobiphenyl-2,2'-dicarboxylic acid, 4,4'-bis(3-aminophenoxy)biphenyl (BAPB-M), and bis(4-aminophenyl)terephthalate (BAPT). The structures of 6FODA, BAPP, HFBAPP, 4,4'-diaminobiphenyl-2,2'-dicarboxylic acid, BAPB-M, and BAPT are shown below:

[0067]

[0068] Therefore, after the above-mentioned types of dibasic anhydrides and diamines undergo polymerization reaction, a polyimide spinning solution with a large number of hydrogen bond acceptors can be formed, which lays the foundation for its subsequent combination with microcapsules containing phase change materials through hydrogen bonds and van der Waals forces.

[0069] In some embodiments of the present application, the first solvent includes at least one of N-methylpyrrolidone (NMP), m-cresol and dimethylacetamide (DMAc). Thus, the above-mentioned types of solvents have high boiling points, can meet the requirements of high temperature polymerization, and can completely dissolve dibasic anhydride and diamine.

[0070] In some embodiments of the present application, the polymerization reaction is carried out under a protective atmosphere, thereby suppressing the occurrence of side reactions and avoiding the oxidation of the polymer by oxygen, thereby improving the performance of the polymer.

[0071] Exemplarily, the protective atmosphere may be nitrogen.

[0072] In some embodiments of the present application, the polymerization reaction is carried out at 150° C. to 200° C. for 4 h to 12 h. This can promote the reaction of dibasic anhydride and diamine, make the reaction more complete, and improve the yield.

[0073] For example, the polymerization reaction temperature may be 150° C., 160° C., 170° C., 180° C., 190° C., 200° C., etc., or may be a range consisting of any of the above values.

[0074] For example, the polymerization reaction time may be 4 h, 8 h, 12 h, etc., or may be within a range consisting of any of the above values.

[0075] S200: Hybrid Processing

[0076] In this step, the temperature regulating and heat insulating material is obtained by mixing the polyimide spinning stock solution generated by the polymerization reaction with microcapsules, wherein the microcapsules contain phase change materials.

[0077] In some embodiments of the present application, the mass concentration of the microcapsules in the spinning solution is 10%-50%. For example, it can be 10%, 20%, 30%, 40%, 50%, etc., or it can be a range composed of any of the above values. Therefore, by making the mass concentration of the microcapsules within the above range, the microcapsules can be fully combined with the hydrogen bond donors on the surface of the wall material and the hydrogen bond acceptors in the polyimide structure in the spinning solution, so that the microcapsules are evenly and firmly combined into the polyimide aerogel polymer solution matrix.

[0078] In some embodiments of the present application, the phase change material includes at least one of higher aliphatic hydrocarbons, fatty acids and their esters, polyols, and crystalline hydrated salts. Therefore, the above-mentioned types of phase change materials can not only improve the thermal insulation performance of the material, but also absorb and release heat within a certain temperature range, thereby playing a role in temperature regulation.

[0079] Illustratively, the higher aliphatic hydrocarbons include, but are not limited to, one or more of n-hexadecane, n-octadecane, and paraffin.

[0080] Illustratively, the fatty acids and their esters include, but are not limited to, one or more of stearic acid and palmitic acid.

[0081] Illustratively, the polyols include, but are not limited to, one or more of pentaerythritol, neopentyl glycol and trimethylolethane.

[0082] Illustratively, the crystalline hydrated salts include, but are not limited to, one or more of Na2SO4·10H2O, Mn(NO3)2·6H2O.

[0083] In some embodiments of the present application, the wall material of the microcapsule is melamine-formaldehyde resin. Therefore, the melamine-formaldehyde resin can combine with a large number of hydrogen bond acceptors in the polyimide structure through surface hydrogen bond donors, so that the microcapsules containing the phase change material are evenly and stably distributed in the polyimide aerogel fiber, ensuring that the material can effectively absorb and release heat under different temperature conditions, not only achieving the temperature regulation effect, but also enhancing the thermal insulation performance.

[0084] In some embodiments of the present application, the particle size of the microcapsule is 20 μm-80 μm. For example, it can be 20 μm, 40 μm, 60 μm, 80 μm, etc., or it can be a range composed of any of the above values. Therefore, by making the particle size of the microcapsule within the above range, the microcapsule can be combined with the polyimide, so that the microcapsule is evenly and firmly dispersed in the polyimide aerogel fiber.

[0085] In some embodiments of the present application, the mixing process is performed under stirring conditions, thereby promoting full combination of microcapsules and polyimide to form a polyimide aerogel fiber material with temperature regulating and heat insulating properties.

[0086] In some embodiments of the present application, the mixing treatment is carried out at 130° C.-180° C. for 1 h-4 h. This can promote the full combination of microcapsules and polyimide to form a polyimide aerogel fiber material with temperature regulation and heat insulation.

[0087] Illustratively, the temperature of the mixing treatment may be 130° C., 140° C., 150° C., 160° C., 170° C., 180° C., etc., or may be a range consisting of any of the above values.

[0088] For example, the mixing treatment time may be 1 h, 2 h, 3 h, 4 h, etc., or may be a range consisting of any of the above values.

[0089] In some embodiments of the present application, reference Figure 3 , after the spinning solution and the microcapsules are mixed, the process further includes: spinning the mixed product; drying the spun product to obtain the temperature regulating and heat insulating material. Thus, the mixed product can be formed into polyimide aerogel fibers after spinning and drying, and the polyimide aerogel fibers contain the above-mentioned microcapsules.

[0090] S300: Spinning process

[0091] In this process, the mixed processing product is subjected to a spinning process, and the mixed processing product can be transformed into a solid fiber through the spinning process.

[0092] In some embodiments of the present application, the spinning process is to extrude the mixed processed product through a spinneret to form a thin stream; the thin stream enters a coagulation bath to form fibers.

[0093] In some embodiments of the present application, the diameter of the spinneret hole is 100 μm-200 μm, for example, 100 μm, 120 μm, 140 μm, 160 μm, 200 μm, etc., or any range of the above values, thereby obtaining uniform fibers.

[0094] In some embodiments of the present application, the coagulation bath is at least one of water, acetone, methanol, and ethanol. Thus, the mixed treatment product can be solidified into fibers in the coagulation bath.

[0095] In some embodiments of the present application, the coagulation bath is a mixture of water and acetone, and the volume ratio of water to acetone is (5-9):5. For example, it can be 5:5, 6:5, 7:5, 8:5, 9:5, etc., or can be a range of any of the above values. In this way, the mixed treatment product can be promoted to solidify into fibers.

[0096] In some embodiments of the present application, the temperature of the coagulation bath is 0°C-30°C. For example, it can be 0°C, 5°C, 10°C, 15°C, 20°C, 30°C, etc., or can be a range of any of the above values. In this way, the coagulation process of the mixed treatment product can be promoted to transform it into fibers.

[0097] S400: Drying

[0098] In this process, the spinning product transformed into fiber after spinning is dried, which can form a porous structure in the fiber. This structure can not only effectively reduce the thermal conductivity of the fiber and improve the thermal insulation performance of the material; it can also reduce the density of the material and reduce its weight.

[0099] In some embodiments of the present application, the drying process is a freeze-drying process.

[0100] In some embodiments of the present application, the drying temperature is -30°C to -90°C. For example, it can be -30°C, -50°C, -70°C, -90°C, etc., or can be any range of the above values. In this way, the fiber can form a porous structure.

[0101] In some embodiments of the present application, the pressure of the drying process is 0.1Pa-50Pa. For example, it can be 0.1Pa, 1Pa, 10Pa, 20Pa, 50Pa, etc., or can be a range of any of the above values. Thus, the fibers can be promoted to form a porous structure.

[0102] In some embodiments of the present application, the drying time is 24 hours to 72 hours, for example, 24 hours, 30 hours, 50 hours, 72 hours, etc., or any range of the above values, thereby promoting the fibers to fully form a porous structure.

[0103] In some embodiments of the present application, the temperature regulating and heat insulating material prepared by the above method has a sparse-dense structure, wherein the cortex of the fiber is a dense structure, the interior is a spatial reticular structure, and the fiber diameter is 100 μm-200 μm. For example, it can be 100 μm, 120 μm, 140 μm, 160 μm, 180 μm, 200 μm, etc., or can be a range composed of any of the above values.

[0104] application

[0105] In the third aspect of the present application, the present application proposes the use of the temperature-regulating and heat-insulating material described in the first aspect or the temperature-regulating and heat-insulating material prepared by the method described in the second aspect in the preparation of automotive parts, textiles, spacecraft parts and / or rocket parts. As mentioned above, the temperature-regulating and heat-insulating material of the present application not only has the characteristics of light weight, high strength, weather resistance and environmental protection, but also can perform temperature regulation and heat insulation. Therefore, the use of the temperature-regulating and heat-insulating material of the present application to prepare products can reduce the weight of the final product, while giving it the dual functions of temperature regulation and heat insulation. Those skilled in the art can understand that this application has all the characteristics and advantages of the temperature-regulating and heat-insulating materials described above, and will not be elaborated on here.

[0106] It should be noted that the temperature regulating and heat insulating material of the present application may refer to a single fiber material or a fiber cloth formed by weaving a plurality of fiber materials (see Figure 4 ), or other forms. There is no limitation on the size, shape, pattern, etc. of the fiber cloth, and those skilled in the art can select according to specific needs.

[0107] In the fourth aspect of the present application, the present application proposes a car roof. According to an embodiment of the present application, the car roof includes the temperature-regulating and heat-insulating material of the first aspect or the temperature-regulating and heat-insulating material prepared by the method described in the second aspect. As mentioned above, the temperature-regulating and heat-insulating material of the present application has excellent temperature-regulating and heat-insulating properties. When it is applied to the car ceiling, it can effectively isolate the influence of the outside temperature on the interior of the cabin, improve thermal comfort, reduce air-conditioning energy consumption, and thus extend the battery life of new energy vehicles. Those skilled in the art can understand that this application has all the characteristics and advantages of the temperature-regulating and heat-insulating materials described above, and will not be elaborated on here.

[0108] In some embodiments of the present application, the automobile roof further includes an outer decorative layer and a polypropylene skeleton layer (PP skeleton layer), and the polypropylene skeleton layer is arranged on one side of the outer decorative layer.

[0109] It should be noted that in the automobile roof, the temperature regulating and heat insulating material of the present application is in the form of fiber cloth. The fiber cloth can be one layer or multiple layers. When the fiber cloth is one layer, the fiber cloth is arranged on the side of the polypropylene skeleton layer away from the outer decorative layer; when the fiber cloth is two layers, refer to Figure 5 A layer of fiber cloth 02 is arranged on a side of the polypropylene skeleton layer 03 away from the outer decorative layer 01 , and another layer is arranged between the polypropylene skeleton layer 03 and the outer decorative layer 01 .

[0110] The scheme of the present application will be explained below in conjunction with the embodiments. It will be appreciated by those skilled in the art that the following embodiments are only used to illustrate the present application and should not be considered as limiting the scope of the present application. If no specific technology or conditions are indicated in the embodiments, the technology or conditions described in the literature in this area or the product specification are carried out. The reagents used or the instruments that do not indicate the manufacturer are all conventional products that can be obtained commercially.

[0111] Example 1

[0112] 1. Preparation of spinning solution

[0113] Under nitrogen atmosphere, in a 500ml three-necked flask, 54.651g (105mmol) of BPADA (Sinopharm Reagent, analytical grade) and 33.623g (100mmol) of 6FODA (Sinopharm Reagent, analytical grade) were dissolved in 353mL of NMP, reacted at 180℃ for 8h, and then naturally cooled to room temperature to obtain spinning solution.

[0114] 2. Preparation of composite spinning solution

[0115] Microcapsules with a particle size of 80 μm are dispersed in 400 g of spinning solution. The mass concentration of the microcapsules in the spinning solution is 30 wt %. The phase change materials of the microcapsules are n-hexadecane and paraffin (the mass ratio of n-hexadecane to paraffin is 1:1), and the wall material is melamine-formaldehyde resin. The mixture is fully stirred at 150° C. for 2 hours, and then naturally cooled to room temperature under stirring to obtain a composite spinning solution.

[0116] 3. Preparation of polyimide aerogel fibers

[0117] The composite spinning solution was spun by dry-jet wet spinning technology (coagulation bath was acetone, spinning rate was 50 m / min, air section height was 5 mm, and 100-hole spinneret was used), washed with deionized water, and freeze-dried at -70°C and 10Pa for 48 hours to obtain polyimide aerogel fiber.

[0118] Example 2

[0119] The polyimide aerogel fiber was prepared according to the method described in Example 1, except that the phase change material of the microcapsule was n-hexadecane and neopentyl glycol (the mass ratio of n-hexadecane to neopentyl glycol was 1:1).

[0120] Example 3

[0121] The polyimide aerogel fiber was prepared according to the method described in Example 1, except that the phase change material of the microcapsule was n-hexadecane and stearic acid (the mass ratio of n-hexadecane to stearic acid was 1:1).

[0122] Example 4

[0123] Polyimide aerogel fibers were prepared according to the method described in Example 1, except that the phase change materials of the microcapsules were paraffin and Mn(NO3)2·6H2O (the mass ratio of paraffin to Mn(NO3)2·6H2O was 1:1).

[0124] Example 5

[0125] The polyimide aerogel fiber was prepared according to the method described in Example 1, except that the diamine was BAPP.

[0126] Example 6

[0127] The polyimide aerogel fiber was prepared according to the method described in Example 1, except that the diamine was HFBAPP.

[0128] Example 7

[0129] Polyimide aerogel fibers were prepared according to the method described in Example 1, except that the diamine was BAPT.

[0130] Example 8

[0131] The polyimide aerogel fiber was prepared according to the method described in Example 1, except that the diamine was 4,4'-diaminobiphenyl-2,2'-dicarboxylic acid.

[0132] Example 9

[0133] Polyimide aerogel fibers were prepared according to the method described in Example 1, except that the diamine was BAPB-M.

[0134] Example 10

[0135] Polyimide aerogel fibers were prepared according to the method described in Example 1, except that the dibasic anhydride was 6FDA.

[0136] Embodiment 11

[0137] The polyimide aerogel fiber was prepared according to the method described in Example 1, except that the mass concentration of the microcapsules in the spinning solution was 10%.

[0138] Example 12

[0139] The polyimide aerogel fiber was prepared according to the method described in Example 1, except that the mass concentration of the microcapsules in the spinning solution was 20%.

[0140] Embodiment 13

[0141] The polyimide aerogel fiber was prepared according to the method described in Example 1, except that the mass concentration of the microcapsules in the spinning solution was 40%.

[0142] Embodiment 14

[0143] The polyimide aerogel fiber was prepared according to the method described in Example 1, except that the mass concentration of the microcapsules in the spinning solution was 50%.

[0144] Comparative Example 1

[0145] The polyimide aerogel fiber without microcapsules is prepared as follows:

[0146] 1. Preparation of spinning solution

[0147] Under nitrogen atmosphere, in a 500ml three-necked flask, 54.651g (105mmol) of BPADA (Sinopharm Reagent, analytical grade) and 33.623g (100mmol) of 6FODA (Sinopharm Reagent, analytical grade) were dissolved in 353mL of NMP, reacted at 180℃ for 8h, and then naturally cooled to room temperature to obtain spinning solution.

[0148] 2. Preparation of polyimide aerogel fibers

[0149] The spinning solution was spun by dry-jet wet spinning technology (the coagulation bath used DMF and deionized water in a volume ratio of 3:1, the spinning rate was 50 m / min, the air section height was 5 mm, and a 100-hole spinneret was used), washed with deionized water, and then freeze-dried at -70°C and 10 Pa for 48 hours to obtain polyimide aerogel fibers.

[0150] Comparative Example 2

[0151] The reference application number is 201910773066.7, and the patent name is "An antibacterial lightweight textile fabric and its preparation method". The antibacterial temperature-regulating aerogel fiber is prepared. The specific process is: the polyester chips are melted to obtain the polyester spinning solution, and then the modified aerogel and the negative ion temperature-regulating material are added to the spinning solution. After mixing evenly, it is sprayed out through the spinneret, and then the fiber is formed, the primary fiber is stretched and oriented, the fiber is heat-set and wound to obtain the antibacterial temperature-regulating aerogel fiber.

[0152] The differences between Examples 1-14 and Comparative Examples 1-2 are shown in Table 1.

[0153] Table 1

[0154]

[0155]

[0156] Performance Testing

[0157] 1. Temperature control test: Weave the fiber into cloth (the cloth structure is plain weave, and the density of warp and weft yarns is 20×20 / 10cm), place the fiber cloth sample on the hot table and the sample table surface respectively, and measure the temperature change on the surface of the polyimide aerogel fiber. The fiber cloth sample specification is 50*50*1mm

[0158] Heating: Place the sample on a constant temperature hot plate (50°C) and let it stand for 30 minutes. Use a digital thermometer to measure the sample surface heating rate and the sample surface temperature after standing.

[0159] Cooling: Place the sample on a constant temperature sample table (0°C) and let it stand for 30 minutes. Use a digital thermometer to measure the sample surface heating rate and the sample surface temperature after standing.

[0160] 2. Thermal conductivity: The thermal conductivity of the fiber sample is tested in accordance with the national standard GT / T5990-2021 "Test method for thermal conductivity, specific heat capacity and thermal diffusion coefficient of refractory materials".

[0161] 3. Density test: The density of fiber samples is tested according to the national standard GB / T 4472 "Determination of density and relative density of chemical products".

[0162] The experimental results are shown in Table 2. The results show that:

[0163] 1. All examples show low density (15.79-32.46 kg / m 3 ) and low thermal conductivity (0.07~0.46W / mk), which can effectively achieve lightweight and exert thermal insulation performance in practical applications.

[0164] 2. The test results of temperature regulation performance show that, compared with comparative example 1, the addition of microcapsules can significantly slow down the temperature change rate of the sample and increase the temperature difference between the sample and the environment, thereby exerting excellent heat insulation and temperature regulation functions.

[0165] 3. As the mass fraction of microcapsules increases, the temperature change rate of the sample further decreases, and the temperature difference between the sample and the environment further expands. When the mass fraction of microcapsules reaches 50wt%, the temperature change rate of the sample and the temperature difference with the environment both reach the optimal state. However, the inventors found that when the mass fraction of microcapsules is further increased, the physical properties of the polyimide aerogel (such as strength and elongation at break) will be reduced, and the microcapsules will be unevenly distributed in the aerogel and the binding force will be insufficient, resulting in the leakage of the loosely bound parts of the microcapsules from the aerogel fiber structure. Therefore, it is necessary to control the mass fraction of the microcapsules to 50% or less.

[0166] 4. Compared with other matrix materials (such as comparative example 2), polyimide aerogel fibers exhibit better thermal insulation performance due to their lower thermal conductivity. Through the large number of hydrogen bonds formed between microcapsules and polyimide molecular chains, the molecular structure system is stably enhanced, thereby achieving a better temperature regulation effect.

[0167] Table 2

[0168]

[0169] Although the embodiments of the present application have been shown and described above, it can be understood that the above embodiments are exemplary and cannot be understood as limitations on the present application. Ordinary technicians in this field can change, modify, replace and modify the above embodiments within the scope of the present application.

Claims

1. A temperature regulating and heat insulating material, characterized in that: include: The polyimide aerogel fiber contains microcapsules, and the microcapsules contain phase change materials.

2. The temperature regulating and heat insulating material according to claim 1, characterized in that: The phase change material includes at least one of higher aliphatic hydrocarbons, fatty acids and their esters, polyols, and crystalline hydrated salts; And / or, the wall material of the microcapsule is melamine-formaldehyde resin.

3. The temperature regulating and heat insulating material according to claim 2, characterized in that: The higher aliphatic hydrocarbons include at least one of n-hexadecane, n-octadecane and paraffin; And / or, the fatty acid and its esters include at least one of stearic acid and palmitic acid; And / or, the polyols include at least one of pentaerythritol, neopentyl glycol, and trimethylolethane; And / or, the crystalline hydrated salt includes at least one of Na2SO4·10H2O and Mn(NO3)2·6H2O.

4. A method for preparing the temperature regulating and heat insulating material according to any one of claims 1 to 3, characterized in that: include: The dibasic anhydride and the diamine are polymerized in a first solvent to obtain a spinning solution; Mixing the spinning solution with microcapsules to obtain the temperature-regulating and heat-insulating material; Wherein, the microcapsule contains phase change material.

5. The method according to claim 4, characterized in that The mass concentration of the microcapsules in the spinning solution is 10%-50%; and / or, the molar ratio of the diamine to the dibasic anhydride is 1:(1-1.2); And / or, the total mass of the diamine and the dibasic anhydride accounts for 5%-25% of the total mass of the diamine, the dibasic anhydride and the first solvent.

6. The method according to claim 5, characterized in that The dibasic anhydride includes at least one of bisphenol A diether dianhydride and hexafluoro dianhydride; And / or, the diamine includes at least one of 2,2'-bis(trifluoromethyl)-4,4'-diaminophenyl ether, 2,2'-bis[4-(4-aminophenoxy)phenyl]propane, 2,2'-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 4,4'-diaminobiphenyl-2,2'-dicarboxylic acid, 4,4'-bis(3-aminophenoxy)biphenyl, and bis(4-aminophenyl)terephthalate; And / or, the phase change material includes at least one of higher aliphatic hydrocarbons, fatty acids and their esters, polyols, and crystalline hydrated salts; And / or, the wall material of the microcapsule is melamine-formaldehyde resin; And / or, the particle size of the microcapsule is 20 μm-80 μm; And / or, the first solvent includes at least one of N-methylpyrrolidone, m-cresol, and dimethylacetamide.

7. The method according to claim 4, characterized in that The polymerization reaction is carried out under a protective atmosphere; And / or, the polymerization reaction is carried out at 150° C.-200° C. for 4 h-12 h; And / or, the mixing process is carried out under stirring conditions; And / or, the mixing treatment is carried out at 130° C.-180° C. for 1 h-4 h.

8. The method according to claim 4, characterized in that After the mixing process, the method further includes: spinning and drying the mixed product to obtain the temperature regulating and heat insulating material.

9. Use of the temperature regulating and heat insulating material according to any one of claims 1 to 3 or the temperature regulating and heat insulating material prepared by the method according to any one of claims 4 to 8 in the preparation of automobile parts, textiles, spacecraft parts and / or rocket parts.

10. A car roof, characterized in that: The invention comprises the temperature regulating and heat insulating material as described in any one of claims 1 to 3 or the temperature regulating and heat insulating material prepared by the method as described in any one of claims 4 to 8; optionally, the automobile roof further comprises an outer decorative layer and a polypropylene skeleton layer.

Images