Thermal insulation composite material as well as preparation method and application thereof

Abstract

The invention discloses a thermal insulation composite material as well as a preparation method and application thereof, and relates to the technical field of high polymer materials. The preparation method of the thermal insulation composite material comprises the following steps: providing a first prepolymer; providing a polyethylene glycol dispersion liquid, wherein the polyethylene glycol dispersion liquid comprises polyethylene glycol and a first solvent; mixing a polyethylene glycol dispersion liquid with the first prepolymer, and reacting to obtain a second prepolymer; and providing fluorinated hollow glass microspheres and a first fluorosilane compound, mixing the fluorinated hollow glass microspheres and the first fluorosilane compound with the second prepolymer, and carrying out a reaction to obtain the thermal insulation composite material. The thermal insulation composite material prepared by the preparation method of the thermal insulation composite material provided by the invention has excellent corrosion resistance, flame retardance, thermal insulation and phase change thermal insulation properties, and has wide application prospects in the fields of oil and gas transportation, building thermal insulation and energy conservation and the like.

Description

Technical Field

[0001] This application relates to the technical field of polymer materials, and particularly to a thermal insulation composite material, a preparation method thereof, and an application thereof. Background Art

[0002] Thermal insulation materials play a crucial role in oil and gas transportation. They not only need to possess functionality (such as maintaining a stable temperature, corrosion resistance, and compressive strength), but also economic efficiency (such as energy conservation and consumption reduction, and extended service life). These characteristics make thermal insulation materials an important part of ensuring the safety and efficiency of energy transportation.

[0003] Among many materials, polyurethane has gradually become the mainstream choice in the industry due to its excellent comprehensive properties, such as low thermal conductivity and easy construction. However, traditional polyurethane foams have some non-negligible defects. First, its limiting oxygen index is only 19%, which means that it will release toxic gases such as carbon monoxide (CO) and hydrogen cyanide (HCN) when burning, posing a threat to the environment and safety. Although conventional first prepolymers (such as aluminum hydroxide) can improve the flame retardancy of polyurethane, they will also cause an increase in the thermal conductivity coefficient and reduce the thermal insulation effect of the material. In addition, due to the high polarity and porous structure of traditional polyurethane foams, they are easily penetrated and corroded by oil or natural gas, thus shortening the service life and reducing the performance. At the same time, the compressive strength of polyurethane foam is significantly lower than that of polyurethane plastics, which further limits its use in the process of oil and gas transportation.

[0004] Therefore, solving the above problems is crucial for improving the applicability of traditional polyurethane foams in the application of thermal insulation materials. Summary of the Invention

[0005] In view of this, this application provides a thermal insulation composite material, a preparation method thereof, and an application thereof.

[0006] The embodiments of this application are implemented as follows. In the first aspect, the embodiments of this application provide a preparation method of a thermal insulation composite material, including the following steps: Provide a first prepolymer, and the structural formula of the first prepolymer is shown as the following formula: ; Provide a polyethylene glycol dispersion liquid, where the polyethylene glycol dispersion liquid includes polyethylene glycol and a first solvent; mix the polyethylene glycol dispersion liquid and the first prepolymer, and react to obtain a second prepolymer; Provide fluorinated hollow glass microspheres and a first fluorosilane compound, mix them with the second prepolymer, and react to obtain a thermal insulation composite material.

[0007] Optionally, in some embodiments of this application, the preparation method of the first prepolymer includes: Provide a 4-isocyanatobenzoyl chloride dispersion and a 2,2-bis[4-(2-hydroxyethoxy)-3,5-dibromophenyl]propane dispersion. The 4-isocyanatobenzoyl chloride dispersion includes a 4-isocyanatobenzoyl chloride dispersion and a second solvent. The 2,2-bis[4-(2-hydroxyethoxy)-3,5-dibromophenyl]propane dispersion includes a 2,2-bis[4-(2-hydroxyethoxy)-3,5-dibromophenyl]propane dispersion and a third solvent; Mix the 4-isocyanatobenzoyl chloride dispersion and the 2,2-bis[4-(2-hydroxyethoxy)-3,5-dibromophenyl]propane dispersion, and react to obtain a first prepolymer.

[0008] Optionally, in some embodiments of the present application, the second solvent and the third solvent are each independently selected from one or more of tetrahydrofuran, 2-methyltetrahydrofuran, 1,4-dioxane, diethylene glycol dimethyl ether, tert-butyl methyl ether, and cyclopentyl methyl ether; and / or, In the 4-isocyanatobenzoyl chloride dispersion, the molar concentration of 4-isocyanatobenzoyl chloride is 0.1 mol / L to 1 mol / L; and / or, In the 2,2-bis[4-(2-hydroxyethoxy)-3,5-dibromophenyl]propane dispersion, the molar concentration of 2,2-bis[4-(2-hydroxyethoxy)-3,5-dibromophenyl]propane is 0.1 mol / L to 1 mol / L; and / or, The molar ratio of 4-isocyanatobenzoyl chloride to 2,2-bis[4-(2-hydroxyethoxy)-3,5-dibromophenyl]propane is (2 to 10):(1 to 5); and / or, The 4-isocyanatobenzoyl chloride dispersion further includes an acid-binding agent; and / or, The reaction of 4-isocyanatobenzoyl chloride and 2,2-bis[4-(2-hydroxyethoxy)-3,5-dibromophenyl]propane includes a first reaction and a second reaction that are carried out in sequence. The temperature of the first reaction is lower than the temperature of the second reaction.

[0009] Optionally, in some embodiments of the present application, the acid-binding agent includes one or more of triethylamine and pyridine; and / or, The reaction temperature of the first reaction is -5°C to 5°C; the reaction time of the first reaction is 1 h to 5 h; and / or, The reaction temperature of the second reaction is 35°C to 45°C; the reaction time of the second reaction is 1 h to 5 h.

[0010] Optionally, in some embodiments of the present application, the polyethylene glycol is selected from polyethylene glycol-4000; and / or, The first solvent is selected from one or more of N,N-dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone, N,N-dimethylacetamide, acetonitrile, and acetone; and / or, In the polyethylene glycol dispersion, the molar concentration of the polyethylene glycol is 0.05 mol / L to 0.5 mol / L; and / or, The mixing of the polyethylene glycol dispersion and the first prepolymer further includes: adding a catalyst; the catalyst includes one or more of dibutyltin dilaurate, stannous octoate, dibutyltin oxide, and tin bis(2-ethylhexanoate); and / or, The mass ratio of the polyethylene glycol to the first prepolymer is (2 to 10):(1 to 5); and / or, The reaction temperature of the polyethylene glycol and the first prepolymer is 30°C to 80°C; the reaction time of the polyethylene glycol and the first prepolymer is 5 h to 10 h.

[0011] Optionally, in some embodiments of the present application, the method for preparing the fluorinated hollow glass microspheres includes: Providing a hollow glass microsphere dispersion and 1H,1H,2H,2H-perfluorodecyltrichlorosilane, the hollow glass microsphere dispersion includes a hollow glass microsphere dispersion and a fourth solvent; Mixing the hollow glass microsphere dispersion and 1H,1H,2H,2H-perfluorodecyltrichlorosilane, and reacting to obtain fluorinated hollow glass microspheres.

[0012] Optionally, in some embodiments of the present application, the fourth solvent is selected from one or more of n-hexane, n-heptane, n-octane, isooctane, cyclohexane, benzene, toluene, xylene, ethylbenzene, carbon tetrachloride, chloroform, and dichloromethane; and / or, In the hollow glass microsphere dispersion, the mass concentration of the hollow glass microspheres is 100 g / L to 300 g / L; and / or, The mass ratio of the hollow glass microspheres to 1H,1H,2H,2H-perfluorodecyltrichlorosilane is (10 to 30):1; and / or, The reaction temperature of the hollow glass microspheres and 1H,1H,2H,2H-perfluorodecyltrichlorosilane is 20°C to 40°C; the reaction time of the hollow glass microspheres and 1H,1H,2H,2H-perfluorodecyltrichlorosilane is 1 h to 5 h.

[0013] Optionally, in some embodiments of the present application, the fluorosilane compound includes 1H,1H,2H,2H-perfluorodecyltrichlorosilane; and / or, The mass ratio of the polyethylene glycol, the fluorinated hollow glass microspheres, and the fluorosilane compound is 40:(1 - 5):(10 - 40); and / or, The reaction temperature of the polyethylene glycol, the fluorinated hollow glass microspheres, and the fluorosilane compound is 30°C - 80°C; the reaction time of the polyethylene glycol, the fluorinated hollow glass microspheres, and the fluorosilane compound is 0.5 h - 5 h; and / or, After the reaction of the polyethylene glycol, the fluorinated hollow glass microspheres, and the fluorosilane compound, it further includes: drying treatment; the temperature of the drying treatment is 30°C - 80°C; the time of the drying treatment is 10 h - 15 h.

[0014] In a second aspect, an embodiment of the present application further provides a thermal insulation composite material, which is prepared by the above preparation method.

[0015] In a third aspect, an embodiment of the present application further provides an application of the thermal insulation composite material prepared by the above preparation method in oil and gas transportation and building thermal insulation.

[0016] In the preparation method of the thermal insulation composite material provided by the present application, polyethylene glycol is selected as the phase change functional unit for heat storage, so that the thermal insulation composite material has a phase change function and can perform heat storage to prevent heat loss during oil and gas transportation; at the same time, polyethylene glycol is used as the structural unit of the thermal insulation composite material. When it undergoes phase change energy storage, the thermal insulation composite material still remains solid, preventing the leakage problem of traditional solid-liquid phase change materials during use; a first prepolymer unit is introduced into the molecular structure to endow the material with intrinsic flame retardant properties; chain extension is carried out using a fluorine-containing compound to increase the surface energy of the second prepolymer material and improve its corrosion resistance; and surface fluorinated hollow glass microspheres are filled to reduce the thermal conductivity of the thermal insulation composite material and further improve its thermal insulation performance; in addition, the fluorinated hollow glass microspheres and the second prepolymer treated with the fluorosilane compound have excellent compatibility, ensuring that the composite material has excellent mechanical properties.

[0017] The thermal insulation composite material prepared by the preparation method of the thermal insulation composite material provided by the present application has excellent anti-corrosion performance, flame retardant performance, heat insulation, and phase change thermal insulation performance, and has broad application prospects in the fields of oil and gas transportation and building thermal insulation and energy conservation. Description of the Drawings

[0018] In order to more clearly illustrate the technical solutions in the embodiments of the present application, the following will briefly introduce the drawings required for the description of the embodiments. Obviously, the following drawings are only some embodiments of the present application. For those skilled in the art, without creative efforts, other drawings can be obtained based on these drawings.

[0019] Figure 1 It is a flowchart of a preparation method of a heat-insulating composite material provided by an embodiment of the present application. Detailed implementation manners

[0020] Next, the technical solutions in the embodiments of the present application will be clearly and completely described in conjunction with the accompanying drawings in the embodiments of the present application. Obviously, the described embodiments are only a part of the embodiments of the present application, rather than all the embodiments. Based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without creative efforts belong to the scope of protection of the present application. In addition, it should be understood that the specific implementation manners described herein are only used to illustrate and explain the present application, and are not used to limit the present application.

[0021] In the present application, unless otherwise stated, the orientation terms such as "upper" and "lower" generally refer to the upper and lower in the actual use or working state of the device, specifically the drawing direction in the accompanying drawings; and "inner" and "outer" refer to the outline of the device. In addition, in the description of the present application, the term "including" means "including but not limited to". The use of terms such as first, second, and third is only for marking purposes, and does not impose a numerical requirement or establish an order.

[0022] In the present application, "and / or" describes the association relationship of associated objects, indicating that three relationships can exist. For example, A and / or B can represent: A exists alone, A and B exist simultaneously, and B exists alone. Where A and B can be singular or plural.

[0023] In the present application, "at least one" means one or more, and "a plurality" means two or more. "One or several", "at least one (item)" or similar expressions below refer to any combination of these items, including any combination of single item (item) or plural items (items). For example, "at least one (item) of a, b, or c", or, "at least one (item) of a, b, and c" can both represent: a, b, c, a-b (that is, a and b), a-c, b-c, or a-b-c, where a, b, and c can be single or multiple respectively.

[0024] The various embodiments of the present application may exist in the form of a range; it should be understood that the description in the form of a range is only for convenience and brevity, and should not be construed as a rigid limitation on the scope of the present application; therefore, it should be considered that the range description has specifically disclosed all possible sub-ranges and the individual values within the range. For example, it should be considered that the range description from 1 to 6 has specifically disclosed sub-ranges, such as from 1 to 3, from 1 to 4, from 1 to 5, from 2 to 4, from 2 to 6, from 3 to 6, etc., and the individual numbers within the range, such as 1, 2, 3, 4, 5, and 6, which applies regardless of the range. Additionally, whenever a numerical range is indicated herein, it means including any cited number (fraction or integer) within the indicated range.

[0025] The structural formulas and molecular weights of some chemical reagents used in the present application are described as follows: Polyethylene glycol 4000 (PEG - 4000): , where n is an integer from 60 to 120, and the number average molecular weight = 4000; 4 - Isocyanatobenzoyl chloride: , and the molecular weight = 181.58; 2,2 - Bis[4 - (2 - hydroxyethoxy) - 3,5 - dibromophenyl]propane: , and the molecular weight = 631.98; 1H,1H,2H,2H - Perfluorodecyltrichlorosilane: , and the molecular weight = 581.56; Triethylamine: The molecular weight = 101.19.

[0026] The technical solution of the present application is as follows: In a first aspect, please refer to Figure 1 , an embodiment of the present application provides a method for preparing a thermal insulation composite material, including the following steps: Step S11: Provide a first prepolymer, and the structural formula of the first prepolymer is shown as follows: ; Step S12: Provide a polyethylene glycol dispersion, which includes polyethylene glycol and a first solvent; mix the polyethylene glycol dispersion and the first prepolymer, and react to obtain a second prepolymer; Step S13: Provide fluorinated hollow glass microspheres and a fluorosilane compound, mix them with the second prepolymer, and react to obtain a thermal insulation composite material.

[0027] It should be noted that hollow glass microspheres, also known as hollow glass microspheres, are tiny, hollow spherical powders, and their main component is borosilicate. As the name implies, the fluorinated hollow glass microspheres refer to the introduction of -F on the hollow glass microspheres.

[0028] It should also be noted that a fluorosilane compound refers to a compound in which at least one H in a silane compound is replaced by F.

[0029] In the preparation method of the thermal insulation composite material provided by this application, polyethylene glycol is selected as the phase change functional unit for heat storage, so that the thermal insulation composite material has a phase change function and can store heat to prevent heat loss during oil and gas transportation; at the same time, polyethylene glycol is used as the structural unit of the thermal insulation composite material. When it undergoes phase change energy storage, the thermal insulation composite material still remains solid, preventing the leakage problem of traditional solid-liquid phase change materials during use; a first prepolymer unit is introduced into the molecular structure, and the 2,2-bis[4-(2-hydroxyethoxy)-3,5-dibromophenyl]propane unit structure endows the material with intrinsic flame retardancy; a fluorine-containing compound is used for chain extension to increase the surface energy of the second prepolymer material and improve its corrosion resistance; and surface fluorinated hollow glass microspheres are filled to reduce the thermal conductivity of the thermal insulation composite material and further improve its thermal insulation performance; in addition, the fluorinated hollow glass microspheres and the second prepolymer treated with a fluorosilane compound have excellent compatibility, ensuring that the composite material has excellent mechanical properties.

[0030] The thermal insulation composite material prepared by the preparation method of the thermal insulation composite material provided by this application has excellent anti-corrosion performance, flame retardancy, heat insulation and phase change thermal insulation performance, and has broad application prospects in the fields of oil and gas transportation and building thermal insulation and energy conservation.

[0031] In the said step S11: In some embodiments, the preparation method of the first prepolymer includes: Step S111: Provide a 4-isocyanatobenzoyl chloride dispersion and a 2,2-bis[4-(2-hydroxyethoxy)-3,5-dibromophenyl]propane dispersion. The 4-isocyanatobenzoyl chloride dispersion includes 4-isocyanatobenzoyl chloride and a second solvent, and the 2,2-bis[4-(2-hydroxyethoxy)-3,5-dibromophenyl]propane dispersion includes 2,2-bis[4-(2-hydroxyethoxy)-3,5-dibromophenyl]propane and a third solvent; Step S112: Mix the 4-isocyanatobenzoyl chloride dispersion and the 2,2-bis[4-(2-hydroxyethoxy)-3,5-dibromophenyl]propane dispersion and react to obtain a first prepolymer.

[0032] In some embodiments, the second solvent and the third solvent are each independently selected from one or more of tetrahydrofuran, 2-methyltetrahydrofuran, 1,4-dioxane, diethylene glycol dimethyl ether, tert-butyl methyl ether, and cyclopentyl methyl ether.

[0033] In some embodiments, in the 4-isocyanatobenzoyl chloride dispersion, the molar concentration of 4-isocyanatobenzoyl chloride is 0.1 mol / L to 1 mol / L, and for example, it can be 0.1 mol / L, 0.2 mol / L, 0.4 mol / L, 0.6 mol / L, 0.8 mol / L, 1 mol / L, or the range between any two of the above values, etc. Within the range of the molar concentration, it is beneficial to the uniform dissolution and dispersion of 4-isocyanatobenzoyl chloride.

[0034] In some embodiments, in the 2,2-bis[4-(2-hydroxyethoxy)-3,5-dibromophenyl]propane dispersion, the molar concentration of 2,2-bis[4-(2-hydroxyethoxy)-3,5-dibromophenyl]propane is 0.1 mol / L to 1 mol / L, and for example, it can be 0.1 mol / L, 0.2 mol / L, 0.4 mol / L, 0.6 mol / L, 0.8 mol / L, 1 mol / L, or the range between any two of the above values, etc. Within the range of the molar concentration, it is beneficial to the uniform dissolution and dispersion of 2,2-bis[4-(2-hydroxyethoxy)-3,5-dibromophenyl]propane.

[0035] In some embodiments, the 4-isocyanatobenzoyl chloride dispersion further includes an acid-binding agent. The acid-binding agent can accelerate the reaction rate and improve the reaction quality.

[0036] Further, the acid-binding agent includes one or more of triethylamine and pyridine.

[0037] In some embodiments, the molar ratio of 4-isocyanatobenzoyl chloride to 2,2-bis[4-(2-hydroxyethoxy)-3,5-dibromophenyl]propane is (2 to 10):(1 to 5), and for example, it can be 5:1, 5:3, 5:3, 5:4, 5:5, or the range between any two of the above ratios, etc. Within the range of the molar ratio, it is beneficial for 4-isocyanatobenzoyl chloride and 2,2-bis[4-(2-hydroxyethoxy)-3,5-dibromophenyl]propane to react efficiently to form the first prepolymer and improve the yield of the first prepolymer.

[0038] In some embodiments, the reaction of 4-isocyanatobenzoyl chloride and 2,2-bis[4-(2-hydroxyethoxy)-3,5-dibromophenyl]propane includes a first reaction and a second reaction that are carried out in sequence, and the temperature of the first reaction is lower than the temperature of the second reaction.

[0039] In some embodiments, the reaction temperature of the first reaction is -5°C to 5°C, for example, it can be -5°C, -2°C, 0°C, 2°C, 5°C, or a range between any two of the above values, etc.; the reaction time of the first reaction is 1 h to 5 h, for example, it can be 1 h, 2 h, 3 h, 4 h, 5 h, or a range between any two of the above values, etc.

[0040] In some embodiments, the reaction temperature of the second reaction is 35°C to 45°C, for example, it can be 35°C, 38°C, 40°C, 42°C, 45°C, or a range between any two of the above values, etc.; the reaction time of the second reaction is 1 h to 5 h, for example, it can be 1 h, 2 h, 3 h, 4 h, 5 h, or a range between any two of the above values, etc.

[0041] Thus, under the reaction conditions of the first reaction and the second reaction, it is beneficial to efficiently generate the first prepolymer.

[0042] In some embodiments, the synthesis route of the reaction of 4-isocyanatobenzoyl chloride and 2,2-bis[4-(2-hydroxyethoxy)-3,5-dibromophenyl]propane to form a crosslinking agent is shown in the following formula: 。

[0043] In step S12: In some embodiments, the polyethylene glycol is selected from polyethylene glycol-4000.

[0044] In some embodiments, the first solvent is selected from one or more of N,N-dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone, N,N-dimethylacetamide, acetonitrile, and acetone.

[0045] In some embodiments, in the polyethylene glycol dispersion, the molar concentration of the polyethylene glycol is 0.05 mol / L to 0.5 mol / L, for example, it can be 0.05 mol / L, 0.1 mol / L, 0.2 mol / L, 0.3 mol / L, 0.4 mol / L, 0.5 mol / L, or a range between any two of the above values, etc. Within the range of the molar concentration, it is beneficial to the uniform dissolution and dispersion of the polyethylene glycol.

[0046] In some embodiments, the mixing of the polyethylene glycol dispersion and the first prepolymer further includes: adding a catalyst.

[0047] Furthermore, the catalyst includes one or more of dibutyltin dilaurate, stannous octoate, dibutyltin oxide, and tin bis(2-ethylhexanoate). The catalyst can improve the reaction efficiency.

[0048] In some embodiments, the mass ratio of the polyethylene glycol to the first prepolymer is (2 to 10):(1 to 5), for example, it can be 5:1, 5:3, 5:3, 5:4, 5:5 or the range between any two of the above ratios, etc. Within the range of the mass ratio, it is beneficial for the polyethylene glycol and the first prepolymer to react efficiently to generate the second prepolymer, thereby increasing the yield of the second prepolymer.

[0049] In some embodiments, the reaction temperature of the polyethylene glycol and the first prepolymer is 30°C to 80°C, for example, it can be 30°C, 40°C, 50°C, 60°C, 70°C, 80°C or the range between any two of the above values, etc.; the reaction time of the polyethylene glycol and the first prepolymer is 5 h to 10 h, for example, it can be 5 h, 6 h, 7 h, 8 h, 9 h, 10 h or the range between any two of the above values, etc. Thus, under the above reaction conditions, it is beneficial to efficiently generate the second prepolymer.

[0050] In some embodiments, the structural formula of the second prepolymer is as shown in the following formula: ; wherein, n represents the degree of polymerization and is an integer selected from 60 - 120.

[0051] In step S13: In some embodiments, the method for preparing the fluorinated hollow glass microspheres includes: Step S131: Provide a hollow glass microsphere dispersion and 1H,1H,2H,2H - perfluorodecyltrichlorosilane. The hollow glass microsphere dispersion includes a hollow glass microsphere dispersion and a fourth solvent; Step S132: Mix the hollow glass microsphere dispersion and 1H,1H,2H,2H - perfluorodecyltrichlorosilane, and react to obtain fluorinated hollow glass microspheres.

[0052] In some embodiments, the fourth solvent is selected from one or more of n - hexane, n - heptane, n - octane, isooctane, cyclohexane, benzene, toluene, xylene, ethylbenzene, carbon tetrachloride, chloroform, dichloromethane.

[0053] In some embodiments, in the hollow glass microsphere dispersion, the mass concentration of the hollow glass microspheres is 100 g / L to 300 g / L, for example, it can be 100 g / L, 150 g / L, 200 g / L, 250 g / L, 300 g / L or the range between any two of the above values, etc. Within the range of the mass concentration, it is beneficial for the uniform dissolution and dispersion of the hollow glass microspheres.

[0054] In some embodiments, the mass ratio of the hollow glass microspheres to the 1H,1H,2H,2H-perfluorodecyltrichlorosilane is (10 to 30):1. For example, it can be 10:1, 15:1, 20:1, 25:1, 30:1, or a range between any two of the above ratios, etc. Within the range of the mass ratio, it is beneficial for the hollow glass microspheres and the 1H,1H,2H,2H-perfluorodecyltrichlorosilane to react efficiently to produce fluorinated hollow glass microspheres, thereby increasing the yield of the fluorinated hollow glass microspheres.

[0055] In some embodiments, the reaction temperature of the hollow glass microspheres and the 1H,1H,2H,2H-perfluorodecyltrichlorosilane is 20°C to 40°C. For example, it can be 20°C, 25°C, 30°C, 35°C, 40°C, or a range between any two of the above values, etc.; the reaction time of the hollow glass microspheres and the 1H,1H,2H,2H-perfluorodecyltrichlorosilane is 1 h to 5 h. For example, it can be 1 h, 2 h, 3 h, 4 h, 5 h, or a range between any two of the above values, etc.

[0056] Thus, under the above reaction conditions, it is beneficial for the 1H,1H,2H,2H-perfluorodecyltrichlorosilane to modify the hollow glass microspheres and efficiently produce the fluorinated hollow glass microspheres.

[0057] It should be noted that in step S13, the chain extension reaction of the second prepolymer is mainly carried out by using the substitution reaction between the terminal hydroxyl group of the second prepolymer and the silicon chlorine group, and a micro-crosslinked structure is locally formed.

[0058] In some embodiments, the fluorosilane compound includes 1H,1H,2H,2H-perfluorodecyltrichlorosilane.

[0059] In some embodiments, the mass ratio of the polyethylene glycol, the fluorinated hollow glass microspheres, and the fluorosilane compound is 40:(1 to 5):(10 to 40). For example, it can be 40:2:10, 40:2:10, 40:2:20, 40:2:30, 40:2:40, 40:3:10, 40:4:10, 40:1:10, or a range between any two of the above ratios, etc. Within the range of the mass ratio, it is beneficial to increase the yield of the thermal insulation composite material.

[0060] In some embodiments, the reaction temperature of the polyethylene glycol, the fluorinated hollow glass microspheres and the fluorosilane compound is 30°C to 80°C, for example, it can be 30°C, 40°C, 50°C, 60°C, 70°C, 80°C or the range between any two of the above values, etc.; the reaction time of the polyethylene glycol, the fluorinated hollow glass microspheres and the fluorosilane compound is 0.5 h to 5 h, for example, it can be 0.5 h, 1 h, 2 h, 3 h, 4 h, 5 h or the range between any two of the above values, etc. Thus, under the above reaction conditions, it is beneficial to efficiently generate the thermal insulation composite material.

[0061] In some embodiments, after the reaction of the polyethylene glycol, the fluorinated hollow glass microspheres and the fluorosilane compound, it further includes: drying treatment.

[0062] Furthermore, the temperature of the drying treatment is 30°C to 80°C, for example, it can be 30°C, 40°C, 50°C, 60°C, 70°C, 80°C or the range between any two of the above values, etc.; the time of the drying treatment is 10 h to 15 h, for example, it can be 10 h, 11 h, 12 h, 13 h, 14 h, 15 h or the range between any two of the above values, etc. Thus, under the conditions of the drying treatment, it is beneficial to remove the solvent and reaction by-products in the reaction system and improve the purity of the thermal insulation composite material.

[0063] In some embodiments, the thermal insulation composite material includes a polyurethane compound and fluorinated hollow glass microspheres, wherein the structural formula of the polyurethane compound is as shown in the following formula: ; wherein, n represents the degree of polymerization and is an integer selected from 60 - 120.

[0064] It should be noted that " " in the above formula can represent a molecular chain or a substituent. In some embodiments, can represent a Cl atom; in some embodiments can represent: ; wherein represents the connection site of the molecular chain and the silicon atom. Further, the two bonded to one Si atom in the above formula can both be molecular chains, and at this time, a micro-crosslinked structure can be formed locally. The two bonded to one Si atom in the above formula can also be one molecular chain and the other Cl atom, and at this time, a linear structure can be formed.

[0065] In a second aspect, the embodiments of the present application further provide a thermal insulation composite material, and the thermal insulation composite material can be prepared by the above preparation method.

[0066] The heat-insulating composite material provided by this application has excellent anti-corrosion performance, flame retardancy, heat insulation, and phase change heat-insulating performance, and has broad application prospects in the fields of oil and gas transportation, building heat insulation and energy conservation, etc.

[0067] In a third aspect, the embodiments of this application also provide the heat-insulating composite material prepared by the above preparation method or the application of the above heat-insulating composite material.

[0068] Specifically, the above heat-insulating composite material can be applied to oil and gas transportation and building heat insulation.

[0069] The following will specifically illustrate this application through specific embodiments. The following embodiments are only partial embodiments of this application and do not limit this application.

[0070] Example 1: This embodiment provides a heat-insulating composite material, and its preparation method includes the following steps: Step 1: Weigh 0.05 mol of 4-isocyanatobenzoyl chloride, 0.05 mol of triethylamine, and 100 mL of anhydrous dioxane and add them to a 250 mL three-necked flask. Start stirring, introduce flowing nitrogen for protection, and mix the reactants evenly under an ice bath (0 °C); weigh 12.6 g of 2,2-bis[4-(2-hydroxyethoxy)-3,5-dibromophenyl]propane (0.02 mol) and dissolve it in 50 mL of anhydrous dioxane. Under the condition of an ice bath, gradually drop the 2,2-bis[4-(2-hydroxyethoxy)-3,5-dibromophenyl]propane solution into the 4-isocyanatobenzoyl chloride / dioxane solution through a constant pressure funnel. During this period, continuously introduce flowing nitrogen for protection. After the dropping is completed, react for 2 h under an ice bath, and then raise the temperature to 40 °C and react for 2 h. During this period, a by-product white powder precipitates; after the reaction is completed, filter by suction to remove the by-product; perform rotary evaporation on the filtrate at 80 °C to remove the residual dioxane and excessive 4-isocyanatobenzoyl chloride in the system to obtain a first prepolymer; Step 2: Weigh 40 g of polyethylene glycol 4000 (PEG-4000) and 100 g of anhydrous DMF and add them to a 250 mL three-necked flask. Start stirring, heat to 60 °C until PEG-4000 is completely dissolved, then add 4.6 g of the first prepolymer obtained in Step 1 and 0.1 g of dibutyltin dilaurate (catalyst), keep stirring, introduce nitrogen for protection, and react at 60 °C for 8 h to obtain a second prepolymer; Step 3: Stir a mixture of 20 g of hollow glass microspheres (3M hollow glass microspheres VS500, purchased from Shanghai Xianglan Chemical Co., Ltd.) and 100 mL of n-hexane in an ultrasonic bath for 1 h, then add 1 g of 1H,1H,2H,2H-perfluorodecyltrichlorosilane and stir for 3 h to obtain a suspension of surface fluorinated hollow glass microspheres; centrifuge the suspension for 20 min and take the lower precipitate; wash it successively with n-hexane and deionized water, then centrifuge again for 20 min and take the lower precipitate; finally, dry it in a forced-air oven at 90 °C for 4 h to obtain fluorinated hollow glass microspheres; Step 4: Take 10 g of the fluorinated hollow glass microspheres obtained in Step 3 and 50 g of anhydrous DMF, stir them in an ultrasonic bath at 60 °C for 2 h to obtain a uniformly dispersed suspension, then add it to the polyurethane second prepolymer solution obtained in Step 2 and stir and mix evenly at 60 °C; then add 2 g of 1H,1H,2H,2H-perfluorodecyltrichlorosilane to it, react at 60 °C for 1 h under nitrogen protection, then pour the reaction solution into a polytetrafluoroethylene tray and place it in a vacuum oven for vacuum drying at 80 °C for 12 h to remove the residual anhydrous DMF and by-products in the system to obtain a thermal insulation composite material.

[0071] Example 2: This example is basically the same as Example 1, except that the amount of fluorinated hollow glass microspheres in Step 4 is 20 g.

[0072] Example 3: This example is basically the same as Example 1, except that the amount of fluorinated hollow glass microspheres in Step 4 is 30 g.

[0073] Example 4: This example is basically the same as Example 1, except that the amount of fluorinated hollow glass microspheres in Step 4 is 40 g.

[0074] Comparative Example: This comparative example provides a thermal insulation composite material, which is a commercially available thermal insulation material: rigid foamed polyurethane (purchased from Shandong Liuchuanfeng Environmental Protection Technology Co., Ltd.).

[0075] Test the mechanical properties, anti-corrosion properties, flame retardancy properties, heat insulation properties and phase change properties of the thermal insulation composite materials of Examples 1 to 4 and the thermal insulation composite material of the comparative example. The test results are shown in Table 1.

[0076] Among them, the compressive strength test is carried out in accordance with the standard GB / T6343-2009.

[0077] The water contact angle test is carried out in accordance with the standard GB / T 30693-2014.

[0078] The anti-corrosion performance is tested according to the standard GB / T 10125-2012 "Artificial Atmosphere Corrosion Test - Salt Spray Test". The acetic acid salt spray (AASS) is used, the pH value of the salt solution is controlled within 3.0 - 3.1, the pH value of the collected liquid in the salt spray chamber is 3.1 - 3.3, the test period is 240 h, and the mass loss before and after the test is used to evaluate the corrosion resistance performance.

[0079] The flame retardancy performance test is carried out according to the standard UL94.

[0080] The determination of the thermal conductivity is carried out according to the standard GB / T 42919.1-2023.

[0081] The determination of the melting and crystallization temperatures and the heat enthalpy is carried out according to the standard GB / T 19466.3-2004; 。

[0082] As can be seen from Table 1, the compressive strength of the thermal insulation composite materials provided in Examples 1 - 4 is 25 Mpa and above, the water contact angle is 146° and above, the flame retardancy grades are all V-0, the thermal conductivity is maintained in a relatively low range: 0.035 - 0.051 W / (m·K), and they have good phase change thermal insulation performance. The composite materials provided in the embodiments of the present application exhibit excellent anti-corrosion performance, flame retardancy performance, heat insulation and phase change thermal insulation performance.

[0083] The technical solutions provided in the embodiments of the present application have been introduced in detail above. Specific examples are used in this article to elaborate on the principle and implementation manner of the present application. The description of the above embodiments is only used to help understand the method and its core idea of the present application; at the same time, for those skilled in the art, based on the idea of the present application, there will be changes in the specific implementation manner and application scope. In summary, the content of this specification should not be construed as a limitation to the present application.

Claims

1. A method for preparing a thermal insulation composite material, characterized in that: The steps include: A first prepolymer is provided, wherein the structural formula of the first prepolymer is shown below: ； Providing a polyethylene glycol dispersion, wherein the polyethylene glycol dispersion comprises polyethylene glycol and a first solvent; mixing the polyethylene glycol dispersion and the first prepolymer, reacting them, to obtain a second prepolymer; Fluorinated hollow glass microspheres and a first fluorosilane compound are provided, mixed with the second prepolymer, and reacted to obtain a thermal insulation composite material.

2. The preparation method according to claim 1, characterized in that: The preparation method of the first prepolymer comprises: Providing a 4-isocyanobenzoyl chloride dispersion and a 2,2-bis[4-(2-hydroxyethoxy)-3,5-dibromophenyl]propane dispersion, wherein the 4-isocyanobenzoyl chloride dispersion comprises a 4-isocyanobenzoyl chloride dispersion and a second solvent, and the 2,2-bis[4-(2-hydroxyethoxy)-3,5-dibromophenyl]propane dispersion comprises a 2,2-bis[4-(2-hydroxyethoxy)-3,5-dibromophenyl]propane dispersion and a third solvent; The 4-isocyanobenzoyl chloride dispersion and the 2,2-bis[4-(2-hydroxyethoxy)-3,5-dibromophenyl]propane dispersion are mixed and reacted to obtain a first prepolymer.

3. The preparation method according to claim 2, characterized in that: The second solvent and the third solvent are each independently selected from one or more of tetrahydrofuran, 2-methyltetrahydrofuran, 1,4-dioxane, diethylene glycol dimethyl ether, tert-butyl methyl ether, and cyclopentyl methyl ether; and / or, In the 4-isocyanobenzoyl chloride dispersion, the molar concentration of the 4-isocyanobenzoyl chloride is 0.1 mol / L to 1 mol / L; and / or, In the 2,2-bis[4-(2-hydroxyethoxy)-3,5-dibromophenyl]propane dispersion, the molar concentration of the 2,2-bis[4-(2-hydroxyethoxy)-3,5-dibromophenyl]propane is 0.1 mol / L to 1 mol / L; and / or, The molar ratio of the 4-isocyanobenzoyl chloride to the 2,2-bis[4-(2-hydroxyethoxy)-3,5-dibromophenyl]propane is (2-10):(1-5); and / or, The 4-isocyanobenzoyl chloride dispersion also includes an acid binding agent; and / or, The reaction of 4-isocyanobenzoyl chloride and 2,2-bis[4-(2-hydroxyethoxy)-3,5-dibromophenyl]propane includes a first reaction and a second reaction performed sequentially, and the temperature of the first reaction is lower than the temperature of the second reaction.

4. The preparation method according to claim 3, characterized in that: The acid binding agent includes one or more of triethylamine and pyridine; and / or, The reaction temperature of the first reaction is -5°C to 5°C; the reaction time of the first reaction is 1h to 5h; and / or, The reaction temperature of the second reaction is 35° C. to 45° C.; the reaction time of the second reaction is 1 h to 5 h.

5. The preparation method according to claim 1, characterized in that: The polyethylene glycol is selected from polyethylene glycol-4000; and / or, The first solvent is selected from one or more of N,N-dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone, N,N-dimethylacetamide, acetonitrile and acetone; and / or, In the polyethylene glycol dispersion, the molar concentration of the polyethylene glycol is 0.05 mol / L to 0.5 mol / L; and / or, The mixing of the polyethylene glycol dispersion and the first prepolymer further comprises: adding a catalyst; The catalyst includes one or more of dibutyltin dilaurate, stannous octoate, dibutyltin oxide, bis(2-ethylhexanoate)tin; and / or, The mass ratio of the polyethylene glycol to the first prepolymer is (2-10): (1-5); and / or, The reaction temperature of the polyethylene glycol and the first prepolymer is 30° C. to 80° C.; the reaction time of the polyethylene glycol and the first prepolymer is 5 h to 10 h.

6. The preparation method according to claim 1, characterized in that: The preparation method of the fluorinated hollow glass microspheres comprises: Providing a hollow glass microsphere dispersion and 1H,1H,2H,2H-perfluorodecyltrichlorosilane, wherein the hollow glass microsphere dispersion comprises the hollow glass microsphere dispersion and a fourth solvent; The hollow glass microsphere dispersion liquid and 1H,1H,2H,2H-perfluorodecyltrichlorosilane are mixed and reacted to obtain fluorinated hollow glass microspheres.

7. The preparation method according to claim 6, characterized in that: The fourth solvent is selected from one or more of n-hexane, n-heptane, n-octane, isooctane, cyclohexane, benzene, toluene, xylene, ethylbenzene, carbon tetrachloride, chloroform, and dichloromethane; and / or, In the hollow glass microsphere dispersion, the mass concentration of the hollow glass microspheres is 100 g / L to 300 g / L; and / or, The mass ratio of the hollow glass microspheres to the 1H,1H,2H,2H-perfluorodecyltrichlorosilane is (10-30):1; and / or, The reaction temperature of the hollow glass microspheres and the 1H,1H,2H,2H-perfluorodecyltrichlorosilane is 20°C to 40°C; the reaction time of the hollow glass microspheres and the 1H,1H,2H,2H-perfluorodecyltrichlorosilane is 1h to 5h.

8. The preparation method according to claim 1, characterized in that: The fluorosilane compound includes 1H,1H,2H,2H-perfluorodecyltrichlorosilane; and / or, The mass ratio of the polyethylene glycol, the fluorinated hollow glass microspheres and the fluorosilane compound is 40:(1-5):(10-40); and / or, The reaction temperature of the polyethylene glycol, the fluorinated hollow glass microspheres and the fluorosilane compound is 30° C. to 80° C.; the reaction time of the polyethylene glycol, the fluorinated hollow glass microspheres and the fluorosilane compound is 0.5 h to 5 h; and / or, After the polyethylene glycol, the fluorinated hollow glass microspheres and the fluorosilane compound react, the process further comprises: drying; The temperature of the drying treatment is 30° C. to 80° C.; the time of the drying treatment is 10 h to 15 h.

9. A thermal insulation composite material, characterized in that: The thermal insulation composite material is prepared by the preparation method according to any one of claims 1 to 8.

10. Application of the thermal insulation composite material prepared by the preparation method according to any one of claims 1 to 8 in oil and gas transportation and building insulation.

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