Super-hydrophobic thermal insulation composite material, and preparation method and application thereof

Abstract

The application relates to the technical field of chemical materials, and discloses a super-hydrophobic heat-insulating composite material, a preparation method and application thereof. Raw materials for preparing the super-hydrophobic heat-insulating composite material contain styrene, divinylbenzene, functionalized styrene, hollow glass microbeads modified by a silane coupling agent, inorganic fillers, an initiator, an emulsifier and water; the super-hydrophobic heat-insulating composite material has a thermal conductivity coefficient of less than or equal to 0.03 W / m.K and a water contact angle of more than 150 DEG. The composite material has excellent heat-insulating performance and super-hydrophobicity, and has the characteristics of high mechanical performance and uniform pore size distribution, and has a good application prospect in the fields of heat insulation, heat preservation, waterproofing and the like.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of chemical materials, in particular to a super-hydrophobic thermal insulation composite material and a preparation method and application thereof. BACKGROUND

[0002] At present, reducing the heat loss of high-temperature pipelines is an important part of the carbon emission reduction trend. The outer side of the high-temperature pipeline of a refining and chemical enterprise is usually coated with a thick thermal insulation material, which can effectively reduce the energy consumption of the enterprise and reduce carbon emissions. However, after the pipeline using conventional thermal insulation materials such as calcium silicate, composite silicate, rock wool, and slag wool is operated for a long period of time, the thermal insulation performance of the thermal insulation material decreases, which increases the heat loss and leads to an increase in the energy consumption of the device. On the other hand, the decrease in the thermal insulation performance increases the temperature of the outer surface of the pipeline, which increases the possibility of scalding accidents. In addition, materials such as rock wool and aluminum silicate are prone to water absorption, which leads to a loss of thermal insulation and affects the normal operation of the device.

[0003] Aerogel is a new generation of high-efficiency energy-saving thermal insulation material, which exhibits excellent performance in multiple fields such as heat, acoustics, optics, electricity, and mechanics. Currently, the commercialized aerogel mainly focuses on its high-efficiency heat-blocking ability, and is used in multiple fields such as petroleum and chemical industry, heat pipe network, lithium battery, building materials, outdoor clothing, aerospace, and military industry.

[0004] For example, patent application CN114100534A discloses a preparation method of a silicon-aluminum binary aerogel composite material, which adopts a method of mixing short-chain alcohol and long-chain alcohol to reduce the phase separation of the gel material, and then prepares the aerogel material through supercritical drying. Patent CN110282947B discloses a high-strength composite aerogel thermal insulation material and a preparation method thereof, which uniformly distributes carbon nitride fibers on the surface or inside of the aerogel, effectively improves the mechanical properties of the silicon dioxide aerogel, and further modifies the silicon dioxide aerogel by using the softness and thermal insulation performance of the aluminum silicate fiber, thereby enhancing the flexibility of the silicon dioxide aerogel and reducing its thermal conductivity. Patent application CN113416028A discloses a production process of a water-resistant aerogel thermal insulation material, which uses silicon dioxide sol, modified graphene, and chitosan as the matrix, modifies the surface of the aerogel by using the hydrophobic modifier prepared from the modified graphene, and obtains a hydrophobic surface, with a water repellency of up to 99%.

[0005] However, the aerogel material needs a supercritical carbon dioxide drying process in the preparation process, and the wet gel needs to withstand a drying stress of up to 100 MPa-200 MPa in the drying process. This stress will continuously shrink and crack the gel structure, which is easy to cause the structure to collapse, so the aerogel material is prone to pulverization and residue, which affects the service life of the aerogel material. SUMMARY

[0006] The present application aims to overcome the problems of poor mechanical strength, easy powdering, low hydrophobicity, easy hydrolysis, and high production cost of traditional aerogel thermal insulation materials in the prior art, and provide a super-hydrophobic thermal insulation composite material, a preparation method and application thereof.

[0007] To achieve the above-mentioned object, the present application provides a super-hydrophobic thermal insulation composite material in one aspect, and raw materials for preparing the super-hydrophobic thermal insulation composite material contain styrene, divinylbenzene, functionalized styrene, hollow glass microbeads modified by a silane coupling agent, inorganic fillers, an initiator, an emulsifier, and water.

[0008] The thermal conductivity of the super-hydrophobic thermal insulation composite material is ≤0.03 W / m.K, and the water contact angle is >150°.

[0009] Preferably, the compressive strength of the super-hydrophobic thermal insulation composite material is ≥1 MPa.

[0010] Preferably, the most probable pore size of the super-hydrophobic thermal insulation composite material is 10-200 nm.

[0011] Preferably, the inorganic fillers are selected from one or two or more of silicon carbide, titanium nitride, titanium dioxide, vermicular graphite, graphene, and carbon black.

[0012] Preferably, the silane coupling agent is selected from one or two or more of tetraethoxysilane, vinyltriethoxysilane, aminopropyltrimethoxysilane, glycidyl ether oxypropyltrimethoxysilane, vinyltrimethoxysilane, and γ-methacryloyloxypropyltrimethoxysilane.

[0013] Preferably, the functionalized styrene is selected from one or two or more of N,N-dimethylstyrene, N,N-diethylstyrene, N,N-diphenylstyrene, methoxystyrene, methylthio styrene, p-chlorostyrene, and p-bromostyrene.

[0014] Preferably, the weight ratio of the use amounts of styrene, divinylbenzene, functionalized styrene, emulsifier, hollow glass microbeads modified by a silane coupling agent, inorganic fillers, and initiator is 1:0.5-6:0.1-3:0.5-3:0.01-0.5:0.01-0.1:0.2-1, and the weight ratio of the use amounts of water and styrene is 20-100:1.

[0015] The present application provides a preparation method of a super-hydrophobic thermal insulation composite material in a second aspect, and the method comprises the following steps:

[0016] (1) mixing styrene, divinylbenzene, functionalized styrene, an emulsifier, and water to obtain a mixture A;

[0017] (2) mixing the mixture A, the hollow glass microspheres modified by silane coupling agent and the inorganic filler to obtain a mixture B;

[0018] (3) mixing the mixture B with an initiator solution containing an initiator and water, then performing a reaction, and then performing washing and drying.

[0019] Preferably, the inorganic filler is selected from one or more of silicon carbide, titanium nitride, titanium dioxide, vermicular graphite, graphene and carbon black.

[0020] Preferably, the silane coupling agent is selected from one or more of tetraethoxysilane, vinyltriethoxysilane, aminopropyltrimethoxysilane, glycidyloxypropyltrimethoxysilane, vinyltrimethoxysilane and γ-methacryloxypropyltrimethoxysilane.

[0021] Preferably, the functionalized styrene is selected from one or more of N,N-dimethylstyrene, N,N-diethylstyrene, N,N-diphenylstyrene, methoxystyrene, methylthio styrene, p-chlorostyrene and p-bromostyrene.

[0022] Preferably, the weight ratio of the amounts of styrene, divinylbenzene, functionalized styrene, emulsifier, hollow glass microspheres modified by silane coupling agent, inorganic filler and initiator is 1:0.5-6:0.1-3:0.5-3:0.01-0.5:0.01-0.1:0.2-1.

[0023] Preferably, the weight ratio of the sum of the amounts of water in steps (1) and (3) to styrene is 20-100:1.

[0024] Preferably, in step (1), the weight ratio of the amounts of water to styrene is 20-80:1.

[0025] Preferably, the emulsifier is selected from one or more of Tween 80, sodium dodecylbenzenesulfonate and polyvinyl alcohol.

[0026] Preferably, the initiator is selected from potassium persulfate, ammonium persulfate or hydrogen peroxide.

[0027] Preferably, in step (3), the reaction conditions include a temperature of 65-85℃ and a time of 3-6h.

[0028] Preferably, in step (3), the drying is vacuum drying.

[0029] The third aspect of the present application provides a super-hydrophobic thermal insulation composite material prepared by the method described above.

[0030] The fourth aspect of the present application provides the application of the super-hydrophobic thermal insulation composite material or the super-hydrophobic thermal insulation composite material prepared by the method described above in the field of heat insulation, thermal insulation, sound insulation or waterproof.

[0031] Compared with the prior art, the present application has the following advantages:

[0032] 1. The present application provides a super-hydrophobic thermal insulation composite material, which has a thermal conductivity of ≤0.03 W / m.K and a water contact angle of >150°, indicating that the composite material has excellent thermal insulation performance and super-hydrophobicity; at the same time, it has high mechanical properties and uniform pore size distribution, and has good application prospects in the fields of heat insulation, thermal insulation, waterproofing, etc.

[0033] 2. In the method described in the present application, styrene, divinylbenzene and functionalized styrene are used as monomers, and silane coupling agents are added to modify hollow glass microspheres and inorganic fillers, so that the prepared composite material has excellent thermal insulation performance and super-hydrophobicity; has high mechanical properties and uniform pore size distribution; at the same time, based on the selection of raw materials, various drying methods commonly used in the field can be used to complete drying during the preparation process, overcoming the problem of high production cost and harsh conditions caused by the use of complex supercritical carbon dioxide drying process in traditional aerogel materials. BRIEF DESCRIPTION OF DRAWINGS

[0034] Figure 1 is a picture taken of the product prepared in Example 1;

[0035] Figure 2 is a SEM characterization result graph of the product prepared in Example 2;

[0036] Figure 3 is a water contact angle test photo of the product prepared in Example 1;

[0037] Figure 4 is a BET pore size distribution graph of the product prepared in Examples 1-3. DETAILED DESCRIPTION

[0038] The specific embodiments of the present application will be described in detail below with reference to the accompanying drawings. It should be understood that the specific embodiments described herein are only used to illustrate and explain the present application, and are not used to limit the present application.

[0039] The endpoints of the ranges and any values in the ranges disclosed herein are not limited to the precise values stated. The ranges and values should be construed to be approximations that are used in the art. For numerical ranges, the endpoints are included in the ranges, and the ranges between the endpoints are also included in the ranges. The ranges and values should be construed to be approximations that are used in the art. For numerical ranges, the endpoints are included in the ranges, and the ranges between the endpoints are also included in the ranges.

[0040] The present application provides a super-hydrophobic thermal insulation composite material, and raw materials for preparing the super-hydrophobic thermal insulation composite material include styrene, divinylbenzene, functionalized styrene, hollow glass microspheres modified by a silane coupling agent, inorganic fillers, an initiator, an emulsifier and water.

[0041] The super-hydrophobic thermal insulation composite material has a thermal conductivity of ≤0.03 W / m.K and a water contact angle of >150°.

[0042] The super-hydrophobic thermal insulation composite material has excellent thermal insulation performance and super-hydrophobic performance, and has high mechanical performance and uniform pore size distribution, and has a good application prospect in the fields of thermal insulation, heat preservation, waterproofing and the like.

[0043] In a preferred embodiment, the super-hydrophobic thermal insulation composite material has a compressive strength of ≥1 MPa.

[0044] In a preferred embodiment, the super-hydrophobic thermal insulation composite material has a most probable pore size of 10-200 nm.

[0045] In the present application, the most probable pore size refers to the pore size of the gap with the largest probability in a series of gaps present in the material. In the test process, the peak value corresponding to the pore size on the differential distribution curve of the pore size obtained by BET test is the most probable pore size.

[0046] In a preferred embodiment, the inorganic fillers are selected from one or more than two of silicon carbide, titanium nitride, titanium dioxide, vermicular graphite, graphene and carbon black.

[0047] In order to further improve the thermal insulation performance, mechanical performance and hydrophobicity of the super-hydrophobic thermal insulation composite material, in a preferred embodiment, the silane coupling agent is selected from one or more than two of tetraethoxysilane, vinyltriethoxysilane, aminopropyltrimethoxysilane, glycidyl ether propyltrimethoxysilane, vinyltrimethoxysilane and γ-methacryloyloxypropyltrimethoxysilane.

[0048] In a specific embodiment, the silane coupling agent is γ-methacryloyloxypropyltrimethoxysilane (KH570).

[0049] In the present application, the hollow glass microspheres modified by the silane coupling agent are obtained by modifying the hollow glass microspheres with the silane coupling agent.

[0050] In a preferred embodiment, the weight ratio of the silane coupling agent to the hollow glass microspheres in the raw materials for preparing the hollow glass microspheres modified by the silane coupling agent is 0.01-0.03:1; specifically, it can be 0.01:1, 0.0.2:1 or 0.03:1.

[0051] In the present application, the preparation method of the hollow glass microsphere modified by the silane coupling agent comprises the following steps: mixing the hollow glass microsphere with a solvent, then mixing with the silane coupling agent, then performing a reaction, and then performing filtration and drying.

[0052] Preferably, the solvent is ethanol or ethyl acetate, etc.

[0053] Preferably, the reaction conditions include: the temperature is 40-60℃, and the time is 0.5-2h; specifically, the reaction temperature can be 40℃, 45℃, 50℃, 55℃ or 60℃; and the reaction time can be 0.5h, 1h, 1.5h or 2h.

[0054] In order to further improve the thermal insulation performance, mechanical properties and hydrophobicity of the super-hydrophobic thermal insulation composite material, in the preferred embodiment, the functionalized styrene is selected from one or two or more of N,N-dimethylstyrene, N,N-diethylstyrene, N,N-diphenylstyrene, methoxystyrene, methylthio styrene, p-chlorostyrene and p-bromostyrene.

[0055] In order to further improve the thermal insulation performance, mechanical properties and hydrophobicity of the super-hydrophobic thermal insulation composite material, the ratio of each component in the raw materials can be reasonably controlled. In the preferred embodiment, the weight ratio of the use amount of styrene, divinylbenzene, functionalized styrene, emulsifier, hollow glass microsphere modified by silane coupling agent, inorganic filler and initiator in the raw materials is 1:0.5-6:0.1-3:0.5-3:0.01-0.5:0.01-0.1:0.2-1; and the weight ratio of the use amount of water to styrene is 20-100:1.

[0056] In a specific embodiment, the weight ratio of the use amount of styrene to divinylbenzene can be 1:0.5, 1:1, 1:1.5, 1:2, 1:2.5, 1:3, 1:3.5, 1:4, 1:4.5, 1:5, 1:5.5 or 1:6.

[0057] In a specific embodiment, the weight ratio of the use amount of styrene to functionalized styrene can be 1:0.1, 1:0.2, 1:0.3, 1:0.5, 1:0.6, 1:0.8, 1:1, 1:1.2, 1:1.4, 1:1.5, 1:1.8, 1:2, 1:2.5 or 1:3.

[0058] In a specific embodiment, the weight ratio of the use amount of styrene to emulsifier can be 1:0.5, 1:0.6, 1:0.7, 1:0.8, 1:0.9, 1:1, 1:1.1, 1:1.2, 1:1.5, 1:2, 1:2.5 or 1:3.

[0059] In a specific embodiment, the weight ratio of the amount of styrene to the amount of silane coupling agent modified hollow glass beads can be 1:0.01, 1:0.02, 1:0.03, 1:0.04, 1:0.05, 1:0.08, 1:0.1, 1:0.15, 1:0.2, 1:0.25, 1:0.3, 1:0.36, 1:0.4, 1:0.45, or 1:0.5.

[0060] In a specific embodiment, the weight ratio of the amount of styrene to the amount of inorganic filler can be 1:0.01, 1:0.02, 1:0.03, 1:0.04, 1:0.05, 1:0.06, 1:0.07, 1:0.08, 1:0.09, or 1:0.1.

[0061] In a specific embodiment, the weight ratio of the amount of styrene to the amount of initiator can be 1:0.2, 1:0.3, 1:0.4, 1:0.5, 1:0.6, 1:0.7, 1:0.8, 1:0.9, or 1:1.

[0062] In a specific embodiment, the weight ratio of the amount of water to the amount of styrene can be 20:1, 25:1, 30:1, 35:1, 40:1, 45:1, 50:1, 55:1, 60:1, 65:1, 70:1, 75:1, 80:1, 85:1, 90:1, 95:1, or 100:1.

[0063] The second aspect of the present application provides a method for preparing a super-hydrophobic thermal insulation composite material, the method comprising the following steps:

[0064] (1) mixing styrene, divinylbenzene, functionalized styrene, emulsifier, and water to obtain a mixture A;

[0065] (2) mixing the mixture A, silane coupling agent modified hollow glass beads, and inorganic filler to obtain a mixture B;

[0066] (3) mixing the mixture B with an initiator solution, followed by reaction, then washing and drying, wherein the initiator solution contains an initiator and water.

[0067] In the method described in the present application, a super-hydrophobic thermal insulation composite aerogel material is obtained by using styrene, divinylbenzene, and functionalized styrene as monomers, simultaneously adding silane coupling agent modified hollow glass beads and inorganic filler, and then through in-situ polymerization of high internal phase emulsion. The material has high mechanical properties and thermal insulation properties at the same time, with a thermal conductivity of ≤0.03 W / m.K, a compressive strength of ≥1 MPa, and a super-hydrophobic surface with a water contact angle of >150°. The material has a most probable pore size of 10-200 nm, and a uniform pore size distribution.

[0068] To further improve the thermal insulation performance, mechanical properties and hydrophobicity of the super-hydrophobic thermal insulation composite, in a preferred embodiment, the inorganic filler is selected from one or more of silicon carbide, titanium nitride, titanium dioxide, vermicular graphite, graphene and carbon black.

[0069] To further improve the thermal insulation performance, mechanical properties and hydrophobicity of the super-hydrophobic thermal insulation composite, in a preferred embodiment, the silane coupling agent is selected from one or more of tetraethoxysilane, vinyltriethoxysilane, aminopropyltrimethoxysilane, glycidyl ether propyltrimethoxysilane, vinyltrimethoxysilane and γ-methacryloxypropyltrimethoxysilane.

[0070] In a preferred embodiment, the weight ratio of the silane coupling agent to the hollow glass microbeads in the raw material for preparing the silane coupling agent modified hollow glass microbeads is 0.01-0.03:1; specifically, it can be 0.01:1, 0.0.2:1 or 0.03:1.

[0071] In the present application, the method for preparing the silane coupling agent modified hollow glass microbeads comprises the following steps: mixing the hollow glass microbeads with a solvent, then mixing with a silane coupling agent, then performing a reaction, and then performing filtration and drying.

[0072] Preferably, the solvent is ethanol or ethyl acetate.

[0073] Preferably, the hollow glass microbeads are mixed with the solvent by ultrasonic mixing; further preferably, the time for ultrasonic mixing is 1 h.

[0074] Preferably, the reaction conditions include a temperature of 40-60℃ and a time of 0.5-2 h; specifically, the reaction temperature can be 40℃, 45℃, 50℃, 55℃ or 60℃; and the reaction time can be 0.5 h, 1 h, 1.5 h or 2 h.

[0075] In a specific embodiment, the silane coupling agent is γ-methacryloxypropyltrimethoxysilane (KH570).

[0076] In the method of the present application, by using styrene, divinylbenzene and functionalized styrene as monomers, the dispersibility of the hollow microbeads and the inorganic filler in the polymer matrix is increased, and the thermal insulation performance and infrared radiation barrier property of the material are improved.

[0077] In a preferred embodiment, the functionalized styrene is selected from one or more of N,N-dimethylstyrene, N,N-diethylstyrene, N,N-diphenylstyrene, methoxystyrene, methylthio styrene, p-chlorostyrene and p-bromostyrene.

[0078] To further improve the thermal insulation performance, mechanical properties and hydrophobicity of the super-hydrophobic thermal insulation composite material, the ratio of the raw materials used in the preparation process can be reasonably controlled. In a preferred embodiment, the weight ratio of the amounts of styrene, divinylbenzene, functionalized styrene, emulsifier, hollow glass microsphere modified by silane coupling agent, inorganic filler and initiator is 1:0.5-6:0.1-3:0.5-3:0.01-0.5:0.01-0.1:0.2-1.

[0079] In a specific embodiment, the weight ratio of the amounts of styrene and divinylbenzene can be 1:0.5, 1:1, 1:1.5, 1:2, 1:2.5, 1:3, 1:3.5, 1:4, 1:4.5, 1:5, 1:5.5 or 1:6.

[0080] In a specific embodiment, the weight ratio of the amounts of styrene and functionalized styrene can be 1:0.1, 1:0.2, 1:0.3, 1:0.5, 1:0.6, 1:0.8, 1:1, 1:1.2, 1:1.4, 1:1.5, 1:1.8, 1:2, 1:2.5 or 1:3.

[0081] In a specific embodiment, the weight ratio of the amounts of styrene and emulsifier can be 1:0.5, 1:0.6, 1:0.7, 1:0.8, 1:0.9, 1:1, 1:1.1, 1:1.2, 1:1.5, 1:2, 1:2.5 or 1:3.

[0082] In a specific embodiment, the weight ratio of the amounts of styrene and hollow glass microsphere modified by silane coupling agent can be 1:0.01, 1:0.02, 1:0.03, 1:0.04, 1:0.05, 1:0.08, 1:0.1, 1:0.15, 1:0.2, 1:0.25, 1:0.3, 1:0.36, 1:0.4, 1:0.45 or 1:0.5.

[0083] In a specific embodiment, the weight ratio of the amounts of styrene and inorganic filler can be 1:0.01, 1:0.02, 1:0.03, 1:0.04, 1:0.05, 1:0.06, 1:0.07, 1:0.08, 1:0.09 or 1:0.1.

[0084] In a specific embodiment, the weight ratio of the amounts of styrene and initiator can be 1:0.2, 1:0.3, 1:0.4, 1:0.5, 1:0.6, 1:0.7, 1:0.8, 1:0.9 or 1:1.

[0085] In a preferred embodiment, the weight ratio of the total amount of water used in step (1) and step (3) to the amount of styrene is 20-100:1; wherein the amount of water used in step (3) refers to the amount of water contained in the initiator solution in step (3).

[0086] More preferably, in step (1), the weight ratio of the amount of water used to the amount of styrene is 20-80:1; specifically, it can be 20:1, 25:1, 30:1, 35:1, 40:1, 45:1, 50:1, 55:1, 60:1, 65:1, 70:1, 75:1 or 80:1.

[0087] More preferably, in step (3), the weight ratio of the amount of water used to the amount of styrene is 1-10:1.

[0088] In the method described in the present application, there is no special requirement for the selection of emulsifier, which can be various emulsifiers commonly used in emulsion polymerization in the art. In a preferred embodiment, the emulsifier is selected from one or more than two of Tween 80, sodium dodecyl benzene sulfonate and polyvinyl alcohol.

[0089] In a preferred embodiment, the initiator is selected from potassium persulfate, ammonium persulfate or hydrogen peroxide.

[0090] In a preferred embodiment, in step (1), the mixing can be stirring mixing.

[0091] In a preferred embodiment, in step (2), the mixing is stirring mixing. Further preferably, the temperature of stirring mixing is 25-35℃, and the time of stirring mixing is 30-60 min.

[0092] In a preferred embodiment, in step (3), the specific process of mixing mixture B with the initiator solution includes: adding the initiator solution dropwise into mixture B under stirring; further preferably, the time of dropwise adding is 20-40 min.

[0093] In a specific embodiment, the initiator solution is added dropwise using a constant pressure low liquid funnel.

[0094] In a preferred embodiment, in step (3), the initiator solution further contains calcium chloride, which is beneficial to the dissolution of the initiator. There is no special requirement for the amount of calcium chloride, which can be the amount commonly used in the art. Further preferably, in the initiator solution, the weight ratio of calcium chloride to the sum of the weights of calcium chloride and water is 1-3%.

[0095] In a specific embodiment, the configuration process of the initiator solution is: mixing water and calcium chloride, and then adding the initiator.

[0096] In a preferred embodiment, in step (3), the reaction conditions include: temperature of 65-85℃, time of 3-6h. Specifically, the temperature can be 65℃, 70℃, 75℃, 80℃ or 85℃; the time can be 3h, 3.5h, 4h, 4.5h, 5h, 5.5h or 6h.

[0097] In a preferred embodiment, the washing uses an ethanol as the washing agent, which can remove water and residual monomers.

[0098] In the method described in the present application, in step (3), the washed material can be dried by using various drying methods in the art, which overcomes the problem of high production cost caused by the use of complex supercritical carbon dioxide drying process in traditional aerogel materials, and has the characteristics of simple process and low cost.

[0099] In a preferred embodiment, in step (3), the drying is vacuum drying.

[0100] In a specific embodiment, the process for preparing the super-hydrophobic thermal insulation composite material comprises the following steps:

[0101] (1) stirring and mixing styrene, divinylbenzene, functionalized styrene, emulsifier and water to obtain a mixture A;

[0102] (2) stirring and mixing the mixture A, silane coupling agent modified hollow glass microbeads and inorganic fillers to obtain a mixture B;

[0103] (3) under stirring, adding an initiator solution to the mixture B, followed by reaction, then washing and vacuum drying, wherein the initiator solution contains an initiator, water and calcium chloride.

[0104] The third aspect of the present application provides a super-hydrophobic thermal insulation composite material prepared by the method described above.

[0105] The fourth aspect of the present application provides an application of the super-hydrophobic thermal insulation composite material described above or the super-hydrophobic thermal insulation composite material prepared by the method described above in the field of thermal insulation, heat preservation, sound insulation or waterproofing.

[0106] For example, the thermal insulation layer structure between power batteries, the waterproof thermal insulation layer of low-temperature cooling pipeline, etc.

[0107] The present application will be described in detail below through examples, but the scope of protection of the present application is not limited thereto.

[0108] The reagents used in the following examples and comparative examples are all commercially available products unless otherwise specified.

[0109] Example 1

[0110] Preparation of super-hydrophobic thermal insulation composite material S1 includes the following steps:

[0111] (1) 2 g of styrene, 6 g of divinylbenzene, functionalized styrene (2 g of N,N-dimethylstyrene), 3 g of emulsifier (Tween 80) and 80 g of water were stirred and mixed to obtain a mixture A;

[0112] (2) Mixture A, 0.3 g of silane coupling agent-modified hollow glass microspheres a1, and 0.1 g of inorganic filler (silicon carbide) were stirred and mixed for 30 min at a stirring temperature of 25° C. to obtain mixture B;

[0113] (3) Under stirring, the initiator solution was added dropwise to the mixture B using a constant pressure dropping funnel for 30 min. After sealing, the mixture was polymerized at 80° C. After 6 hours of reaction, a solid block product was obtained, which was then washed with ethanol and then vacuum dried. The initiator solution consisted of 1 g of initiator (potassium persulfate), 9.9 g of water, and 0.1 g of calcium chloride.

[0114] Among them, the weight ratio of styrene, divinylbenzene, functionalized styrene, emulsifier, silane coupling agent modified hollow glass microspheres a1, inorganic filler and initiator is 1:3:1:1.5:0.15:0.05:0.5; the weight ratio of the amount of water used in step (1) to the amount of styrene used is 40:1; and the ratio of the weight of water contained in the initiator solution in step (3) to the weight of styrene is 4.95:1.

[0115] The preparation process of the silane coupling agent-modified hollow glass microspheres a1 includes the following steps: ultrasonically mixing the hollow glass microsphere powder with anhydrous ethanol for 1 hour, then mixing with a silane coupling agent (KH570), then reacting at 60°C for 1 hour, then filtering, and then drying the filter residue at 100°C for 24 hours; wherein the weight ratio of the hollow glass microsphere powder, anhydrous ethanol, and silane coupling agent is 1:100:0.02.

[0116] Example 2

[0117] The preparation of the super-hydrophobic thermal insulation composite material S2 comprises the following steps:

[0118] (1) 3 g of styrene, 6 g of divinylbenzene, functionalized styrene (1 g of N,N-diethylstyrene), 4 g of an emulsifier (sodium dodecylbenzenesulfonate), and 80 g of water were stirred and mixed to obtain a mixture A;

[0119] (2) Mixture A, 0.1 g of silane coupling agent-modified hollow glass microspheres a1, and 0.1 g of inorganic filler (titanium dioxide) were stirred and mixed for 30 min at a temperature of 25° C. to obtain mixture B;

[0120] (3) under stirring, the initiator solution was added into the mixture B using a constant pressure dropping funnel, the dropping time was 40 min, the polymerization reaction was carried out at 70℃ after sealing, the solid block product was obtained after 8 hours of reaction, then washed using ethanol, and then vacuum dried; the initiator solution was composed of 1.5 g initiator (ammonium persulfate), 9.9 g water and 0.1 g calcium chloride;

[0121] The weight ratio of the amount of styrene, divinylbenzene, functionalized styrene, emulsifier, hollow glass microspheres a1 modified by silane coupling agent, inorganic filler and initiator is 3:6:1:4:0.1:0.1:1.5; the weight ratio of the amount of water used in step (1) to the amount of styrene is 80:3; the weight ratio of the amount of water in the initiator solution to the amount of styrene in step (3) is 3.3:1.

[0122] Example 3

[0123] The super-hydrophobic thermal insulation composite material S3 was prepared, including the following steps:

[0124] (1) 5 g of styrene, 4 g of divinylbenzene, functionalized styrene (1 g of N,N-diphenylstyrene), 3 g of emulsifier (polyvinyl alcohol) and 100 g of water were stirred and mixed to obtain a mixture A;

[0125] (2) The mixture A, 0.2 g of hollow glass microspheres a1 modified by silane coupling agent and 0.05 g of inorganic filler (titanium nitride) were stirred and mixed, the stirring time was 30 min, and the stirring temperature was 25℃, to obtain a mixture B;

[0126] (3) under stirring, the initiator solution was added into the mixture B using a constant pressure dropping funnel, the dropping time was 40 min, the polymerization reaction was carried out at 70℃ after sealing, the solid block product was obtained after 8 hours of reaction, then washed using ethanol, and then vacuum dried; the initiator solution was composed of 1.5 g initiator (ammonium persulfate), 9.9 g water and 0.1 g calcium chloride;

[0127] The weight ratio of the amount of styrene, divinylbenzene, functionalized styrene, emulsifier, hollow glass microspheres a1 modified by silane coupling agent, inorganic filler and initiator is 3:6:1:4:0.1:0.1:1.5; the weight ratio of the amount of water used in step (1) to the amount of styrene is 80:3; the weight ratio of the amount of water in the initiator solution to the amount of styrene in step (3) is 3.3:1.

[0128] Example 4

[0129] Preparation of super-hydrophobic thermal insulation composite material S4 includes the following steps:

[0130] (1) 1 g of styrene, 6 g of divinylbenzene, functionalized styrene (3 g of N,N-diethylstyrene), 3 g of emulsifier (Tween 80) and 80 g of water were stirred and mixed to obtain a mixture A;

[0131] (2) Mixture A, 0.5 g of silane coupling agent-modified hollow glass microspheres a1, and 0.1 g of inorganic filler (titanium nitride) were stirred and mixed for 30 min at a stirring temperature of 25° C. to obtain mixture B;

[0132] (3) Under stirring, the initiator solution was added dropwise to the mixture B using a constant pressure dropping funnel for 20 min. After sealing, the mixture was polymerized at 80° C. After 6 hours of reaction, a solid block product was obtained, which was then washed with ethanol and then vacuum dried. The initiator solution contained 1 g of initiator (potassium persulfate), 9.9 g of water, and 0.1 g of calcium chloride.

[0133] Among them, the weight ratio of styrene, divinylbenzene, functionalized styrene, emulsifier, silane coupling agent modified hollow glass microspheres a1, inorganic filler and initiator is 1:6:3:3:0.5:0.1:1; the weight ratio of the amount of water used in step (1) to the amount of styrene used is 80:1; and the ratio of the weight of water contained in the initiator solution in step (3) to the weight of styrene is 9.9:1.

[0134] Example 5

[0135] Preparation of super-hydrophobic thermal insulation composite material S5 includes the following steps:

[0136] (1) 4 g of styrene, 4 g of divinylbenzene, functionalized styrene (2 g of methoxystyrene), 3 g of emulsifier (Tween 80) and 80 g of water were stirred and mixed to obtain a mixture A;

[0137] (2) Mixture A, 0.1 g of silane coupling agent-modified hollow glass microspheres a1, and 0.1 g of inorganic filler (graphene) were stirred and mixed for 30 min at a stirring temperature of 25° C. to obtain mixture B;

[0138] (3) Under stirring, the initiator solution was added dropwise to the mixture B using a constant pressure dropping funnel for 30 min. After sealing, the mixture was polymerized at 80° C. After 6 hours of reaction, a solid block product was obtained, which was then washed with ethanol and then vacuum dried. The initiator solution contained 1 g of initiator (potassium persulfate), 9.9 g of water, and 0.1 g of calcium chloride.

[0139] The weight ratio of the amounts of styrene, divinylbenzene, functionalized styrene, emulsifier, hollow glass microbeads a1 modified by silane coupling agent, inorganic filler and initiator is 1:1:0.5:0.75:0.025:0.025:0.25; the weight ratio of the amount of water used in step (1) to the amount of styrene is 20:1; and the ratio of the weight of water to the weight of styrene in the initiator solution in step (3) is 2.475:1.

[0140] Example 6

[0141] The super-hydrophobic thermal insulation composite material S6 is prepared by the following steps:

[0142] (1) 3 g of styrene, 5 g of divinylbenzene, 2 g of functionalized styrene (p-bromostyrene), 3 g of emulsifier (polyvinyl alcohol) and 60 g of water are stirred and mixed to obtain a mixture A;

[0143] (2) The mixture A, 0.3 g of hollow glass microbeads a1 modified by silane coupling agent and 0.1 g of inorganic filler (carbon black) are stirred and mixed, the stirring time is 30 min and the stirring temperature is 25°C to obtain a mixture B;

[0144] (3) The initiator solution is added dropwise into the mixture B using a constant pressure dropping funnel under stirring, the dropping time is 30 min, and the sealed mixture is subjected to a polymerization reaction at 80°C for 6 hours to obtain a solid block-shaped product, which is then washed with ethanol and vacuum dried; the initiator solution contains 1 g of initiator (potassium persulfate), 9.9 g of water and 0.1 g of calcium chloride;

[0145] The weight ratio of the amounts of styrene, divinylbenzene, functionalized styrene, emulsifier, hollow glass microbeads a1 modified by silane coupling agent, inorganic filler and initiator is 3:5:2:3:0.3:0.1:1; the weight ratio of the amount of water used in step (1) to the amount of styrene is 20:1; and the ratio of the weight of water to the weight of styrene in the initiator solution in step (3) is 3.3:1.

[0146] Example 7

[0147] The super-hydrophobic thermal insulation composite material S7 is prepared by the following steps:

[0148] (1) 2 g of styrene, 6 g of divinylbenzene, 2 g of functionalized styrene (methylthiostyrene), 3 g of emulsifier (Tween 80) and 80 g of water are stirred and mixed to obtain a mixture A;

[0149] (2) mixing the mixed material A, 0.3 g of the hollow glass microsphere a2 modified by the silane coupling agent and 0.1 g of the inorganic filler (silicon carbide) to obtain a mixed material B, wherein the stirring time is 30 min and the stirring temperature is 25℃;

[0150] (3) adding the initiator solution to the mixed material B drop by drop under stirring using a constant pressure dropping funnel, wherein the dropping time is 30 min, and then carrying out a polymerization reaction at 80℃ after being sealed, and then obtaining a solid block product after 6 hours of reaction, and then carrying out washing using ethanol, and then carrying out vacuum drying, wherein the initiator solution contains 1 g of the initiator (potassium persulfate), 9.9 g of water and 0.1 g of calcium chloride;

[0151] The weight ratio of the use amount of the styrene, the di-vinyl benzene, the functionalized styrene, the emulsifier, the hollow glass microsphere a2 modified by the silane coupling agent, the inorganic filler and the initiator is 1:3:1:1.5:0.15:0.05:0.5; the weight ratio of the use amount of the water to the use amount of the styrene in step (1) is 40:1; and the ratio of the weight of the water contained in the initiator solution to the weight of the styrene in step (3) is 4.95:1.

[0152] The preparation process of the hollow glass microsphere a2 modified by the silane coupling agent includes the following steps: mixing the hollow glass microsphere powder with anhydrous ethanol under ultrasonic mixing for 1 h, then mixing with the silane coupling agent (vinyl triethoxysilane), then reacting at 60℃ for 1 h, then filtering, and then drying the filter residue at 100℃ for 24 h; wherein the weight ratio of the use amount of the hollow glass microsphere powder, the anhydrous ethanol and the silane coupling agent is 1:100:0.02.

[0153] Example 8

[0154] The super-hydrophobic thermal insulation composite material S8 is prepared, including the following steps:

[0155] (1) mixing 2 g of styrene, 6 g of di-vinyl benzene, functionalized styrene (1 g of methoxy styrene + 1 g of methylthio styrene), 3 g of emulsifier (Tween 80) and 80 g of water to obtain a mixed material A;

[0156] (2) mixing the mixed material A, 0.3 g of the hollow glass microsphere a2 modified by the silane coupling agent and 0.1 g of the inorganic filler (silicon carbide) to obtain a mixed material B, wherein the stirring time is 30 min and the stirring temperature is 25℃;

[0157] (3) under stirring, the initiator solution was added into the mixture B using a constant pressure dropping funnel, the dropping time was 30 min, the polymerization reaction was carried out at 80℃ after sealing, the solid block product was obtained after 6 hours of reaction, then washed using ethanol, and then vacuum dried; the initiator solution contained 1 g initiator (potassium persulfate), 9.9 g water and 0.1 g calcium chloride;

[0158] The weight ratio of the amounts of styrene, divinylbenzene, functionalized styrene, emulsifier, silane coupling agent modified hollow glass microbeads a3, inorganic filler and initiator is 1:3:1:1.5:0.15:0.05:0.5; the weight ratio of the amount of water used in step (1) to the amount of styrene used is 40:1; the ratio of the weight of water contained in the initiator solution in step (3) to the weight of styrene is 4.95:1.

[0159] The preparation process of the silane coupling agent modified hollow glass microbeads a3 includes the following steps: mixing hollow glass microbead powder with anhydrous ethanol, then mixing with silane coupling agent (KH570), then reacting at 60℃ for 1h, then filtering, and then drying the filter residue at 100℃ for 24h; wherein the weight ratio of the amounts of hollow glass microbead powder, anhydrous ethanol and silane coupling agent is 1:100:0.03.

[0160] Example 9

[0161] The super-hydrophobic thermal insulation composite material S9 was prepared, including the following steps:

[0162] (1) 2 g of styrene, 6 g of divinylbenzene, functionalized styrene (1 g of methoxystyrene + 1 g of N,N-dimethylstyrene), 3 g of emulsifier (polyvinyl alcohol) and 60 g of water were stirred and mixed to obtain a mixture A;

[0163] (2) The mixture A, 0.3 g of silane coupling agent modified hollow glass microbeads a1 and 0.1 g of inorganic filler (vermicular graphite) were stirred and mixed, the stirring time was 30 min, and the stirring temperature was 25℃, to obtain a mixture B;

[0164] (3) under stirring, the initiator solution was added into the mixture B using a constant pressure dropping funnel, the dropping time was 30 min, the polymerization reaction was carried out at 80℃ after sealing, the solid block product was obtained after 6 hours of reaction, then washed using ethanol, and then vacuum dried; the initiator solution contained 1 g initiator (potassium persulfate), 9.9 g water and 0.1 g calcium chloride;

[0165] The weight ratio of the amounts of styrene, divinylbenzene, functionalized styrene, emulsifier, hollow glass microbeads a1 modified by silane coupling agent, inorganic filler and initiator is 1:3:1:1.5:0.15:0.05:0.5; the weight ratio of the amount of water used in step (1) to the amount of styrene is 30:1; and the ratio of the weight of water to the weight of styrene in the initiator solution in step (3) is 4.85:1.

[0166] Example 10

[0167] The super-hydrophobic thermal insulation composite material S10 is prepared by the following steps:

[0168] (1) 2 g of styrene, 5 g of divinylbenzene, 3 g of functionalized styrene (3 g of p-chlorostyrene), 3 g of emulsifier (polyvinyl alcohol) and 60 g of water are stirred and mixed to obtain a mixture A;

[0169] (2) The mixture A, 0.3 g of hollow glass microbeads a1 modified by silane coupling agent and 0.1 g of inorganic filler (silicon carbide) are stirred and mixed, the stirring time is 30 min and the stirring temperature is 25°C to obtain a mixture B;

[0170] (3) The initiator solution is added dropwise into the mixture B using a constant pressure dropping funnel under stirring, the dropping time is 30 min, the reaction is carried out at 80°C after being sealed, and a solid block product is obtained after 6 hours of reaction, then the product is washed using ethanol and then vacuum dried; the initiator solution contains 1 g of initiator (potassium persulfate), 9.9 g of water and 0.1 g of calcium chloride;

[0171] The weight ratio of the amounts of styrene, divinylbenzene, functionalized styrene, emulsifier, hollow glass microbeads a1 modified by silane coupling agent, inorganic filler and initiator is 1:2.5:1.5:1.5:0.15:0.05:0.5; the weight ratio of the amount of water used in step (1) to the amount of styrene is 20:1; and the ratio of the weight of water to the weight of styrene in the initiator solution in step (3) is 4.95:1.

[0172] Comparative Example 1

[0173] The method described in Example 1 is implemented, except that the hollow glass microbeads a1 modified by silane coupling agent are not used.

[0174] Comparative Example 2

[0175] The method described in Example 1 is implemented, except that the functionalized styrene (N,N-dimethylstyrene) is not used.

[0176] Comparative Example 3

[0177] The procedure described in Example 1 was followed except that no divinylbenzene was used.

[0178] Comparative Example 4

[0179] The procedure described in Example 1 was followed except that no inorganic filler was used.

[0180] Comparative Example 5

[0181] The procedure described in Example 1 was followed except that the same weight of hollow glass microsphere powder was used to replace the hollow glass microspheres a1 modified by silane coupling agent.

[0182] Test Example 1

[0183] The picture of placing the product prepared in Example 1 on the flower stem for shooting is shown in Figure 1 .

[0184] As can be seen from Figure 1 , the product prepared in Example 1 is very light and can be placed on the flower stem without crushing the flower stem.

[0185] The product prepared in Example 2 was characterized by SEM, and the results are shown in Figure 2 .

[0186] As can be seen from Figure 2 , the product prepared in Example 2 is a kind of nano-porous material with low thermal conductivity, which is suitable for use as a thermal insulation material.

[0187] Test Example 2

[0188] The compressive strength of the products obtained in the examples and comparative examples was tested by the method recorded in the national standard GB / T 8813-2020, and the results are shown in Table 1.

[0189] Table 1

[0190]

[0191]

[0192] As can be seen from Table 1, except for Comparative Example 3, the products all have good mechanical properties, and the compressive strength is more than 1 MPa, indicating that they have strong resistance to external force damage.

[0193] Test Example 3

[0194] The thermal conductivity of the products obtained in the examples and comparative examples was tested by the method recorded in the national standard GB / T 10294-2008, and the results are shown in Table 2.

[0195] Table 2

[0196] No. Thermal conductivity W / m.K No. Thermal conductivity W / m.K Example 1 0.018 Example 9 0.033 Example 2 0.027 Example 10 0.038 Example 3 0.021 Comparative Example 1 0.058 Example 4 0.022 Comparative Example 2 0.066 Example 5 0.028 Comparative Example 3 0.077 Example 6 0.038 Comparative Example 4 0.047 Example 7 0.035 Comparative Example 5 0.044 Example 8 0.034

[0197] As shown in Table 2, the products prepared in the examples have lower thermal conductivity, which is basically between 0.018-0.028 W / m.K, and have good heat conduction blocking performance, and can be applied to various thermal insulation projects.

[0198] Test Example 4

[0199] The infrared reflection performance of the products obtained in the examples and the comparative examples was tested by the method recorded in the standard JG / T 235-2014, and the results are shown in Table 3.

[0200] Table 3

[0201] No. Infrared reflectance % No. Infrared reflectance % Example 1 0.91 Example 9 0.85 Example 2 0.87 Example 10 0.87 Example 3 0.85 Comparative Example 1 0.78 Example 4 0.88 Comparative Example 2 0.88 Example 5 0.85 Comparative Example 3 0.89 Example 6 0.87 Comparative Example 4 0.68 Example 7 0.88 Comparative Example 5 0.85 Example 8 0.87

[0202] As shown in Table 3, the products prepared in the examples have higher infrared radiation reflection performance, and the infrared reflection ratio is greater than 0.85, which can effectively block the penetration of infrared radiation and prevent the diffusion of heat by radiation.

[0203] Test Example 5

[0204] The water contact angle of the products prepared in the examples and the comparative examples was detected by using a contact angle measuring instrument.

[0205] The contact angle test photo of the product prepared in Example 1 is shown in Figure 3 , and the contact angle test results are shown in Table 4.

[0206] Table 4

[0207]

[0208]

[0209] As shown in Table 4, the products prepared in the examples have higher hydrophobic performance, and the water contact angle is greater than 150°, which can well prevent water from penetrating into the inside of the material and affecting the thermal insulation performance of the material.

[0210] Test Example 6

[0211] The products prepared in the examples and the comparative examples were detected by using the BET method.

[0212] The pore size distribution of the products prepared in Examples 1-3 is shown in Figure 4 , and the most probable pore size of the products prepared in the examples and the comparative examples is shown in Table 5.

[0213] Table 5

[0214] No. Most probable pore diameter nm No. Most probable pore diameter nm Example 1 40 Example 9 200 Example 2 80 Example 10 150 Example 3 90 Comparative Example 1 300 Example 4 100 Comparative Example 2 500 Example 5 60 Comparative Example 3 - Example 6 150 Comparative Example 4 100 Example 7 100 Comparative Example 5 500 Example 8 100

[0215] From table 5, it can be seen that the most probable pore size distribution of the material is uniform, and is basically between 40-200nm, and the smaller pore size is conducive to inhibiting air convection and reducing heat loss through air convection, and can ensure good heat preservation performance.

[0216] The preferred embodiments of the application are described in detail above, but the application is not limited thereto. Within the technical concept of the application, various simple modifications can be made to the technical solutions of the application, including the combination of various technical features in any other suitable manner, and these simple modifications and combinations should also be considered as disclosed by the application and fall within the protection scope of the application.

Claims

1. A super-hydrophobic thermal insulation composite material, characterized in that: The raw materials for preparing the super-hydrophobic thermal insulation composite material include styrene, divinylbenzene, functionalized styrene, silane coupling agent modified hollow glass microspheres, inorganic filler, initiator, emulsifier and water; The super-hydrophobic thermal insulation composite material has a thermal conductivity of ≤0.03W / mK and a water contact angle of >150°; The functionalized styrene is selected from one or more of methoxystyrene, methylthiostyrene, p-chlorostyrene and p-bromostyrene.

2. The super-hydrophobic thermal insulation composite material according to claim 1, characterized in that: The compressive strength of the super-hydrophobic thermal insulation composite material is ≥1 MPa.

3. The super-hydrophobic thermal insulation composite material according to claim 1 or 2, characterized in that: The maximum pore diameter of the super-hydrophobic thermal insulation composite material is 10-200 nm.

4. The super-hydrophobic thermal insulation composite material according to claim 1 or 2, characterized in that: The inorganic filler is selected from one or more of silicon carbide, titanium nitride, titanium dioxide, worm graphite, graphene and carbon black.

5. The super-hydrophobic thermal insulation composite material according to claim 1, characterized in that: The silane coupling agent is selected from one or more of tetraethoxysilane, vinyltriethoxysilane, aminopropyltrimethoxysilane, glycidoxypropyltrimethoxysilane, vinyltrimethoxysilane and γ-methacryloxypropyltrimethoxysilane.

6. The super-hydrophobic thermal insulation composite material according to claim 1, characterized in that: The weight ratio of styrene, divinylbenzene, functionalized styrene, emulsifier, silane coupling agent modified hollow glass microspheres, inorganic filler and initiator is 1:0.5-6:0.1-3:0.5-3:0.01-0.5:0.01-0.1:0.2-1, and the weight ratio of water to styrene is 20-100:

1.

7. A method for preparing a super-hydrophobic thermal insulation composite material, characterized in that: The method comprises the following steps: (1) Mixing styrene, divinylbenzene, functionalized styrene, an emulsifier, and water to obtain a mixture A; (2) Mixing the mixture A, the silane coupling agent-modified hollow glass microspheres and the inorganic filler to obtain a mixture B; (3) mixing the mixed material B with an initiator solution containing an initiator and water, followed by reaction, and then washing and drying; The functionalized styrene is selected from one or more of methoxystyrene, methylthiostyrene, p-chlorostyrene and p-bromostyrene.

8. The method according to claim 7, characterized in that The inorganic filler is selected from one or more of silicon carbide, titanium nitride, titanium dioxide, worm graphite, graphene and carbon black.

9. The method according to claim 7 or 8, characterized in that The silane coupling agent is selected from one or more of tetraethoxysilane, vinyltriethoxysilane, aminopropyltrimethoxysilane, glycidoxypropyltrimethoxysilane, vinyltrimethoxysilane and γ-methacryloxypropyltrimethoxysilane.

10. The method according to claim 7, characterized in that The weight ratio of styrene, divinylbenzene, functionalized styrene, emulsifier, silane coupling agent modified hollow glass microspheres, inorganic filler and initiator is 1:0.5-6:0.1-3:0.5-3:0.01-0.5:0.01-0.1:0.2-1.

11. The method according to claim 7 or 10, characterized in that The weight ratio of the sum of the amounts of water used in step (1) and step (3) to styrene is 20-100:

1.

12. The method according to claim 11, characterized in that In step (1), the weight ratio of water to styrene is 20-80:

1.

13. The method according to claim 7, characterized in that The emulsifier is selected from one or more of Tween 80, sodium dodecylbenzenesulfonate and polyvinyl alcohol.

14. The method according to claim 7 or 13, characterized in that The initiator is selected from potassium persulfate, ammonium persulfate or hydrogen peroxide.

15. The method according to claim 7, characterized in that In step (3), the reaction conditions include: temperature of 65-85°C and time of 3-6 hours.

16. The method according to claim 7, characterized in that In step (3), the drying is vacuum drying.

17. A super-hydrophobic thermal insulation composite material prepared by the method according to any one of claims 7 to 16.

18. Use of the super-hydrophobic thermal insulation composite material according to any one of claims 1 to 6 or the super-hydrophobic thermal insulation composite material prepared by the method according to any one of claims 7 to 16 in the fields of heat insulation, thermal insulation, sound insulation or waterproofing.

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