Antistatic thermal insulation coating and preparation method thereof
Through anti-static insulating coatings with specific components and preparation methods, combined with Vitrimer xylose polyacrylate and anti-static insulating composite materials, the existing coatings have solved the problems of insufficient anti-static, thermal insulation, mechanical and thermal resistance performance, and achieved high-performance applications of coatings.
Patent Information
- Application Number
- CN202510157696.7
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- Filing Date
- 2025-02-13
- Publication Date
- 2025-08-29
- Estimated Expiration
- 2045-02-13
AI Technical Summary
Existing antistatic insulating coatings are difficult to meet high requirements in terms of antistatic properties, thermal insulation properties, mechanical properties and heat resistance, and there are fewer coating products.
Antistatic insulating coatings made of polyacrylate, antistatic heat insulating fillers, hydrophilic aerogels, diatomaceous earth, defoaming agents, film-forming additives and water are formed through specific component ratios and preparation methods, combined with the use of Vitrimer xylose polyacrylate and antistatic heat insulating composite materials to form a composite micro-layer structure of lightweight material surface composite conductive polymer and carbon material.
It significantly improves the mechanical properties, thermal stability and durability of the paint, ensures uniform dispersion of the paint, and has good anti-static and thermal insulation properties, and is suitable for a variety of application scenarios.
Smart Images

Figure CN119614003B_ABST
Abstract
Description
Technical Field
[0001] The invention belongs to the technical field of coatings, and particularly relates to an antistatic thermal insulation coating and a preparation method thereof. Background Art
[0002] Antistatic thermal insulation coatings are specialized coatings that combine antistatic and thermal insulation properties. The antistatic property effectively conducts electricity, preventing the potential safety hazards caused by static electricity accumulation. This is particularly important for the storage and transportation of flammable and explosive materials. The thermal insulation property, on the other hand, reduces heat conduction, helping to maintain a stable internal temperature and reduce energy consumption. These properties have led to widespread application in a variety of fields, including electronic equipment, construction, automotive, and aerospace.
[0003] With the development of technology and the increase in its application, the requirements for the antistatic, thermal insulation, mechanical, and heat resistance properties of antistatic thermal insulation coatings are becoming increasingly stringent. However, among current coating products, there are still few products that combine these properties and meet these high requirements. Therefore, the antistatic, thermal insulation, mechanical, and heat resistance properties of coatings need to be further improved.
[0004] In view of this, the present invention is proposed. Summary of the Invention
[0005] The present invention aims to provide an antistatic heat-insulating (thermal insulation) coating, a preparation method and a coating, so as to improve one of the above-mentioned problems existing in the prior art.
[0006] In order to achieve the above purpose, the following technical solutions are adopted:
[0007] The first object of the present invention is to provide an antistatic thermal insulation coating, which comprises the following components in the following mass fractions, based on the total mass of the antistatic thermal insulation coating being 100%:
[0008] Polyacrylate 30%-40%, titanium dioxide 10%-15%, antistatic thermal insulation filler 0.2%-3%, hydrophilic aerogel 0.1%-0.2%, diatomaceous earth 1%-4%, defoamer 1%-4%, film-forming aid 1%-5%, dispersant 0.1%-1.5% and water 30%-55%;
[0009] Furthermore, based on the above technical solution of the present invention, the polyacrylate includes Vitrimer xylose polyacrylate, and the structural formula of Vitrimer xylose polyacrylate is specifically shown in formula (a):
[0010]
[0011] In formula (a), R is selected from an alkyl group having 1 to 3 carbon atoms.
[0012] Furthermore, based on the above technical solution of the present invention, the preparation method of Vitrimer xylose polyacrylate comprises the following steps:
[0013] S1. Mixing an alcohol solution containing xylose and acryloyl chloride and reacting them in the presence of a basic catalyst to obtain xylose acrylate;
[0014] S2. xylose acrylate, acrylate monomer, initiator and solvent are mixed and polymerized under nitrogen atmosphere. A precipitation promoting agent is added to the obtained polymerization reaction product so that the xylose polyacrylate generated by the polymerization reaction is precipitated in the form of a precipitate, which is then filtered, washed and dried to obtain xylose polyacrylate;
[0015] S3. Xylose polyacrylate and 2,2'-dithiodiethanol are mixed and reacted with each other under the action of a cross-linking agent to obtain Vitrimer xylose polyacrylate.
[0016] Furthermore, based on the above technical solution of the present invention, the molecular weight of Vitrimer xylose polyacrylate is 10,000-150,000 g / mol.
[0017] Furthermore, based on the above technical solution of the present invention, in step S1, the mass ratio of xylose and acryloyl chloride in the alcohol solution containing xylose is (1-3):(1-3);
[0018] and / or, in step S1, the alkaline catalyst comprises sodium hydroxide;
[0019] and / or, in step S1, the reaction temperature is 50-100° C., and the reaction time is 2-6 h;
[0020] and / or, in step S2, the molar ratio of xylose acrylate to acrylate monomer is (1-3):(1-3);
[0021] and / or, in step S2, the polymerization reaction temperature is 50-100° C., the reaction time is 2-10 h, and the polymerization reaction is terminated by adding a terminator, hydroquinone;
[0022] and / or, in step S3, the molar ratio of xylose polyacrylate to 2,2'-dithiodiethanol is (1-4):(2-4);
[0023] and / or, in step S3, the cross-linking agent comprises cystamine;
[0024] And / or, in step S3, the reaction temperature is 50-100° C., and the reaction time is 2-6 h.
[0025] Furthermore, based on the above technical solution of the present invention, the antistatic thermal insulation filler includes an antistatic thermal insulation composite material, which is mainly composed of a lightweight material, polypyrrole and a carbon material. The composite material is prepared by an in-situ polymerization method and has a structure of a composite microlayer of polypyrrole and carbon material on the surface of the lightweight material;
[0026] The lightweight material includes at least one of aerogel, hollow glass microspheres, expanded microspheres, floating beads or perlite;
[0027] The carbon material includes at least one of carbon nanotubes, modified carbon nanotubes, graphene, or modified graphene.
[0028] Furthermore, based on the above technical solution of the present invention, the lightweight material includes at least one of aerogel, hollow glass microspheres or expanded microspheres.
[0029] Furthermore, based on the above technical solution of the present invention, the carbon material includes carbon nanotubes and / or graphene oxide;
[0030] And / or, the mass ratio of the lightweight material, polypyrrole and carbon material is (1.2-1.5):(0.5-0.8):(0.08-0.2).
[0031] Furthermore, based on the above technical solution of the present invention, a method for preparing an antistatic heat-insulating composite material comprises the following steps:
[0032] (a) providing a pyrrole aqueous solution, a ferric chloride p-toluenesulfonic acid mixed solution, and a carbon material dispersion;
[0033] (b) mixing the lightweight material with the pyrrole aqueous solution, then adding the ferric chloride p-toluenesulfonic acid mixed solution and the carbon material dispersion to carry out a polymerization reaction, and after the reaction is completed, performing solid-liquid separation on the obtained product, and drying the separated solid product to obtain an antistatic heat-insulating composite material composed of the lightweight material, polypyrrole and carbon material.
[0034] Furthermore, based on the above technical solution of the present invention, in step (a), the molar concentration of pyrrole in the pyrrole aqueous solution is 0.1M-0.8M;
[0035] And / or, in the ferric chloride and p-toluenesulfonic acid mixed solution, the molar concentration of ferric chloride is 0.1M-0.8M, and the molar concentration of p-toluenesulfonic acid is 0.1M-0.8M;
[0036] And / or, the mass concentration of the carbon material in the carbon material dispersion is 1-10 mg / ml.
[0037] Furthermore, based on the above technical solution of the present invention, in step (b), the mass ratio of the lightweight material to the mass ratio of the pyrrole aqueous solution is 5-10%;
[0038] and / or, the total mass ratio of ferric chloride and p-toluenesulfonic acid in the ferric chloride-p-toluenesulfonic acid mixed solution to the mass ratio of the pyrrole aqueous solution is 45-60%;
[0039] and / or, the mass ratio of the carbon material dispersion to the pyrrole aqueous solution is 5-15%;
[0040] And / or, the polymerization reaction temperature is 15-30° C., and the polymerization reaction time is 1-3 hours;
[0041] And / or, the drying is vacuum drying, and the vacuum drying temperature is 50-90°C.
[0042] Furthermore, based on the above technical solution of the present invention, the hydrophilic aerogel includes silica aerogel;
[0043] and / or, the defoaming agent comprises at least one of n-butanol, an organosilicon defoaming agent or a polyether defoaming agent;
[0044] and / or, the film-forming aid comprises at least one of ethylene glycol, propylene glycol butyl ether, hydrocarbons or dodecyl alcohol ester;
[0045] And / or, the dispersant includes at least one of SN5040 dispersant, a cationic wetting dispersant or a nonionic dispersant.
[0046] The second object of the present invention is to provide a method for preparing the above-mentioned antistatic thermal insulation coating, comprising the following steps:
[0047] Titanium dioxide, hydrophilic aerogel, diatomaceous earth and a portion of the formulated amount of water are stirred and mixed once to obtain a mixed solution I;
[0048] Adding a portion of the defoaming agent and a portion of the film-forming aid to the mixed solution I and stirring and mixing them a second time to obtain a mixed solution II;
[0049] Adding polyacrylate to the mixed solution II and stirring for three times to obtain a mixed solution III;
[0050] Add a dispersion formed by an antistatic thermal insulation filler and the remaining amount of water, a dispersant, the remaining amount of a defoamer and the remaining amount of a film-forming aid to the mixed solution III and stir and mix four times to obtain an antistatic thermal insulation coating.
[0051] Furthermore, based on the above technical solution of the present invention, the stirring and mixing time is 1-10 minutes, and the stirring speed is 500-800 r / min;
[0052] And / or, the secondary stirring and mixing time is 10-30 min, and the stirring speed is 500-800 r / min;
[0053] And / or, the three stirring and mixing times are 30-60 min, and the stirring speed is 500-800 r / min;
[0054] And / or, the time for the four stirring and mixing is 60-120 min, and the stirring speed is 450-750 r / min.
[0055] The third object of the present invention is to provide a coating, which is formed by coating the antistatic thermal insulation coating provided by the first object of the present invention or the antistatic thermal insulation coating prepared by the preparation method provided by the second object of the present invention.
[0056] Compared with the prior art, the technical solution of the present invention has at least the following technical effects:
[0057] (1) The present invention provides an antistatic thermal insulation coating, which is mainly made of raw materials such as polyacrylate, titanium dioxide, antistatic thermal insulation filler, hydrophilic aerogel, diatomaceous earth, defoaming agent, film-forming aid, dispersant and water, wherein the polyacrylate includes Vitrimer xylose polyacrylate with a specific structure. The xylose structure and disulfide bond are simultaneously introduced into the structure of Vitrimer xylose polyacrylate, which can improve the mechanical properties and heat resistance of the polymer itself, thereby significantly improving the mechanical properties (hardness, adhesion, wear resistance, etc.), thermal stability and durability of the coating (coating).
[0058] (2) The present invention also provides a method for preparing the above-mentioned antistatic thermal insulation coating. By adopting a specific adding sequence, the coating can be well dispersed and is not easy to form particles or lumps, which is beneficial to improving the overall performance of the coating.
[0059] (3) The present invention also provides an antistatic heat-insulating composite material. By combining a lightweight material, polypyrrole, and a carbon material, a unique structure of a composite microlayer of a conductive polymer (polypyrrole) and a carbon material is formed on the surface of the lightweight material. The synergistic effect of the three materials and the specific composite structure formed make the composite material have good heat-insulating and antistatic properties, and can be used as an antistatic heat-insulating filler for coatings (especially antistatic heat-insulating coatings).
[0060] Furthermore, the antistatic thermal insulation composite material provided by the present invention is used as an antistatic thermal insulation filler, and cooperates with other raw materials such as polyacrylate to make the prepared antistatic thermal insulation coating have both good antistatic and thermal insulation properties, which can meet the different needs of various application scenarios.
[0061] (4) The present invention also provides a method for preparing an antistatic heat-insulating composite material, which realizes the composite of a lightweight material, polypyrrole and a carbon material by an in-situ polymerization method, thereby forming a unique structure of a composite microlayer of a conductive polymer (polypyrrole) and a carbon material on the surface of the lightweight material; in addition, the in-situ polymerization technology can form a thin and uniform conductive polymer (polypyrrole), so when polymerizing the lightweight material, the carbon material and the pyrrole, the polypyrrole and the carbon material can be effectively polymerized on the surface of the lightweight material, thereby enhancing the common properties of the materials. BRIEF DESCRIPTION OF THE DRAWINGS
[0062] Figure 1 Schematic diagram of the preparation process of the antistatic thermal insulation composite material and the antistatic thermal insulation coating of the present invention;
[0063] Figure 2 SEM images of the antistatic thermal insulation composite material (HPG) provided in Example 1 of the present invention at different scanning magnifications, wherein (a) is scanned at 100 times, and (b) is scanned at 450 times;
[0064] Figure 3 SEM images of the antistatic thermal insulation composite material (TPG) provided in Example 2 of the present invention at different scanning magnifications, wherein (a) is scanned at 100 times, and (b) is scanned at 450 times;
[0065] Figure 4 SEM images of the antistatic thermal insulation coating (P-HPG) provided in Example 3 of the present invention at different scanning magnifications, wherein (a) is scanned at 100 times, and (b) is scanned at 450 times;
[0066] Figure 5 SEM images of the antistatic thermal insulation coating (P-TPG) provided in Example 7 of the present invention at different scanning magnifications, wherein (a) is scanned at 100 times, and (b) is scanned at 450 times;
[0067] Figure 6 The infrared spectra of the antistatic thermal insulation coatings provided in Examples 3 to 6 of the present invention and Comparative Example 1;
[0068] Figure 7 The infrared spectra of the antistatic thermal insulation coatings provided in Examples 7 to 10 of the present invention and Comparative Example 2;
[0069] Figure 8 This is a graph showing the thermal insulation temperature difference performance of the antistatic thermal insulation coatings provided in Examples 3 to 6 of the present invention and Comparative Example 1 after 60 minutes;
[0070] Figure 9 This is a graph showing the thermal insulation temperature difference performance of the antistatic thermal insulation coatings provided in Examples 7 to 10 of the present invention and Comparative Example 2 after 60 minutes;
[0071] Figure 10 A graph showing the antistatic resistance values of the antistatic thermal insulation coatings provided in Examples 3 to 6 of the present invention and Comparative Example 1;
[0072] Figure 11 A graph showing the antistatic resistance values of the antistatic thermal insulation coatings provided in Examples 7 to 10 of the present invention and Comparative Example 2;
[0073] Figure 12 A comparison chart of the adhesion of the antistatic thermal insulation coatings provided in Examples 3 to 6 of the present invention and Comparative Example 1;
[0074] Figure 13 A comparison chart of the adhesion of the antistatic thermal insulation coatings provided in Examples 7 to 10 of the present invention and Comparative Example 2;
[0075] Figure 14 IR spectra of Vitrimer xylose polyacrylate in Examples 11 and 12 of the present invention;
[0076] Figure 15 This is a comparison chart of the heat resistance of the Vitrimer xylose polyacrylate provided by the present invention and conventional polyacrylate. DETAILED DESCRIPTION
[0077] In order to make the purpose, technical solutions and advantages of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention. It should be understood by those skilled in the art that the embodiments are merely to help understand the present invention and should not be regarded as specific limitations of the present invention. Based on the embodiments in the present invention, all other embodiments obtained by those of ordinary skill in the art without making creative work are within the scope of protection of the present invention. The process parameters for which specific conditions are not specified in the following examples are generally in accordance with conventional conditions.
[0078] The endpoints of the ranges and any values disclosed herein are not limited to the precise ranges or values, and these ranges or values should be understood to include values close to these ranges or values. For numerical ranges, the endpoints of each range, the endpoints of each range and individual point values, and the individual point values can be combined with each other to form one or more new numerical ranges, and these numerical ranges should be considered to be specifically disclosed in the present invention.
[0079] According to a first aspect of the present invention, an antistatic heat-insulating composite material is provided. The composite material is mainly composed of a lightweight material, polypyrrole, and a carbon material. The composite material is prepared by an in-situ polymerization method and has a structure of a composite microlayer of polypyrrole and carbon material on the surface of the lightweight material.
[0080] The lightweight material includes at least one of aerogel, hollow glass microspheres, expanded microspheres, floating beads or perlite;
[0081] The carbon material includes at least one of carbon nanotubes, modified carbon nanotubes, graphene, or modified graphene (eg, graphene oxide).
[0082] Specifically, the lightweight materials of the present invention are generally selected from lightweight, porous materials with thermal insulation properties. Among them, aerogel has the characteristics of improving the thermal insulation performance of coatings, reducing coating density, enhancing the adhesion, anti-permeability and durability of coatings, and improving construction performance. Its role in antistatic thermal insulation composite materials is to improve thermal insulation performance and enhance adhesion; hollow glass microspheres have the advantages of reducing weight, improving dielectric properties, improving flow properties, reducing oil absorption rate, reducing volume cost and thermal insulation, etc., and have a thermal insulation effect in antistatic thermal insulation composite materials; expanded microspheres have the functions of enhancing the mechanical properties of materials, improving strength and durability, as well as thermal insulation, shock absorption and flame retardancy, and mainly play the role of thermal insulation and enhancing the durability of materials in antistatic thermal insulation composite materials; floating beads have the functions of thermal insulation and enhancing adhesion, and have the function of improving coating adhesion in antistatic thermal insulation coatings; perlite mainly plays the role of improving durability and coating adhesion in antistatic thermal insulation composite materials.
[0083] Polypyrrole has the characteristics of conductivity, stability, porosity and strong processing performance, and has the function of increasing the adhesion of materials in antistatic and thermal insulation composite materials.
[0084] Among carbon materials, modified carbon nanotubes and / or modified graphene products refer to products whose structure or surface has been modified to improve their properties (such as dispersibility or compatibility). Carbon materials are low-cost, corrosion-resistant, and possess excellent electrical conductivity. Adding them to antistatic and thermal-insulating composite materials can enhance the composite's electrical conductivity. Structural or surface modifications can also improve their water dispersibility. Consequently, they require less addition to the polymer matrix material (such as polyacrylate) of subsequent coatings, and the resulting coatings exhibit superior electrical conductivity and mechanical properties.
[0085] The antistatic thermal insulation composite material of the present invention is formed by compounding a lightweight material, polypyrrole and a carbon material to form a unique structure of a composite microlayer of a conductive polymer (polypyrrole) and a carbon material on the surface of the lightweight material. Through the synergistic effect between the three materials and the specific composite structure formed, the composite material has good thermal insulation and antistatic properties, and can be used as an antistatic thermal insulation filler for coatings (especially antistatic thermal insulation coatings).
[0086] In a preferred embodiment of the present invention, the carbon material includes carbon nanotubes and / or graphene oxide. Selecting carbon nanotubes, graphene oxide, and the like further improves the coating's electronic conductivity, mechanical properties, and aging resistance. Even a small amount can effectively improve the polymer's electrical conductivity, impact resistance, and aging resistance.
[0087] As an optional embodiment of the technical solution of the present invention, the mass ratio between the lightweight material, polypyrrole and carbon material is (1.2-1.5): (0.5-0.8): (0.08-0.2), preferably (1.2-1.4): (0.5-0.7): (0.1-0.2), and more preferably 1.3: 0.6: 0.1. When the mass ratio between the lightweight material, polypyrrole and carbon material is within the above-mentioned specific range, it is beneficial for the polypyrrole and carbon material to be better composited on the lightweight material, maximizing the composite efficiency and thus reducing unnecessary waste of materials, and the composite material formed is better dispersed in the coating as an antistatic and thermal insulation filler, which helps to improve the antistatic and thermal insulation properties of the coating. However, when the mass ratio between the lightweight material, polypyrrole and carbon material is not within the above-mentioned specific range, it is not conducive to the polypyrrole and carbon material to be better composited on the lightweight material, or when there is too much carbon material, the color of the coating will become irreversible black, thereby limiting the application of the coating. Therefore, typical but non-limiting mass ratios of lightweight material, polypyrrole and carbon material are 1.2:0.5:0.08, 1.2:0.5:0.1, 1.2:0.5:0.15, 1.2:0.5:0.2, 1.2:0.6:0.1, 1.2:0.6:0.2, 1.2:0.7:0.1, 1.2:0.7:0.2, 1.2:0.8:0.1, 1.2:0.8:0.2, 1.3:0.5:0.08, 1.3:0.5:0.1, 1.3:0 .5:0.2, 1.3:0.6:0.1, 1.3:0.6:0.2, 1.3:0.7:0.1, 1.3:0.7:0.2, 1.3:0.8:0.1, 1.3:0.8:0.2, 1.4:0.5:0.08, 1.4:0.6:0.1, 1.4:0.7:0.1, 1.4:0.8:0.2, 1.5:0.6:0.1, 1.5:0.6:0.2, 1.5:0.7:0.2 or 1.5:0.8:0.2, etc.
[0088] By further limiting the mass ratio of each component in the antistatic thermal insulation composite material, the lightweight material is composited more evenly with the polypyrrole and carbon material, thereby better improving the thermal insulation and antistatic properties of the coating.
[0089] According to a second aspect of the present invention, there is provided a method for preparing the above-mentioned antistatic heat-insulating composite material, comprising the following steps:
[0090] (a) providing a pyrrole aqueous solution, a ferric chloride p-toluenesulfonic acid mixed solution, and a carbon material dispersion;
[0091] (b) mixing the lightweight material with the pyrrole aqueous solution, then adding the ferric chloride p-toluenesulfonic acid mixed solution and the carbon material dispersion to carry out a polymerization reaction, after the reaction is completed, the obtained product is subjected to solid-liquid separation, and the separated solid product is dried to obtain an antistatic heat-insulating composite material composed of the lightweight material, polypyrrole and carbon material. The process flow diagram is shown in FIG. Figure 1 shown.
[0092] Specifically, the ferric chloride-toluenesulfonic acid mixed solution mainly uses ferric chloride as an oxidant and p-toluenesulfonic acid (TsOH) as a dopant, which is beneficial to the in-situ polymerization of pyrrole.
[0093] This preparation method realizes the composite of lightweight material, polypyrrole and carbon material by in situ polymerization, forming a unique structure of composite microlayer of conductive polymer (polypyrrole) and carbon material on the surface of lightweight material. Through the synergistic effect between the three materials and the specific composite structure formed, the composite material has good thermal insulation and antistatic properties, and can be used as an antistatic thermal insulation filler for coatings (especially antistatic thermal insulation coatings). The composite material prepared by this method has excellent mechanical properties and interfacial strength, can enhance the effect of polypyrrole and carbon material on coating, and improve its comprehensive performance. In addition, the in situ polymerization technology can form a thin and uniform polymer electrolyte (polypyrrole), so when polymerizing lightweight material, carbon material and pyrrole, polypyrrole and carbon material can be effectively polymerized on the surface of lightweight material, enhancing the common performance of the material.
[0094] As an optional embodiment of the technical solution of the present invention, in step (a), the pyrrole aqueous solution is prepared by mixing water (e.g., deionized water) with pyrrole, and then ultrasonicating the mixed solution in an ultrasonic instrument for 15-30 minutes (e.g., 15 minutes, 20 minutes, 25 minutes, or 30 minutes, etc.) to fully mix the water and pyrrole.
[0095] As an optional embodiment of the technical solution of the present invention, in step (a), the molar concentration of pyrrole in the pyrrole aqueous solution is 0.1M-0.8M; typical but non-limiting molar concentrations are 0.1M, 0.2M, 0.3M, 0.4M, 0.5M, 0.6M, 0.7M or 0.8M, etc.
[0096] As an optional embodiment of the technical solution of the present invention, in step (a), the preparation of the ferric chloride and p-toluenesulfonic acid mixed solution: water (such as deionized water) is mixed with ferric chloride and p-toluenesulfonic acid to prepare a ferric chloride and p-toluenesulfonic acid mixed solution with a molar concentration of 0.1-0.8M.
[0097] As an optional embodiment of the technical solution of the present invention, in step (a), in the ferric chloride and p-toluenesulfonic acid mixed solution, the molar concentration of ferric chloride is 0.1M-0.8M, and the molar concentration of p-toluenesulfonic acid is 0.1M-0.8M. Typical but non-limiting molar concentrations of ferric chloride are 0.1M, 0.2M, 0.3M, 0.4M, 0.5M, 0.6M, 0.7M or 0.8M, etc. Typical but non-limiting molar concentrations of p-toluenesulfonic acid are 0.1M, 0.2M, 0.3M, 0.4M, 0.5M, 0.6M, 0.7M or 0.8M, etc.
[0098] As an optional embodiment of the technical solution of the present invention, in step (a), the method for preparing the carbon material dispersion includes: mixing the carbon material with water (e.g., deionized water), and then ultrasonically dispersing the mixture for 20-40 minutes (e.g., 20 minutes, 25 minutes, 30 minutes, 35 minutes or 40 minutes, etc.) to obtain a carbon material dispersion.
[0099] As an optional embodiment of the technical solution of the present invention, in step (a), the mass concentration of the carbon material in the carbon material dispersion is 1-10 mg / ml, and a typical but non-limiting mass concentration is 1 mg / ml, 2 mg / ml, 5 mg / ml, 6 mg / ml, 8 mg / ml or 10 mg / ml, etc.
[0100] As an optional embodiment of the technical solution of the present invention, in step (b), the mass ratio of the lightweight material to the mass ratio of the pyrrole aqueous solution is 5%-10%, and a typical but non-limiting mass ratio is 5%, 6%, 7%, 8%, 9% or 10%, etc.
[0101] As an optional embodiment of the technical solution of the present invention, in step (b), the total mass ratio of ferric chloride and p-toluenesulfonic acid in the ferric chloride-p-toluenesulfonic acid mixed solution to the pyrrole aqueous solution is 45-60%. Typical but non-limiting mass ratios are 45%, 48%, 50%, 52%, 55%, 58% or 60%.
[0102] As an optional embodiment of the technical solution of the present invention, in step (b), the mass ratio of the carbon material dispersion to the pyrrole aqueous solution is 5-15%, and a typical but non-limiting mass ratio is 5%, 6%, 7%, 8%, 9%, 10%, 12%, 14% or 15%, etc.
[0103] By limiting the concentrations of the pyrrole aqueous solution, the ferric chloride-toluenesulfonic acid mixed solution, and the carbon material dispersion, as well as the relative amounts of the lightweight material and the above solutions or dispersions, the mass ratio of each component in the obtained antistatic thermal insulation composite material is kept within a specific numerical range, thereby allowing the pyrrole to be more effectively polymerized into the antistatic material polypyrrole and better composited with the carbon material on the lightweight material.
[0104] The polymerization reaction conditions of the present invention do not need to be too harsh and can usually be completed at room temperature. As an optional embodiment of the technical solution of the present invention, in step (b), the polymerization reaction temperature is 15-30°C and the polymerization reaction time is 1-3h. Typical but non-limiting polymerization reaction temperatures are 15°C, 18°C, 20°C, 25°C, 28°C or 30°C, and typical but non-limiting times are 1h, 1.5h, 2h, 2.5h or 3h, etc. The above reaction conditions are mild and easy to implement.
[0105] As an optional embodiment of the technical solution of the present invention, in step (b), the drying is vacuum drying, and the vacuum drying temperature is 50-90°C. Typical but non-limiting vacuum drying temperatures are 50°C, 60°C, 70°C, 80°C or 90°C, etc.
[0106] According to a third aspect of the present invention, there is also provided an antistatic thermal insulation (insulation) coating, which comprises the following components in the following mass fractions, based on the total mass of the antistatic thermal insulation coating being 100%:
[0107] Polyacrylate 30%-40%, titanium dioxide 10%-15%, antistatic thermal insulation filler 0.2%-3%, hydrophilic aerogel 0.1%-0.2%, diatomaceous earth 1%-4%, defoamer 1%-4%, film-forming aid 1%-5%, dispersant 0.1%-1.5% and water 30%-55%;
[0108] Among them, polyacrylate is mainly used as the base material of the antistatic thermal insulation coating to form a film. The polyacrylate can be a conventional polyacrylate emulsion in the art. Preferably, the polyacrylate includes Vitrimer xylose polyacrylate, which was first proposed by the inventors. The structural formula is shown in formula (a):
[0109]
[0110] In formula (a), R is selected from an alkyl group having 1 to 3 carbon atoms, such as -CH3, -CH2CH3 or -CH2CH2CH3.
[0111] The inventors have found through a large number of practices that when the polyacrylate in the coating is partially or entirely made of Vitrimer xylose polyacrylate with a specific structure, the mechanical properties (such as strength, adhesion, hardness, wear resistance, etc.) and thermal stability of the antistatic thermal insulation coating are significantly improved, mainly due to the introduction of xylose structure and disulfide bonds. Among them, the introduction of xylose structure can significantly enhance the bio-based characteristics, mechanical properties, thermal stability, etc. of the polymer. When the Vitrimer xylose polyacrylate containing xylose structure is used as the base material of the coating, the strength, adhesion, hardness and thermal stability of the coating (coating) are significantly improved relative to conventional polyacrylates. At the same time, since the xylose structure is derived from a bio-based material, it is harmless to nature and has a low cost, so the Vitrimer xylose polyacrylate made therefrom is also more environmentally friendly, while also reducing the production cost of the Vitrimer xylose polyacrylate.
[0112] The disulfide bond has high thermal stability and can remain stable within a certain temperature range, which can improve the thermal stability and heat resistance of Vitrimer xylose polyacrylate; at the same time, the introduction of disulfide bonds can increase the cross-linking density of Vitrimer xylose polyacrylate, thereby improving its mechanical properties, such as strength, hardness, adhesion and wear resistance (durability).
[0113] Given the above-mentioned characteristics of xylose structure and disulfide bonds, when Vitrimer xylose polyacrylate is used as the base material of the coating, the mechanical properties such as strength, hardness, adhesion, wear resistance and thermal stability of the coating can be significantly improved, making the coating more suitable for application scenarios with high temperature and high mechanical performance requirements (such as heat-resistant coatings, heat-resistant composite materials, etc.).
[0114] Typical but non-limiting mass fractions of polyacrylate are 30%, 32%, 34%, 35%, 36%, 38% or 40%, etc.
[0115] Titanium dioxide's primary functions in antistatic thermal insulation coatings include whitening, improving hiding power, and enhancing lightfastness and weather resistance. As a pigment, titanium dioxide possesses a high refractive index, strong tinting power, and good hiding power, making coatings more vibrant and enhancing the overall visual quality. Furthermore, titanium dioxide enhances adhesion, prevents sagging, and provides UV shielding, protecting the coating from UV damage. Typical, but not limiting, mass fractions of titanium dioxide are 10%, 11%, 12%, 13%, 14%, or 15%.
[0116] Antistatic thermal insulation fillers mainly use raw materials that can further enhance the antistatic ability and thermal insulation performance of the coating. Preferably, the functional material adopts the antistatic thermal insulation composite material provided by the first aspect of the present invention. Since the antistatic thermal insulation composite material itself has excellent electrical conductivity, when it is added to the coating, a conductive network can be formed in the coating, which can effectively reduce the resistivity of the coating, thereby preventing the occurrence of static electricity accumulation and discharge. At the same time, since the antistatic thermal insulation composite material also has good thermal insulation performance, it is added to the coating as an antistatic thermal insulation filler, which can not only increase the antistatic ability of the coating, but also improve the thermal insulation performance of the coating. The mass fraction of the antistatic thermal insulation filler should not be too low (less than 0.2%), otherwise it will easily lead to a decrease in thermal insulation performance and antistatic performance. The mass fraction of the antistatic thermal insulation filler should not be too high (higher than 3%), otherwise it will easily cause the coating to crack and fall off after drying and film formation. Therefore, the typical but non-restrictive mass fraction of the antistatic thermal insulation filler is 0.2%, 0.4%, 0.5%, 0.6%, 0.8%, 1.0%, 1.2%, 1.4%, 1.5%, 1.6%, 1.8%, 2%, 2.2%, 2.4%, 2.5%, 2.6%, 2.8% or 3.0%, etc.
[0117] The main function of the hydrophilic aerogel in the antistatic thermal insulation coating is to improve the thermal insulation performance of the coating. The typical but non-limiting mass fraction of the hydrophilic aerogel is 0.1%, 0.12%, 0.14%, 0.15%, 0.18% or 0.2%, etc.
[0118] Diatomaceous earth is primarily used as a filler in antistatic thermal insulation coatings. Its porosity effectively removes harmful substances from the air. Typical, but not limiting, mass fractions of diatomaceous earth are 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, or 4%.
[0119] In addition to adding the above-mentioned main ingredients, a certain amount of functional additives, such as defoaming agents, film-forming agents or dispersants, also need to be added.
[0120] Typical but non-limiting mass fractions of defoamers are 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, or 4%, etc. Typical but non-limiting mass fractions of film-forming aids are 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, or 5%, etc. Typical but non-limiting mass fractions of dispersants are 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1%, 1.1%, 1.2%, 1.4%, or 1.5%, etc.
[0121] The antistatic thermal insulation coating provided by the present invention is mainly made of raw materials such as polyacrylate, titanium dioxide, antistatic thermal insulation filler, hydrophilic aerogel, diatomaceous earth, defoaming agent, film-forming aid, dispersant and water. Preferably, the polyacrylate includes Vitrimer xylose polyacrylate with a specific structure. The xylose structure and disulfide bond are simultaneously introduced into the structure of Vitrimer xylose polyacrylate, which can improve the mechanical strength, hardness, adhesion and heat resistance of the polymer itself, thereby significantly improving the mechanical properties, thermal stability and durability of the coating (coating); and / or the antistatic thermal insulation filler is the antistatic thermal insulation composite material provided by the first aspect of the present invention or the antistatic thermal insulation composite material prepared by the method of the second aspect.
[0122] Furthermore, the present invention adopts antistatic thermal insulation composite materials as antistatic thermal insulation fillers. The antistatic thermal insulation fillers cooperate with other raw materials such as polyacrylate to make the prepared coating have both good antistatic and thermal insulation properties, which can meet the needs of application scenarios with higher requirements for antistatic and thermal insulation properties.
[0123] As a preferred embodiment of the technical solution of the present invention, based on the total mass of the antistatic thermal insulation coating as 100%, the antistatic thermal insulation coating includes the following components in mass fractions: 35%-40% polyacrylate, 12%-15% titanium dioxide, 0.5%-2.5% antistatic thermal insulation filler, 0.1%-0.2% hydrophilic aerogel, 2%-4% diatomaceous earth, 2%-4% defoaming agent, 2%-5% film-forming aid, 0.5%-1.5% dispersant, and water makes up the balance.
[0124] As an optional implementation of the technical solution of the present invention, the hydrophilic aerogel includes silica aerogel.
[0125] As an optional implementation of the technical solution of the present invention, the defoaming agent includes at least one of n-butanol, silicone defoaming agent or polyether defoaming agent, and is preferably n-butanol.
[0126] As an optional embodiment of the technical solution of the present invention, the film-forming aid includes at least one of ethylene glycol, propylene glycol butyl ether, hydrocarbons or dodecyl alcohol esters, etc., preferably ethylene glycol.
[0127] As an optional embodiment of the technical solution of the present invention, the dispersant includes at least one of SN5040 dispersant, a cationic wetting dispersant or a non-ionic dispersant, preferably SN5040 dispersant.
[0128] The polyacrylate in the coating can be entirely Vitrimer xylose polyacrylate with a specific cross-linked structure, or part of it can be Vitrimer xylose polyacrylate and the other part can be conventional polyacrylate commercially available in the art. As a preferred embodiment of the technical solution of the present invention, the polyacrylate is Vitrimer xylose polyacrylate.
[0129] As an optional embodiment of the technical solution of the present invention, the preparation method of Vitrimer xylose polyacrylate comprises the following steps:
[0130] S1. Mixing an alcohol solution containing xylose and acryloyl chloride and reacting them in the presence of an alkaline catalyst, wherein the specific reaction formula is shown in formula (1) to obtain xylose acrylate;
[0131]
[0132] S2 xylose acrylate, acrylate monomer, initiator and solvent are mixed and polymerized under a nitrogen atmosphere. The specific reaction formula is shown in formula (2) to obtain a polymerization product.
[0133] adding a precipitation-promoting agent to the obtained polymerization product to precipitate the xylose polyacrylate generated by the polymerization reaction, and then filtering, washing and drying to obtain the xylose polyacrylate;
[0134]
[0135] S3. Xylose polyacrylate and 2,2'-dithiodiethanol are mixed and reacted under the action of a cross-linking agent. The specific reaction formula is shown in formula (3), thereby obtaining Vitrimer xylose polyacrylate.
[0136]
[0137] In step S3, dithiodiethanol can react with the hydroxyl groups in the polymer (xylose polyacrylate) chain through its disulfide bond, introducing the disulfide bond into the main chain or side chain to form a cross-linked structure. 2,2'-dithiodiethanol can be purchased or prepared by yourself. Taking self-preparation as an example, the following description is provided:
[0138] a. Select a sulfur-containing monomer: using a monomer with a thiol group (-SH), such as dimercaptoethanol;
[0139] b. Oxidation: The thiol groups on the thiol-bearing monomers are oxidized to form disulfide bonds. Common oxidants include oxygen, hydrogen peroxide, or iodine. The reaction conditions must be mild to avoid damaging other functional groups, as shown in Formula (4):
[0140]
[0141] As an optional embodiment of the technical solution of the present invention, in step S1, the mass ratio of xylose and acryloyl chloride in the alcohol solution containing xylose is (1-3): (1-3), for example, 1:1, 1:2, 1:3, 2:1, 2:3, 3:1 or 3:2;
[0142] and / or, in step S1, the alkaline catalyst comprises sodium hydroxide;
[0143] And / or, in step S1, the reaction temperature is 50-100°C, for example, 50°C, 60°C, 70°C, 80°C, 90°C or 100°C, preferably 60°C, and the reaction time is 2-6h, for example, 2h, 3h, 4h, 5h or 6h.
[0144] As an optional embodiment of the technical solution of the present invention, in step S2, the molar ratio of xylose acrylate and acrylate monomer is (1-3): (1-3), for example, 1:1, 1:2, 1:3, 2:1, 2:3, 3:1 or 3:2, etc., preferably 1:1;
[0145] And / or, in step S2, the polymerization reaction temperature is 50-100°C, for example, 50°C, 60°C, 70°C, 80°C, 90°C or 100°C, preferably 60°C, and the reaction time is 2-10h, for example, 2h, 3h, 4h, 5h, 6h, 7h, 8h, 9h or 10h, and the polymerization reaction is terminated by adding a terminator such as hydroquinone.
[0146] As an optional embodiment of the technical solution of the present invention, in step S3, the molar ratio of xylose polyacrylate and 2,2'-dithiodiethanol is (1-4): (2-4), for example, 1:2, 1:3, 1:4, 2:2, 2:3, 2:4, 3:2, 3:4, 4:2 or 4:3;
[0147] and / or, in step S3, the cross-linking agent comprises cystamine;
[0148] And / or, in step S3, the reaction temperature is 50-100° C., for example, 50° C., 60° C., 70° C., 80° C., 90° C., or 100° C., and the reaction time is 2-6 hours, for example, 2 hours, 3 hours, 4 hours, 5 hours, or 6 hours. There is no specific limitation on the molecular weight of the Vitrimer xylose polyacrylate. The mechanical properties and thermal stability of the polymer can be controlled by adjusting the structure and ratio of structural units such as xylose and acrylate structures according to actual needs, so that it can meet the needs of more different application scenarios. As an optional embodiment of the technical solution of the present invention, the molecular weight of Vitrimer xylose polyacrylate is 10,000-150,000 g / mol, for example, 10,000 g / mol, 40,000 g / mol, 50,000 g / mol, 80,000 g / mol, 100,000 g / mol, 120,000 g / mol, 140,000 g / mol or 150,000 g / mol, etc.
[0149] As an optional embodiment of the technical solution of the present invention, the antistatic resistance value of the antistatic thermal insulation coating is 10 6 -10 9 Ω, for example, 10 6 Ω, 10 7 Ω, 10 8 Ω or 10 9 Ω, etc., preferably 10 6 -10 8 Ω.
[0150] According to a fourth aspect of the present invention, there is also provided a method for preparing the above-mentioned antistatic thermal insulation coating, comprising the following steps:
[0151] Titanium dioxide, hydrophilic aerogel, diatomaceous earth and a portion of the formulated amount of water are stirred and mixed once to obtain a mixed solution I;
[0152] Adding a portion of the defoaming agent and a portion of the film-forming aid to the mixed solution I and stirring and mixing them a second time to obtain a mixed solution II;
[0153] Adding polyacrylate to the mixed solution II and stirring for three times to obtain a mixed solution III;
[0154] Add the dispersion formed by the antistatic thermal insulation filler and the remaining amount of water, the dispersant, the remaining amount of defoaming agent and the remaining amount of film-forming aid to the mixed solution III and stir and mix them four times to obtain the antistatic thermal insulation coating. The preparation process diagram is shown in FIG. Figure 1 shown.
[0155] The preparation method of the antistatic thermal insulation coating provided by the present invention adopts a specific adding sequence, which is conducive to the coating being well dispersed and not easy to form particles or lumps, and is conducive to improving the overall performance of the coating.
[0156] As an optional embodiment of the technical solution of the present invention, the time for a single stirring and mixing is 1-10 minutes, and the stirring speed is 500-800 r / min. Typical but non-limiting stirring and mixing times are 1 minute, 2 minutes, 3 minutes, 5 minutes, 6 minutes, 8 minutes, or 10 minutes, and typical but non-limiting stirring speeds are 500 r / min, 550 r / min, 600 r / min, 650 r / min, 700 r / min, 750 r / min, or 800 r / min, etc.
[0157] As an optional embodiment of the technical solution of the present invention, the secondary stirring and mixing time is 10-30 minutes, and the stirring speed is 500-800 r / min. Typical but non-limiting secondary stirring and mixing times are 10 minutes, 15 minutes, 20 minutes, 25 minutes, 28 minutes, or 30 minutes, and typical but non-limiting stirring speeds are 500 r / min, 550 r / min, 600 r / min, 650 r / min, 700 r / min, 750 r / min, or 800 r / min.
[0158] As an optional embodiment of the technical solution of the present invention, the three stirring and mixing times are 30-60 minutes, and the stirring speed is 500-800 r / min. Typical but non-limiting three stirring and mixing times are 30 minutes, 35 minutes, 40 minutes, 45 minutes, 50 minutes, 55 minutes or 60 minutes, and typical but non-limiting stirring speeds are 500 r / min, 550 r / min, 600 r / min, 650 r / min, 700 r / min, 750 r / min or 800 r / min, etc.
[0159] As an optional embodiment of the technical solution of the present invention, the time for the four stirring and mixing is 60-120 minutes, and the stirring speed is 450-750 r / min. Typical but non-limiting examples of the four stirring and mixing times are 60 minutes, 70 minutes, 80 minutes, 90 minutes, 100 minutes, 110 minutes, or 120 minutes, and typical but non-limiting examples of the stirring speed are 450 r / min, 500 r / min, 550 r / min, 600 r / min, 650 r / min, 700 r / min, or 750 r / min, etc.
[0160] According to the fifth aspect of the present invention, there is also provided a coating, which is formed by coating the antistatic thermal insulation coating provided by the third aspect of the present invention or the antistatic thermal insulation coating prepared by the preparation method provided by the fourth aspect of the present invention.
[0161] The coating provided by the present invention can be a single-layer coating or a multi-layer coating. The multi-layer coating can be obtained by applying the antistatic thermal insulation coating of the present invention multiple times, or the antistatic thermal insulation coating of the present invention can be used as a primer and other coating compositions can be used as a topcoat, or other coating compositions can be used as a primer and the antistatic thermal insulation coating of the present invention can be used as a topcoat.
[0162] The coating provided by the present invention not only has good antistatic and thermal insulation properties, but also has good mechanical properties such as adhesion to the substrate (base material) or primer, and is not prone to peeling off after long-term use.
[0163] The present invention will be further described in detail below with reference to specific examples and comparative examples. It should be noted that in the following examples and comparative examples, the density of the defoaming agent n-butanol is 0.808 g / ml, the density of the film-forming aid ethylene glycol is 1.111 g / ml, and the density of the dispersant SN5040 is 1.25 g / cm 3 .
[0164] Example 1
[0165] This embodiment provides an antistatic heat-insulating composite material (hollow glass microspheres / polypyrrole / graphene oxide, abbreviated as HPG), which is mainly composed of lightweight materials, polypyrrole and carbon materials;
[0166] Among them, the lightweight material is hollow glass microspheres (average particle size 80μm), the carbon material is graphene oxide (sheet diameter 60-200nm), and the mass ratio of the lightweight material, polypyrrole and carbon material is 1.3:0.6:0.1.
[0167] This embodiment provides a method for preparing an antistatic heat-insulating composite material, comprising the following steps:
[0168] S1. Preparation of pyrrole aqueous solution: Add 50 ml of deionized water and 1750 μl of pyrrole to a clean beaker, and ultrasonicate the mixed solution for 15 min to fully mix the water and pyrrole to obtain a 0.5 M pyrrole aqueous solution.
[0169] S2. Preparation of ferric chloride p-toluenesulfonic acid solution: Weigh 13.52 g of ferric chloride and 9.51 g of p-toluenesulfonic acid in a beaker, add 40 ml of water to dissolve, pour into a 100 ml volumetric flask and adjust to volume to obtain 100 ml of ferric chloride p-toluenesulfonic acid solution, the molar concentration of ferric chloride in the ferric chloride p-toluenesulfonic acid solution is 0.5 M, and the molar concentration of p-toluenesulfonic acid is 0.5 M.
[0170] S3. Carbon material dispersion: A graphene oxide aqueous dispersion in a liquid state is used, and the concentration of graphene oxide in the graphene oxide aqueous dispersion is 2 mg / mL.
[0171] S4. In situ polymerization of pyrrole: Weigh 3g of hollow glass microspheres and put them into the pyrrole aqueous solution and stir them evenly in a magnetic stirrer for 30min. Then, take 50ml of the mixed solution of ferric chloride and p-toluenesulfonic acid and slowly pour it into the pyrrole aqueous solution. Then, add 6mL of graphene oxide aqueous dispersion and slowly stir on the stirrer at room temperature (15-25℃) for 2h to carry out the polymerization reaction. After the reaction is completed, the sample needs to be taken out and the water needs to be filtered with a vacuum pump. Then, it is dried in a vacuum drying oven at 70℃. After drying, the sample is ground into powder (particle size is 50-90μm) to obtain an antistatic thermal insulation composite material.
[0172] Example 2
[0173] This embodiment provides an antistatic heat-insulating composite material (expanded microspheres / polypyrrole / graphene oxide, abbreviated as TPG), which is mainly composed of a lightweight material, polypyrrole, and a carbon material;
[0174] Among them, the lightweight material is expanded microspheres (particle size range is 15-25μm), the carbon material is graphene oxide (sheet diameter is 60-200nm), and the mass ratio of the lightweight material, polypyrrole and carbon material is 1.3:0.6:0.1.
[0175] The preparation method of the antistatic heat-insulating composite material of this embodiment is the same as that of Example 1, except that the hollow glass microspheres in the preparation method of Example 1 are replaced by expanded microspheres. Other raw materials, amounts used, and preparation methods are the same as those of Example 1.
[0176] Example 3
[0177] This embodiment provides an antistatic thermal insulation coating (abbreviated as P-HPG (2.0)), which includes the following components in the following mass fractions, based on the total mass of the antistatic thermal insulation coating being 100%:
[0178] Polyacrylate 38.7%, titanium dioxide 13.2%, antistatic thermal insulation filler 2.0%, hydrophilic aerogel 0.2%, diatomaceous earth 3.1%, defoamer 3.3%, film-forming aid 4.5%, dispersant 1.3%, and water makes up the balance.
[0179] The antistatic heat-insulating composite material provided in Example 1 is used as the antistatic heat-insulating filler, and the polyacrylate is a polyacrylate with a solid content of 55% (acrylate copolymer emulsion, purchased from Jiangsu Sanmu Group Co., Ltd., product brand: SM-100), the hydrophilic aerogel is silica aerogel (particle size range is 15-50 μm), the defoaming agent is n-butanol, the film-forming aid is ethylene glycol, and the dispersant is SN5040 dispersant.
[0180] The preparation method of the antistatic thermal insulation coating comprises the following steps:
[0181] (a) Weighing 13 g of titanium dioxide, 0.2 g of hydrophilic aerogel, and 3 g of diatomaceous earth, sequentially poured into a three-necked flask, added 23 mL of deionized water, and then turned on the stirrer and stirred once for 10 minutes at a stirring speed of 650 r / min to obtain a mixed solution I;
[0182] (b) adding 2 mL of defoamer and 2 mL of film-forming aid to the mixed solution I, and stirring for a second time (high speed) for 30 minutes at a stirring speed of 650 r / min to obtain a mixed solution II;
[0183] (c) Adding 38 mL of polyacrylate to mixed solution II, stirring and dispersing the mixture three times (at a low speed), stirring and dispersing the mixture for 60 minutes, and then stirring at a speed of 450 rpm to obtain mixed solution III;
[0184] (d) Add 2.0 g of antistatic thermal insulation filler to the mixed solution III. The antistatic thermal insulation filler needs to be added after ultrasonic dispersion with 10 mL of deionized water. Finally, add 1 mL of dispersant, 2 mL of defoaming agent and 2 mL of film-forming aid. Stir at a low speed for 120 minutes. The stirring speed is 450 r / min, and the mixture is poured out to obtain an antistatic thermal insulation coating (about 98.1 g).
[0185] Example 4
[0186] This embodiment provides an antistatic thermal insulation coating (abbreviated as P-HPG (1.5)), which includes the following components in the following mass fractions, based on the total mass of the antistatic thermal insulation coating being 100%:
[0187] Polyacrylate 38.7%, titanium dioxide 13.2%, antistatic thermal insulation filler 1.5%, hydrophilic aerogel 0.2%, diatomaceous earth 3.1%, defoamer 3.3%, film-forming aid 4.5%, dispersant 1.3%, and water makes up the balance.
[0188] The antistatic heat-insulating composite material provided in Example 1 is used as the antistatic heat-insulating filler, and the polyacrylate is a polyacrylate with a solid content of 55% (acrylate copolymer emulsion, purchased from Jiangsu Sanmu Group Co., Ltd., product brand: SM-100), the hydrophilic aerogel is silica aerogel (particle size range is 15-50 μm), the defoaming agent is n-butanol, the film-forming aid is ethylene glycol, and the dispersant is SN5040 dispersant.
[0189] The preparation method of the antistatic thermal insulation coating is the same as that of Example 3, except that the amount of antistatic thermal insulation filler in step (d) is adjusted from 2.0 g to 1.5 g, and the amount of deionized water is adjusted accordingly to keep the total mass of the antistatic thermal insulation coating unchanged.
[0190] Example 5
[0191] This embodiment provides an antistatic thermal insulation coating (abbreviated as P-HPG (1.0)), which includes the following components in the following mass fractions, based on the total mass of the antistatic thermal insulation coating being 100%:
[0192] Polyacrylate 38.7%, titanium dioxide 13.2%, antistatic thermal insulation filler 1.0%, hydrophilic aerogel 0.2%, diatomaceous earth 3.1%, defoaming agent 3.3%, film-forming aid 4.5%, dispersant 1.3%, water makes up the balance.
[0193] The antistatic heat-insulating composite material provided in Example 1 is used as the antistatic heat-insulating filler, and the polyacrylate is a polyacrylate with a solid content of 55% (acrylate copolymer emulsion, purchased from Jiangsu Sanmu Group Co., Ltd., product brand: SM-100), the hydrophilic aerogel is silica aerogel (particle size range is 15-50 μm), the defoaming agent is n-butanol, the film-forming aid is ethylene glycol, and the dispersant is SN5040 dispersant.
[0194] The preparation method of the antistatic thermal insulation coating is the same as that of Example 3, except that the amount of antistatic thermal insulation filler in step (d) is adjusted from 2.0 g to 1.0 g, and the amount of deionized water is adjusted accordingly to keep the total mass of the antistatic thermal insulation coating unchanged.
[0195] Example 6
[0196] This embodiment provides an antistatic thermal insulation coating (abbreviated as P-HPG (0.5)), which includes the following components in the following mass fractions, based on the total mass of the antistatic thermal insulation coating being 100%:
[0197] Polyacrylate 38.7%, titanium dioxide 13.2%, antistatic thermal insulation filler 0.5%, hydrophilic aerogel 0.2%, diatomaceous earth 3.1%, defoamer 3.3%, film-forming aid 4.5%, dispersant 1.3%, and water makes up the balance.
[0198] The antistatic heat-insulating composite material provided in Example 1 is used as the antistatic heat-insulating filler, and the polyacrylate is a polyacrylate with a solid content of 55% (acrylate copolymer emulsion, purchased from Jiangsu Sanmu Group Co., Ltd., product brand: SM-100), the hydrophilic aerogel is silica aerogel (particle size range is 15-50 μm), the defoaming agent is n-butanol, the film-forming aid is ethylene glycol, and the dispersant is SN5040 dispersant.
[0199] The preparation method of the antistatic thermal insulation coating is the same as that of Example 3, except that the amount of antistatic thermal insulation filler in step (d) is adjusted from 2.0 g to 0.5 g, and the amount of deionized water is adjusted accordingly to keep the total mass of the antistatic thermal insulation coating unchanged.
[0200] Example 7
[0201] This embodiment provides an antistatic thermal insulation coating (abbreviated as P-TPG (2.0)), which includes the following components in the following mass fractions, based on the total mass of the antistatic thermal insulation coating being 100%:
[0202] Polyacrylate 38.7%, titanium dioxide 13.2%, antistatic thermal insulation filler 2%, hydrophilic aerogel 0.2%, diatomaceous earth 3.1%, defoaming agent 3.3%, film-forming aid 4.5%, dispersant 1.3%, water makes up the balance.
[0203] The antistatic heat-insulating composite material provided in Example 2 is used as the antistatic heat-insulating filler, and the polyacrylate is a polyacrylate with a solid content of 55% (acrylate copolymer emulsion, purchased from Jiangsu Sanmu Group Co., Ltd., product brand: SM-100), the hydrophilic aerogel is silica aerogel (particle size range is 15-50 μm), the defoaming agent is n-butanol, the film-forming aid is ethylene glycol, and the dispersant is SN5040 dispersant.
[0204] The preparation method of the antistatic thermal insulation coating is the same as that of Example 3, except that in step (d), the type of antistatic thermal insulation filler is adjusted from the antistatic thermal insulation composite material HPG provided in Example 1 to the antistatic thermal insulation composite material TPG provided in Example 2, and the mass of the antistatic thermal insulation filler remains 2.0 g. The remaining raw materials, amounts and preparation methods are the same as those of Example 3.
[0205] Example 8
[0206] This embodiment provides an antistatic thermal insulation coating (abbreviated as P-TPG (1.5)), which includes the following components in the following mass fractions, based on the total mass of the antistatic thermal insulation coating being 100%:
[0207] Polyacrylate 38.7%, titanium dioxide 13.2%, antistatic thermal insulation filler 1.5%, hydrophilic aerogel 0.2%, diatomaceous earth 3.1%, defoamer 3.3%, film-forming aid 4.5%, dispersant 1.3%, and water makes up the balance.
[0208] The antistatic heat-insulating composite material provided in Example 2 is used as the antistatic heat-insulating filler, and the polyacrylate is a polyacrylate with a solid content of 55% (acrylate copolymer emulsion, purchased from Jiangsu Sanmu Group Co., Ltd., product brand: SM-100), the hydrophilic aerogel is silica aerogel (particle size range is 15-50μm), the defoaming agent is n-butanol, the film-forming aid is ethylene glycol, and the dispersant is SN5040 dispersant.
[0209] The preparation method of the antistatic thermal insulation coating is the same as that of Example 7, except that the amount of antistatic thermal insulation filler in step (d) is adjusted from 2.0 g to 1.5 g, and the amount of deionized water is adjusted accordingly to keep the total mass of the antistatic thermal insulation coating unchanged.
[0210] Example 9
[0211] This embodiment provides an antistatic thermal insulation coating (abbreviated as P-TPG (1.0)), which includes the following components in the following mass fractions, based on the total mass of the antistatic thermal insulation coating being 100%:
[0212] Polyacrylate 38.7%, titanium dioxide 13.2%, antistatic thermal insulation filler 1.0%, hydrophilic aerogel 0.2%, diatomaceous earth 3.1%, defoaming agent 3.3%, film-forming aid 4.5%, dispersant 1.3%, water makes up the balance.
[0213] The antistatic heat-insulating composite material provided in Example 2 is used as the antistatic heat-insulating filler, and the polyacrylate is a polyacrylate with a solid content of 55% (acrylate copolymer emulsion, purchased from Jiangsu Sanmu Group Co., Ltd., product brand: SM-100), the hydrophilic aerogel is silica aerogel (particle size range is 15-50 μm), the defoaming agent is n-butanol, the film-forming aid is ethylene glycol, and the dispersant is SN5040 dispersant.
[0214] The preparation method of the antistatic thermal insulation coating is the same as that of Example 7, except that the amount of antistatic thermal insulation filler in step (d) is adjusted from 2.0 g to 1.0 g, and the amount of deionized water is adjusted accordingly to keep the total mass of the antistatic thermal insulation coating unchanged.
[0215] Example 10
[0216] This embodiment provides an antistatic thermal insulation coating (abbreviated as P-TPG (0.5)), which includes the following components in the following mass fractions, based on the total mass of the antistatic thermal insulation coating being 100%:
[0217] Polyacrylate 38.7%, titanium dioxide 13.2%, antistatic thermal insulation filler 0.5%, hydrophilic aerogel 0.2%, diatomaceous earth 3.1%, defoamer 3.3%, film-forming aid 4.5%, dispersant 1.3%, and water makes up the balance.
[0218] The antistatic heat-insulating composite material provided in Example 2 is used as the antistatic heat-insulating filler, and the polyacrylate is a polyacrylate with a solid content of 55% (acrylate copolymer emulsion, purchased from Jiangsu Sanmu Group Co., Ltd., product brand: SM-100), the hydrophilic aerogel is silica aerogel (particle size range is 15-50 μm), the defoaming agent is n-butanol, the film-forming aid is ethylene glycol, and the dispersant is SN5040 dispersant.
[0219] The preparation method of the antistatic thermal insulation coating is the same as that of Example 7, except that the amount of antistatic thermal insulation filler in step (d) is adjusted from 2.0 g to 0.5 g, and the amount of deionized water is adjusted accordingly to keep the total mass of the antistatic thermal insulation coating unchanged.
[0220] Example 11
[0221] This embodiment provides an antistatic thermal insulation coating, except that the type of polyacrylate in Example 5 (P-HPG (1.0)) is changed to polyacrylate with a solid content of 55% (acrylate copolymer emulsion, purchased from Jiangsu Sanmu Group Co., Ltd., product brand: SM-100) was replaced by Vitrimer xylose polyacrylate, and the remaining raw materials, amounts and preparation method were the same as those in Example 5.
[0222] The structural formula of Vitrimer xylose polyacrylate in this embodiment is shown below:
[0223] Wherein R is -CH3.
[0224] The preparation method of Vitrimer xylose polyacrylate comprises the following steps:
[0225] S1. 3 g of xylose was placed in a 100 mL three-necked flask and dissolved in 12 mL of ethanol solvent to obtain an alcohol solution containing xylose;
[0226] The alcohol solution containing xylose was mixed with 4 mL of acryloyl chloride, and 0.03 g of alkaline catalyst sodium hydroxide was added, and the mixture was stirred to react at 60°C for 4 h to obtain xylose acrylate.
[0227] S2. 20.41 g of xylose acrylate (0.1 mol) and 8.609 g of methyl acrylate monomer (0.1 mol) were mixed in a three-necked flask in a molar ratio of 1:1. An appropriate amount of water was added as a solvent and stirred evenly. Then, 0.2 g of initiator benzoyl peroxide was added to the reaction solution. The reaction temperature was raised to 60°C and the reaction was carried out for 6 h. Nitrogen was required to be purged during the reaction to avoid contact with oxygen. When the reaction time was reached, the terminator hydroquinone was added to terminate the polymerization reaction. The reaction mixture was poured into a large amount of non-solvent methanol or acetone to precipitate the polymer. The precipitate was filtered and washed to remove unreacted monomer and initiator. The polymer was dried in a vacuum oven to obtain xylose polyacrylate.
[0228] S3. 20.18 g of xylose polyacrylate (0.1 mol) and 30.85 g of 2,2'-dithiodiethanol (0.2 mol) were mixed and reacted in the presence of 0.1 g of a cross-linking agent at 60°C for 6 hours to obtain Vitrimer xylose polyacrylate. Testing revealed that the molecular weight of Vitrimer xylose polyacrylate was approximately 80,000.
[0229] Example 12
[0230] This embodiment provides an antistatic thermal insulation coating, except that the type of polyacrylate in Example 9 (P-TPG (1.0)) is changed to polyacrylate with a solid content of 55% (acrylate copolymer emulsion, purchased from Jiangsu Sanmu Group Co., Ltd., product brand: SM-100) was replaced by Vitrimer xylose polyacrylate (the structure and specific preparation method were the same as those in Example 11), and the remaining raw materials, amounts and preparation methods were the same as those in Example 9.
[0231] Comparative Example 1
[0232] This comparative example provides an antistatic thermal insulation coating (abbreviated as PHPG), which includes the following components in the following mass fractions, based on the total mass of the antistatic thermal insulation coating being 100%:
[0233] Polyacrylate 38.7%, titanium dioxide 13.2%, hollow glass microspheres 1.3%, graphene oxide 0.1%, polypyrrole 0.6%, hydrophilic aerogel 0.2%, diatomaceous earth 3.1%, defoaming agent 3.3%, film-forming aid 4.5%, dispersant 1.3%, and water makes up the balance.
[0234] Among them, hollow glass microspheres, graphene oxide, and polypyrrole are used together as antistatic thermal insulation fillers, polyacrylate is polyacrylate with a solid content of 55% (acrylate copolymer emulsion), the hydrophilic aerogel is silica aerogel (particle size range is 15-50μm), the defoaming agent is n-butanol, the film-forming aid is ethylene glycol, and the dispersant is SN5040 dispersant.
[0235] The preparation method of the antistatic thermal insulation coating comprises the following steps:
[0236] (a) Weighing 13 g of titanium dioxide, 0.2 g of hydrophilic aerogel, and 3 g of diatomaceous earth, sequentially poured into a three-necked flask, added 23 mL of deionized water, and then turned on the stirrer and stirred once for 10 minutes at a stirring speed of 650 r / min to obtain a mixed solution I;
[0237] (b) adding 2 mL of defoamer and 2 mL of film-forming aid to the mixed solution I, and stirring for a second time (high speed) for 30 minutes at a stirring speed of 650 r / min to obtain a mixed solution II;
[0238] (c) Adding 38 mL of polyacrylate to mixed solution II, stirring and dispersing the mixture three times (at a low speed), stirring and dispersing the mixture for 60 minutes, and then stirring at a speed of 450 rpm to obtain mixed solution III;
[0239] (d) Add 0.1 g of graphene oxide, 0.6 g of polypyrrole and 1.3 g of hollow glass microspheres to the mixed solution III as antistatic thermal insulation fillers. The antistatic thermal insulation fillers need to be ultrasonically dispersed with 10 mL of deionized water before being added. Finally, 1 mL of dispersant, 2 mL of defoaming agent and 2 mL of film-forming aid are added and stirred at a low speed for 120 minutes. The stirring speed is 450 r / min and the mixture is poured out to obtain a preparation method for an antistatic thermal insulation coating.
[0240] Comparative Example 2
[0241] This comparative example provides an antistatic thermal insulation coating (abbreviated as THPG), which includes the following components in the following mass fractions, based on the total mass of the antistatic thermal insulation coating being 100%:
[0242] Polyacrylate 38.7%, titanium dioxide 13.2%, expanded microspheres 1.3%, graphene oxide 0.1%, polypyrrole 0.6%, hydrophilic aerogel 0.2%, diatomaceous earth 3.1%, defoaming agent 3.3%, film-forming aid 4.5%, dispersant 1.3%, and water makes up the balance.
[0243] Among them, expanded microspheres, graphene oxide, and polypyrrole are used together as antistatic thermal insulation fillers, polyacrylate is polyacrylate with a solid content of 55% (acrylate copolymer emulsion), hydrophilic aerogel is silica aerogel (particle size range is 15-50μm), defoaming agent is n-butanol, film-forming aid is ethylene glycol, and dispersant is SN5040 dispersant.
[0244] The preparation method of the antistatic thermal insulation coating is the same as that of Comparative Example 1, except that 0.1 g of graphene oxide, 0.6 g of polypyrrole and 1.3 g of expanded microspheres are used as antistatic thermal insulation fillers in step (d). Other raw materials, amounts and preparation methods are the same as those of Comparative Example 1.
[0245] In order to compare the technical effects of the above embodiments and comparative examples, the following experimental examples are specially set up. It should be noted that in the experimental results, P-HPG (2.0), P-HPG (1.5), P-HPG (1.0), P-HPG (0.5) and PHPG refer to the antistatic thermal insulation coatings provided in Example 3, Example 4, Example 5, Example 6 and Comparative Example 1, respectively. P-TPG (2.0), P-TPG (1.5), P-TPG (1.0), P-TPG (0.5) and PTPG refer to the antistatic thermal insulation coatings provided in Example 7, Example 8, Example 9, Example 10 and Comparative Example 2, respectively.
[0246] Experimental Example 1
[0247] The morphologies of the antistatic thermal insulation composite material (HPG) provided in Example 1 and the antistatic thermal insulation composite material (TPG) provided in Example 2 were detected, and their SEM images were as follows: Figure 2 and Figure 3 As shown. Figure 2 As can be seen from (a) and (b), polypyrrole and graphene oxide composites are aggregated on the surface of the hollow glass microspheres, which indicates that the in-situ composite is successful and the shape is basically spherical. Figure 3 As can be seen from (a) and (b), polypyrrole and graphene oxide composites are also aggregated on the surface of the expanded microspheres, indicating that the in situ composite is successful and the shape is basically spherical.
[0248] Taking the antistatic thermal insulation coating (P-HPG) provided in Example 3 and the antistatic thermal insulation coating (P-TPG) provided in Example 7 as examples, their morphologies were detected, and their SEM images were as follows: Figure 4 and Figure 5 As shown. Figure 4 and Figure 5 It can be seen that the composite formed by hollow glass microspheres or expanded microspheres, polypyrrole and graphene oxide is encapsulated inside the polyacrylate. After magnification 450 times, raised hollow glass microspheres or expanded microspheres can be seen on the surface, indicating that the hollow glass microsphere polymer and the expanded microsphere polymer are evenly dispersed inside the coating.
[0249] Experimental Example 2
[0250] (1) The antistatic thermal insulation coatings provided in Examples 3 to 6 and Comparative Example 1 were used as a control group, and the antistatic thermal insulation coatings provided in Examples 7 to 10 and Comparative Example 2 were used as a control group, and their infrared spectra were detected respectively. Figure 6 shown.
[0251] from Figure 6 In the infrared spectrum, graphene oxide has a wavelength of 3357 cm -1 There is a strong and broad absorption peak at 1725cm -1 Assigned to C=O stretching vibration peak. 1650cm -1 is the stretching vibration peak of C=C; 1034cm -1 The stretching vibration peak attributed to -CH is derived from the characteristic peak of polypyrrole, 2950cm -1 Assigned to -CH2 stretching vibration peak; 1147cm -1 The stretching vibration peak attributed to CO is a characteristic peak of polyacrylate. -1 The C=C characteristic peak of the pyrrole ring and the OH characteristic peak C=O stretching vibration peak of graphene oxide can also be found in the comparison sample PHPG.
[0252] from Figure 7 In the infrared spectrum, graphene oxide has a wavelength of 3357 cm -1 There is a strong and broad absorption peak at 1723cm -1 Assigned to C=O stretching vibration peak. 1650cm -1 is the stretching vibration peak of C=C; 1040cm -1 The stretching vibration peak attributed to -CH is derived from the infrared characteristic peak of polypyrrole. 2932cm -1 Assigned to -CH2 stretching vibration peak. 1162cm -1 It is attributed to CO, which is a characteristic peak of polyacrylate. As can be seen from the figure, the characteristic peaks of carbon materials, polyacrylates and graphene oxide in the comparative sample also correspond to the characteristic peaks of the sample, indicating that the polymer materials of the comparative sample are all present.
[0253] (2) The antistatic thermal insulation coatings provided in Examples 3 to 6 and Comparative Example 1 were used as a control group, and the antistatic thermal insulation coatings provided in Examples 7 to 10 and Comparative Example 2 were used as a control group, and their thermal insulation temperature difference performance was tested. The specific testing method includes: (1) Two homemade insulation boxes, each with a temperature display and a 7×15cm tinplate-sized hole on the insulation box; (2) 7×15cm blank tinplate (blank sample) and tinplate coated with 6mm thick coating (coating sample) were placed on the insulation sealing box respectively; (3) Irradiated with a 350W infrared lamp, and recorded the temperature of the blank sample and coating sample every 5 minutes. After 1 hour, the infrared lamp irradiation was stopped, and the reference temperature was calculated. Reference temperature calculation method: The temperature difference is obtained by subtracting the temperature of the coating sample from the temperature of the blank sample. The specific results are as follows: Figure 8 and Figure 9 shown.
[0254] from Figure 8 and Figure 9 It can be seen that by increasing the amount of in-situ polymerized antistatic thermal insulation filler HPG or TPG, the thermal insulation performance of the coating can be improved to a certain extent, and compared with PHPG or PTPG directly added with polypyrrole, hollow glass microspheres or expanded microspheres, and graphene oxide coating samples, the antistatic thermal insulation coating (P-HPG or P-TPG) introduced with antistatic thermal insulation filler HPG or TPG of the present invention has better thermal insulation performance.
[0255] (3) The antistatic thermal insulation coatings provided in Examples 3 to 6 and Comparative Example 1 were used as a control group, and the antistatic thermal insulation coatings provided in Examples 7 to 10 and Comparative Example 2 were used as a control group. The antistatic properties were tested in accordance with the ASTM standard D-257 test method. The specific results are shown in FIG. Figure 10 and Figure 11 shown.
[0256] from Figure 10 and Figure 11 As can be seen, the antistatic resistance values of Comparative Example 1 (PHPG) are all higher than those of Examples 3-6, and the antistatic resistance values of Comparative Example 2 (PTPG) are all higher than those of Examples 7-10. The larger the resistance value, the worse the antistatic effect. Therefore, the introduction of in-situ polymerized antistatic insulation fillers is beneficial to enhancing the antistatic effect of the coating.
[0257] (4) The antistatic thermal insulation coatings provided in Examples 3 to 6 and Comparative Example 1 were used as a control group, and the antistatic thermal insulation coatings provided in Examples 7 to 10 and Comparative Example 2 were used as a control group. The adhesion of the coatings was tested in accordance with GB / T 5210-2006 "Adhesion test for paints and varnishes by pull-off method". The specific results are shown in the figure below. Figure 12 and Figure 13 shown.
[0258] from Figure 12 It can be seen that the adhesion of the coating with antistatic thermal insulation filler is basically better than that of the coating with the comparison sample PHPG. Since the polypyrrole is wrapped in the hollow glass microspheres through in-situ polymerization, the antistatic thermal insulation filler is better and more tightly adhered to the base material polyacrylate, thereby effectively increasing its adhesion.
[0259] from Figure 13 It can be seen that the adhesion of coatings with different amounts of antistatic thermal insulation fillers is different. The adhesion of coatings with antistatic thermal insulation fillers is basically better than that of coatings with the comparison sample PTPG. Since the polypyrrole is wrapped in the expanded microspheres through in-situ polymerization, the antistatic thermal insulation filler is better and more tightly adhered to the base material polyacrylate, thereby effectively increasing its adhesion.
[0260] (5) The antistatic thermal insulation coatings provided in Examples 3 to 6 and Comparative Example 1 were used as a control group, and the antistatic thermal insulation coatings provided in Examples 7 to 10 and Comparative Example 2 were used as a control group, and their hardness was tested. The specific testing method was based on GB / T 6739-1996 "Determination of Coating Hardness by Pencil Method." Hardness test standard: Pencil numbers are 6H, 5H, 4H, 3H, 2H, H, F, HB, B, 2B, 3B, 4B, 5B, and 6B, with 6H being the hardest and 6B being the softest, with the hardness decreasing from 6H to 6B. The specific results are shown in Tables 1 and 2.
[0261] Table 1
[0262]
[0263] Table 2
[0264]
[0265] Note: "+250g" means that the original test instrument is loaded with 250g of weight, indicating that the hardness is one level higher.
[0266] As can be seen from the hardness test data in Tables 1 and 2, in Examples 3-6, the hardness reaches its highest when the amount of antistatic and thermal insulating filler is increased to 1g (corresponding to the composite material P-HPG (1.0)). The hardness of the coatings incorporating antistatic and thermal insulating fillers is substantially higher than that of Comparative Example 1. As can be seen in Examples 7-10, the hardness of the coatings gradually increases with increasing amounts of antistatic and thermal insulating filler, and all are higher than that of Comparative Example 2. This also demonstrates that coatings with different amounts of antistatic and thermal insulating fillers have different hardness levels, meeting the needs of different application scenarios.
[0267] (6) The infrared spectra of the Vitrimer xylose polyacrylate in Example 11 and Example 12 were detected. Figure 14 shown.
[0268] from Figure 14 As can be seen, 1725cm -1 、1240-1260cm -1 and 1160-1180cm -1 These are the characteristic absorption peaks of polyacrylate. -1 The stretching vibration of C=O on the ester bond, 1240-1260 cm -1 and 1160-1180cm -1 Represent the asymmetric and symmetric stretching vibrations of CO on the ester bond. 1020-1100cm -1 and 3000-3600cm -1 The stretching vibration peaks of xylose structure, 1020-1100 cm -1 COC stretching vibration, 3000-3600cm -1 The broad characteristic peak is the OH stretching vibration.
[0269] At the same time, in order to compare the performance of the Vitrimer xylose polyacrylate in Examples 11 and 12 with the conventional polyacrylate emulsion in Examples 3-10, the Vitrimer xylose polyacrylate and the conventional polyacrylate emulsion were coated on a substrate with the same surface roughness. The coating area and coating thickness of the two were the same. The substrate samples of the Vitrimer xylose polyacrylate and the conventional polyacrylate emulsion after coating were placed in an oven at 100°C for 12 hours. The surface appearance of the substrate after drying is shown in the following photograph: Figure 15 As shown, Figure 15 The substrate sample at the top of the picture is a substrate sample coated with a conventional polyacrylate emulsion, and the substrate sample at the bottom of the picture is a substrate sample coated with Vitrimer xylose polyacrylate. As can be seen from the figure, the surface of the substrate sample coated with conventional polyacrylate emulsion shows obvious cracking, while the surface of the substrate sample coated with Vitrimer xylose polyacrylate is smooth and intact without any cracks. It can be seen from this that the Vitrimer xylose polyacrylate provided by the present invention exhibits good mechanical strength and heat resistance, and its application in coatings (coatings) can also improve the mechanical properties and thermal stability of the coating.
[0270] In addition, using Examples 5 and 11 as a comparative group, and Examples 9 and 12 as a comparative group, the effect of the structure of the polyacrylate on the coating performance was investigated from the perspectives of adhesion and hardness. The adhesion test method is as described in Section (4) above, and the hardness test method and test standards are as described in Section (5) above, which will not be repeated here.
[0271] Table 3
[0272]
[0273] From the data in Table 3, it can be seen that when Vitrimer xylose polyacrylate containing xylose structure is used as the base material of the coating, the adhesion and hardness properties of the coating (coating) are significantly improved compared with conventional polyacrylates, which is beneficial to extending the service life of the coating (coating).
[0274] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and principles of the present invention are within the scope of protection of the pending claims of the present invention.
Claims
1. An antistatic thermal insulation coating, characterized in that: Taking the total mass of the antistatic thermal insulation coating as 100%, it includes the following components in mass fractions: Polyacrylate 30%-40%, titanium dioxide 10%-15%, antistatic thermal insulation filler 1.4%-1.6%, hydrophilic aerogel 0.1%-0.2%, diatomaceous earth 1%-4%, defoamer 1%-4%, film-forming aid 1%-5%, dispersant 0.1%-1.5% and water 30%-55%; The antistatic heat-insulating filler comprises an antistatic heat-insulating composite material, which is mainly composed of a lightweight material, polypyrrole and a carbon material, and is prepared by an in-situ polymerization method; the antistatic heat-insulating composite material has a structure of a composite microlayer of polypyrrole and carbon material on the surface of a lightweight material; Wherein, the lightweight material is hollow glass microspheres; The carbon material includes at least one of carbon nanotubes, modified carbon nanotubes, graphene, or modified graphene; The mass ratio of the lightweight material, polypyrrole and carbon material is (1.2-1.4): (0.5-0.7): (0.1-0.2).
2. The antistatic thermal insulation coating according to claim 1, characterized in that: The preparation method of the antistatic heat-insulating composite material comprises the following steps: (a) providing a pyrrole aqueous solution, a ferric chloride p-toluenesulfonic acid mixed solution, and a carbon material dispersion; (b) mixing the lightweight material with the pyrrole aqueous solution, then adding the ferric chloride p-toluenesulfonic acid mixed solution and the carbon material dispersion to carry out a polymerization reaction, and after the reaction is completed, performing solid-liquid separation on the obtained product, and drying the separated solid product to obtain an antistatic heat-insulating composite material composed of the lightweight material, polypyrrole and carbon material.
3. The antistatic thermal insulation coating according to claim 2, characterized in that: In step (a), the molar concentration of pyrrole in the pyrrole aqueous solution is 0.1M-0.8M; And / or, in step (a), in the ferric chloride and p-toluenesulfonic acid mixed solution, the molar concentration of ferric chloride is 0.1M-0.8M, and the molar concentration of p-toluenesulfonic acid is 0.1M-0.8M; and / or, in step (a), the mass concentration of the carbon material in the carbon material dispersion is 1-10 mg / ml; and / or, in step (b), the mass ratio of the lightweight material to the mass ratio of the pyrrole aqueous solution is 5-10%; And / or, in step (b), the total mass ratio of ferric chloride and p-toluenesulfonic acid in the ferric chloride-p-toluenesulfonic acid mixed solution to the mass ratio of the pyrrole aqueous solution is 45-60%; and / or, in step (b), the mass ratio of the carbon material dispersion to the pyrrole aqueous solution is 5-15%; And / or, in step (b), the polymerization reaction temperature is 15-30° C., and the polymerization reaction time is 1-3 hours; And / or, in step (b), the drying is vacuum drying, and the vacuum drying temperature is 50-90°C.
4. The antistatic thermal insulation coating according to any one of claims 1 to 3, characterized in that: The hydrophilic aerogel comprises silica aerogel; and / or, the defoaming agent comprises at least one of n-butanol, an organosilicon defoaming agent or a polyether defoaming agent; and / or, the film-forming aid comprises at least one of ethylene glycol, propylene glycol butyl ether, hydrocarbons or dodecyl alcohol ester; And / or, the dispersant includes at least one of SN5040 dispersant, a cationic wetting dispersant or a nonionic dispersant.
5. The method for preparing the antistatic thermal insulation coating according to any one of claims 1 to 4, characterized in that: The following steps are involved: Titanium dioxide, hydrophilic aerogel, diatomaceous earth and a portion of the formulated amount of water are stirred and mixed once to obtain a mixed solution I; Adding a portion of the defoaming agent and a portion of the film-forming aid to the mixed solution I and stirring and mixing them a second time to obtain a mixed solution II; Adding polyacrylate to the mixed solution II and stirring for three times to obtain a mixed solution III; Add a dispersion formed by an antistatic thermal insulation filler and the remaining amount of water, a dispersant, the remaining amount of a defoamer and the remaining amount of a film-forming aid to the mixed solution III and stir and mix four times to obtain an antistatic thermal insulation coating.
6. The method for preparing the antistatic thermal insulation coating according to claim 5, characterized in that: The mixing time is 1-10 minutes, and the stirring speed is 500-800r / min; And / or, the secondary stirring and mixing time is 10-30 min, and the stirring speed is 500-800 r / min; And / or, the three stirring and mixing times are 30-60 min, and the stirring speed is 500-800 r / min; And / or, the time for the four stirring and mixing is 60-120 min, and the stirring speed is 450-750 r / min.
7. A coating, characterized in that The antistatic thermal insulation coating is coated with the antistatic thermal insulation coating according to any one of claims 1 to 4 or the antistatic thermal insulation coating prepared by the preparation method according to any one of claims 5 to 6.
Citation Information
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