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WO2024216667A1 - Base de schiff de biomasse, polymère de base de schiff de biomasse, revêtement photothermique et procédé de préparation - Google Patents

Base de schiff de biomasse, polymère de base de schiff de biomasse, revêtement photothermique et procédé de préparation Download PDF

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Publication number
WO2024216667A1
WO2024216667A1 PCT/CN2023/091236 CN2023091236W WO2024216667A1 WO 2024216667 A1 WO2024216667 A1 WO 2024216667A1 CN 2023091236 W CN2023091236 W CN 2023091236W WO 2024216667 A1 WO2024216667 A1 WO 2024216667A1
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biomass
schiff base
coating
photothermal
titanium nitride
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Chinese (zh)
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顾嫒娟
李秋逸
梁国正
袁莉
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Suzhou University
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Suzhou University
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/62—Alcohols or phenols
    • C08G59/64—Amino alcohols
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
    • C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D307/38—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
    • C07D307/52—Radicals substituted by nitrogen atoms not forming part of a nitro radical
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere
    • C09K3/18—Materials not provided for elsewhere for application to surfaces to minimize adherence of ice, mist or water thereto; Thawing or antifreeze materials for application to surfaces
    • C09K3/185—Thawing materials
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/32—Phosphorus-containing compounds
    • C08K2003/321—Phosphates
    • C08K2003/327—Aluminium phosphate
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/70—Wind energy
    • Y02E10/72—Wind turbines with rotation axis in wind direction

Definitions

  • the present invention belongs to polymer material technology, and specifically relates to a biomass Schiff base and its polymer, a photothermal coating and a preparation method.
  • Photothermal super-hydrophobic anti-icing coating is one of the effective ways to solve the problem of icing of wind turbine blades.
  • the photothermal filler of the coating is often distributed on the surface of the material.
  • external factors such as wind and sand cause serious wear on the surface of the material, which will not only affect the super-hydrophobic properties of the material, and then affect the passive anti-icing performance of the material, but also have a greater impact on the photothermal performance of the material. Therefore, wear resistance is particularly important for photothermal anti-icing materials.
  • the present invention designs and synthesizes a biomass Schiff base monomer HD containing hydroxyl groups at both ends, and prepares a biomass epoxy resin system HD-EP through a ring-opening reaction between the hydroxyl groups and the epoxy groups of the epoxy resin TDE-85.
  • the curing behavior and wetting properties of HD-EP are systematically studied; HD-EP, a mixed solution of ⁇ TiN and nTiN, and a mixed solution of ADP and FAS are sprayed layer by layer on a glass slide substrate by a simple spraying method, and a photothermal anti-icing coating (HD-EP@yTiN x /FADP z ) with high wear resistance is prepared. This is a new type of photothermal anti-icing coating with high wear resistance.
  • a biomass Schiff base which is ((decane-1,10-diacylbis(nitrene vinylidene))bis(methyl vinylidene)bis(furan-5,2-diacyl))dimethanol.
  • the invention discloses a method for preparing the biomass Schiff base, comprising the following steps: using 5-hydroxymethylfurfural and 1,10-diaminodecane as raw materials, reacting at 90-120°C for 0.5-3h to obtain the biomass Schiff base; preferably, using 5-hydroxymethylfurfural and 1,10-diaminodecane as raw materials, reacting at a molar ratio of 1:1 at 100-120°C for 0.5-2h to obtain the biomass Schiff base.
  • the present invention discloses a biomass Schiff base polymer, which is obtained by curing epoxy resin with the above-mentioned biomass Schiff base. Specifically, the above-mentioned biomass Schiff base is mixed with the epoxy resin and then cured to obtain the biomass Schiff base polymer.
  • the curing temperature is 180-220°C
  • the time is 5-8 hours
  • the curing adopts step-by-step temperature increase, such as 180°C/2h+200°C/2h+220°C/2h.
  • the present invention discloses a biomass Schiff base photothermal coating and a preparation method thereof, comprising the following steps: sequentially preparing a biomass Schiff base prepolymer-titanium nitride layer and a biomass Schiff base prepolymer-aluminum dihydrogen phosphate-fluorosilicone layer on a biomass Schiff base prepolymer film, and then curing to obtain a biomass Schiff base photothermal coating.
  • the curing temperature is 180-220°C
  • the time is 5-8 hours
  • the curing adopts a step-by-step temperature increase, such as 180°C/2h+200°C/2h+220°C/2h.
  • the titanium nitride in the biomass Schiff base prepolymer-titanium nitride layer, is composed of micron titanium nitride and nano titanium nitride; in the biomass Schiff base prepolymer-aluminum dihydrogen phosphate-fluorosilicone layer, the fluorosilicone is tridecafluorooctylsiloxane.
  • the mass ratio of micron titanium nitride to nano titanium nitride is 1: (0.25-1).
  • the biomass Schiff base prepolymer is a mixture of the above-mentioned biomass Schiff base and epoxy resin; and then solidified to obtain a biomass Schiff base polymer.
  • the above-mentioned biomass Schiff base and epoxy resin are mixed in a solvent, and then divided into three parts, namely, mixed solution A, mixed solution B, and mixed solution C;
  • the mixed solution B is mixed with titanium nitride in a solvent to obtain a biomass Schiff base-titanium nitride mixed solution;
  • the mixed solution C is mixed with aluminum dihydrogen phosphate and fluorosilicone in a solvent to obtain a biomass Schiff base-aluminum dihydrogen phosphate-fluorosilicone mixed solution;
  • the mixed solution A is dried to obtain a biomass Schiff base prepolymer film;
  • the biomass Schiff base-titanium nitride mixed solution is dried to obtain a biomass Schiff base prepolymer-titanium nitride layer;
  • the total volume of mixed liquid A, mixed liquid B and mixed liquid C is 100%, wherein the volume of mixed liquid B is 20-40%, the volume of mixed liquid C is 15-30%, and the remainder is mixed liquid A;
  • the mass sum of the biomass Schiff base and the epoxy resin is the mass of the resin matrix, and the mass ratio of the resin matrix, titanium nitride, aluminum dihydrogen phosphate and fluorosilicone is 100: (55-80): (3-9): (30-40).
  • the invention discloses a photothermal anti-icing material, comprising a substrate and a biomass Schiff base photothermal coating on the surface thereof, wherein the biomass Schiff base photothermal coating is the above-mentioned biomass Schiff base photothermal coating.
  • the present invention discloses the use of the above-mentioned biomass Schiff base, biomass Schiff base polymer, and biomass Schiff base photothermal coating in the preparation of anti-icing coating; and the use of the above-mentioned photothermal anti-icing material in the preparation of wind turbine blade materials, especially coating materials.
  • the present invention uses biomass 5-hydroxymethylfurfural and 1,10-diaminodecane as raw materials, and adopts a one-step method to synthesize a Schiff base (HD) containing a hydroxymethyl structure.
  • HD is used as a curing agent to construct an epoxy resin system with a trifunctional epoxy resin (for example, 4,5-epoxyhexane-1,2-dicarboxylic acid diglycidyl ester, TDE-85).
  • a resin coating (HD-EP) was prepared on a glass slide by spraying, and the contact angle of HD-EP was 95.7°, showing a hydrophobic state.
  • the surface energy was calculated to be 16.66 mN/m by the two-liquid method (Owens-Wendt-Kaelble method). In an environment of -20°C, the droplet freezes after staying on the glass slide for only 37 seconds, while it needs to stay on the HD-EP surface for 120 seconds before freezing, and the freezing time is extended by 2.24 times.
  • the present invention adopts a layer-by-layer spraying method, wherein the first layer is a HD/EP resin solution, the second layer is a HD/EP resin-micron titanium nitride ( ⁇ TiN), nano TiN (nTiN) mixed solution, and the third layer is a HD/EP resin-aluminum dihydrogen phosphate (ADP)-tridecafluorooctylsiloxane (FAS) mixed solution, and a new resin-based composite coating (referred to as HD-EP@yTiN x /FADP z ) is prepared, wherein HD-EP@cTiN 75 /FADP 7 has excellent super-hydrophobicity, WCA is 165.5°, SA is 4°, and has excellent wear resistance.
  • ADP aluminum dihydrogen phosphate
  • FAS tridecafluorooctylsiloxane
  • the coating After 100 wear tests on 1200# sandpaper, the coating still has super-hydrophobicity. The coating has good anti-deicing function. At -20°C, the droplet freezing time is as long as 446s, and the frozen droplets can be completely melted in only 10s under 808nm near-infrared light. The excellent wear resistance of the coating comes from the synergistic effect of the resin system and the filler protective layer.
  • the icing problem of wind turbine blades has seriously hindered the development of wind power energy, and photothermal super-hydrophobic anti-icing coatings are an important strategy to solve this problem.
  • existing photothermal super-hydrophobic anti-icing coatings generally have the problem of low wear resistance.
  • the present invention conducts research on a new type of highly wear-resistant photothermal super-hydrophobic anti-icing resin-based composite coating, which improves the wear resistance of the coating without affecting the anti-icing performance of the coating.
  • FIG1 is a schematic diagram of the synthesis of Schiff base HD.
  • Figure 2 is the characterization of HD, where A is the H-NMR spectrum, B is the C-NMR spectrum, and C is the FT-IR spectrum of HMF and HD.
  • Figure 3 shows pictures of HD-EP before and after self-repair, where a is before self-repair and b is after self-repair, both magnified 200 times under an ultra-depth-of-field microscope.
  • Figure 4 shows the WCA and SA of the coating HD-EP@yTiNx/FADP.
  • Figure 5 is the SEM images of different coatings, where a is HD-EP@ ⁇ TiN 75 /FADP 7 , b is HD-EP@dTiN 75/ FADP 7 , c is HD-EP@cTiN 75 /FADP 7 , d is HD-EP@bTiN 75 /FADP 7 , e is HD-EP@aTiN 75 /FADP 7 and f is HD-EP@nTiN 75 /FADP 7 .
  • Figure 6 is a schematic diagram of the changes in WCA and SA of the composite coating with wear cycles.
  • Figure 7 shows the SEM images of HD-EP@cTiN 75 and HD-EP@cTiN 75 /FADP 7 before and after 100 wear tests, where a is the HD-EP@cTiN 75 coating before wear, b is the HD-EP@cTiN 75 coating after wear, c is the HD-EP@cTiN 75 /FADP 7 coating before wear, and d is the HD-EP@cTiN 75 /FADP 7 coating after wear.
  • Figure 8 shows the icing delay time test and deicing test of the glass slide, HD-EP resin coating, and HD-EP@cTiN 75 /FADP 7 coating.
  • Figure 9 shows the ice delay time test of different coatings.
  • Figure 10 is a schematic diagram of the change of surface temperature of different coatings with time. Taking the highest temperature of each curve in the figure as the standard, from top to bottom are HD-EP@cTiN 75 /FADP, HD-EP@cTiN 70 /FADP, HD-EP@cTiN 65 /FADP, HD-EP@cTiN 60 /FADP, HD-EP@cTiN 55 /FADP, HD-EP@cTiN 50 /FADP, and HD-EP@ ⁇ TiN 75 /FADP.
  • Figure 11 shows the photos of HD-EP@cTiN 75 /FADP 7 before and after self-repair.
  • FIG. 12 is a schematic diagram of the self-cleaning function of HD-EP@cTiN 75 /FADP 7 .
  • a feasible way to increase the service life of anti-icing coatings is to introduce self-repairing properties into the resin coating.
  • the self-repairing properties of anti-icing coatings usually include two meanings. One is that when the coating surface loses its super-hydrophobic properties due to structural damage, oxygen erosion, etc., the super-hydrophobic properties can be restored under certain conditions. The other is that the coating can self-repair surface scratches under certain conditions. At present, there is relatively little public information about self-repairing anti-icing coatings.
  • the self-repairing properties of existing super-hydrophobic anti-icing coatings with self-repairing properties are limited to the recovery of super-hydrophobic properties. This self-repair is achieved by the migration of low surface energy segments to the surface of the material.
  • the curing agents containing dynamic covalent bonds used in the prior art are all petroleum-based raw materials, and no renewable biomass raw materials are used.
  • the present invention uses biomass raw materials to synthesize a new biomass Schiff base, and uses it as an epoxy resin curing agent to prepare an epoxy resin with self-healing properties for preparing a photothermal super-hydrophobic anti-icing coating.
  • HD long alkyl chain Schiff base
  • the key performance in passive anti-icing - super-hydrophobic performance comes from the synergistic effect of the surface structure of the coating material and the low surface energy.
  • the long-term wear of the coating material surface by wind and sand is difficult to ignore, especially for the anti-icing coating of outdoor equipment such as wind turbine blades that are exposed to wind and sand erosion for a long time. Due to the continuous wear and damage of the surface structure, the super-hydrophobic performance of the coating will continue to decrease, thus greatly affecting the anti-icing performance of the coating.
  • the present invention discloses a photothermal super-hydrophobic anti-icing resin-based composite coating with both self-repairing performance and high wear resistance.
  • the solution is to use ⁇ TiN and nTiN to construct a surface micro-nano structure combined with fluorinated ADP, and use the self-repairing epoxy resin prepared above to strengthen the bonding between the filler and the substrate.
  • the obtained coating has excellent structure and performance, super-hydrophobic performance, good wear resistance and anti-icing performance.
  • 1,10-Diaminodecane (DAD) and petroleum ether were purchased from Shanghai Aladdin Biochemical Technology Co., Ltd. (China)
  • 4,5-epoxytetrahydrophthalic acid diglycidyl ester (TDE-85) and 5-hydroxymethylfurfural (HMF) were purchased from Shanghai McLean Biochemical Technology Co., Ltd. (China)
  • anhydrous ethanol was purchased from Yonghua Chemical Co., Ltd. (China).
  • Tridecafluorooctylsiloxane (FAS) was purchased from Shanghai Aladdin Biochemical Technology Co., Ltd.
  • nano titanium nitride (nTiN, 20-100 nanometers) and micron titanium nitride ( ⁇ TiN, 2-10 microns) were purchased from Shanghai Yuanye Biotechnology Co., Ltd. (China), and aluminum dihydrogen phosphate (ADP) was purchased from Shanghai Adamas Reagent Co., Ltd. (China). All reagents were not treated otherwise.
  • the raw materials involved in the present invention are existing products, and the specific preparation operations and testing methods are conventional techniques.
  • AVANCE III HD-400 nuclear magnetic resonance spectrometer was used to record hydrogen nuclear magnetic resonance ( 1 H-NMR) and carbon nuclear magnetic resonance ( 13 C-NMR).
  • Deuterated chloroform CDCl 3
  • TMS tetramethylsilane
  • Vertex 70 intelligent Fourier transform infrared spectrometer was used to test infrared spectrum (FTIR), with a test scanning range of 600-4000cm -1 and a resolution of 4cm -1 .
  • the reactivity of the resin prepolymer was measured using a Q200 differential scanning calorimeter (DSC) under nitrogen atmosphere (flow rate: 50 mL min -1 ) and heating rates of 5 °C min -1 , 10 °C min -1 , 15 °C min -1 and 20 °C min -1 .
  • DSC differential scanning calorimeter
  • About 4 mg of the sample was weighed in an aluminum crucible and sealed, and the scanning temperature range was from room temperature to 300 °C.
  • VHX-7000 An ultra-depth-of-field camera (VHX-7000) was used to record the scratch images before and after the coating self-repair, with a magnification of 200 times.
  • the water contact angle (WCA) and sliding angle (SA) of the coating were measured using an LSA60Pro contact angle meter.
  • the ambient temperature during the test was 25°C
  • the droplet volume used in the WCA test was 4 ⁇ L
  • the droplet volume used in the SA test was 6 ⁇ L.
  • Hitachi S-4700 cold field emission scanning electron microscope (SEM) was used to analyze the surface morphology of the coating.
  • UV3600 ultraviolet-visible-near-infrared spectrophotometer
  • the photothermal conversion performance of the coating was measured and recorded using an infrared thermal imager (PI640i).
  • the 808nm near-infrared light used in the measurement process came from an infrared laser (MDL-H-808-5W) with an energy density of 1W/ cm2 .
  • the anti-icing performance of the coating was tested on a freezing table with an ambient temperature of 20°C, a humidity of 47%, and a surface temperature of -20°C.
  • the test method is as follows: the coating sample to be tested is placed flat on the freezing table, 10 ⁇ L of deionized water is added to the coating surface using a pipette, and the passive anti-icing performance of the coating is evaluated by measuring the time when the droplet begins to appear at the solid-liquid interface and the time when the droplet is completely frozen.
  • the coating is vertically irradiated with near-infrared light with an energy density of 1 W/cm 2 , and the photothermal deicing performance of the coating is evaluated by recording the time when 10 ⁇ L of completely frozen droplets turn back into liquid.
  • the mechanical durability of the coating was studied by sandpaper abrasion test.
  • the coating was dragged on 1200# sandpaper at a constant speed for 10 cm under a load of 100g, and the contact angle and rolling angle after abrasion were measured.
  • the abrasion resistance of the coating was evaluated by recording the number of cycles before the coating completely lost its superhydrophobic properties.
  • the all-bio-based Schiff base curing agent HD was synthesized by a solvent-free method. 2.649 g HMF was added to a round-bottom flask, and placed in a magnetic stirring oil bath with a water separator and a condensation reflux device, and magnetic stirring was turned on. Then 1.721 g DAD was evenly added in 5 batches, and the reaction was carried out at 110 ° C for 1 h. After the reaction, 200 mL of deionized water and 200 mL of petroleum ether were used to wash in turn, and then the water and the remaining reactants were removed by vacuum evaporation at 80 ° C. After drying, the biomass Schiff base HD was obtained with a yield of 95%; the reaction diagram and the chemical structure of the product are shown in Figure 1.
  • Figure 2 A is the 1 H NMR (400 MHz, Chloroform- d ) map of HD;
  • Figure 2 B is the 13 C NMR (101 MHz, Chloroform-d) map of HD.
  • the measured molecular mass is 411.2252, which is consistent with the theoretical value of HD 411.2260.
  • Example 2 HD-EP resin coating.
  • HD and TDE-85 were mixed in a molar ratio of 1:1 and stirred at 180°C for 30 minutes to obtain HD-EP prepolymer.
  • the DSC curves with different heating rates were used to study the curing behavior of HD-EP prepolymer.
  • Each curve had an obvious curing exothermic peak in the range of 200-250°C.
  • the tangent method was used for the curing exothermic peak to know the curing starting temperature (T i ), curing peak temperature (T p ) and curing termination temperature (T f ) of each curve, as shown in Table 1.
  • T p and T f are 180°C, 198°C and 222°C respectively.
  • the WCA test of the HD-EP resin coating was carried out using a contact angle meter.
  • the WCA of a water drop on the HD-EP surface was 95°, indicating that the coating was a hydrophobic surface. Since the wetting properties of the coating are closely related to the surface energy of the material, the surface energy of HD-EP was analyzed using the two-liquid method.
  • the WCA of water and formamide on the HD-EP surface were tested, which were 95°C and 86°, respectively.
  • a scratch was made on the HD-EP resin coating with a scalpel, with a width of 65.03 ⁇ m and a depth of 20.18 ⁇ m.
  • the scratched coating was then placed at 180°C for 30 minutes and observed again under an ultra-depth microscope. It was found that the width of the scratch was reduced to 28.93 ⁇ m and the depth was 5.65 ⁇ m. See Figure 3, the pictures of HD-EP before and after self-repair, magnified 200 times under an ultra-depth microscope.
  • the substrate is a 75 ⁇ 25 mm microscope slide, which is cleaned with deionized water and ethanol in sequence before use and set aside.
  • ⁇ TiN was added into a beaker, and 5 mL of anhydrous ethanol and 3 mL of spray liquid A were added, and the mixture was dispersed in an ultrasonic instrument for 30 min to obtain spray liquid B.
  • Spray liquid C was obtained by mixing 0.05 g ADP, 0.25 g FAS, 2 mL spray liquid A, and 3 mL anhydrous ethanol.
  • spray liquid A (the remaining spray liquid A), spray liquid B, and spray liquid C are sprayed layer by layer on a clean glass slide. After each layer is sprayed, it is kept at 80°C for 2 minutes to evaporate the solvent.
  • the sprayed coating is cured according to the process of 180°C/2h+200°C/2h+220°C/2h to obtain a ⁇ TiN-based coating, which is recorded as HD-EP@ ⁇ TiN x /FADP 7 , where x is the mass percentage of ⁇ TiN relative to HD-EP resin (actually x%, for simplicity, % is omitted in the name), and FADP 7 means that the mass percentage of ADP relative to HD-EP resin is 7% (for simplicity, % is omitted in the name), see Table 2 for details.
  • the mass of HD-EP resin is 0.7g and the mass of ⁇ TiN is 0.35g, then x is 50%, abbreviated as 50.
  • spray liquid C i.e., a biomass Schiff base-aluminum dihydrogen phosphate-fluorosilicone mixed liquid.
  • ⁇ TiN and nTiN were added into a beaker, and 5 mL of anhydrous ethanol and 3 mL of spray liquid A were added, and dispersed in an ultrasonic instrument for 30 minutes to obtain spray liquid D, i.e., a biomass Schiff base-titanium nitride mixed liquid.
  • spray liquid D i.e., a biomass Schiff base-titanium nitride mixed liquid.
  • spray liquid A (the remaining spray liquid A), spray liquid D, and spray liquid C are sprayed layer by layer on the clean glass slide. After each layer is sprayed, keep it at 80°C for 2 minutes to evaporate the solvent. The sprayed coating is cured according to the process of 180°C/2h+200°C/2h+220°C/2h.
  • the WCA of HD-EP@ ⁇ TiN 75 /FADP 7 is the maximum (125.2°) and the SA is the minimum (21.2°), which does not meet the superhydrophobic performance requirements, that is, the coating surface has a WCA greater than 150° and a SA less than 10°.
  • the surface structure of the coating HD-EP@nTiN 75 /FADP 7 containing only nTiN is very fragile, and droplets can easily penetrate into the coating, making the coating non-hydrophobic (WCA less than 90°). Obviously, the composite coating with only ⁇ TiN or nTiN does not have superhydrophobic properties.
  • Figure 4 shows the WCA and SA of HD-EP@yTiN 0.75 /FADP 7. It can be seen that when the micro-nano ratio gradually decreases, the WCA of the coating shows a trend of first increasing and then decreasing, while the SA shows the opposite trend. When the micro-nano ratio is 1:0.25, the WCA and SA of the coating are 153° and 7.5°, respectively, and it has superhydrophobic properties. When the micro-nano ratio reaches 1:0.5, the coating has the best superhydrophobic properties, with WCA reaching 165.5° and SA reaching 4°.
  • WCA and SA show a decreasing and increasing trend, respectively, which are 151° and 9°.
  • the WCA and SA of the coating are 128.2° and 26.4°, respectively, and the coating no longer has superhydrophobic properties.
  • the surface SEM characterization of the coating was carried out (Figure 5). At a magnification of 2.5K, it can be found that the structure of the coating HD-EP@ ⁇ TiN 0.75 /FADP 7 does not meet the conditions for superhydrophobicity, and the test contact angle is only 125.2°. When the micro-nano ratio changes from 1:0 to 1:0.25, many tiny nano-scale protrusions can be observed on the micron-scale protrusion structure. When the micro-nano ratio reaches 1:0.5, the structure of the coating surface becomes more complicated, and many gully-like cracks appear. At this time, the coating has the best superhydrophobic performance.
  • the superhydrophobic performance continues to decrease with the increase of nTiN content, and even loses the superhydrophobic performance.
  • the surface structure of the coating is very fragile at this time, and the droplets will penetrate into the scratches after the coating is repaired, making the coating not have superhydrophobic performance.
  • ADP aluminum dihydrogen phosphate
  • FIG. 6 is a schematic diagram of the changes in WCA and SA of HD-EP@cTiN 75 /FADP z with the increase in the number of wear test cycles. It can be found that with the increase in the number of cycles, the WCA of the coating gradually shows a downward trend, and the SA shows an upward trend. When the mass fraction of ADP reaches 7%, even if the wear cycle reaches 100 times, the WCA and SA of the coating HD-EP@cTiN 75 /FADP 7 are still 152.1° and 7.6°. This shows that the coating has excellent wear resistance.
  • the WCA and SA are 155° and 6.5° respectively.
  • the SA is greater than 10°; after more than 50 times, the WCA is also less than 150°.
  • Figure 7 shows the SEM images of HD-EP@cTiN 75 and HD-EP@cTiN 75 /FADP 7 before and after the wear test.
  • HD-EP@cTiN 75 had obvious ups and downs, which made it appear distinctly light and dark, that is, it had a high roughness; however, after 100 wear cycles, the micro-nanostructure on the coating surface was severely damaged, and a large area of flat area appeared in the field of view.
  • HD-EP@cTiN 75 /FADP 7 has a high-low, dense surface. After 100 wear tests, the surface structure composed of obvious protrusions and grooves can still be observed.
  • AFM is used to characterize the roughness of HD-EP@cTiN 75 and HD-EP@cTiN 75 /FADP 7 before and after the wear test. After 100 wear cycles, the structure of HD-EP@cTiN 75 is severely damaged, and the roughness is greatly reduced from 539nm to 178nm. After 100 wear cycles, the roughness of HD-EP@cTiN 75 /FADP 7 is only reduced from 534nm to 467nm. This shows that the coating has excellent wear resistance.
  • the coating HD-EP@cTiN 75 /FADP 7 of the present invention has relatively better wear resistance and comprehensive performance, and the number of wear cycles is greater than that of most existing technologies, which solves the problem that although the existing coatings have good wear cycle performance, they have poor anti-icing performance and short freezing termination time, making them difficult to be used as surface coatings for wind turbine blades.
  • Anti-icing and de-icing performance of the coating were studied by measuring the ice delay time.
  • the contact angles of the droplets on the glass slides and resin coatings were less than 90°, while on the surface of HD-EP@cTiN 75 /FADP 7 , they were greater than 150°, showing a relatively complete spherical shape, indicating that the coating still has superhydrophobic properties even at a low temperature of -20°C.
  • the time when a clear solid-liquid interface appears inside the droplets is selected as the starting freezing time of the droplets, and the time when the liquid phase is completely frozen into the solid phase is the freezing end time.
  • the results show that the initial freezing time and the final freezing time of the blank component glass slide are 4s and 37s respectively, while those of HD-EP are 91s and 120s, and those of HD-EP@cTiN 75 /FADP 7 are 289s and 446s. Even if completely frozen, the droplets on the coating still maintain a spherical shape.
  • the freezing time of the HD-EP@cTiN 75 /FADP 7 coating is extended by 12 times compared to the blank sample, indicating that it has good passive anti-icing ability.
  • the freezing time of HD-EP@aTiN 75 /FADP 7 , HD-EP@bTiN 75 /FADP 7 , HD-EP@dTiN 75 /FADP 7 and HD-EP@ ⁇ TiN 75 /FADP 7 were also tested. As shown in Figure 9, the initial freezing time and the final freezing time of the coating HD-EP@dTiN 75 /FADP 7 were 285 s and 375 s, respectively, and those of HD-EP@bTiN 75 /FADP 7 were 262 s and 364 s, respectively.
  • Figure 11 is an ultra-depth microscope image of the scratches on the surface of the coating HD-EP@cTiN 75 /FADP 7 before and after repair.
  • a scalpel scratched the coating surface with a width of 71.05 ⁇ m and a depth of 29.85 ⁇ m.
  • the scratch area was irradiated with 808nm near-infrared light with an energy density of 2W/ cm2 for 30 minutes, and then the picture after near-infrared light repair was taken. After 30 minutes of coating repair, it can be observed that the scratches on the resin are no longer obvious, and the middle of the scratch is healed after repair, and it is not a continuous scratch.
  • Figure 12 is a schematic diagram of the self-cleaning function of the coating HD-EP@cTiN 75 /FADP 7.
  • 1g of sand was sprinkled on the surface of the coating, and the coating was placed in a petri dish at an inclination angle of about 10°.
  • 3mL of deionized water was dripped on the top of the coating with a dropper. It can be observed that the sand on the surface of the coating was removed from the coating as the droplets rolled down and finally flowed into the petri dish. After the 3mL of deionized water was dripped, it can be found that there was basically no sand left on the coating, indicating that HD-EP@cTiN 75 /FADP 7 has a good self-cleaning function.
  • photothermal anti-icing coatings Compared with other anti-icing technologies, photothermal anti-icing coatings have the advantages of energy saving and high efficiency. They are the most promising representatives of anti-icing materials, and their applications cover many fields such as aerospace, energy industry, and civil transportation.
  • wear resistance has always been one of the most important properties of photothermal anti-icing coating materials. Therefore, it is of great significance to develop resin-based photothermal anti-icing coatings with high wear resistance.
  • the icing problem of wind turbine blades has seriously hindered the development of wind power energy, and photothermal super-hydrophobic anti-icing coatings are an important strategy to solve this problem.
  • existing photothermal super-hydrophobic anti-icing coatings generally have the problem of low wear resistance.
  • the present invention adopts green biomass raw materials and a solvent-free method to synthesize a biomass Schiff base, and reacts it with epoxy resin TDE-85 to prepare an epoxy resin HD-EP with self-healing function; using resin HD-EP as a coating adhesive, using two scales of TiN (nTiN and ⁇ TiN) as fillers and surface micro-nano structure construction materials, and using fluorinated ADP, a photothermal superhydrophobic anti-icing coating HD-EP@yTiN x /FADP z with high wear resistance and self-healing performance is prepared by a layer-by-layer spraying method.
  • the coating has excellent superhydrophobic performance, WCA of 165.5°, SA of 4°, good wear resistance of the coating, and can maintain superhydrophobic performance after 100 sandpaper wear tests; the coating HD-EP@cTiN 75 /FADP 7 has good anti-icing performance, and its freezing time at -20°C is extended to 446s. Compared with the glass slide substrate, the freezing delay time is 12 times.
  • the coating HD-EP@cTiN 75 /FADP 7 has a certain optical self-repair ability, and can achieve a repair rate of 35.7% within 30 minutes under 808nm near-infrared light irradiation; in addition, the coating has excellent self-cleaning function, and can complete the self-cleaning function of 1g of sand with 3mL of deionized water.

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Abstract

L'invention concerne une base de Schiff de biomasse, un polymère de base de Schiff de biomasse, un revêtement photothermique et un procédé de préparation. La base de Schiff de biomasse est obtenue à l'aide de 5-hydroxyméthylfurfural et de 1,10-diaminodécane en tant que matières premières et par réaction à 90-120°C pendant 0,5 à 3 heures. Le polymère de base de Schiff de biomasse est obtenu par durcissement de résine époxy avec la base de Schiff de biomasse. Le revêtement photothermique est obtenu par préparation séquentielle d'une couche de prépolymère de base de Schiff de biomasse-nitrure de titane et d'une couche de prépolymère de base de Schiff de biomasse-phosphate de dihydrogène-fluorosilicone sur un film de prépolymère de base de Schiff de biomasse, puis durcissement. Le revêtement préparé dans la présente invention a une excellente résistance à l'usure, en particulier permet d'obtenir une auto-réparation, et en particulier, peut prolonger significativement le temps de givrage, ce qui permet de résoudre efficacement les problèmes de mauvaise résistance à l'usure et de résistance au givrage d'un revêtement hydrophobe résistant à l'usure existant.
PCT/CN2023/091236 2023-04-21 2023-04-27 Base de schiff de biomasse, polymère de base de schiff de biomasse, revêtement photothermique et procédé de préparation Pending WO2024216667A1 (fr)

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