A self-sealing coating, a self-sealing coating layer, and a preparation method and application thereof

Abstract

The present application relates to a kind of self-sealing coating, self-sealing coating and its preparation method and application, belong to functional coating technical field.Self-sealing coating includes healing coating and intumescent coating;The preparation material of healing coating includes: A liquid, raw material includes polyester polyol 40-80 parts, isocyanate 20-60 parts;B liquid, raw material includes polyether amine 40-70 parts, chain extender 10-20 parts, flame retardant 10-25 parts;The preparation material of intumescent coating includes: C liquid, raw material includes polyether polyol 50-80 parts, isocyanate 20-50 parts;D liquid, raw material includes polyether polyol 70-80 parts;E liquid includes fatty acid ester 40-70 parts, acrylate 20-48 parts.A liquid is mixed with B liquid to make coating have good extensibility and resilience;C liquid, D liquid and E liquid are mixed to have oil absorption intumescent capacity.Application is used to the protection of oil product storage device such as gasoline, diesel, kerosene etc..

Description

Technical Field

[0001] This invention belongs to the field of functional coatings technology, specifically relating to a self-sealing coating, a self-sealing coating layer, its preparation method, and its application. Background Technology

[0002] The information disclosed in this background section is intended only to enhance understanding of the overall background of the invention and is not necessarily to be construed as an admission or in any way implying that such information constitutes prior art known to those skilled in the art.

[0003] Fuel is the power source for transportation vehicles, and it is also a flammable and explosive liquid. When fuel storage devices such as fuel tanks (or oil tanks) containing liquid fuels like gasoline and diesel are damaged, and the tank (or oil tank) walls are penetrated, it will lead to a large-scale fuel leak. Continuous leakage will not only cause the transportation vehicle to lose power, but it can also easily cause catastrophic accidents such as explosions and fires. Currently, the protective capabilities of fuel storage devices are generally weak, and there is a lack of protective measures in the event of penetration of the fuel tank (or oil tank) walls. Summary of the Invention

[0004] The purpose of this invention is to provide a self-sealing coating, a self-sealing coating layer, a preparation method thereof, and an application thereof. Based on the self-sealing coating provided by this invention, a coating with good self-sealing ability can be prepared, thereby improving the protective capability of oil tanks (oil containers).

[0005] To achieve the above objectives, the technical solution of the present invention is as follows:

[0006] In a first aspect, a self-sealing coating includes a healing coating and an intumescent coating;

[0007] The materials for preparing the healing coating include liquid A and liquid B. The raw materials for preparing liquid A include the following components in parts by weight: 40-80 parts of polyester polyol and 20-60 parts of isocyanate. The raw materials for preparing liquid B include 40-70 parts of polyetheramine, 10-20 parts of chain extender and 10-25 parts of flame retardant.

[0008] The materials for preparing the intumescent coating include liquid C, liquid D, and liquid E. The raw materials for preparing liquid C include the following components in parts by weight: 50-80 parts of polyether polyol and 20-50 parts of isocyanate; the raw materials for preparing liquid D include the following components in parts by weight: 70-80 parts of polyether polyol; and liquid E includes the following components in parts by weight: 40-70 parts of fatty acid ester and 20-48 parts of acrylate.

[0009] The isocyanate composition in solution A and solution C may be the same or different;

[0010] The polyether polyols in solution C and solution D may have the same or different compositions.

[0011] Optionally, the isocyanate includes one or more of toluene diisocyanate, diphenylmethane diisocyanate, and 1,6-hexanediisocyanate.

[0012] Optionally, the polyether polyol includes one or more of polypropylene oxide diol, polytetrahydrofuran diol, and tetrahydrofuran-propylene oxide copolydiol.

[0013] Optionally, the polyester polyol includes one or more of polycaprolactone polyol, polycarbonate diol, and polyester diol.

[0014] Optionally, the polyetheramine includes one or more of terminal amino polyoxypropylene ether and terminal amino polyoxyethylene ether.

[0015] Optionally, the chain extender includes one or more of 1,4-butanediol, 1,6-hexanediol, and trimethylolpropane.

[0016] Optionally, the flame retardant includes one or more of aluminum hydroxide flame retardants or magnesium hydroxide flame retardants.

[0017] The acrylates include one or more of methyl acrylate, ethyl acrylate, methyl 2-methacrylate, and ethyl 2-methacrylate.

[0018] Optionally, the raw materials for preparing liquid B further include the following components in parts by weight: 5-10 parts plasticizer, 1-5 parts reactive diluent, and 1-10 parts additives; the raw materials for preparing liquid D further include the following components in parts by weight: 20-30 parts additives; and the raw materials for preparing liquid E further include the following components in parts by weight: 10-15 parts additives.

[0019] The additives in solution B, solution D, and solution E may have the same or different additive components.

[0020] Optionally, the plasticizer is a phthalate plasticizer;

[0021] The reactive diluent is a multifunctional reactive diluent;

[0022] The additives include one or more of leveling agents, defoamers, wetting agents, catalysts, and emulsifiers, wherein the catalyst is an azo catalyst.

[0023] Optionally, liquid A and liquid B are packaged separately; liquids C, D and E are packaged separately.

[0024] In a second aspect, a self-sealing coating includes an inner healing layer disposed on the surface of a substrate, an expansion layer disposed outside the inner healing layer, and an outer healing layer disposed outside the expansion layer; the layer thickness ratio of the inner healing layer, the expansion layer, and the outer healing layer is 1:1:1 to 3:2:3.

[0025] The coating for the inner healing layer is made by mixing liquid A and liquid B in a mass ratio of 2:1 to 7:1.

[0026] The coating of the expansion layer is made by mixing liquid C, liquid D and liquid E in a mass ratio of 1:1:1 to 10:7:5.

[0027] The coating for the outer healing layer is made by mixing liquid A and liquid B in a mass ratio of 2:1 to 7:1.

[0028] After liquid A and liquid B are mixed, the isocyanate groups in the material react with the amine and hydroxyl groups, giving the coating good extensibility and resilience. When damaged by external impact, it can rely on its own extensibility and resilience to gradually reduce the impact hole in a short time.

[0029] After liquid C and liquid D are mixed, the isocyanate and hydroxyl groups in the material react to give the coating good extensibility. The lipophilic monomers in liquid E are moderately cross-linked to form an acrylate copolymer with a three-dimensional network structure. It has a stable macroporous network structure and a high specific surface area, which can provide storage space for the absorbed oil pollutants and form a three-dimensional network structure to surround the absorbed oil molecules.

[0030] Thirdly, the method for preparing the aforementioned self-sealing coating includes the following steps:

[0031] Weigh the polyester polyol and put it into a heating container. Stir at 20-60 rpm and heat to 100-160°C. After reaching the set temperature, keep it at the temperature for 1-3 hours and then lower the temperature of the heating container to room temperature. Add isocyanate to the above solution, stir at 80-120 rpm and heat to 60-90°C. Keep it at 1-2 hours to obtain solution A.

[0032] After weighing the polyetheramine and chain extender, add them to a container and stir and disperse them thoroughly at 700-1000 rpm for 30-60 minutes. Then add the plasticizer, reactive diluent, additives, and flame retardant and stir and disperse them thoroughly at 1800-2200 rpm for 30-60 minutes. After grinding, test the fineness to be <30 μm and filter it through a 100-400 mesh screen to obtain solution B.

[0033] Weigh the polyether polyol and add it to a heating container. Stir at 20-60 rpm and heat to 100-160°C. After reaching a certain temperature, keep it at that temperature for 1-3 hours and then lower the temperature of the heating container to room temperature. Add a certain weight of isocyanate to the above solution, stir at 80-120 rpm and heat to 60-90°C. Keep it at that temperature for 1-2 hours to obtain solution C.

[0034] Weigh the polyether polyol and add it to a container. Stir and disperse it thoroughly at 700-1000 rpm for 30-60 min. Add the additive and stir and disperse it thoroughly at 1800-2200 rpm for 30-60 min. Grind it and test the fineness to be <30 μm. Filter it through a 100-400 mesh screen to obtain liquid D.

[0035] After weighing the fatty acid ester, acrylate, and additives, add them to a heating container and stir and heat at 1200-1800 rpm to 40-80℃. After reaching a certain temperature, keep it at that temperature for 3-6 hours. Then, cool the temperature inside the heating container to room temperature and grind it. Test the fineness to be <30μm and filter it with a 100-400 mesh filter to obtain liquid E.

[0036] During construction, separately packaged liquid A and liquid B are mixed in a mass ratio of 2:1 to 7:1 to obtain the coating for the inner healing layer. Separately packaged liquid A and liquid B are mixed in a mass ratio of 2:1 to 7:1 to obtain the coating for the outer healing layer. Separately packaged liquid C, liquid D and liquid E are mixed in a mass ratio of 1:1:1 to 10:7:5 to obtain the coating for the expansion layer.

[0037] A self-sealing coating is obtained by applying a layer with a thickness ratio of 1:1:1 to 3:2:3 for the healing layer: expansion layer: healing layer.

[0038] Optionally, the total thickness of the self-sealing coating is 6 to 12 mm.

[0039] Thirdly, the application of the aforementioned self-sealing coatings and / or coatings in the field of oil storage devices.

[0040] Optionally, it can be used for the protection of oil storage devices for gasoline, diesel, kerosene, and other oil products.

[0041] Optionally, the coating can be applied to the surface of the oil storage device by spraying, brushing, roller coating, or by attaching pre-made patches.

[0042] The beneficial effects of this invention are as follows:

[0043] 1. In the self-sealing coating of the present invention, after the healing coating A and B are mixed, the isocyanates in the material react with the amino and hydroxyl groups, giving the coating good extensibility and resilience. When damaged by external impact, it can gradually reduce the impact hole in a short time by relying on its own extensibility and resilience. After the expanding coating C and D are mixed, the isocyanates in the material react with the hydroxyl groups, giving the coating good extensibility. The lipophilic monomers in the added E material are moderately cross-linked to form an acrylate copolymer with a three-dimensional network structure. It has a stable macroporous network structure and a high specific surface area, which can provide storage space for absorbed oil contaminants, forming a three-dimensional network structure that surrounds the absorbed oil molecules. The combination of the changes in the healing coating and the expanding coating can achieve a self-sealing effect after the oil storage device is damaged.

[0044] 2. The self-sealing coating of this invention has a multi-layered composite structure. The inner / outer healing layers heal rapidly upon impact, immediately mitigating oil leakage from the storage device. Simultaneously, the expansion layer rapidly absorbs oil and expands, working together to quickly heal pores, thus protecting storage devices for gasoline, diesel, kerosene, and other oil products. This technology integrates the healing process of the healing layer and the expansion process of the expansion layer as continuous parts of the self-sealing process, participating together in the healing process. Compared to traditional oil-swellable rubber, it has better oil absorption performance and higher adsorption capacity. Furthermore, the healing layers inside and outside the expansion layer provide support, resulting in faster self-sealing and less residual healing.

[0045] 3. The self-sealing coating of the present invention is suitable for various working conditions and construction processes. In addition to spraying, brushing, and roller coating, it can also be prefabricated into patches and directly applied to the oil storage device using an adhesive. It can be used on various substrates and surfaces of various shapes, improving construction efficiency and applicability.

[0046] 4. The preparation method of the self-sealing coating and coating of the present invention is simple and highly compatible. The raw materials are prepared in advance and packaged separately. The packaged raw materials take effect after mixing. After mixing, it can be applied to the substrate or the original coating. Other functional coatings, such as camouflage coatings, can also be applied to the surface of the multifunctional self-sealing coating without affecting the relevant performance. It can effectively reduce the oil leakage rate and fire rate of oil storage devices under impact. Detailed Implementation

[0047] It should be noted that the following detailed descriptions are exemplary and intended to provide further illustration of the invention. Unless otherwise specified, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention pertains.

[0048] It should be noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to limit the scope of exemplary embodiments according to the invention. As used herein, the singular form is intended to include the plural form as well, unless the context clearly indicates otherwise. Furthermore, it should be understood that when the terms "comprising" and / or "including" are used in this specification, they indicate the presence of features, steps, operations, devices, components, and / or combinations thereof.

[0049] This invention provides a self-sealing coating, comprising a healing coating and an intumescent coating;

[0050] The materials for preparing the healing coating include liquid A and liquid B. Liquid A is prepared from the following components in parts by weight: 40-80 parts polyester polyol and 20-60 parts isocyanate. Liquid B is prepared from the following components in parts by weight: 40-70 parts polyetheramine, 10-20 parts chain extender, 5-10 parts plasticizer B, 1-5 parts reactive diluent, 1-10 parts additives, and 10-25 parts flame retardant.

[0051] The materials for preparing the intumescent coating include liquid C, liquid D, and liquid E. The raw materials for preparing liquid C include the following components in parts by weight: 50-80 parts of polyether polyol and 20-50 parts of isocyanate; the raw materials for preparing liquid D include the following components in parts by weight: 70-80 parts of polyether polyol and 20-30 parts of additives; liquid E includes the following components in parts by weight: 40-70 parts of fatty acid ester, 20-48 parts of acrylate and 10-15 parts of additives.

[0052] Polyester polyols include one or more of polycaprolactone polyols, polycarbonate diols, and polyester diols. Polyester polyol molecules contain a large number of polar groups such as ester groups and amino groups, resulting in strong cohesive strength and adhesion, as well as high strength and abrasion resistance.

[0053] Isocyanates include one or more of toluene diisocyanate, diphenylmethane diisocyanate, and 1,6-hexane diisocyanate; isocyanates include monoisocyanates (R—N=C=O) and diisocyanates (O=C=N—R—N=C=O). Because isocyanates contain unsaturated bonds in their structure, they are highly reactive and readily react with some organic or inorganic substances containing active groups (such as hydroxyl, amino, carboxyl, etc.).

[0054] Polyetheramines include one or more types of amino-terminated polypropylene ethers and amino-terminated polyethylene oxide ethers. Polyetheramines are polymers with a polyether backbone and amino groups as terminal active functional groups. The amino groups provide polyetheramines with the possibility of reacting with various compounds, and their unique molecular structure gives them excellent overall properties. Chain extenders are low-molecular-weight, multifunctional compounds containing hydroxyl or amino groups. Through reaction with polyetheramines, they form "bridges" between molecular chains, diffusing and extending the molecular chains, increasing molecular weight, and improving the viscosity of the system.

[0055] Chain extenders include one or more of 1,4-butanediol, 1,6-hexanediol, and trimethylolpropane. Chain extenders, also known as chain growth agents, extend molecular chains and increase molecular weight through reactions, thereby improving the mechanical and processing properties of products, ensuring extensibility, and imparting a certain tensile strength to the coating.

[0056] The plasticizer is a phthalate plasticizer. As an additive for polymer materials, it can effectively improve the performance of polymer materials and enhance the flexibility of coatings.

[0057] Reactive diluents are multifunctional reactive diluents, which are substances with epoxy functional groups in their molecular structure. They can dissolve or disperse film-forming substances and participate in the film-forming reaction during the coating film-forming process, forming non-volatile components that remain in the coating, thus maintaining the coating's performance and also playing a toughening role.

[0058] The additives include one or more of leveling agents, defoamers, wetting agents, catalysts, and emulsifiers; the leveling agent is an organosilicon leveling agent, specifically a polyether-modified organosilicon leveling agent or a polyester-modified organosilicon leveling agent; the defoamer is an organosilicon defoamer, specifically a polydimethylsiloxane defoamer; the wetting agent is a wetting and dispersing wetting agent, and the catalyst is an azo catalyst.

[0059] Flame retardants include one or more of aluminum hydroxide flame retardants or magnesium hydroxide flame retardants;

[0060] Polyether polyols include one or more of polypropylene oxide diol, polytetrahydrofuran diol, and tetrahydrofuran-propylene oxide copolydiol;

[0061] Acrylates include one or more of methyl acrylate, ethyl acrylate, methyl 2-methacrylate, and ethyl 2-methacrylate;

[0062] Preferably, in the healing coating, liquid A and liquid B are packaged separately; in the expanding coating, liquids C, D and E are packaged separately.

[0063] The present invention provides a self-sealing coating comprising an inner healing layer disposed on the surface of a substrate, an expansion layer disposed outside the inner healing layer, and an outer healing layer disposed outside the expansion layer; the layer thickness ratio of the inner healing layer, the expansion layer, and the outer healing layer is 1:1:1 to 3:2:3, and the total thickness is 6 to 12 mm.

[0064] The coating for the inner healing layer is made by mixing liquid A and liquid B in a mass ratio of 2:1 to 7:1.

[0065] The coating of the expansion layer is made by mixing liquid C, liquid D and liquid E in a mass ratio of 1:1:1 to 10:7:5.

[0066] The coating for the outer healing layer is made by mixing liquid A and liquid B in a mass ratio of 2:1 to 7:1.

[0067] After liquid A and liquid B are mixed, the isocyanate group of isocyanate A reacts with the amino and hydroxyl groups of polyetheramine, giving the coating good extensibility and resilience. When damaged by external impact, it can gradually reduce the impact hole in a short time by relying on its own extensibility and resilience.

[0068] When liquid C and liquid D are mixed, an expansion layer with oil absorption and expansion capacity is formed. The isocyanate group in isocyanate C reacts with the hydroxyl group of polyether polyol, giving the coating good extensibility. The lipophilic monomers (fatty acid esters) in liquid E are moderately cross-linked to form an acrylate copolymer with a three-dimensional network structure. It has a stable macroporous network structure and a high specific surface area, which can provide storage space for the absorbed oil pollutants (gasoline, diesel, etc.) and form a three-dimensional network structure that surrounds the oil molecules.

[0069] This invention provides a method for preparing the above-mentioned self-sealing coating, comprising the following steps:

[0070] Weigh the polyester polyol and put it into a heating container. Stir at 20-60 rpm and heat to 100-160°C. After reaching the set temperature, keep it at the temperature for 1-3 hours and then cool the temperature inside the heating container to room temperature. Add isocyanate A to the above solution, stir at 80-120 rpm and heat to 60-90°C. Keep it at 1-2 hours to obtain solution A.

[0071] Preferably, the polyester polyol is weighed and placed into a heating container, stirred at 50 rpm and heated to 120°C, kept at that temperature for 2 hours and then cooled to room temperature; after adding isocyanate, the mixture is stirred at 100 rpm and heated to 70°C, and kept at that temperature for 2 hours.

[0072] In this process, polyester polyol molecules contain a large number of polar groups such as ester and amino groups, resulting in strong cohesive strength and adhesion, and high strength and abrasion resistance. Isocyanates include monoisocyanates (R—N=C=O) and diisocyanates (O=C=N—R—N=C=O). Due to the presence of unsaturated bonds in their structure, isocyanates are highly reactive and readily react with some organic or inorganic substances containing active groups (such as hydroxyl, amino, and carboxyl groups).

[0073] After weighing the polyetheramine and chain extender, add them to a container and stir and disperse them thoroughly at 700-1000 rpm for 30-60 minutes. Then add the plasticizer, reactive diluent, additives, and flame retardant and stir and disperse them thoroughly at 1800-2200 rpm for 30-60 minutes. After grinding, test the fineness to be <30 μm and filter it through a 100-400 mesh screen to obtain solution B.

[0074] Preferably, polyetheramine and chain extender are weighed and added to a container, and stirred and dispersed at 800 rpm for 40 min. After dispersion, plasticizer, reactive diluent, additives and flame retardant are added and stirred and dispersed at 2000 rpm for 40 min. After dispersion, the mixture is ground and the fineness is tested to be <30 μm. After filtration through a 200 mesh filter, liquid B is obtained.

[0075] In this process, polyetheramines are polymers with a polyether backbone and amine groups as terminal active functional groups. The amine groups provide polyetheramines with the possibility of reacting with various compounds, and their unique molecular structure gives them excellent overall performance. Chain extenders are low-molecular-weight, multifunctional compounds containing hydroxyl or amino groups. Through reaction with polyetheramines, they form "bridges" between molecular chains, diffusing and extending the molecular chains, increasing molecular weight, and improving the viscosity of the system.

[0076] Weigh the polyether polyol and add it to a heating container. Stir at 20-60 rpm and heat to 100-160°C. After reaching a certain temperature, keep it at that temperature for 1-3 hours and then lower the temperature of the heating container to room temperature. Add a certain weight of isocyanate to the above solution, stir at 80-120 rpm and heat to 60-90°C. Keep it at that temperature for 1-2 hours to obtain solution C.

[0077] Preferably, the polyether polyol is weighed and added to a heating container, stirred at 50 rpm and heated to 120°C, kept at that temperature for 2 hours, and then the temperature inside the heating container is lowered to room temperature; a certain weight of isocyanate is added to the above solution, stirred at 100 rpm and heated to 70°C, and kept at that temperature for 2 hours to obtain solution C.

[0078] In this process, the main chain of the polyether polyol contains ether bonds (—R—O—R—), and the terminal or side groups contain more than two hydroxyl groups (—OH). Isocyanates include monoisocyanates (R—N=C=O) and diisocyanates (O=C=N—R—N=C=O). Because isocyanates contain unsaturated bonds, they are highly reactive and readily react with some organic or inorganic substances containing active groups (such as hydroxyl, amino, and carboxyl groups).

[0079] After weighing polyether polyol D, add it to a container and stir and disperse it thoroughly at 700-1000 rpm for 30-60 min. Then add auxiliary agent D and stir and disperse it thoroughly at 1800-2200 rpm for 30-60 min. After dispersing, grind it and test the fineness to be <30 μm. Filter it through a 100-400 mesh screen to obtain liquid D.

[0080] Preferably, the polyether polyol is weighed and added to a container, and then stirred and dispersed at 800 rpm for 40 minutes. After dispersion, the additives are added and stirred and dispersed at 2000 rpm for another 40 minutes. The mixture is then ground, and after the fineness is tested to be <30 μm, it is filtered through a 200-mesh filter to obtain solution D.

[0081] In this process, the main chain of the polyether polyol contains ether bonds (—R—O—R—), and the end groups or side groups contain more than two hydroxyl groups (—OH), which readily react with isocyanates.

[0082] After weighing the fatty acid ester, acrylate, and additives, add them to a heating container and stir and heat at 1200-1800 rpm to 40-80℃. After reaching a certain temperature, keep it at that temperature for 3-6 hours. Then, cool the temperature inside the heating container to room temperature and grind it. Test the fineness to be <30μm and filter it with a 100-400 mesh filter to obtain liquid E.

[0083] Preferably, fatty acid ester, acrylate, and additives are weighed and added to a heating container. The mixture is stirred and heated to 55°C at 1500 rpm and kept at that temperature for 4 hours. The temperature inside the heating container is then lowered to room temperature, followed by grinding. After testing the fineness to be <30 μm, the mixture is filtered through a 200-mesh filter to obtain liquid E.

[0084] In this process, lipophilic monomers undergo appropriate cross-linking to form acrylate copolymers with a three-dimensional network structure. These copolymers have a stable macroporous network structure and a high specific surface area, which can provide storage space for absorbed oil pollutants. The three-dimensional network structure surrounds the oil molecules within it.

[0085] During construction, separately packaged liquid A and liquid B are mixed in a mass ratio of 2:1 to 7:1 to obtain the coating for the inner healing layer. Separately packaged liquid A and liquid B are mixed in a mass ratio of 2:1 to 7:1 to obtain the coating for the outer healing layer. Separately packaged liquid C, liquid D and liquid E are mixed in a mass ratio of 1:1:1 to 10:7:5 to obtain the coating for the expansion layer.

[0086] A self-sealing coating is obtained by applying the healing layer: expansion layer: healing layer in a ratio of 1:1:1 to 3:2:3. The thickness range of the layer is selected as 6 to 12 mm.

[0087] This invention provides the application of the above-mentioned self-sealing coatings and / or coatings in the field of oil storage devices.

[0088] The coating can be applied to the surface of the oil storage device by spraying, brushing, rolling, or by attaching pre-made patches.

[0089] The coating can be applied to protect oil storage devices for gasoline, diesel, kerosene and other oil products.

[0090] Example 1

[0091] The preparation method of the multi-self-sealing coating described in this embodiment is as follows:

[0092] S1. Weigh 40 parts of polycaprolactone polyol, add it to a heating container, stir at 50 rpm and heat to 120°C, keep warm for 2 hours and then cool to room temperature; add 25 parts of diphenylmethane diisocyanate and 35 parts of 1,6-hexanediisocyanate to the container, stir at 100 rpm and heat to 70°C, keep warm for 2 hours to obtain solution A.

[0093] S2. Weigh 40 parts of amino-terminated polyoxypropylene ether, 6 parts of 1,4-butanediol, and 4 parts of trimethylolpropane and add them to a container. Stir and disperse thoroughly at 800 rpm for 40 min. Add 10 parts of plasticizer, 5 parts of reactive diluent, 4 parts of leveling agent, 6 parts of defoamer, and 25 parts of flame retardant to the container and stir and disperse thoroughly at 2000 rpm for 40 min. Grind the mixture and test the fineness to <30 μm. Filter the mixture through a 200-mesh screen to obtain solution B.

[0094] S3. Weigh 50 parts of polyoxypropylene glycol and add it to a heating container. Stir at 50 rpm and heat to 120°C. Keep warm for 2 hours and then cool to room temperature. Add 22 parts of toluene diisocyanate and 28 parts of diphenylmethane diisocyanate to the container. Stir at 100 rpm and heat to 70°C. Keep warm for 2 hours to obtain liquid C.

[0095] S4. Weigh 75 parts of tetrahydrofuran-propylene oxide copolymer glycol and add it to a container. Stir and disperse it thoroughly at 800 rpm for 40 min. Add 11 parts of defoamer and 14 parts of wetting agent to the container. Stir and disperse it thoroughly at 2000 rpm for 40 min. Grind it and test the fineness to be <30 μm. Filter it through a 200-mesh filter to obtain liquid D.

[0096] S5. Weigh 53 parts of fatty acid ester, 14 parts of methyl acrylate, 18 parts of ethyl 2-methacrylate, 3 parts of wetting agent, 5 parts of catalyst, and 7 parts of emulsifier and add them to a heating container. Stir at 1500 rpm and heat to 55°C. Keep at this temperature for 4 hours and then cool to room temperature. Grind the above solution and test the fineness to be <30 μm. Filter the solution through a 200-mesh filter to obtain solution E.

[0097] S6. Mix liquid A and liquid B in a 2:1 ratio to obtain the coating for the inner / outer healing layer, apply it to the sample and wait for curing; mix liquid C, liquid D and liquid E in a 10:7:5 ratio to obtain the coating for the expansion layer, apply it to the sample and wait for curing.

[0098] S7. The cured inner healing layer, expansion layer and outer healing layer are composited in a layer thickness ratio of 2:1:2, with a total thickness of 7mm, to obtain a self-sealing coating system.

[0099] In Example 1, the number of portions weighed is by weight.

[0100] Example 2

[0101] The self-sealing coating described in this embodiment is prepared using the following multi-component raw materials in parts by weight:

[0102] Solution A: 35 parts polycaprolactone polyol, 45 parts polyester diol, and 20 parts 1,6-hexamethylene diisocyanate.

[0103] Solution B: 29 parts amino-terminated polyoxypropylene ether, 41 parts amino-terminated polyoxyethylene ether, 8 parts 1,4-butanediol, 5 parts 1,6-hexanediol, 5 parts plasticizer, 1 part reactive diluent, 0.5 parts defoamer, 0.5 parts wetting agent, and 10 parts flame retardant.

[0104] Solution C: 28 parts of polytetrahydrofuran diol, 42 parts of tetrahydrofuran-propylene oxide copolymer diol, and 30 parts of diphenylmethane diisocyanate.

[0105] Liquid D: 31 parts polypropylene glycol, 39 parts polytetrahydrofuran glycol, 14 parts leveling agent, and 16 parts defoamer.

[0106] Liquid E: 70 parts fatty acid ester, 12 parts ethyl acrylate, 8 parts methyl 2-methacrylate, 2 parts leveling agent, 3 parts catalyst, and 5 parts emulsifier.

[0107] Wherein, "parts" refers to the number of parts by weight.

[0108] The mixing ratio of liquid A and liquid B is 2:1, and the mixing ratio of liquid C, liquid D and liquid E is 1:1:1. The inner healing layer, expansion layer and outer healing layer are composited according to a layer thickness of 1:1:1.

[0109] The preparation method is the same as in Example 1, except that the temperature and holding time are different:

[0110] In S1, the temperature is initially raised to 100℃ and held for 3 hours, then cooled to room temperature, and then raised to 60℃ again and held for 2 hours to prepare solution A.

[0111] In S3, the temperature is initially raised to 100℃ and held for 3 hours, then cooled to room temperature, and then raised to 60℃ again and held for 2 hours to prepare solution C.

[0112] In S5, during the preparation of liquid E, the temperature is raised to 40℃ and kept at that temperature for 6 hours to obtain liquid E.

[0113] The self-sealing coating system II was obtained according to the mixing ratio of each liquid and the thickness ratio of each layer in this embodiment, with the total thickness being the same as in Example 1.

[0114] Example 3

[0115] The self-sealing coating described in this embodiment is prepared using the following multi-component raw materials in parts by weight:

[0116] Solution A: 28 parts polycarbonate diol, 35 parts polyester diol, 17 parts toluene diisocyanate, and 20 parts diphenylmethane diisocyanate.

[0117] Component B: 51 parts amino-terminated polyoxyethylene ether, 13 parts 1,6-hexanediol, 7 parts trimethylolpropane, 7 parts plasticizer, 3 parts reactive diluent, 2 parts leveling agent, 1 part defoamer, 2 parts wetting agent, and 14 parts flame retardant.

[0118] Solution C: 32 parts polypropylene glycol, 48 parts polytetrahydrofuran glycol, 5 parts toluene diisocyanate, 7 parts diphenylmethane diisocyanate, and 8 parts 1,6-hexanediisocyanate.

[0119] Liquid D: 30 parts polyoxypropylene glycol, 50 parts tetrahydrofuran-propylene oxide copolymer glycol, 8 parts leveling agent, 6 parts defoamer, and 6 parts wetting agent.

[0120] Liquid E: 40 parts fatty acid ester, 21 parts methyl acrylate, 12 parts methyl 2-methacrylate, 15 parts ethyl 2-methacrylate, 1.5 parts leveling agent, 2.5 parts defoamer, 3 parts catalyst, and 5 parts emulsifier.

[0121] Wherein, "parts" refers to the number of parts by weight.

[0122] The mixing ratio of liquid A and liquid B is 7:1, and the mixing ratio of liquid C, liquid D and liquid E is 7:5:3. The inner healing layer, expansion layer and outer healing layer are composited according to a thickness ratio of 3:2:3.

[0123] The preparation method is the same as in Example 1, except that the temperature and holding time are different:

[0124] In S1, the temperature is initially raised to 160℃ and held for 1 hour, then cooled to room temperature, and then raised to 90℃ again and held for 1 hour to prepare solution A.

[0125] In S3, the temperature is initially raised to 160℃ and held for 1 hour, then cooled to room temperature, and then raised to 90℃ again and held for 1 hour to prepare solution C.

[0126] In S5, during the preparation of liquid E, the temperature is raised to 80℃ and kept at that temperature for 3 hours to obtain liquid E.

[0127] The self-sealing coating system III was obtained according to the mixing ratio of each liquid and the thickness ratio of each layer in this embodiment, with the total thickness being the same as in Example 1.

[0128] Comparative Example 1

[0129] The self-healing material provided in this comparative example consists of a recovery unit, a swelling and filling unit, and a self-healing and reinforcing unit.

[0130] The recovery unit comprises 5-10 parts of amino-terminated polyether and 4-6 parts of isocyanate; the swelling and filling unit comprises 4-10 parts of olefin and 3-5 parts of alkyl acrylate; the self-healing and reinforcing unit is composed of a capsule wall and a core material, wherein the capsule wall comprises 3-5 parts of paraffin, 5-8 parts of polyvinyl alcohol and 2-5 parts of polyacrylate; and the core material comprises 5-10 parts of epoxy-containing polysiloxane and 3-5 parts of tetramethylsilane.

[0131] The preparation method is as follows:

[0132] The recovery unit is obtained by uniformly mixing and cross-linking and curing amino-terminated polyether and isocyanate;

[0133] A swelling filler unit is obtained by uniformly mixing and cross-linking olefins and alkyl acrylates and then curing them.

[0134] Paraffin, polyvinyl alcohol and polyacrylate are mixed evenly and cross-linked to obtain the capsule wall. Epoxy-containing polysiloxane and tetramethylsilane are mixed evenly and cross-linked to obtain the capsule core. The capsule wall and capsule core are mixed evenly to obtain the self-healing and reinforcing unit.

[0135] The self-repairing and reinforcing unit was mixed evenly with the recovery unit and the swelling and filling unit to obtain a thickness of 7mm.

[0136] The same performance tests were performed on Examples 1-3 and Comparative Example 1, and the results are shown in Table 1.

[0137] Table 1

[0138]

[0139]

[0140] The tensile direction for the tensile strength test is parallel to the coating plane.

[0141] The partial test method for saturated oil absorption ratio is as follows: Weigh a certain mass (m) of material into a nylon bag, and record its weight as m1. Immerse it in a bottle containing 100mL of the oil to be tested. After 1 hour, remove it, drip it for 5 minutes, and record its weight as m2. Then immerse it in the oil to be tested again. Repeat this process continuously until the oil absorption reaches saturation, at which point record its weight as m3. Measure the oil absorption of the empty bag as m0. The formula for calculating the saturated oil absorption ratio is:

[0142] Saturated oil absorption ratio = Net oil absorption / Material mass

[0143] =(m3-m1-m0) / m

[0144] The oil resistance test method is as follows: after immersing in standard oil B at 40℃ for 1 month, observe whether there are any bubbles or peeling off of the coating.

[0145] As shown in Table 1, the bullet of Example 1 has the smallest diameter after being punctured, has a large rebound ability, and is not easily broken, which reflects its highest tensile strength.

[0146] Due to the protective effect of the healing layer, Examples 1-3 all exhibit good oil resistance, meeting the requirement of no blistering or peeling of the coating over a long period of time, and preventing oil leakage at the damaged location for an extended period of time.

[0147] The reason why it is difficult to evaluate all indicators in ratio 1 is that it does not have this function and it is difficult to complete the relevant tests.

[0148] Examples 1-3 all have high performance and can meet the protection requirements of oil storage devices.

[0149] The above description is merely a preferred embodiment of this application and is not intended to limit this application. Various modifications and variations can be made to this application by those skilled in the art. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of this application should be included within the protection scope of this application.

Claims

1. A self-sealing coating, characterized in that, Including healing coatings and expanding coatings; The materials for preparing the healing coating include liquid A and liquid B. Liquid A is prepared from the following components in parts by weight: 40-80 parts of polyester polyol and 20-60 parts of isocyanate. Liquid B is prepared from the following components in parts by weight: 40-70 parts of polyetheramine, 10-20 parts of chain extender and 10-25 parts of flame retardant. The materials for preparing the intumescent coating include liquid C, liquid D, and liquid E. The raw materials for preparing liquid C include the following components in parts by weight: 50-80 parts of polyether polyol and 20-50 parts of isocyanate; the raw materials for preparing liquid D include the following components in parts by weight: 70-80 parts of polyether polyol; and liquid E includes the following components in parts by weight: 40-70 parts of fatty acid ester and 20-48 parts of acrylate. The isocyanate composition in solution A and solution C may be the same or different; The polyether polyols in solution C and solution D may have the same or different compositions.

2. The self-sealing coating as described in claim 1, characterized in that, The polyester polyol includes one or more of polycaprolactone polyol, polycarbonate diol, and polyester diol; The isocyanate includes one or more of toluene diisocyanate, diphenylmethane diisocyanate, and 1,6-hexanediisocyanate. The polyether polyol includes one or more of polypropylene oxide diol, polytetrahydrofuran diol, and tetrahydrofuran-propylene oxide copolydiol. The polyetheramine includes one or more of terminal amino polyoxypropylene ether and terminal amino polyethylene oxide ether; The chain extender includes one or more of 1,4-butanediol, 1,6-hexanediol, and trimethylolpropane; The flame retardant includes one or more of aluminum hydroxide flame retardant or magnesium hydroxide flame retardant; The acrylates include one or more of methyl acrylate, ethyl acrylate, methyl 2-methacrylate, and ethyl 2-methacrylate.

3. The self-sealing coating as described in claim 1, characterized in that, Liquid A and liquid B are packaged separately; liquids C, D and E are packaged separately.

4. The self-sealing coating as described in claim 1, characterized in that, The raw materials for preparing liquid B include the following components in parts by weight: 5-10 parts plasticizer, 1-5 parts reactive diluent, and 1-10 parts additives; the raw materials for preparing liquid D include the following components in parts by weight: 20-30 parts additives; the raw materials for preparing liquid E include the following components in parts by weight: 10-15 parts additives. The additives in solution B, solution D, and solution E may have the same or different additive components.

5. The self-sealing coating as described in claim 4, characterized in that, The plasticizer is a phthalate plasticizer; The reactive diluent is a multifunctional reactive diluent; The additives include one or more of leveling agents, defoamers, wetting agents, catalysts, and emulsifiers, wherein the catalyst is an azo catalyst.

6. A self-sealing coating, characterized in that, The materials used in the preparation include the self-sealing coatings described in any one of claims 1-5; The self-sealing coating includes an inner healing layer disposed on the surface of the substrate, an expansion layer disposed outside the inner healing layer, and an outer healing layer disposed outside the expansion layer; the layer thickness ratio of the inner healing layer, the expansion layer, and the outer healing layer is 1:1:1 to 3:2:3; the total thickness is 6 to 12 mm. The coating for the inner healing layer is made by mixing liquid A and liquid B in a mass ratio of 2:1 to 7:

1. The coating of the expansion layer is composed of liquid C, liquid D and liquid E mixed in a mass ratio of 1:1:1 to 10:7:

5. The coating for the outer healing layer is made by mixing liquid A and liquid B in a mass ratio of 2:1 to 7:

1.

7. A method for preparing a self-sealing coating as described in any one of claims 1-5 and / or a self-sealing coating as described in claim 6, characterized in that, Weigh the polyester polyol and put it into a heating container. Stir at 20-60 rpm and heat to 100-160°C. After reaching the set temperature, keep it at the temperature for 1-3 hours and then lower the temperature of the heating container to room temperature. Add isocyanate to the above solution, stir at 80-120 rpm and heat to 60-90°C. Keep it at 1-2 hours to obtain solution A. After weighing the polyetheramine and chain extender, add them to a container and stir and disperse them thoroughly at 700-1000 rpm for 30-60 minutes. Then add the plasticizer, reactive diluent, additives, and flame retardant and stir and disperse them thoroughly at 1800-2200 rpm for 30-60 minutes. After grinding, test the fineness to be <30 μm and filter it through a 100-400 mesh screen to obtain solution B. Weigh the polyether polyol and add it to a heating container. Stir at 20-60 rpm and heat to 100-160°C. After reaching a certain temperature, keep it at that temperature for 1-3 hours and then lower the temperature of the heating container to room temperature. Add a certain weight of isocyanate to the above solution, stir at 80-120 rpm and heat to 60-90°C. Keep it at that temperature for 1-2 hours to obtain solution C. Weigh the polyether polyol and add it to a container. Stir and disperse it thoroughly at 700-1000 rpm for 30-60 min. Add the additive and stir and disperse it thoroughly at 1800-2200 rpm for 30-60 min. Grind it and test the fineness to be <30 μm. Filter it through a 100-400 mesh screen to obtain liquid D. After weighing the fatty acid ester, acrylate, and additives, add them to the heating container and stir and heat at 1200-1800 rpm to 40-80℃. After reaching a certain temperature, keep it at that temperature for 3-6 hours, then cool the temperature inside the heating container to room temperature, and then grind it. The fineness is tested to be <30μm and filtered through a 100-400 mesh filter to obtain liquid E. During construction, separately packaged liquid A and liquid B are mixed in a mass ratio of 2:1 to 7:1 to obtain the coating for the inner healing layer. Separately packaged liquid A and liquid B are mixed in a mass ratio of 2:1 to 7:1 to obtain the coating for the outer healing layer. Separately packaged liquid C, liquid D and liquid E are mixed in a mass ratio of 1:1:1 to 10:7:5 to obtain the coating for the expansion layer.

8. The preparation method according to claim 7, characterized in that, A self-sealing coating is obtained by applying a layer with a thickness ratio of 1:1:1 to 3:2:3 for the healing layer: expansion layer: healing layer.

9. The preparation method according to claim 7, characterized in that, After weighing the polyester polyol, put it into a heating container, stir at 50 rpm and heat to 120°C, keep at this temperature for 2 hours and then cool to room temperature; after adding isocyanate, stir at 100 rpm and heat to 70°C, keep at this temperature for 2 hours to obtain solution A. After weighing the polyetheramine and chain extender, add them to the container and stir and disperse them at 800 rpm. After dispersing for 40 min, add the plasticizer, reactive diluent, additives, and flame retardant and stir and disperse them at 2000 rpm. After dispersing for 40 min, grind them and filter them through a 200-mesh screen after testing the fineness to <30 μm to obtain liquid B. After weighing the polyether polyol, add it to the heating container, stir at 50 rpm and heat to 120°C, keep it at this temperature for 2 hours, and then lower the temperature of the heating container to room temperature; add a certain weight of isocyanate to the above solution, stir at 100 rpm and heat to 70°C, keep it at this temperature for 2 hours to obtain solution C. After weighing the polyether polyol, add it to the container and stir and disperse it at 800 rpm. After dispersing for 40 min, add the additive and stir and disperse it at 2000 rpm. After dispersing for 40 min, grind it. After testing the fineness to be <30 μm, filter it through a 200 mesh filter to obtain liquid D. After weighing the fatty acid ester, acrylate, and additives, add them to a heating container. Stir and heat at 1500 rpm to 55°C, then keep at that temperature for 4 hours. After cooling the temperature inside the heating container to room temperature, grind the mixture. After testing the fineness to be <30 μm, filter the mixture through a 200-mesh filter to obtain liquid E.

10. The preparation method according to claim 7, characterized in that, The total thickness of the self-sealing coating is 7mm.

11. The application of a self-sealing coating according to any one of claims 1-5 and / or a self-sealing coating according to claim 6 and / or a preparation method according to any one of claims 7-8 in the field of oil storage devices.

12. The application in the field of oil storage devices as described in claim 11, characterized in that, It is applied to the surface of the oil storage device by spraying, brushing, roller coating, or by attaching pre-made patches.

13. The application in the field of oil storage devices as described in claim 11, characterized in that, It is used for the protection of oil storage devices for gasoline, diesel, and kerosene.

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