Thermal insulation composite material and preparation method and application thereof

Abstract

The present application discloses a thermal insulation composite material and its preparation method and application, which relate to the field of polymer material technology. The preparation method of the thermal insulation composite material includes the following steps: providing a first prepolymer; providing a polyethylene glycol dispersion, the polyethylene glycol dispersion including polyethylene glycol and a first solvent; mixing the polyethylene glycol dispersion and the first prepolymer, reacting to obtain a second prepolymer; providing fluorinated hollow glass microspheres and fluorosilane compounds, mixing with the second prepolymer, reacting to obtain a thermal insulation composite material. The thermal insulation composite material prepared by the preparation method of the thermal insulation composite material provided in the present application has excellent anti-corrosion properties, flame retardant properties, heat insulation and phase change thermal insulation properties, and has broad application prospects in the fields of oil and gas transportation and building thermal insulation and energy saving.

Description

Technical Field

[0001] The present application relates to the technical field of polymer materials, and in particular to a thermal insulation composite material and a preparation method and application thereof. Background Art

[0002] Thermal insulation materials play a vital role in oil and gas transportation. They must not only be functional (such as maintaining stable temperature, corrosion resistance and pressure resistance), but also economical (such as energy saving and consumption reduction and extended service life). These characteristics make thermal insulation materials an important component of ensuring the safety and efficiency of energy transportation.

[0003] Among numerous materials, polyurethane (PU) has gradually become the industry's mainstream choice due to its superior overall performance, such as low thermal conductivity and easy construction. However, traditional PU foam has some significant drawbacks. First, its limiting oxygen index is only 19%, which means that when burned, it releases toxic gases such as carbon monoxide (CO) and hydrogen cyanide (HCN), posing a threat to the environment and safety. While conventional primary prepolymers (such as aluminum hydroxide) can enhance the flame retardancy of PU, they also increase thermal conductivity, reducing the material's insulation effectiveness. Furthermore, the high polarity and porous structure of traditional PU foam make it susceptible to corrosion from the penetration of oil or natural gas, shortening its service life and reducing its performance. Furthermore, the compressive strength of PU foam is significantly lower than that of PU plastic, further limiting its use in oil and gas transportation.

[0004] Therefore, solving the above problems is crucial to improving the applicability of traditional polyurethane foam in insulation material applications. Summary of the Invention

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

[0006] The embodiments of the present application are implemented as follows. In a first aspect, the embodiments of the present application provide a method for preparing a thermal insulation composite material, comprising the following steps:

[0007] A first prepolymer is provided, wherein the structural formula of the first prepolymer is shown below: ;

[0008] 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, and reacting them to obtain a second prepolymer;

[0009] Fluorinated hollow glass microspheres and fluorosilane compounds are provided, mixed with the second prepolymer, and reacted to obtain a thermal insulation composite material.

[0010] Optionally, in some embodiments of the present application, the method for preparing the first prepolymer includes:

[0011] Providing a 4-isocyanatobenzoyl chloride dispersion and a 2,2-bis[4-(2-hydroxyethoxy)-3,5-dibromophenyl]propane dispersion, wherein the 4-isocyanatobenzoyl chloride dispersion comprises a 4-isocyanatobenzoyl 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;

[0012] 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.

[0013] 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,

[0014] In the 4-isocyanatobenzoyl chloride dispersion, the molar concentration of the 4-isocyanatobenzoyl chloride is 0.1 mol / L to 1 mol / L; and / or,

[0015] 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,

[0016] 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,

[0017] The 4-isocyanatobenzoyl chloride dispersion further comprises an acid binding agent; and / or,

[0018] 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.

[0019] Optionally, in some embodiments of the present application, the acid binding agent includes one or more of triethylamine and pyridine; and / or,

[0020] 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,

[0021] 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.

[0022] Optionally, in some embodiments of the present application, the polyethylene glycol is selected from polyethylene glycol-4000; and / or,

[0023] 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,

[0024] In the polyethylene glycol dispersion, the molar concentration of the polyethylene glycol is 0.05 mol / L to 0.5 mol / L; and / or,

[0025] The mixing of the polyethylene glycol dispersion and the first prepolymer further comprises: adding a catalyst; the catalyst comprises one or more of dibutyltin dilaurate, stannous octoate, dibutyltin oxide, and bis(2-ethylhexanoate)tin; and / or,

[0026] The mass ratio of the polyethylene glycol to the first prepolymer is (2-10): (1-5); and / or,

[0027] 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.

[0028] Optionally, in some embodiments of the present application, the method for preparing the fluorinated hollow glass microspheres includes:

[0029] 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;

[0030] The hollow glass microsphere dispersion liquid and 1H,1H,2H,2H-perfluorodecyltrichlorosilane are mixed and reacted to obtain fluorinated hollow glass microspheres.

[0031] 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,

[0032] In the hollow glass microsphere dispersion, the mass concentration of the hollow glass microspheres is 100 g / L to 300 g / L; and / or,

[0033] The mass ratio of the hollow glass microspheres to the 1H,1H,2H,2H-perfluorodecyltrichlorosilane is (10-30):1; and / or,

[0034] 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 1 hour to 5 hours.

[0035] Optionally, in some embodiments of the present application, the fluorosilane compound includes 1H,1H,2H,2H-perfluorodecyltrichlorosilane; and / or,

[0036] The mass ratio of the polyethylene glycol, the fluorinated hollow glass microspheres and the fluorosilane compound is 40:(1-5):(10-40); and / or,

[0037] 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,

[0038] After the polyethylene glycol, the fluorinated hollow glass microspheres and the fluorosilane compound react, the method further comprises: drying treatment; the drying treatment temperature is 30° C. to 80° C.; and the drying treatment time is 10 hours to 15 hours.

[0039] In a second aspect, an embodiment of the present application further provides a thermal insulation composite material, which is prepared by the above-mentioned preparation method.

[0040] In a third aspect, an embodiment of the present application further provides an application of the thermal insulation composite material prepared by the above-mentioned preparation method in oil and gas transportation and building insulation.

[0041] The preparation method of the thermal insulation composite material provided in the present application selects polyethylene glycol as a 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 a structural unit of the thermal insulation composite material. When phase change energy storage occurs, the thermal insulation composite material remains in a solid state, preventing the leakage problem of traditional solid-liquid phase change materials during use; a first prepolymer unit is introduced into the molecular structure to give the material intrinsic flame retardant properties; fluorine-containing compounds are 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 have excellent compatibility with the second prepolymer treated with fluorosilane compounds, ensuring that the composite material has excellent mechanical properties.

[0042] The thermal insulation composite material prepared by the preparation method of the thermal insulation composite material provided in the present application has excellent corrosion resistance, flame retardancy, heat insulation and phase change thermal insulation properties, and has broad application prospects in the fields of oil and gas transportation and building insulation and energy saving. BRIEF DESCRIPTION OF THE DRAWINGS

[0043] In order to more clearly illustrate the technical solutions in the embodiments of the present application, the following briefly introduces the drawings required for use in the description of the embodiments. Obviously, the drawings described below are only some embodiments of the present application. For those skilled in the art, other drawings can be obtained based on these drawings without creative work.

[0044] Figure 1 This is a flow chart of a method for preparing a thermal insulation composite material provided in an embodiment of the present application. DETAILED DESCRIPTION

[0045] The following will be combined with the drawings in the embodiments of the present application to clearly and completely describe the technical solutions in the embodiments of the present application. Obviously, the described embodiments are only 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 making creative work are within the scope of protection of this application. In addition, 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.

[0046] In this application, unless otherwise indicated, directional terms such as "upper" and "lower" generally refer to the upper and lower positions of a device in actual use or operation, specifically in the drawing directions of the accompanying drawings; whereas "inner" and "outer" refer to the outline of the device. Furthermore, in the description of this application, the term "including" means "including but not limited to." Terms such as first, second, and third are used merely as designations and do not impose numerical requirements or establish a sequential order.

[0047] In this application, "and / or" describes the association relationship between associated objects, indicating that three relationships can exist. For example, A and / or B can mean: A exists alone, A and B exist at the same time, and B exists alone. A and B can be singular or plural.

[0048] In this application, "at least one" means one or more, and "plurality" means two or more. "One or more," "at least one of the following," or similar expressions refer to any combination of these items, including any combination of single or plural items. For example, "at least one of a, b, or c" or "at least one of a, b and c" can all mean: a, b, c, ab (i.e., a and b), ac, bc, or abc, where a, b, and c can each be single or plural.

[0049] Various embodiments of the present application may be presented 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 hard limitation on the scope of the present application; therefore, the range description should be considered to have specifically disclosed all possible sub-ranges and single numbers within the range. For example, the description of a range from 1 to 6 should be considered to have 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., as well as single numbers within the range, such as 1, 2, 3, 4, 5 and 6, which applies regardless of the range. In addition, whenever a numerical range is indicated herein, it is meant to include any cited number (fractional or integer) within the indicated range.

[0050] The structural formulas and molecular weights of some chemical reagents used in this application are described below:

[0051] Polyethylene glycol 4000 (PEG-4000): , n is an integer from 60 to 120, number average molecular weight = 4000;

[0052] 4-Isocyanobenzoyl chloride: , molecular weight = 181.58;

[0053] 2,2-Bis[4-(2-hydroxyethoxy)-3,5-dibromophenyl]propane: , molecular weight = 631.98;

[0054] 1H,1H,2H,2H-Perfluorodecyltrichlorosilane: , molecular weight = 581.56;

[0055] Triethylamine: Molecular weight = 101.19.

[0056] The technical solution of this application is as follows:

[0057] First, see Figure 1 The present invention provides a method for preparing a thermal insulation composite material, comprising the following steps:

[0058] Step S11: providing a first prepolymer, wherein the structural formula of the first prepolymer is shown below: ;

[0059] Step S12, 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, and reacting them to obtain a second prepolymer;

[0060] Step S13: providing fluorinated hollow glass microspheres and a fluorosilane compound, mixing them with the second prepolymer, and reacting them to obtain a thermal insulation composite material.

[0061] It should be noted that hollow glass microspheres, also known as hollow glass microspheres, are tiny, hollow spherical powders whose main component is borosilicate. As the name suggests, the fluorinated hollow glass microspheres refer to hollow glass microspheres with -F introduced into them.

[0062] It should also be noted that the fluorosilane compound refers to a compound in which at least one H in the silane compound is replaced by F.

[0063] The preparation method of the thermal insulation composite material provided in the present application selects polyethylene glycol as a 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 a structural unit of the thermal insulation composite material. When phase change energy storage occurs, the thermal insulation composite material remains in a solid state, preventing the leakage problem of traditional solid-liquid phase change materials during use; a first prepolymer unit is introduced into the molecular structure, in which the 2,2-bis[4-(2-hydroxyethoxy)-3,5-dibromophenyl]propane unit structure gives the material intrinsic flame retardant properties; fluorine-containing compounds are 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 have excellent compatibility with the second prepolymer treated with fluorosilane compounds, ensuring that the composite material has excellent mechanical properties.

[0064] The thermal insulation composite material prepared by the preparation method of the thermal insulation composite material provided in the present application has excellent corrosion resistance, flame retardancy, heat insulation and phase change thermal insulation properties, and has broad application prospects in the fields of oil and gas transportation and building insulation and energy saving.

[0065] In the step S11:

[0066] In some embodiments, the method for preparing the first prepolymer comprises:

[0067] Step S111, providing a 4-isocyanatobenzoyl chloride dispersion and a 2,2-bis[4-(2-hydroxyethoxy)-3,5-dibromophenyl]propane dispersion, wherein the 4-isocyanatobenzoyl chloride dispersion comprises a 4-isocyanatobenzoyl 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;

[0068] Step S112: mixing the 4-isocyanatobenzoyl chloride dispersion and the 2,2-bis[4-(2-hydroxyethoxy)-3,5-dibromophenyl]propane dispersion, and reacting them to obtain a first prepolymer.

[0069] 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.

[0070] In some embodiments, the molar concentration of 4-isocyanatobenzoyl chloride in the 4-isocyanatobenzoyl chloride dispersion is 0.1 mol / L to 1 mol / L, for example, 0.1 mol / L, 0.2 mol / L, 0.4 mol / L, 0.6 mol / L, 0.8 mol / L, 1 mol / L, or a range between any two of the above values. Within the molar concentration range, the 4-isocyanatobenzoyl chloride is facilitated to be uniformly dissolved and dispersed.

[0071] In some embodiments, the molar concentration of the 2,2-bis[4-(2-hydroxyethoxy)-3,5-dibromophenyl]propane in the 2,2-bis[4-(2-hydroxyethoxy)-3,5-dibromophenyl]propane dispersion is 0.1 mol / L to 1 mol / L, for example, 0.1 mol / L, 0.2 mol / L, 0.4 mol / L, 0.6 mol / L, 0.8 mol / L, 1 mol / L, or a range between any two of the foregoing values. Within this molar concentration range, uniform dissolution and dispersion of the 2,2-bis[4-(2-hydroxyethoxy)-3,5-dibromophenyl]propane is facilitated.

[0072] In some embodiments, the 4-isocyanatobenzoyl chloride dispersion further comprises an acid binding agent, which can accelerate the reaction rate and improve the reaction quality.

[0073] Furthermore, the acid binding agent includes one or more of triethylamine and pyridine.

[0074] In some embodiments, the molar ratio of the 4-isocyanatobenzoyl chloride to the 2,2-bis[4-(2-hydroxyethoxy)-3,5-dibromophenyl]propane is (2-10):(1-5), for example, 5:1, 5:3, 5:3, 5:4, 5:5, or a range between any two of the above ratios. Within this molar ratio range, the 4-isocyanatobenzoyl chloride and the 2,2-bis[4-(2-hydroxyethoxy)-3,5-dibromophenyl]propane efficiently react to form the first prepolymer, thereby increasing the yield of the first prepolymer.

[0075] In some embodiments, 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.

[0076] In some embodiments, the reaction temperature of the first reaction is -5°C~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; the reaction time of the first reaction is 1h~5h, for example, it can be 1h, 2h, 3h, 4h, 5h or a range between any two of the above values.

[0077] In some embodiments, the reaction temperature of the second reaction is 35°C~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; the reaction time of the second reaction is 1h~5h, for example, it can be 1h, 2h, 3h, 4h, 5h or a range between any two of the above values.

[0078] In this way, under the reaction conditions of the first reaction and the second reaction, it is conducive to the efficient production of the first prepolymer.

[0079] In some embodiments, the synthesis route of the reaction of the 4-isocyanatobenzoyl chloride and the 2,2-bis[4-(2-hydroxyethoxy)-3,5-dibromophenyl]propane to form a cross-linking agent is shown in the following formula:

[0080] .

[0081] In the step S12:

[0082] In some embodiments, the polyethylene glycol is selected from polyethylene glycol-4000.

[0083] 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.

[0084] In some embodiments, the polyethylene glycol dispersion has a molar concentration of polyethylene glycol of 0.05 mol / L to 0.5 mol / L, for example, 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 foregoing values. Within the molar concentration range, the polyethylene glycol is facilitated to be uniformly dissolved and dispersed.

[0085] In some embodiments, mixing the polyethylene glycol dispersion and the first prepolymer further comprises: adding a catalyst.

[0086] Furthermore, the catalyst includes one or more of dibutyltin dilaurate, stannous octoate, dibutyltin oxide, and bis(2-ethylhexanoate)tin. The catalyst can improve reaction efficiency.

[0087] In some embodiments, the mass ratio of the polyethylene glycol to the first prepolymer is (2-10):(1-5), for example, 5:1, 5:3, 5:3, 5:4, 5:5, or a range between any two of the above ratios. Within this mass ratio range, the polyethylene glycol and the first prepolymer efficiently react to form the second prepolymer, thereby increasing the yield of the second prepolymer.

[0088] In some embodiments, the reaction temperature of the polyethylene glycol and the first prepolymer is 30° C. to 80° C., for example, 30° C., 40° C., 50° C., 60° C., 70° C., 80° C., or a range between any two of the foregoing values; the reaction time of the polyethylene glycol and the first prepolymer is 5 h to 10 h, for example, 5 h, 6 h, 7 h, 8 h, 9 h, 10 h, or a range between any two of the foregoing values. Thus, under the aforementioned reaction conditions, the second prepolymer is efficiently produced.

[0089] In some embodiments, the structural formula of the second prepolymer is as shown below:

[0090] ;

[0091] Wherein, n represents the degree of polymerization, which is an integer selected from 60-120.

[0092] In step S13:

[0093] In some embodiments, the method for preparing the fluorinated hollow glass microspheres comprises:

[0094] Step S131, 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;

[0095] Step S132: mixing the hollow glass microsphere dispersion and 1H,1H,2H,2H-perfluorodecyltrichlorosilane, and reacting them to obtain fluorinated hollow glass microspheres.

[0096] 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, and dichloromethane.

[0097] In some embodiments, the mass concentration of the hollow glass microspheres in the hollow glass microsphere dispersion is 100 g / L to 300 g / L, for example, 100 g / L, 150 g / L, 200 g / L, 250 g / L, 300 g / L, or a range between any two of the foregoing values. Within this mass concentration range, the hollow glass microspheres are facilitated to uniformly dissolve and disperse.

[0098] In some embodiments, the mass ratio of the hollow glass microspheres to the 1H,1H,2H,2H-perfluorodecyltrichlorosilane is (10-30):1, for example, 10:1, 15:1, 20:1, 25:1, 30:1, or a range between any two of these ratios. Within this mass ratio range, the hollow glass microspheres and 1H,1H,2H,2H-perfluorodecyltrichlorosilane efficiently react to form fluorinated hollow glass microspheres, thereby increasing the yield of the fluorinated hollow glass microspheres.

[0099] 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, 20°C, 25°C, 30°C, 35°C, 40°C, or a range between any two of the above values; the reaction time of the hollow glass microspheres and the 1H,1H,2H,2H-perfluorodecyltrichlorosilane is 1h to 5h, for example, 1h, 2h, 3h, 4h, 5h, or a range between any two of the above values.

[0100] Thus, under the reaction conditions, it is favorable for the 1H,1H,2H,2H-perfluorodecyltrichlorosilane to modify the hollow glass microspheres, and the fluorinated hollow glass microspheres are efficiently generated.

[0101] It should be noted that in step S13, the second prepolymer is subjected to a chain extension reaction mainly by utilizing the substitution reaction between the terminal hydroxyl groups of the second prepolymer and the silicon chloride groups, thereby partially forming a micro-crosslinked structure.

[0102] In some embodiments, the fluorosilane compound includes 1H,1H,2H,2H-perfluorodecyltrichlorosilane.

[0103] In some embodiments, the mass ratio of the polyethylene glycol, the fluorinated hollow glass microspheres, and the fluorosilane compound is 40:(1-5):(10-40), for example, 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 foregoing ratios. Within this mass ratio range, the yield of the thermal insulation composite material is advantageously improved.

[0104] 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, 30°C, 40°C, 50°C, 60°C, 70°C, 80°C, or a range between any two of the foregoing values; the reaction time of the polyethylene glycol, the fluorinated hollow glass microspheres, and the fluorosilane compound is 0.5h to 5h, for example, 0.5h, 1h, 2h, 3h, 4h, 5h, or a range between any two of the foregoing values. Thus, under the aforementioned reaction conditions, the thermal insulation composite material is efficiently produced.

[0105] In some embodiments, after the polyethylene glycol, the fluorinated hollow glass microspheres, and the fluorosilane compound react, the method further includes: drying treatment.

[0106] Furthermore, the drying temperature is 30°C to 80°C, for example, 30°C, 40°C, 50°C, 60°C, 70°C, 80°C, or a range between any two of the above values; the drying time is 10 hours to 15 hours, for example, 10 hours, 11 hours, 12 hours, 13 hours, 14 hours, 15 hours, or a range between any two of the above values. Thus, under the above drying conditions, the solvent and reaction by-products in the reaction system are removed, thereby improving the purity of the thermal insulation composite material.

[0107] 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 shown below:

[0108] ;

[0109] Wherein, n represents the degree of polymerization, which is an integer selected from 60-120.

[0110] It should be noted that the “ " can represent a molecular chain or a substituent. In some embodiments, Can represent a Cl atom; in some embodiments Can be expressed , where "*" represents the connection site between the molecular chain and the silicon atom. They can all be molecular chains, in which case a micro-crosslinked structure can be formed locally. Alternatively, one can be a molecular chain and the other a Cl atom, in which case a linear structure can be formed.

[0111] In a second aspect, an embodiment of the present application further provides a thermal insulation composite material, which can be prepared by the above-mentioned preparation method.

[0112] The thermal insulation composite material provided in this application has excellent anti-corrosion, flame retardant, heat insulation and phase change thermal insulation properties, and has broad application prospects in the fields of oil and gas transportation and building insulation and energy saving.

[0113] In a third aspect, embodiments of the present application further provide a thermal insulation composite material prepared by the above-mentioned preparation method or an application of the above-mentioned thermal insulation composite material.

[0114] Specifically, the thermal insulation composite material can be applied to oil and gas transportation and building insulation.

[0115] The present application will be described in detail below through specific examples. The following examples are only some examples of the present application and are not limitations of the present application.

[0116] Example 1

[0117] This embodiment provides a thermal insulation composite material, the preparation method of which includes the following steps:

[0118] Step 1: Weigh 0.05 mol of 4-isocyanatobenzoyl chloride, 0.05 mol of triethylamine and 100 mL of anhydrous dioxane into a 250 mL three-necked flask, start stirring, introduce nitrogen protection, and mix the reactants evenly in an ice bath (0°C); weigh 12.6 g 2,2-bis[4-(2-hydroxyethoxy)-3,5-dibromophenyl]propane (0.02 mol) was dissolved in 50 mL of anhydrous dioxane. The 2,2-bis[4-(2-hydroxyethoxy)-3,5-dibromophenyl]propane solution was gradually added dropwise to the 4-isocyanobenzoyl chloride / dioxane solution through a constant pressure funnel under ice bath conditions, with nitrogen continuously flowing through the funnel during the process. After the dropwise addition was completed, the mixture was reacted under ice bath for 2 hours, and then heated to 40°C and reacted for 2 hours, during which time a white powder by-product precipitated. After the reaction was completed, the by-product was removed by filtration. The filtrate was rotary evaporated at 80°C to remove residual dioxane and excess 4-isocyanobenzoyl chloride in the system, thereby obtaining a first prepolymer.

[0119] Step 2: Weigh 40 g of polyethylene glycol 4000 (PEG-4000) and 100 g of anhydrous DMF into a 250 mL three-necked flask, start stirring, and 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 protection, and react at 60°C for 8 h to obtain a second prepolymer.

[0120] Step 3: 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 was stirred in an ultrasonic bath for 1 h, and then 1 g of 1H,1H,2H,2H-perfluorodecyltrichlorosilane was added and stirred for 3 h to obtain a suspension of surface-fluorinated hollow glass microspheres. The suspension was centrifuged for 20 min, and the precipitate was removed. The suspension was then rinsed with n-hexane and deionized water, followed by another centrifugation for 20 min, and the precipitate was removed. Finally, the suspension was dried in a 90°C forced air oven for 4 h to obtain fluorinated hollow glass microspheres.

[0121] 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 the suspension to the second polyurethane prepolymer solution obtained in step 2, and stir and mix them evenly at 60° C.; then add 2 g of 1H,1H,2H,2H-perfluorodecyltrichlorosilane thereto, react at 60° C. for 1 h under nitrogen protection, pour the reaction solution into a polytetrafluoroethylene tray, place it in a vacuum oven at 80° C. and vacuum dry it for 12 h to remove residual anhydrous DMF and by-products in the system to obtain a thermal insulation composite material.

[0122] Example 2

[0123] This embodiment is basically the same as embodiment 1, except that the amount of fluorinated hollow glass microspheres used in step 4 is 20 g.

[0124] Example 3

[0125] This embodiment is basically the same as embodiment 1, except that the amount of fluorinated hollow glass microspheres used in step 4 is 30 g.

[0126] Example 4

[0127] This embodiment is substantially the same as embodiment 1, except that the amount of fluorinated hollow glass microspheres used in step 4 is 40 g.

[0128] Comparative Example

[0129] 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.).

[0130] The thermal insulation composite materials of Examples 1 to 4 and the thermal insulation composite material of the comparative example were tested for mechanical properties, corrosion resistance, flame retardancy, thermal insulation properties, and phase change properties. The test results are shown in Table 1.

[0131] Among them, the compressive strength test is carried out in accordance with the standard GB / T6343-2009.

[0132] The water contact angle test was performed in accordance with the standard GB / T 30693-2014.

[0133] The corrosion resistance test was carried out in accordance with the standard GB / T 10125-2012 "Artificial Atmosphere Corrosion Experiment Salt Spray Test". Acetic acid salt spray (AASS) was used, the pH of the salt solution was controlled at 3.0-3.1, the pH value of the liquid collected in the salt spray chamber was 3.1-3.3, the test cycle was 240 hours, and the corrosion resistance was evaluated by the mass loss before and after the test.

[0134] The flame retardant performance test is carried out in accordance with the UL94 standard.

[0135] The thermal conductivity coefficient is determined in accordance with the standard GB / T 42919.1-2023.

[0136] The melting and crystallization temperatures and enthalpy were determined in accordance with GB / T 19466.3-2004.

[0137] Table 1:

[0138] Example 1 Example 2 Example 3 Example 4 Comparative Example Tensile and compressive strength (MPa) 25 37 44 58 0.22 Water contact angle (°) 146 148 151 155 107 Mass loss before and after salt spray test (%) 4.7 4.1 3.4 2.3 28 Flame retardant grade V-0 V-0 V-0 V-0 HB Thermal conductivity W / (m·K) 0.051 0.046 0.042 0.035 0.033 Melting temperature (℃) 49 48 48 49 - Melting enthalpy (J / g) 75 64 55 49 - Crystallization temperature (℃) 38 38 37 39 - Crystallization enthalpy (J / g) 67 57 50 44 -

[0139] As shown in Table 1, the thermal insulation composite materials provided in Examples 1-4 have a compressive strength of 25 MPa or greater, a water contact angle of 146° or greater, a flame retardancy rating of V-0, a relatively low thermal conductivity of 0.035-0.051 W / (m·K), and good phase-change thermal insulation performance. The composite materials provided in the examples of this application exhibit excellent corrosion resistance, flame retardancy, thermal insulation, and phase-change thermal insulation properties.

[0140] The above is a detailed introduction to the technical solutions provided in the embodiments of the present application. Specific examples are used herein to illustrate the principles and implementation methods of the present application. The description of the above embodiments is only used to help understand the method of the present application and its core idea. At the same time, for those skilled in the art, based on the ideas of the present application, there may be changes in the specific implementation methods and application scope. In summary, the content of this specification should not be understood as a limitation on 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, and reacting them to obtain a second prepolymer; Providing fluorinated hollow glass microspheres and a fluorosilane compound, mixing with the second prepolymer, and reacting to obtain a thermal insulation composite material; Wherein, the fluorosilane compound includes 1H,1H,2H,2H-perfluorodecyltrichlorosilane; The mass ratio of the polyethylene glycol, the fluorinated hollow glass microspheres and the fluorosilane compound is 40:(1-5):(10-40).

2. The preparation method according to claim 1, characterized in that The preparation method of the first prepolymer comprises: Providing a 4-isocyanatobenzoyl chloride dispersion and a 2,2-bis[4-(2-hydroxyethoxy)-3,5-dibromophenyl]propane dispersion, wherein the 4-isocyanatobenzoyl chloride dispersion comprises a 4-isocyanatobenzoyl 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-isocyanatobenzoyl chloride dispersion, the molar concentration of the 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 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-isocyanatobenzoyl chloride dispersion further comprises 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, and 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 1 hour to 5 hours.

8. The preparation method according to claim 1, characterized in that The reaction temperature of the second prepolymer, the fluorinated hollow glass microspheres and the fluorosilane compound is 30° C. to 80° C.; the reaction time of the second prepolymer, the fluorinated hollow glass microspheres and the fluorosilane compound is 0.5 h to 5 h; and / or, After the second prepolymer, the fluorinated hollow glass microspheres and the fluorosilane compound react, the method further comprises: drying treatment; The temperature of the drying process is 30° C. to 80° C.; the time of the drying process 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. Use 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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