High wear-resistant thermal insulation coating, thermal insulation film and preparation method
By preparing a wear-resistant and heat-insulating copolymer and using it in high wear-resistant and heat-insulating coatings, the problem of balancing heat insulation and wear resistance was solved, and the heat insulation performance and tensile strength of the coatings were improved.
Patent Information
- Application Number
- CN202410775324.6
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- Filing Date
- 2024-06-17
- Publication Date
- 2026-02-06
- Estimated Expiration
- 2044-06-17
AI Technical Summary
In existing technologies, it is difficult to achieve both heat insulation and wear resistance in heat insulation coatings, and the tensile strength of heat insulation films is relatively low.
A wear-resistant and heat-insulating copolymer was prepared by grafting carboxylated hollow silica and styrene-maleic anhydride copolymer with aminated carbon nanotubes. This copolymer was then used as a component of a high wear-resistant and heat-insulating coating. The coating was prepared by combining it with film-forming substances, film-forming aids, curing agents, and dispersants.
It significantly improves the thermal insulation performance, near-infrared reflectance and tensile strength of the coating, while also possessing high abrasion resistance, achieving a balance between thermal insulation and abrasion resistance.
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Figure CN118725711B_ABST
Abstract
Description
TECHNICAL FIELD
[0001] The application belongs to the technical field of thermal insulation coatings, and particularly relates to a high-wear-resistance thermal insulation coating, a thermal insulation film and a preparation method. BACKGROUND
[0002] On the surface of a vehicle such as an airplane, a high-speed train and a car or a building, a thermal insulation coating is usually coated on the surface to reduce heat transfer, and the thermal insulation coating also needs to have high wear resistance to ensure a sufficient service life.
[0003] In the prior art, modified silicon dioxide is added to form a crosslinked structure with a resin to obtain a coating with high thermal insulation, and ceramic microparticles (including one or more of silicon carbide, aluminum oxide and boron carbide) are added to improve wear resistance. However, the ceramic microparticles have strong thermal conductivity, greatly reducing the thermal insulation, and have poor fusion with the resin, so that the thermal insulation film made of the coating has low tensile strength, and the wear resistance is low without the ceramic microparticles. SUMMARY
[0004] The application solves the problem that the thermal insulation and wear resistance of the prior art cannot be considered together, and improves the tensile strength of the thermal insulation film.
[0005] The application provides a high-wear-resistance thermal insulation coating, which comprises the following raw materials in parts by weight:
[0006] 35-70 parts of a film-forming substance, 5-30 parts of a wear-resistance thermal insulation copolymer, 1-5 parts of a film-forming aid, 0.5-3 parts of a curing agent and 0.1-5 parts of a dispersing agent;
[0007] The wear-resistance thermal insulation copolymer comprises a copolymer obtained by grafting reaction of carboxylated hollow silicon dioxide and a styrene maleic anhydride copolymer with an aminated carbon nanotube.
[0008] Optionally, the wear-resistance thermal insulation copolymer comprises the following raw materials in parts by weight:
[0009] 10-25 parts of carboxylated hollow silicon dioxide, 5-20 parts of a styrene maleic anhydride copolymer, 10-25 parts of an aminated carbon nanotube and 1-5 parts of an amide condensation agent.
[0010] Optionally, the preparation method of the wear-resistance thermal insulation copolymer comprises the following steps:
[0011] The amino carbon nanotube is mixed in a solvent, the carboxylated hollow silica, styrene maleic anhydride copolymer and amide condensing agent are stirred and mixed, then are added dropwise into the mixture of the amino carbon nanotube and the solvent, and are stirred until the reaction is completed, and then are washed and filtered to obtain the wear-resistant thermal insulation copolymer, wherein the amino carbon nanotube is provided by Changzhou Bogia Biological Medicine Technology Co., Ltd., has a diameter of 1-1.5 nm and a length of 8-20 μm, and the styrene maleic anhydride copolymer is provided by Shanghai Maikelin Biological Technology Co., Ltd., and has a particle size of 100-200 μm.
[0012] Optionally, the amide condensing agent is at least one of HATU, HBTU, PyBOP, HCTU, benzenesulfonic acid, methanesulfonic acid and benzene sulfonic acid.
[0013] Optionally, the solvent is at least one of N,N-dimethylformamide (DMF) and dimethyl sulfoxide.
[0014] Optionally, the preparation method of the carboxylated hollow silica comprises the following steps:
[0015] According to weight parts, 30-50 parts of the amino-modified hollow silica, 5-15 parts of succinic anhydride and 1-5 parts of an organic acid catalyst are added in an organic solvent, and are heated and stirred for 2-5 h, and then are washed, filtered and dried to obtain the carboxylated hollow silica; the organic acid catalyst is at least one of benzenesulfonic acid and benzene sulfonic acid.
[0016] Optionally, the average diameter of the amino-modified hollow silica is 50-200 nm, and the supplier is Xi'an Ruixi Biological Technology Co., Ltd.
[0017] Optionally, the film-forming material is at least one of polyurethane resin, polyacrylate and bisphenol A type epoxy resin, wherein the polyurethane resin is water-based polyurethane resin, and the supplier is Guangzhou Ruilin New Material Co., Ltd., and the model number is RL-8305.
[0018] Optionally, the film-forming aid is at least one of dodecanol ester, hexanediol, hexylene glycol butyl ether acetate and 3-ethoxypropyl acetate.
[0019] Optionally, the curing agent is at least one of cuprous sulfate and cuprous nitrate, and the dispersant is Efka EFKA-4010.
[0020] The application provides a preparation method of a high-wear-resistant thermal insulation coating, comprising the following steps:
[0021] The wear-resistant thermal insulation copolymer, the film-forming aid and the dispersant are added into a solvent, are stirred and dispersed, and then the film-forming material is added and is stirred and mixed uniformly to obtain the wear-resistant thermal insulation coating.
[0022] The application provides a heat insulation film made of the high wear-resistant heat insulation paint.
[0023] The application has the advantages that the carboxylated hollow silica and styrene maleic anhydride copolymer are grafted onto the aminated carbon nanotube to obtain a wear-resistant heat insulation copolymer, which is used as a component of the high wear-resistant heat insulation paint, and the heat insulation performance, near-infrared reflectance and tensile strength of the paint are significantly improved, and the obtained paint has high wear resistance and has both heat insulation and wear resistance. BRIEF DESCRIPTION OF DRAWINGS
[0024] Figure 1 A thermal gravimetric analysis data graph of the embodiment one of the application. DETAILED DESCRIPTION
[0025] Embodiment 1
[0026] Preparation of carboxylated hollow silica:
[0027] The aminated hollow silica 43 parts, succinic anhydride 10 parts and benzenesulfonic acid 2 parts are heated and stirred in DMF for 3 hours, then washed with water for three times and washed with anhydrous ethanol for two times, and each washing is followed by filtration, and then vacuum dried at 50 DEG C for 5 hours to obtain the carboxylated hollow silica, wherein the average diameter of the aminated hollow silica is 50 nm.
[0028] Preparation of wear-resistant heat insulation copolymer:
[0029] The aminated carbon nanotube 20 parts is mixed in DMF, the carboxylated hollow silica 18 parts, styrene maleic anhydride copolymer 12 parts and amide condensing agent HATU 2 parts are stirred and mixed, then added dropwise into the mixture of the aminated carbon nanotube and DMF, and continuously stirred for 6 hours, then washed with water for three times and washed with anhydrous ethanol for two times, and each washing is followed by filtration, and then vacuum dried at 50 DEG C for 5 hours to obtain the wear-resistant heat insulation copolymer.
[0030] Preparation of high wear-resistant heat insulation paint:
[0031] The wear-resistant heat insulation copolymer 5 parts, dodecanol ester 2 parts, cuprous sulfate 1 part and EFKA-4010 1 part are added into a solvent composed of acetone and deionized water in a volume ratio of 1:2, stirred and dispersed, then the water-based polyurethane resin 50 parts is added and stirred and mixed uniformly to obtain the high wear-resistant heat insulation paint.
[0032] The aminated hollow silica, the carboxylated hollow silica and the wear-resistant heat insulation copolymer are subjected to thermal gravimetric test in an argon atmosphere, and the experimental results are shown in Figure 1 , which shows that the carboxylated hollow silica is successfully carboxylated, and the carboxylated hollow silica and the styrene maleic anhydride copolymer are grafted onto the aminated carbon nanotube.
[0033] Example 2
[0034] Preparation of high wear-resistant thermal insulation coating:
[0035] The wear-resistant thermal insulation copolymer obtained in Example 1, dodecanol ester, cuprous sulfate and EFKA-4010 were added into a solvent composed of acetone and deionized water in a volume ratio of 1:2 in parts by weight, stirred and dispersed, then water-based polyurethane resin was added and stirred to mix uniformly, to obtain a high wear-resistant thermal insulation coating.
[0036] Example 3
[0037] Preparation of high wear-resistant thermal insulation coating:
[0038] The wear-resistant thermal insulation copolymer obtained in Example 1, dodecanol ester, cuprous sulfate and EFKA-4010 were added into a solvent composed of acetone and deionized water in a volume ratio of 1:2 in parts by weight, stirred and dispersed, then water-based polyurethane resin was added and stirred to mix uniformly, to obtain a high wear-resistant thermal insulation coating.
[0039] Example 4
[0040] Preparation of carboxylated hollow silica:
[0041] The amino-modified hollow silica, succinic anhydride and benzenesulfonic acid were added into DMF and stirred and reacted at high temperature for 3 h, then washed with water three times and anhydrous ethanol two times, filtered after each washing, and then dried at 50°C under vacuum for 5 h, to obtain carboxylated hollow silica.
[0042] Preparation of wear-resistant thermal insulation copolymer:
[0043] The amino-modified hollow silica, succinic anhydride and benzenesulfonic acid were added into DMF and stirred and reacted at high temperature for 3 h, then washed with water three times and anhydrous ethanol two times, filtered after each washing, and then dried at 50°C under vacuum for 5 h, to obtain carboxylated hollow silica.
[0044] Preparation of high wear-resistant thermal insulation coating:
[0045] The wear-resistant thermal insulation copolymer, hexylene glycol butyl ether acetate, cuprous sulfate and EFKA-4010 were added into a solvent composed of acetone and deionized water in a volume ratio of 1:2 in parts by weight, stirred and dispersed, then water-based polyurethane resin was added and stirred to mix uniformly, to obtain a high wear-resistant thermal insulation coating.
[0046] Comparative Example 1
[0047] Preparation of the coating:
[0048] In parts by weight, dodecanol ester 2 parts, cuprous sulfate 1 part and EFKA-4010 1 part were added into a solvent composed of acetone and deionized water in a volume ratio of 1:2, stirred and dispersed, and then water-based polyurethane resin 50 parts was added and stirred and mixed uniformly to obtain a high wear-resistant thermal insulation coating.
[0049] Comparative Example 2
[0050] Preparation of the coating:
[0051] In parts by weight, amino-functionalized carbon nanotubes 6 parts were mixed in DMF, carboxylated hollow silica 5.4 parts, styrene-maleic anhydride copolymer 3.6 parts, dodecanol ester 2 parts, cuprous sulfate 1 part and EFKA-4010 1 part were added into a solvent composed of acetone and deionized water in a volume ratio of 1:2, stirred and dispersed, and then water-based polyurethane resin 50 parts was added and stirred and mixed uniformly to obtain a high wear-resistant thermal insulation coating.
[0052] Comparative Example 3
[0053] Preparation of the copolymer:
[0054] In parts by weight, amino-functionalized carbon nanotubes 20 parts were mixed in DMF, styrene-maleic anhydride copolymer 12 parts, amide condensing agent HATU 2 parts were stirred and mixed, and then added dropwise into the mixture of amino-functionalized carbon nanotubes and DMF, and stirred for reaction for 6 h, and then washed with water for 3 times, washed with anhydrous ethanol for 2 times, filtered after each washing, and then dried at 50°C under vacuum for 5 h to obtain the copolymer.
[0055] Preparation of the coating:
[0056] In parts by weight, copolymer 15 parts, dodecanol ester 2 parts, cuprous sulfate 1 part and EFKA-4010 1 part were added into a solvent composed of acetone and deionized water in a volume ratio of 1:2, stirred and dispersed, and then water-based polyurethane resin 50 parts was added and stirred and mixed uniformly to obtain a high wear-resistant thermal insulation coating.
[0057] Comparative Example 4
[0058] Preparation of the copolymer:
[0059] In parts by weight, amino-functionalized carbon nanotubes 20 parts were mixed in DMF, carboxylated hollow silica 18 parts, amide condensing agent HATU 2 parts were stirred and mixed, and then added dropwise into the mixture of amino-functionalized carbon nanotubes and DMF, and stirred for reaction for 6 h, and then washed with water for 3 times, washed with anhydrous ethanol for 2 times, filtered after each washing, and then dried at 50°C under vacuum for 5 h to obtain the copolymer.
[0060] Preparation of the paint:
[0061] A copolymer 15 parts, dodecanol ester 2 parts, cuprous sulfate 1 part and efka EFKA-4010 1 part were added into a solvent composed of acetone and deionized water in a volume ratio of 1:2, stirred and dispersed, then waterborne polyurethane resin 50 parts was added and stirred and mixed uniformly to obtain a high wear-resistant thermal insulation paint.
[0062] Comparative Example 5
[0063] Preparation of the copolymer:
[0064] Amino-modified hollow silica 18 parts, styrene maleic anhydride copolymer 12 parts, amide condensing agent HATU 2 parts were stirred and mixed, then added dropwise into the mixture of amino-modified carbon nanotubes and DMF, continuously stirred for 6h, then washed with water three times, washed with anhydrous ethanol twice, filtered after each washing, then vacuum dried at 50°C for 5h to obtain the copolymer.
[0065] Preparation of the paint:
[0066] A copolymer 15 parts, dodecanol ester 2 parts, cuprous sulfate 1 part and efka EFKA-4010 1 part were added into a solvent composed of acetone and deionized water in a volume ratio of 1:2, stirred and dispersed, then waterborne polyurethane resin 50 parts was added and stirred and mixed uniformly to obtain a high wear-resistant thermal insulation paint.
[0067] Comparative Example 6
[0068] Preparation of the copolymer:
[0069] Amino-modified carbon nanotubes 20 parts, carboxyl-modified hollow silica 18 parts, styrene maleic anhydride copolymer 12 parts, amide condensing agent HATU 2 parts were stirred and mixed uniformly in DMF, continuously stirred for 6h, then washed with water three times, washed with anhydrous ethanol twice, filtered after each washing, then vacuum dried at 50°C for 5h to obtain the copolymer.
[0070] Preparation of the paint:
[0071] A copolymer 15 parts, dodecanol ester 2 parts, cuprous sulfate 1 part and efka EFKA-4010 1 part were added into a solvent composed of acetone and deionized water in a volume ratio of 1:2, stirred and dispersed, then waterborne polyurethane resin 50 parts was added and stirred and mixed uniformly to obtain a high wear-resistant thermal insulation paint.
[0072] The coating prepared in each of the above examples and comparative examples was coated on the surface of a cubic container composed of aluminum plates, dried and formed to obtain a heat insulation film, the dry film thickness was 0.5 mm, the temperature insulation performance and near-infrared reflectance were tested according to the standard JG / T235-2014, the wear resistance was tested according to the standard GB / T 23989-2009, and the tensile strength was tested according to the standard GB / T 25261-2018, and the test results are shown in Table 1.
[0073] Table 1
[0074]
[0075] As can be seen from Table 1, by grafting the carboxylated hollow silica and styrene maleic anhydride copolymer onto the aminated carbon nanotubes, a wear-resistant heat-insulating copolymer is obtained, and as a component of a high-wear-resistant heat-insulating coating, the temperature insulation performance, near-infrared reflectance and tensile strength of the coating are significantly improved, and the coating has very high wear resistance, and has both heat insulation and wear resistance.
[0076] Principle: The carboxyl groups of the carboxylated hollow silica and the anhydride groups of the styrene maleic anhydride copolymer are reacted with the amino groups of the aminated carbon nanotubes under the action of an amide condensing agent to form amide bonds, thereby grafting the carboxylated hollow silica and the styrene maleic anhydride copolymer onto the aminated carbon nanotubes.
[0077] By comparing each example with Comparative Example 6, Comparative Example 6 is a simultaneous mixing reaction of aminated carbon nanotubes, carboxylated hollow silica and styrene maleic anhydride copolymer, so that the proportion of carboxylated hollow silica and styrene maleic anhydride copolymer grafted on each monomer aminated carbon nanotube in the system is greatly different, thereby adversely affecting the temperature insulation performance, near-infrared reflectance and tensile strength of the coating.
[0078] Analyzing Comparative Example 5, the aminated carbon nanotubes and the amino-modified hollow silica are grafted onto the styrene maleic anhydride copolymer, resulting in poor temperature insulation performance and near-infrared reflectance of the coating.
[0079] It should be understood by those skilled in the art that the above discussion of any of the embodiments is only exemplary and is not intended to suggest that the scope of protection of the present application is limited to these examples; under the idea of the present application, the technical features of the above embodiments or different embodiments can also be combined, the steps can be implemented in any order, and there are many other changes of different aspects of one or more embodiments of the present application as described above. In order to be brief, they are not provided in detail.
[0080] It is intended that the embodiments of the application herein disclosed meet all the written requirements of the patent statutes and come within the judicial doctrines of equivalents and will not be construed to be limited to the embodiments shown and described and by the keeping within the spirit and scope of the embodiments of the application.
Claims
1. A highly wear-resistant and heat-insulating coating, characterized in that, Including the following parts by weight of raw materials: Film-forming substance 35-70 parts, wear-resistant and heat-insulating copolymer 5-30 parts, film-forming aid 1-5 parts, curing agent 0.5-3 parts, dispersant 0.1-5 parts; The wear-resistant and heat-insulating copolymer includes a copolymer obtained by grafting carboxylated hollow silica and styrene-maleic anhydride copolymer with aminated carbon nanotubes. The wear-resistant and heat-insulating copolymer comprises the following raw materials in parts by weight: 10-25 parts of carboxylated hollow silica, 5-20 parts of styrene-maleic anhydride copolymer, 10-25 parts of aminated carbon nanotubes, and 1-5 parts of amide condensing agent; The method for preparing the carboxylated hollow silica includes the following steps: According to the weight percentage, 30-50 parts of amino-modified hollow silica, 5-15 parts of succinic anhydride and 1-5 parts of organic acid catalyst are heated and stirred in an organic solvent for 2-5 hours. After washing, filtering and drying, carboxylated hollow silica is obtained. The preparation method of the wear-resistant and heat-insulating copolymer includes the following steps: Aminated carbon nanotubes were mixed in a solvent. Carboxylated hollow silica, styrene-maleic anhydride copolymer, and amide condensing agent were stirred and mixed. The mixture was then added dropwise to the mixture of aminated carbon nanotubes and solvent. The reaction was stirred until complete. After washing and filtration, a wear-resistant and heat-insulating copolymer was obtained.
2. The high wear-resistant and heat-insulating coating according to claim 1, characterized in that, The amide condensing agent is at least one of HATU, HBTU, PyBOP, HCTU, benzenesulfonic acid, methanesulfonic acid, and benzosulfonic acid.
3. The high wear-resistant and heat-insulating coating according to claim 1, characterized in that, The solvent is at least one of dimethylformamide and dimethyl sulfoxide.
4. The high wear-resistant and heat-insulating coating according to claim 1, characterized in that, The average diameter of the amino-modified hollow silica is 100-200 nm.
5. The high wear-resistant and heat-insulating coating according to claim 1, characterized in that, The film-forming substance is at least one of polyurethane resin, polyacrylate, and bisphenol A epoxy resin.
6. A method for preparing the high wear-resistant and heat-insulating coating according to any one of claims 1-5, characterized in that, Includes the following steps: The wear-resistant and heat-insulating copolymer, film-forming aid and dispersant are added to the solvent, stirred and dispersed, and then the film-forming substance is added and stirred and mixed evenly to obtain the wear-resistant and heat-insulating coating.
7. A heat insulation film made using the high abrasion-resistant heat insulation coating according to any one of claims 1-6.
Citation Information
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