A super-slippery resin and its application in the preparation of self-cleaning membrane materials

Abstract

This invention relates to a super-lubricating resin and its application in the preparation of self-cleaning film materials. The super-lubricating resin comprises, by weight (100%), the following components in the following percentages: 23%–28% first monomer, 1%–4% second monomer, 10%–16% third monomer, 3%–6% polymeric active silane coupling agent, 6%–10% trifluoro-non-isocyanate polyurethane acrylate, 1%–2% initiator, 0.1%–0.5% chain transfer agent, and the balance being a first solvent; wherein the first monomer is selected from one or more of methacrylic acid and methacrylates in any proportion; the second monomer is selected from fluorinated acrylate monomers; and the third monomer is selected from hydroxyl-containing active crosslinking monomers. The self-cleaning film comprising the super-lubricating resin of this invention can significantly improve the corrosion resistance, stain resistance, animal protein resistance, and mildew resistance of the original paint film on vehicles.

Description

[0001] This application is a divisional application of Chinese invention patent application No. 202211467051.6, filed on November 22, 2022, entitled "A self-cleaning membrane material composition and its preparation method and application". Technical Field

[0002] This invention belongs to the field of polymer materials technology, specifically relating to a super-slippery resin and its application in the preparation of self-cleaning membrane materials, as well as a self-cleaning membrane material composition, its preparation method, and its application. Background Technology

[0003] The cleanliness of the exterior surface of rail transit vehicles (including but not limited to high-speed trains, high-speed EMUs, ordinary railway passenger cars, and urban rail transit vehicles) is an important indicator of the vehicle's aesthetic appearance and a significant factor affecting the passenger experience. During high-speed operation, particulate matter in the air, dust particles along the tracks, and protein residue from insect and bird strikes all contaminate the vehicle's exterior surface. This is particularly pronounced on the bodies of high-speed trains and high-speed EMUs operating at high frequencies. For exterior surface contamination, cleaning agents are commonly used, and cleaning is performed manually or by automated machinery. Manual cleaning is more thorough and effective, but it is also more expensive. Taking an 8-car high-speed EMU as an example, according to railway bureau statistics, an average of 4 exterior cleanings are performed per day, costing 120 yuan each time, while interior cleaning costs 300 yuan per cleaning, totaling 286,160 yuan annually. A railway bureau owns no fewer than 150 EMUs, meaning the annual cleaning cost alone exceeds 50 million yuan, not even considering the costs of other vehicles, water, electricity, and cleaning agents. Meanwhile, manual washing can easily damage the car's paint, leading to common problems such as paint aging, yellowing, and localized peeling, thus reducing the paint's lifespan. Mechanical automated cleaning, on the other hand, often misses many hard-to-reach areas, resulting in incomplete cleaning; furthermore, the long-term accumulation of contaminants can also damage the paint.

[0004] In everyday applications such as automotive glass and building glass facades, as well as high-end fields like optical and optoelectronic devices, reports have documented the use of superhydrophobic coatings for surface self-cleaning. Superhydrophobicity requires a stable contact angle greater than 150° and a roll-off contact angle less than 10° on the material surface. Water droplets on the surface are spherical and roll off under their own weight or external force. For example, patent application CN107513176A discloses a method for preparing a transparent superhydrophobic polymer film, involving supercritical CO2 foaming of a pre-formed transparent thermoplastic polymer film to create a special structure of nanopapillary protrusions and grooves on the polymer film surface, achieving superhydrophobicity and low reflectivity while maintaining transparency. However, this method requires specific process conditions, is difficult to prepare, and is not easily implemented. Patent application CN106835043A discloses a transparent superhydrophobic film comprising a zinc oxide film and a fluorinated carbon film loaded on the surface of the zinc oxide film. The preparation of zinc oxide thin films involves first preparing a zinc film using a radio frequency magnetron sputtering system, followed by annealing. The resulting zinc oxide film then undergoes fluorination treatment, such as using a carbon- and fluorine-containing gas as the working gas in an etching system. Completing this preparation process requires specialized and expensive equipment. Patent application CN101492544A discloses a method where a mixture of tetraethyl orthosilicate, ethanol, ammonia, and water is dried and then self-assembled in a solution of alkyl and fluorinated silane coupling agents to form a superhydrophobic self-cleaning membrane. The inventors found that while the films prepared by this method have high mechanical strength, their weather resistance is poor.

[0005] Applying superhydrophobic films to the exterior surfaces of rail transit vehicles may be an effective way to solve surface contamination and improve the appearance of the vehicles. However, the film must at least meet the relevant standards, such as the technical indicators of Q / CR546.1-2016 "Coatings and Coating Systems for High-Speed ​​Trains - Part 1: Coatings and Coating Systems for Exterior Surfaces of Trains" as shown in Table 1.

[0006] Table 1 Technical Requirements for Surface Clear Coating of High-Speed ​​Trains in my country

[0007]

[0008] Secondly, the film also needs to possess specific properties and characteristics suitable for rail transit, such as low cost, simple and easy preparation method, and excellent adhesion and weather resistance. Clearly, there is currently no superhydrophobic film with self-cleaning properties suitable for preventing fouling on the outer surface of rail transit vehicles, especially high-speed train vehicles. Summary of the Invention

[0009] To overcome the shortcomings of existing technologies, this invention provides a self-cleaning membrane material composition and its preparation method. By coating the composition of this invention onto the surface of a rail vehicle body and undergoing a simple curing process, a firm and uniform self-cleaning membrane with a thickness of 30–50 μm can be formed on the vehicle body surface.

[0010] To achieve the above-mentioned technical effects, the present invention adopts the following technical solution:

[0011] A super-lubricating resin, comprising, by weight percentage, the following components, at 100% of the total mass of the super-lubricating resin:

[0012] The composition includes: 23%–28% first monomer, 1%–4% second monomer, 10%–16% third monomer, 3%–6% polymerizable active silane coupling agent, 6%–10% trifluoro-nonisocyanate polyurethane acrylate (FNIPUA), 1%–2% initiator, 0.1%–0.5% chain transfer agent, and the balance being the first solvent; wherein,

[0013] The first monomer is selected from one or more of methacrylic acid and methacrylate in any proportion;

[0014] The second monomer is selected from fluorinated acrylate monomers;

[0015] The third monomer is selected from hydroxyl-containing active crosslinking monomers.

[0016] Preferably, the methacrylate is selected from one of methyl methacrylate, butyl methyl methacrylate, lauryl methacrylate, isobornyl methacrylate, and octadecyl methacrylate.

[0017] Preferably, the fluorinated acrylate monomer is selected from at least one of trifluoroethyl acrylate, tetrafluoropropyl acrylate, trifluoroethyl methacrylate, tetrafluoropropyl methacrylate, hexafluorobutyl acrylate, hexafluorobutyl methacrylate, hexafluoroisopropyl acrylate, and hexafluoroisopropyl methacrylate.

[0018] More preferably, the fluorinated alkyl acrylate monomer is selected from at least one of hexafluorobutyl acrylate, hexafluorobutyl methacrylate, hexafluoroisopropyl acrylate, and hexafluoroisopropyl methacrylate.

[0019] Preferably, the hydroxyl-containing active crosslinking monomer is selected from at least two of 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, 4-hydroxybutyl methacrylate, 4-hydroxybutyl acrylate, and hydroxyethylcaprolactone acrylate.

[0020] More preferably, the hydroxyl-containing active crosslinking monomer is selected from at least one of 2-hydroxyethyl methacrylate and 2-hydroxyethyl acrylate.

[0021] Preferably, the polymeric active silane coupling agent is selected from at least one of γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-methacrylic acid oxypropylmethyldimethoxysilane, γ-methacryloxypropylmethyldiethoxysilane, γ-acetoxypropyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, and vinyltriisopropoxysilane.

[0022] More preferably, the polymeric active silane coupling agent is selected from at least one of γ-methacrylic acid propylmethyl dimethoxysilane and γ-methacryloyloxypropylmethyl diethoxysilane.

[0023] Preferably, the initiator is selected from at least one of 2,2'-azobis(2-methylpropionitrile) and 2,2'-bisazo-(2,4-dimethylpentanonitrile).

[0024] Preferably, the chain transfer agent is selected from at least one of n-dodecyl mercaptan, secondary dodecyl mercaptan, tertiary dodecyl mercaptan, cyclohexyl mercaptan, isooctyl 3-mercaptopropionate, n-butyl 3-mercaptopropionate, n-octyl mercaptan, mercaptoethanol, and mercaptoacetic acid.

[0025] More preferably, the chain transfer agent is selected from at least one of dodecyl mercaptan, isooctyl 3-mercaptopropionate, and n-butyl 3-mercaptopropionate.

[0026] Preferably, the trifluoro-nonisocyanate polyurethane acrylate (FNIPUA) has the following structure:

[0027]

[0028] R is selected from -H or -CH3.

[0029] Preferably, the first solvent is selected from at least one of benzene solvents, ester solvents, and ketone solvents.

[0030] More preferably, the first solvent is selected from at least one of xylene, butyl acetate, and methyl isobutyl ketone.

[0031] The present invention also provides a method for preparing the above-mentioned superlubricating resin, comprising the following steps:

[0032] I. Prepare each component according to the mass ratio;

[0033] II. Divide the first solvent and the initiator into three parts each. Based on their total mass, the first part accounts for 8% to 12%, the second part accounts for 78% to 82%, and the third part accounts for 10%.

[0034] III. Mix the first part of the first solvent and the first part of the initiator, heat to 75℃~85℃, and dropwise add the mixture of the second part of the first solvent, the second part of the initiator, the first monomer, the second monomer, the third monomer, the polymerizable active silane coupling agent and the trifluoro-nonisocyanate polyurethane acrylate. After the addition is complete, keep the temperature for 2h~4h. Then add the third part of the mixture of the first solvent and the third part of the initiator, and keep the temperature for 1h~3h. Finally, add the chain transfer agent and cool to 20℃~30℃ to obtain the final product.

[0035] Preferably, the method for preparing the superlubricating resin includes the following steps:

[0036] I. Prepare each component according to the mass ratio;

[0037] II. Divide the first solvent and the initiator into three parts each. Based on their total mass, the first part accounts for 8% to 12%, the second part accounts for 78% to 82%, and the third part accounts for 10%.

[0038] III. Mix the first part of the first solvent and the first part of the initiator, heat to 75℃~85℃, and dropwise add the mixture of the second part of the first solvent, the second part of the initiator, the first monomer, the second monomer, the third monomer, the polymerizable active silane coupling agent, and the trifluoro-nonisocyanate polyurethane acrylate. After the addition is complete, maintain the temperature for 2.5h~3.5h. Then add the third part of the mixture of the first solvent and the third part of the initiator, and maintain the temperature for 1.5h~2.5h. Finally, add the chain transfer agent and cool to 20℃~30℃ to obtain the final product.

[0039] Preferably, the mixture of the solvent, initiator, first monomer, second monomer, third monomer, polymerizable active silane coupling agent and trifluoro-nonisocyanate polyurethane acrylate is added dropwise over a period of 1.5 h to 2.5 h.

[0040] The present invention also provides the application of the above-mentioned super-slippery resin in the preparation of self-cleaning membrane materials.

[0041] Therefore, the present invention also provides a self-cleaning membrane material composition comprising the above-mentioned super-slippery resin; the self-cleaning membrane material composition is composed of component A and component B, wherein the mass ratio of component A to component B is 1.5 to 2.5:1; wherein,

[0042] Component A includes: 20-70 parts by weight of the above-mentioned super-slippery resin, 2-15 parts by weight of organosilicon resin, 3-20 parts by weight of silane-modified nano-alumina, 0.01-0.1 parts by weight of catalyst, 0.2-2 parts by weight of surface additives, and 5-20 parts by weight of second solvent.

[0043] Component B comprises: 5-25 parts by weight of isocyanate curing agent and 15-30 parts by weight of third solvent.

[0044] Preferably, the mass ratio of component A to component B is 2:1.

[0045] Preferably, component A comprises: 30-60 parts by weight of the above-mentioned super-lubricating resin, 2-10 parts by weight of the organosilicon resin, 3-15 parts by weight of the silane-modified nano-alumina, 0.01-0.1 parts by weight of the catalyst, 0.2-2 parts by weight of the surface additive, and 5-20 parts by weight of the second solvent.

[0046] More preferably, component A comprises: 40-50 parts by weight of the above-mentioned super-lubricating resin, 3-5 parts by weight of the organosilicon resin, 6-10 parts by weight of the silane-modified nano-alumina, 0.02-0.05 parts by weight of the catalyst, 0.5-1 parts by weight of the surface additive, and 10-15 parts by weight of the second solvent.

[0047] Preferably, component B comprises: 5-20 parts by weight of isocyanate curing agent and 15-30 parts by weight of third solvent.

[0048] More preferably, component B comprises: 10-15 parts by weight of isocyanate curing agent and 20-25 parts by weight of third solvent.

[0049] Preferably, the silicone resin is selected from one or two of MQ silicone resin and polyhedral oligomeric silsesquioxane (POSS).

[0050] Preferably, the M / Q molar ratio of the MQ silicone resin is 0.5 to 2.0:1.

[0051] More preferably, the M / Q molar ratio of the MQ silicone resin is 0.6 to 1.0:1.

[0052] Preferably, the weight-average molecular weight of the MQ silicone resin is 5000 to 30000.

[0053] More preferably, the weight-average molecular weight of the MQ silicone resin is 6000 to 15000.

[0054] Preferably, the polyhedral oligomeric silsesquioxane is Aldrich's Q8M8H.

[0055] Preferably, the silane-modified nano-alumina is prepared by C... 12 -C 18 The surface-modified nano-alumina of long-chain alkyltriethoxysilane has an average particle size of 5–20 nm.

[0056] Preferably, the silane-modified nano-alumina is prepared by the following method:

[0057] Nano-alumina, C 12 -C 18The long-chain alkyltriethoxysilane, isopropanol, and ion exchange resin catalyst are mixed, and the reactants are heated to 70-80°C and refluxed for 4-6 hours. After cooling to room temperature, the mixture is filtered, and the filter cake is dried at 100-110°C for 1-3 hours to obtain the final product. The mass percentage of each component is as follows, based on the total mass of the reactants:

[0058] Nano-alumina 25-35%, C 12 -C 18 It contains 4-6% long-chain alkyltriethoxysilane, 1.5-2.5% ion exchange resin catalyst, and the balance isopropanol.

[0059] Preferably, the ion exchange resin catalyst is K16 ion exchange resin catalyst from the Chemical Research Institute of Guangdong Academy of Sciences.

[0060] Preferably, the catalyst is selected from at least one of organotin catalysts and organobismuth catalysts.

[0061] Preferably, the organotin catalyst is selected from dibutyltin dilaurate, dioctyltin dilaurate, dimethyltin dilaurate, dibutyltin diacetate, dimethyltin diacetate, stannous octanoate, monobutyltin oxide, or dibutyltin maleate.

[0062] Preferably, the organic bismuth catalyst is selected from bismuth neodecanoate, bismuth laurate, bismuth isooctanoate, or bismuth naphthenate.

[0063] Preferably, the surface additive is a wetting agent or a leveling agent.

[0064] More preferably, the surface additive is selected from at least one of the following: Gemini wetting agent SE-5100 and silicone leveling agent BOW-307 containing polyester-modified hydroxyl functional groups. Both of the above surface additives are produced by Guangdong Jinbo Chemical Co., Ltd.

[0065] Preferably, the second solvent and the third solvent are each independently selected from at least one of benzene solvents, ester solvents and ketone solvents.

[0066] More preferably, the second solvent and the third solvent are each independently selected from at least one of toluene, xylene, butyl acetate, ethyl acetate, amyl acetate, isooctyl acetate, butanone, methyl isobutyl ketone, ethylene glycol butyl ether acetate, ethylene glycol diacetate, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, dimethyl succinate, dimethyl glutarate, dimethyl adipate, and dimethyl phthalate.

[0067] Preferably, component A is prepared by the following steps:

[0068] Mix all components in component A according to the specified ratio to obtain the final product.

[0069] Preferably, component B is prepared by the following steps:

[0070] Mix all components in component B according to the specified ratio to obtain the final product.

[0071] Preferably, during the preparation of components A and B, the stirring speed for each component is 50 r / min to 400 r / min, more preferably 100 r / min to 300 r / min.

[0072] Preferably, during the preparation of components A and B, the stirring and mixing temperature is 5°C to 60°C, more preferably 10°C to 40°C, and even more preferably 20°C to 25°C.

[0073] Preferably, during the preparation of component A and component B, the stirring and mixing time for each component is 5 to 40 minutes, more preferably 10 to 20 minutes.

[0074] Another objective of this invention is to provide a self-cleaning membrane material, which is formed by curing the above-mentioned self-cleaning membrane material composition as raw material.

[0075] The present invention also provides a method for preparing the above-mentioned self-cleaning membrane material, comprising the following steps:

[0076] Mix components A and B evenly according to the specified mass ratio, form a film on a carrier, and cure at 30–80°C for 2–48 hours to obtain the final product.

[0077] Preferably, the curing temperature is 40–70°C, more preferably 55–65°C.

[0078] Preferably, the curing time is 12 to 24 hours.

[0079] In addition, another objective of this invention is to provide the application of the above-mentioned self-cleaning membrane material composition in rail transit vehicles, specifically as follows:

[0080] Clean the outer surface of the paint on the rail transit vehicle; mix the components A and B evenly according to the mass ratio, spray the mixture onto the outer surface of the paint on the rail transit vehicle, and cure at 30-80℃ for 2-48 hours to form a self-cleaning film with a thickness of 30-50μm.

[0081] Preferably, the rail transit vehicles include ordinary high-speed trains, high-speed EMU trains, and subway trains.

[0082] The super-slippery resin provided by this invention utilizes the synergistic effect of two isooctyl groups in the fluorinated acrylate monomer and the trifluoro-nonisocyanate polyurethane acrylate (FNIPUA) structural unit to reduce the surface energy of the self-cleaning membrane material, thereby endowing the self-cleaning membrane with excellent hydrophobic and weather-resistant properties.

[0083] The super-slippery resin provided by this invention uses trifluoro-non-isocyanate polyurethane acrylate (FNIPUA) monomer as the main film-forming component. Because FNIPUA contains both amide and ester bonds of polyurethane, it combines the advantages of both polyurethane and polyacrylate, resulting in excellent compatibility and adhesion between the self-cleaning film of this invention and the acrylic-polyurethane paint on the outer surface of rail vehicle bodies. Furthermore, the polymeric active silane coupling agent contained in the super-slippery resin greatly improves the system compatibility between the super-slippery resin and the organosilicon resin and modified nano-alumina of the self-cleaning film material, enhancing the adhesion of the self-cleaning film to the acrylic-polyurethane paint on the outer surface of rail vehicle bodies. It also solves the problem of easy damage and peeling of the paint film (including the paint itself and the self-cleaning film) on rail transit vehicles (especially high-speed trains) during high-speed operation.

[0084] The self-cleaning membrane provided by this invention uses silicone resin and modified nano-alumina as reinforcing materials. The silicone resin is dissolved in the solvent system and fills the gaps between the modified nano-alumina particles during the curing process, thereby improving the membrane's density and strength and ensuring its impact resistance during high-speed train operation. Simultaneously, the long-chain alkyl modification of the nano-alumina surface reduces the dynamic friction coefficient of the membrane material. Attached Figure Description

[0085] The present invention will be further described below with reference to the accompanying drawings.

[0086] Figure 1 The infrared spectrum of the superlubricating resin prepared in Example 1 of this invention.

[0087] Figure 2 The water contact angle of the self-cleaning membrane material prepared in Example 4 of the present invention is shown.

[0088] Figure 3 The water contact angle of the self-cleaning membrane material prepared in Example 5 of the present invention is shown. Detailed Implementation

[0089] The present invention will be described below with reference to specific embodiments. Those skilled in the art will understand that these embodiments are for illustrative purposes only and do not limit the scope of the invention in any way.

[0090] Unless otherwise specified, the experimental methods used in the following examples are conventional methods. Unless otherwise specified, all raw materials and reagents used in the following examples are commercially available products. The purchase details of some reagents and raw materials are as follows:

[0091] Trifluoro-nonisocyanate polyurethane acrylate (FNIPUA), Gemini wetting agent SE-5100, and silicone leveling agent BOW-307 were purchased from Guangdong Jinbo Chemical Co., Ltd.

[0092] Polyhedral oligomeric silsesquioxane (POSS) Q8M8H: Aldrich.

[0093] The silane-modified nano-alumina used in the following examples and comparative examples was prepared by the following method:

[0094] Nano-alumina, C 12 -C 18 The long-chain alkyltriethoxysilane, isopropanol, and ion exchange resin catalyst K16 are mixed. The reactants are heated to 70–80°C and refluxed for 4–6 hours. After cooling to room temperature, the mixture is filtered, and the filter cake is dried at 100–110°C for 1–3 hours to obtain the final product. The mass percentage of each component is as follows, based on the total mass of the reactants:

[0095] Nano-alumina 25-35%, C 12 -C 18 It contains 4-6% long-chain alkyltriethoxysilane, 1.5-2.5% ion exchange resin catalyst, and the balance isopropanol.

[0096] The ion exchange resin catalyst can be K16 produced by the Chemical Research Institute of Guangdong Academy of Sciences.

[0097] Example 1: A super-slippery resin

[0098] The raw material formulation of the super-lubricating resin in this embodiment is shown in Table 2; it is prepared by the following method:

[0099] A mixture of 42.2 g xylene and 1.5 g 2,2'-azobis(2-methylpropionitrile) was heated to 80 °C. A mixture of 337.6 g xylene, 12 g 2,2'-azobis(2-methylpropionitrile), 210 g methyl methacrylate, 10 g methacrylic acid, 50 g methyl methacrylate, 20 g hexafluorobutyl methacrylate, 60 g γ-methacrylate propylmethyldimethoxysilane, 80 g trifluoro-nonisocyanate polyurethane acrylate (FNIPUA), and 130 g 2-hydroxyethyl methacrylate was added dropwise over 2 hours. The reaction was maintained at 85 °C for 3 hours. Then, the mixture of 42.2 g xylene and 1.5 g 2,2'-azobis(2-methylpropionitrile) was added, and the reaction was maintained at 85 °C for 1.5 to 2.5 hours. Finally, 3 g n-dodecyl mercaptan was added, and the temperature was lowered to 25 °C to obtain a super-slippery resin.

[0100] The infrared spectrum of the superlubricating resin obtained in this embodiment is shown in [reference needed]. Figure 1 . Figure 1 Shown: 3485cm -1The broad and strong peak at 2955 cm⁻¹ is the absorption peak of the -OH stretching vibration, indicating that the modified acrylic resin segments have been grafted with hydroxyl-containing structural units (methacrylic acid, 2-hydroxyethyl methacrylate); -1 and 2856cm -1 The corresponding absorption peaks are the stretching vibrations of -CH3 and -CH2-; 1732 cm⁻¹ -1 This is the absorption peak of the asymmetric stretching vibration of the C=O bond on the ester group, which originates from the C=O absorption peak of acrylic resin; 1151 cm⁻¹ -1 The peak at 1263 cm⁻¹ represents the asymmetric stretching peak of COC. -1 The corresponding peaks are the characteristic absorption peaks of -CF3 and -CF2- at 1020 cm⁻¹. -1 and 1093cm -1 The presence of a Si-OC absorption peak indicates that both the organic fluorine monomers (hexafluorobutyl methacrylate and FNIPUA) and the organosilane coupling agent monomers participated in the polymerization reaction, and the absence of a peak at 1680 cm⁻¹ in the spectrum further supports this. -1 1620cm -1 The C=C stretching vibration peak indicates that the monomer polymerization is basically complete, confirming that the desired super-lubricating resin structure has been obtained.

[0101] Example 2: A super-slippery resin

[0102] The raw material formulation of the super-lubricating resin in this embodiment is shown in Table 2; it was prepared by the following method:

[0103] A mixture of 49.5 g butyl acetate and 1 g 2,2'-azobis(2-methylpropionitrile) was heated to 85 °C. A mixture of 396 g butyl acetate, 8 g 2,2'-azobis(2-methylpropionitrile), 130 g methyl methacrylate, 20 g methacrylic acid, 110 g butyl methacrylate, 40 g hexafluorobutyl methacrylate, 30 g γ-methacryloyloxypropylmethyldiethoxysilane, 60 g trifluoro-nonisocyanate polyurethane acrylate (FNIPUA), and 100 g 2-hydroxyethyl acrylate was added dropwise over 1.5 h. The reaction was maintained at 85 °C for 2.5 h. Then, the mixture of 49.5 g butyl acetate and 1 g 2,2'-azobis(2-methylpropionitrile) was added, and the reaction was maintained at 85 °C for 2.5 h. Finally, 5 g isooctyl 3-mercaptopropionate was added, and the temperature was lowered to 20 °C to obtain a super-lubricating resin.

[0104] The infrared spectrum of the super-lubricating resin in this embodiment (spectrum omitted) is similar to that of the super-lubricating resin in Example 1.

[0105] Example 3: A super-slippery resin

[0106] The raw material formulation of the super-lubricating resin in this embodiment is shown in Table 2; it was prepared by the following method:

[0107] Mix 20g butyl acetate, 19.9g methyl isobutyl ketone, and 2g 2,2'-diazo-(2,4-dimethylpentanonitrile), heat to 75℃, and then add dropwise 160g butyl acetate, 159.2g methyl isobutyl ketone, 16g 2,2'-diazo-(2,4-dimethylpentanonitrile), 180g methyl methacrylate, 30g isobornyl methacrylate, 10g methacrylic acid, 60g octadecyl methacrylate, 10g hexafluoroisopropyl methacrylate, and 30g γ-methacrylate oxide. A mixture of methyl dimethoxysilane, 100g of trifluoro-nonisocyanate polyurethane acrylate (FNIPUA), and 160g of 2-hydroxyethyl methacrylate was added dropwise over 2.5 hours. The reaction was maintained at 75°C for 3.5 hours. Then, a mixture of 20g of butyl acetate, 19.9g of methyl isobutyl ketone, and 2g of 2,2'-diazo-(2,4-dimethylpentanonitrile) was added, and the reaction was maintained at 75°C for 1.5 hours. Finally, 1 part of n-butyl 3-mercaptopropionate was added, and the temperature was lowered to 30°C to obtain a super-slippery resin.

[0108] The infrared spectrum of the super-lubricating resin in this embodiment (spectrum omitted) is similar to that of the super-lubricating resin in Example 1.

[0109] Table 2. Raw material formulations of super-slippery resins in Examples 1-3

[0110]

[0111] Example 4: A self-cleaning membrane material composition and the prepared self-cleaning membrane

[0112] The self-cleaning membrane material composition of this embodiment is formed by mixing component A and component B in a mass ratio of 2:1, wherein: the raw material composition of component A is (10g = 1 part by weight):

[0113] 450g of the super-slippery resin from Example 1;

[0114] MQ silicone resin (M / Q = 0.8 (mol / mol), weight average molecular weight 10000) 30g;

[0115] Dodecyltriethoxysilane modified nano-alumina (average particle size 10nm) 80g;

[0116] 0.3g of dibutyltin dilaurate;

[0117] Gemini wetting agent SE-5100 8g;

[0118] 120g of propylene glycol methyl ether acetate;

[0119] The raw material composition of component B is (10g = 1 part by weight):

[0120] 1,6-Hexamethylene diisocyanate 130g;

[0121] 160g of methyl isobutyl ketone;

[0122] 50g of dimethyl glutarate.

[0123] The self-cleaning membrane material composition of this embodiment is prepared by the following steps:

[0124] (1) Stir all the raw materials of component A at room temperature at a speed of 200 r / min for 15 minutes to obtain component A;

[0125] (2) Stir all the raw materials of component B at 100 r / min at room temperature for 10 minutes to obtain component B;

[0126] (3) The A component obtained in step (1) and the B component obtained in step (2) are stirred at a mass ratio of 2:1 at room temperature at a speed of 100 r / min for 10 minutes to obtain a self-cleaning membrane material composition.

[0127] The above-mentioned self-cleaning film material composition was sprayed onto the white exterior paint surface of a rail transit EMU and cured at 60°C for 24 hours to obtain a self-cleaning film with a thickness of 45μm adhering to the exterior paint surface.

[0128] Example 5: A self-cleaning membrane material composition and the prepared self-cleaning membrane

[0129] The self-cleaning membrane material of this embodiment is composed of component A and component B mixed in a mass ratio of 2:1, wherein the raw material composition of component A is (10g = 1 part by weight):

[0130] 500g of super-slippery resin from Example 2;

[0131] MQ silicone resin (M / Q = 0.6 mol / mol, weight-average molecular weight 15000) 30g;

[0132] 60g of hexadecyltriethoxysilane modified nano-alumina (average particle size 5nm);

[0133] Stannous octanoate 0.2g;

[0134] Gemini wetting agent SE-5100 10g;

[0135] 100g of xylene;

[0136] The raw material composition of component B is (10g = 1 part by weight):

[0137] 1,6-Hexamethylene diisocyanate 100g;

[0138] 200g of methyl isobutyl ketone;

[0139] 50g of dimethyl adipic acid.

[0140] The self-cleaning membrane material composition of this embodiment is prepared by the following steps:

[0141] (1) Stir all the raw materials of component A at 100 r / min at room temperature for 20 minutes to obtain component A;

[0142] (2) Stir all the raw materials of component B at 100 r / min at room temperature for 10 minutes to obtain component B;

[0143] (3) The A component obtained in step (1) and the B component obtained in step (2) are stirred at a mass ratio of 2:1 at room temperature at a speed of 100 r / min for 10 minutes to obtain the self-cleaning membrane material composition of this embodiment.

[0144] The above-mentioned self-cleaning film material composition was sprayed onto the white exterior paint surface of a rail transit EMU and cured at 60°C for 12 hours to obtain a self-cleaning film with a thickness of 30 μm adhering to the exterior paint surface.

[0145] Example 6: A self-cleaning membrane material composition and the prepared self-cleaning membrane

[0146] The self-cleaning membrane material of this embodiment is composed of component A and component B mixed in a mass ratio of 2:1, wherein the raw material composition of component A is (10g = 1 part by weight):

[0147] Example 3: 400g of super-slippery resin;

[0148] MQ silicone resin (M / Q = 1.0 (mol / mol), weight-average molecular weight 6000) 50g;

[0149] Octadecyltriethoxysilane modified nano-alumina (average particle size 20nm) 80g;

[0150] 0.5g of dioctyltin dilaurate;

[0151] Polyester-modified hydroxyl-functionalized silicone leveling agent BOW-307 5g;

[0152] 150g of xylene;

[0153] The raw material composition of component B is (10g = 1 part by weight):

[0154] 150g of bis(4-isocyanate-cyclohexyl)methane;

[0155] 140g of xylene;

[0156] 50g of propylene glycol ethyl ether acetate.

[0157] The self-cleaning membrane material composition of this embodiment is prepared by the following steps:

[0158] (1) Stir all the raw materials of component A at room temperature at a speed of 300 r / min for 10 minutes to obtain component A;

[0159] (2) Stir all the raw materials of component B at 100 r / min at room temperature for 10 minutes to obtain component B;

[0160] (3) The A component obtained in step (1) and the B component obtained in step (2) are stirred at a mass ratio of 2:1 at room temperature at a speed of 100 r / min for 10 minutes to obtain the self-cleaning membrane material composition of this embodiment.

[0161] The above-mentioned self-cleaning film material composition was sprayed onto the white exterior paint surface of a rail transit EMU and cured at 60°C for 18 hours to obtain a self-cleaning film with a thickness of 50 μm adhering to the exterior paint surface.

[0162] Example 7: A self-cleaning membrane material composition and the prepared self-cleaning membrane

[0163] The self-cleaning membrane material liquid of this embodiment is composed of component A and component B mixed in a mass ratio of 2:1, wherein: the raw material composition of component A is (10g = 1 part by weight):

[0164] 450g of the super-slippery resin from Example 1;

[0165] 30g of silicone resin (M / Q = 0.8, weight average molecular weight 10000);

[0166] Octadecyltriethoxysilane modified nano-alumina (average particle size 15nm) 100g;

[0167] 0.5g of organic bismuth catalyst;

[0168] Gemini wetting agent SE-5100 8g;

[0169] 120g of propylene glycol methyl ether acetate;

[0170] The raw material composition of component B is (10g = 1 part by weight):

[0171] 1,6-Hexamethylene diisocyanate 130g;

[0172] 160g of methyl isobutyl ketone;

[0173] 50g of dimethyl glutarate.

[0174] The self-cleaning membrane material composition of this embodiment is prepared by the following steps:

[0175] (1) Stir all the raw materials of component A at room temperature at a speed of 200 r / min for 15 minutes to obtain component A;

[0176] (2) Stir all the raw materials of component B at 100 r / min at room temperature for 10 minutes to obtain component B;

[0177] (3) The A component obtained in step (1) and the B component obtained in step (2) are stirred at a mass ratio of 2:1 at room temperature at a speed of 100 r / min for 10 minutes to obtain the self-cleaning membrane material composition of this embodiment.

[0178] The above-mentioned self-cleaning film material composition was sprayed onto the white exterior paint surface of a rail transit EMU and cured at 60°C for 24 hours to obtain a self-cleaning film with a thickness of 45μm adhering to the exterior paint surface.

[0179] Example 8: A self-cleaning membrane material composition and the prepared self-cleaning membrane

[0180] The self-cleaning membrane material composition of this embodiment is formed by mixing component A and component B in a mass ratio of 2:1, wherein: the raw material composition of component A is (10g = 1 part by weight):

[0181] 500g of super-slippery resin from Example 2;

[0182] MQ silicone resin (M / Q = 1.0 (mol / mol), weight average molecular weight 15000) 30g;

[0183] 100g of hexadecyltriethoxysilane modified nano-alumina (average particle size 5nm);

[0184] 0.2 g of dibutyltin diacetate;

[0185] Gemini wetting agent SE-5100 10g;

[0186] 100g of xylene;

[0187] The raw material composition of component B is (10g = 1 part by weight):

[0188] 1,6-Hexamethylene diisocyanate 100g;

[0189] 200g of methyl isobutyl ketone;

[0190] 50g of dimethyl adipic acid.

[0191] The self-cleaning membrane material composition of this embodiment is prepared by the following steps:

[0192] (1) Stir all the raw materials of component A at 100 r / min at room temperature for 20 minutes to obtain component A;

[0193] (2) Stir all the raw materials of component B at 100 r / min at room temperature for 10 minutes to obtain component B;

[0194] (3) The A component obtained in step (1) and the B component obtained in step (2) are stirred at a mass ratio of 2:1 at room temperature at a speed of 100 r / min for 10 minutes to obtain the self-cleaning membrane material composition of this embodiment.

[0195] The above-mentioned self-cleaning film material composition was sprayed onto the white exterior paint surface of a rail transit EMU and cured at 60°C for 12 hours to obtain a self-cleaning film with a thickness of 30 μm adhering to the exterior paint surface.

[0196] Comparative Example 1: A modified hydroxypropyl resin

[0197] A modified hydroxypropyl resin is prepared by the following method: 45.2 g of xylene and 1.5 g of 2,2'-azobis(2-methylpropionitrile) are mixed and heated to 80 °C. A mixture of 361.6 g of xylene, 12 g of 2,2'-azobis(2-methylpropionitrile), 210 g of methyl methacrylate, 10 g of methacrylic acid, 130 g of lauryl methacrylate, 20 g of hexafluorobutyl methacrylate, 20 g of γ-methacrylate oxypropylmethyldimethoxysilane, and 130 g of 2-hydroxyethyl methacrylate is added dropwise over 2 hours. The mixture is then reacted at 85 °C for 3 hours. Next, the mixture of 45.2 g of xylene and 1.5 g of 2,2'-azobis(2-methylpropionitrile) is added, and the reaction is maintained at 85 °C for 1.5 to 2.5 hours. Finally, 3 g of n-dodecyl mercaptan is added, and the mixture is cooled to 25 °C to obtain a super-lubricating resin.

[0198] Comparative Example 2: A self-cleaning membrane material composition and the self-cleaning membrane prepared therefrom

[0199] The self-cleaning membrane material composition of this comparative example is prepared by mixing component A and component B in a mass ratio of 2:1, wherein the raw material composition of component A is (10g = 1 part by weight):

[0200] 450g of modified hydroxypropyl resin (Comparative Example 1);

[0201] MQ silicone resin (M / Q = 0.8 (mol / mol), weight average molecular weight 10000) 30g;

[0202] Dodecyltriethoxysilane modified nano-alumina (average particle size 10nm) 80g;

[0203] 0.3g of dibutyltin dilaurate;

[0204] Gemini wetting agent SE-5100 8g;

[0205] 120g of propylene glycol methyl ether acetate;

[0206] The raw material composition of component B is (10g = 1 part by weight):

[0207] 1,6-Hexamethylene diisocyanate 130g;

[0208] 160g of methyl isobutyl ketone;

[0209] 50g of dimethyl glutarate.

[0210] The self-cleaning membrane material composition of this comparative example was prepared by the following steps:

[0211] (1) Stir all the raw materials of component A at room temperature at a speed of 200 r / min for 15 minutes to obtain component A;

[0212] (2) Stir all the raw materials of component B at 100 r / min at room temperature for 10 minutes to obtain component B;

[0213] (3) The A component obtained in step (1) and the B component obtained in step (2) are stirred at a mass ratio of 2:1 at room temperature at a speed of 100 r / min for 10 minutes to obtain a comparative self-cleaning membrane material composition.

[0214] The above-mentioned self-cleaning film material composition was sprayed onto the white exterior paint surface of a rail transit EMU and cured at 60°C for 24 hours to obtain a film material with a thickness of 45μm adhering to the exterior paint surface.

[0215] Comparative Example 3: A transparent self-cleaning film

[0216] A transparent self-cleaning film was prepared and attached to the outer surface of the vehicle paint according to the method in Example 8 of Chinese Invention Patent CN200810056918, "A Transparent Self-Cleaning Film and Its Preparation Method and Application". Test Examples 4-6 and Comparative Examples 2-3 were used to determine the performance of the self-cleaning films.

[0217] The performance of the self-cleaning membranes prepared in Examples 4-6, Comparative Examples 2 and 3 of this invention was tested, and the test method for resistance to animal proteins was as follows:

[0218] Chicken blood and chicken breast meat were ground three times in a meat grinder at a 1:1 mass ratio to obtain an animal protein mimic. Then, 2g of the animal protein mimic was coated onto a 5cm x 5cm area of ​​the prepared membrane material. The membrane was then placed in a 60℃ oven for 2 hours, followed by direct rinsing with tap water for 1 minute. The degree of animal protein mimic removal was used as the standard for the membrane material's resistance to animal protein, graded from 0 to 5: Grade 0 = all animal protein mimic removed; Grade 1 = 80%–100% removed; Grade 2 = 60%–80% removed; Grade 3 = 40%–60% removed; Grade 4 = 20%–40% removed; Grade 5 = <20% removed.

[0219] The test results are shown in Table 3.

[0220] Table 3. Performance test results of self-cleaning membranes in the examples and comparative examples.

[0221]

[0222]

[0223] As shown in Table 3, the original white paint film on the EMU train basically lacks corrosion resistance, stain resistance, animal protein resistance, and mildew resistance. However, after spraying and curing the self-cleaning film material composition of the present invention onto its surface, the above properties are significantly improved. Specifically, the self-cleaning films prepared in Examples 4-8 have a surface energy of <25mN / m, belonging to low-energy surfaces, exhibiting a high water contact angle and good anti-fouling performance, an extremely low coefficient of dynamic friction, belonging to super-slippery film materials, and possessing stain-resistant and self-cleaning capabilities. The water contact angle measurement results of the self-cleaning films in Examples 4 and 5 are shown in the table below. Figure 2 and Figure 3 As shown.

[0224] Furthermore, the self-cleaning films of Examples 4-8 possess high mechanical properties, high gloss, high adhesion, high weather resistance, water and mildew resistance, and chemical solvent resistance, all of which are significantly superior to those of Comparative Example 2, Comparative Example 3, and the original white paint film of the high-speed train.

[0225] (1) Compared with Examples 4-8 of the present invention, Comparative Example 2 did not use trifluoro-nonisocyanate polyurethane acrylate (FNIPUA) as the super-slippery resin component, and thus had a higher surface energy. It is not a low surface energy film material, and its weather resistance, stain resistance, animal protein resistance, and de-icing strength are all far inferior to the film materials of Examples 4-8 of the present invention. The dynamic friction coefficient U of Examples 4-8 of the present invention... dThe viscosity is approximately 0.05, which is considered a super-slippery film material. This is an order of magnitude lower than that of Comparative Example 2, Comparative Example 3, and the original white paint film of the high-speed train. The reason for this is likely that the two large isooctyl groups at the tail end of the trifluoronon-isocyanate polyurethane acrylate (FNIPUA) molecule can greatly increase the free volume of the film, reduce the cohesive force of the film material, provide a super-slippery effect, reduce the physical adhesion of dirt such as dust and animal protein to the film surface, and achieve a self-cleaning effect.

[0226] (2) Although Comparative Example 3 has a water contact angle greater than 150° and achieves a superhydrophobic effect, it is not suitable for rail transit vehicles, especially high-speed trains, due to its poor mechanical properties such as adhesion and flexibility, as well as its poor acid and alkali resistance and weather resistance.

[0227] Based on this invention and in accordance with the technical requirements of Q / CR546.1-2016, the technical requirements for anti-pollution self-cleaning membrane materials for high-speed trains are proposed, as detailed in Table 4.

[0228] Table 4 Technical Requirements for Self-Cleaning Materials for High-Speed ​​Train Paint Surface

[0229]

[0230]

[0231] In summary, this invention enables the preparation of a self-cleaning film on the exterior of rail transit vehicles (such as EMU trains) through a simple and quick construction method, thereby effectively improving the self-cleaning ability of the vehicle surface against dust and animal protein, reducing the de-icing intensity of the EMU train, improving the weather resistance of the paint film, extending the service life of the vehicle's exterior paint, and reducing the cost of vehicle cleaning and maintenance.

Claims

1. A super-lubricating resin, comprising, by weight percentage, the following components, with the total mass of the super-lubricating resin being 100%: The composition includes: 23%–28% first monomer, 1%–4% second monomer, 10%–16% third monomer, 3%–6% polymerizable active silane coupling agent, 6%–10% trifluoro-nonisocyanate polyurethane acrylate, 1%–2% initiator, 0.1%–0.5% chain transfer agent, and the balance being the first solvent; wherein, The first monomer is selected from one or more of methacrylic acid and methacrylate in any proportion; The second monomer is selected from fluorinated acrylate monomers; The third monomer is selected from hydroxyl-containing active crosslinking monomers; The trifluoro-non-isocyanate polyurethane acrylate has the following structure: R is selected from -H or -CH3.

2. The super-lubricating resin according to claim 1, characterized in that, The methacrylate is selected from one of methyl methacrylate, butyl methyl methacrylate, lauryl methacrylate, isobornyl methacrylate, and octadecyl methacrylate.

3. The super-lubricating resin according to claim 1, characterized in that, The fluorinated acrylate monomer is selected from at least one of trifluoroethyl acrylate, tetrafluoropropyl acrylate, trifluoroethyl methacrylate, tetrafluoropropyl methacrylate, hexafluorobutyl acrylate, hexafluorobutyl methacrylate, hexafluoroisopropyl acrylate, and hexafluoroisopropyl methacrylate.

4. The super-lubricating resin according to claim 3, characterized in that, The fluorinated acrylate monomer is selected from at least one of hexafluorobutyl acrylate, hexafluorobutyl methacrylate, hexafluoroisopropyl acrylate, and hexafluoroisopropyl methacrylate.

5. The super-lubricating resin according to claim 1, characterized in that, The hydroxyl-containing active crosslinking monomer is selected from at least two of 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, 4-hydroxybutyl methacrylate, 4-hydroxybutyl acrylate, and hydroxyethylcaprolactone acrylate.

6. The super-lubricating resin according to claim 5, characterized in that, The hydroxyl-containing active crosslinking monomer is selected from at least one of 2-hydroxyethyl methacrylate and 2-hydroxyethyl acrylate.

7. The super-lubricating resin according to claim 1, characterized in that, The polymeric active silane coupling agent is selected from at least one of γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, γ-methacryloxypropylmethyldiethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, and vinyltriisopropoxysilane.

8. The super-lubricating resin according to claim 7, characterized in that, The polymeric active silane coupling agent is selected from at least one of γ-methacryloxypropylmethyldimethoxysilane and γ-methacryloxypropylmethyldiethoxysilane.

9. The super-lubricating resin according to claim 1, characterized in that, The initiator is selected from at least one of 2,2'-azobis(2-methylpropionitrile) and 2,2'-bisazo-(2,4-dimethylpentanonitrile).

10. The super-lubricating resin according to claim 1, characterized in that, The chain transfer agent is selected from at least one of n-dodecyl mercaptan, tertiary dodecyl mercaptan, cyclohexyl mercaptan, isooctyl 3-mercaptopropionate, n-butyl 3-mercaptopropionate, n-octyl mercaptan, mercaptoethanol, and mercaptoacetic acid.

11. The super-lubricating resin according to claim 10, characterized in that, The chain transfer agent is selected from at least one of dodecyl mercaptan, isooctyl 3-mercaptopropionate, and n-butyl 3-mercaptopropionate.

12. The super-lubricating resin according to claim 1, characterized in that, The first solvent is selected from at least one of benzene solvents, ester solvents, and ketone solvents.

13. The super-lubricating resin according to claim 12, characterized in that, The first solvent is selected from at least one of xylene, butyl acetate and methyl isobutyl ketone.

14. A method for preparing the superlubricating resin according to any one of claims 1 to 13, comprising the following steps: I. Prepare each component according to the mass ratio; II. Divide the first solvent and the initiator into three parts each. Based on their total mass, the first part accounts for 8% to 12%, the second part accounts for 78% to 82%, and the third part accounts for 10%. III. Mix the first part of the first solvent and the first part of the initiator, heat to 75℃~85℃, and dropwise add the mixture of the second part of the first solvent, the second part of the initiator, the first monomer, the second monomer, the third monomer, the polymerizable active silane coupling agent and the trifluoro-nonisocyanate polyurethane acrylate. After the addition is complete, keep the temperature for 2h~4h. Then add the third part of the mixture of the first solvent and the third part of the initiator, and keep the temperature for 1h~3h. Finally, add the chain transfer agent and cool to 20℃~30℃ to obtain the final product.

15. The preparation method according to claim 14, characterized in that, The preparation method of the superlubricating resin includes the following steps: I. Prepare each component according to the mass ratio; II. Divide the first solvent and the initiator into three parts each. Based on their total mass, the first part accounts for 8% to 12%, the second part accounts for 78% to 82%, and the third part accounts for 10%. III. Mix the first part of the first solvent and the first part of the initiator, heat to 75℃~85℃, and dropwise add the mixture of the second part of the first solvent, the second part of the initiator, the first monomer, the second monomer, the third monomer, the polymerizable active silane coupling agent, and the trifluoro-nonisocyanate polyurethane acrylate. After the addition is complete, maintain the temperature for 2.5h~3.5h. Then add the third part of the mixture of the first solvent and the third part of the initiator, and maintain the temperature for 1.5h~2.5h. Finally, add the chain transfer agent and cool to 20℃~30℃ to obtain the final product.

16. The preparation method according to claim 14 or 15, characterized in that, The mixture of the solvent, initiator, first monomer, second monomer, third monomer, polymerizable active silane coupling agent, and trifluoro-nonisocyanate polyurethane acrylate is added dropwise over a period of 1.5 h to 2.5 h.

17. The use of the super-slippery resin according to any one of claims 1 to 13 or the super-slippery resin prepared according to the method of any one of claims 14 to 16 in the preparation of self-cleaning membrane materials.

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