CN116143732A - Biomass Schiff base and polymer, photo-thermal coating and preparation method thereof - Google Patents

Biomass Schiff base and polymer, photo-thermal coating and preparation method thereof Download PDF

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CN116143732A
CN116143732A CN202310432292.5A CN202310432292A CN116143732A CN 116143732 A CN116143732 A CN 116143732A CN 202310432292 A CN202310432292 A CN 202310432292A CN 116143732 A CN116143732 A CN 116143732A
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schiff base
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CN116143732B (en
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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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    • 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
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Abstract

The invention discloses a biomass Schiff base, a polymer thereof, a photo-thermal coating and a preparation method thereof, wherein 5-hydroxymethylfurfural and 1, 10-diaminodecane are used as raw materials and react for 0.5-3 h at 90-120 ℃ to obtain the biomass Schiff base; solidifying the epoxy resin by using biomass Schiff base to obtain a biomass Schiff base polymer; sequentially preparing a biomass Schiff base prepolymer-titanium nitride layer and a biomass Schiff base prepolymer-aluminum dihydrogen phosphate-fluorosilicone layer on the biomass Schiff base prepolymer film, and then solidifying to obtain the biomass Schiff base photo-thermal coating. The coating prepared by the invention has excellent wear resistance, can realize self-repairing, particularly obviously prolongs icing time, and effectively solves the problems of poor wear resistance and poor icing resistance of the existing wear-resistant hydrophobic coating.

Description

Biomass Schiff base and polymer, photo-thermal coating and preparation method thereof
Technical Field
The invention belongs to the technology of high molecular materials, and particularly relates to a biomass Schiff base and a polymer, a photo-thermal coating and a preparation method thereof.
Background
The photo-thermal super-hydrophobic ice preventing and removing coating is one of effective methods for solving the problem of wind power blade icing. In order to better absorb external light energy, the photo-thermal filler of the coating is often distributed on the surface of the material. In the actual use process, external factors such as sand wind and the like have serious abrasion on the surface of the material, so that the super-hydrophobic performance of the material can be influenced, the passive anti-icing performance of the material is further influenced, and the photo-thermal performance of the material can be greatly influenced. Therefore, the abrasion resistance is particularly important for the photothermal deicing material. The prior art has the following problems: firstly, most of the wear cycles of the photo-thermal ice prevention and removal coating can be carried out only about 50 times, so that the super-hydrophobic performance is lost, and the load used in the test process is only 50 g-100 g; the anti-icing performance was also poor, and the freezing time was 288s only (blank 57 s). In addition, sustainable green development is an important direction of development in the field of materials today, however, in the existing technical solutions of polishing-resistant heat control ice coatings, no report on the preparation of coatings using biomass raw materials is seen.
Disclosure of Invention
The invention designs and synthesizes a biomass Schiff base monomer HD with hydroxyl groups at two ends, and prepares a biomass epoxy resin system HD-EP by ring-opening reaction of the hydroxyl groups and epoxy groups of epoxy resin TDE-85. The system researches the curing behavior and the wetting property of the HD-EP; the photo-thermal ice-preventing coating (HD-EP@yTiN) with high wear resistance is prepared by spraying the mixed solution of HD-EP, mu TiN and nTiN and the mixed solution of ADP and FAS on a glass slide substrate layer by a simple spraying method x /FADP z ) Is a novel high-wear-resistance photo-thermal deicing coating.
The invention adopts the following technical scheme:
a biomass schiff base is ((decane-1, 10-diacyldi (azetidinylene)) bis (methylvinylidene) bis (furan-5, 2-diacyl)) dimethanol.
The invention discloses a preparation method of the biomass Schiff base, which comprises the following steps of taking 5-hydroxymethylfurfural and 1, 10-diaminodecane as raw materials, and reacting for 0.5-3 h at 90-120 ℃ to obtain the biomass Schiff base; preferably, 5-hydroxymethyl furfural and 1, 10-diaminodecane are used as raw materials, and the biomass Schiff base is obtained by reacting for 0.5-2 hours at the temperature of 100-120 ℃ in the molar ratio of 1:1.
The invention discloses a biomass Schiff base polymer, which is obtained by solidifying epoxy resin by using biomass Schiff base, specifically, the biomass Schiff base polymer is obtained by mixing the biomass Schiff base with the epoxy resin and then solidifying the mixture. Preferably, the curing temperature is 180-220 ℃ and the time is 5-8 hours, and the curing adopts stepped temperature rise, such as 180 ℃/2h+200 ℃/2h+220 ℃/2h.
The invention discloses a biomass Schiff base photo-thermal coating and a preparation method thereof. Preferably, the curing temperature is 180-220 ℃ and the time is 5-8 hours, and the curing adopts stepped temperature rise, such as 180 ℃/2h+200 ℃/2h+220 ℃/2h.
In the biomass Schiff base prepolymer-titanium nitride layer, titanium nitride consists of micro titanium nitride and nano titanium nitride; in the biomass Schiff base prepolymer-aluminum dihydrogen phosphate-fluorosilicone layer, the fluorosilicone is tridecafluorooctyl siloxane. Preferably, in the titanium nitride, the mass ratio of the micro titanium nitride to the nano titanium nitride is 1: (0.25-1).
In the invention, the biomass Schiff base prepolymer is a mixture of the biomass Schiff base and epoxy resin; and solidifying to obtain the biomass Schiff base polymer. Mixing the biomass Schiff base and epoxy resin in a solvent, and dividing the mixture into three parts, namely a mixed solution A, a mixed solution B and a mixed solution C; mixing the mixed solution B with titanium nitride in a solvent to obtain a biomass Schiff base-titanium nitride mixed solution; mixing the mixed solution C with aluminum dihydrogen phosphate and fluorosilicone in a solvent to obtain a biomass Schiff base-aluminum dihydrogen phosphate-fluorosilicone mixed solution; drying the mixed solution A to obtain a biomass Schiff base prepolymer film; drying the biomass Schiff base-titanium nitride mixed solution to obtain a biomass Schiff base prepolymer-titanium nitride layer; drying the biomass Schiff base-aluminum dihydrogen phosphate-fluorosilicone mixed solution to obtain a biomass Schiff base prepolymer-aluminum dihydrogen phosphate-fluorosilicone layer. Preferably, the drying is carried out at 70-90 ℃ for 1-5 min. The solvent in the solution is a conventional solvent such as ethanol, preferably, the solvents are consistent and all ethanol.
In the invention, the total volume of the mixed solution A, the mixed solution B and the mixed solution C is 100%, wherein the volume of the mixed solution B is 20-40%, the volume of the mixed solution C is 15-30%, and the balance is the mixed solution A; the mass ratio of the biomass Schiff base to the epoxy resin is 100:55-80:3-9:30-40.
The invention discloses a photo-thermal deicing material, which comprises a substrate and a biomass Schiff base photo-thermal coating on the surface of the substrate, wherein the biomass Schiff base photo-thermal coating is the biomass Schiff base photo-thermal coating.
The invention discloses application of the biomass Schiff base, biomass Schiff base polymer and biomass Schiff base photo-thermal coating in preparation of anti-icing coating; the application of the photo-thermal deicing material in preparing fan blade materials, especially coating materials.
The invention synthesizes Schiff base (HD) containing hydroxymethyl structure by using biomass 5-hydroxymethyl furfural and 1, 10-diaminodecane as raw materials and adopting a one-step method. An epoxy resin system is constructed with a trifunctional epoxy resin (e.g., diglycidyl 4, 5-epoxyhexane-1, 2-dicarboxylate, TDE-85) using HD as a curing agent. Using the spray method, a resin coating (HD-EP) was prepared on a glass slide, the contact angle of the HD-EP being 95.7, exhibiting a hydrophobic state. The surface energy was calculated to be 16.66mN/m by the two-fluid method (Owens-Wendt-Kaelble method). In an environment of-20 ℃, the liquid drops are frozen only when staying for 37s on the glass slide, and the liquid drops are frozen only when staying for 120s on the surface of the HD-EP, so that the freezing time is prolonged by 2.24 times.
The invention adopts a layer-by-layer spraying method, according to the first layer being HD/EP resin solution, the second layer being HD/EP resin-micron titanium nitride (mu TiN) and nano TiN (nTiN) mixed solution, the third layer being HD/EP resin-Aluminum Dihydrogen Phosphate (ADP) -tridecafluorooctyl siloxane (FAS) mixed solution, and then spraying in turn, a novel resin-based composite coating (marked as HD-EP@yTiN) is prepared x /FADP z ) Wherein HD-EP@cTiN 75 /FADP 7 The coating has excellent superhydrophobic performance, the WCA is 165.5 degrees, the SA is 4 degrees, and particularly has excellent wear resistance, and the coating still has superhydrophobic performance after 100 times of wear tests are carried out on 1200# abrasive paper. The coating has good ice preventing and removing function, the freezing time of the liquid drops is up to 446s at the temperature of minus 20 ℃, and the frozen liquid drops can be completely melted only for 10s under the irradiation of 808nm near infrared light. The excellent wear resistance of the coating is derived from the synergistic effect of the resin system and the filler protection layer.
The icing problem of wind power blades seriously hinders the development of wind power energy, and a photo-thermal super-hydrophobic ice-preventing and removing coating is an important strategy for solving the problem. However, the existing photo-thermal super-hydrophobic ice control coating has the problem of low wear resistance. The invention develops the research of the novel high-wear-resistance photo-thermal super-hydrophobic deicing resin-based composite coating, and improves the wear resistance of the coating while not affecting the deicing performance of the coating.
Drawings
FIG. 1 is a schematic diagram of the synthesis of Schiff base HD.
FIG. 2 is a representation of HD, where A is the nuclear magnetic hydrogen spectrum, B is the nuclear magnetic carbon spectrum, and C is the FT-IR spectrum of HMF and HD.
Fig. 3 is a picture before and after HD-EP self-repair, where a is before self-repair and b is after self-repair, both magnified 200 times under a super-depth-of-field microscope.
FIG. 4 shows WCA and SA coated with HD-EP@yTiNx/FADP.
FIG. 5 is an SEM image of various coatings, wherein a is HD-EP@. Mu. 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 F is HD-EP@nTiN 75 /FADP 7 。
FIG. 6 is a schematic of the WCA, SA of the composite coating as a function of wear cycle.
FIG. 7 is a diagram of HD-EP@cTiN 75 With HD-EP@cTiN 75 /FADP 7 SEM pictures before and after 100 wear experiments, where a is HD-EP@cTiN 75 Before the coating wears, b is HD-EP@cTiN 75 After the coating is worn, c is HD-EP@cTiN 75 /FADP 7 D is HD-EP@cTiN before coating abrasion 75 /FADP 7 After the coating wears down.
FIG. 8 is a slide glass, HD-EP resin coating, and HD-EP@cTiN 75 /FADP 7 And testing the icing delay time and deicing of the coating.
Fig. 9 is a graph of icing delay time test for different coatings.
FIG. 10 is a graph showing the temperature of the surface of different coatings over time, based on the highest temperature of each curve in the graph, with HD-EP@cTiN in order from top to bottom 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、HD-EP@μTiN 75 /FADP。
FIG. 11 is a diagram of HD-EP@cTiN 75 /FADP 7 Photographs before and after self-repair.
FIG. 12 is a diagram of HD-EP@cTiN 75 /FADP 7 Schematic of self-cleaning function of (c).
Detailed Description
One possible way to increase the useful life of an ice control coating is to introduce self-healing properties into the resin coating. The self-repairing property of the deicing coating generally comprises two meanings, one refers to the property that the superhydrophobic property can be restored through a certain condition after the surface of the coating loses the superhydrophobic property due to structural damage, oxygen corrosion and the like, and the other refers to the property that the coating can restore the surface scratch automatically under a certain condition. The existing self-repairing ice-preventing and removing coating has less public information, the self-repairing performance of the existing super-hydrophobic ice-preventing and removing coating with self-repairing performance is only limited to the recovery of the super-hydrophobic performance, the self-repairing is realized by transferring a low-surface energy chain segment to the surface of a material, and the repairing is realized by melting a low-melting-point component, so that the material has poor heat resistance and cannot be used for preparing the photo-thermal ice-preventing and removing coating. The invention uses biomass raw materials to synthesize a brand new biomass Schiff base, uses the biomass Schiff base as an epoxy resin curing agent to prepare an epoxy resin with self-repairing performance, is used for preparing a photo-thermal super-hydrophobic ice-preventing and removing coating, firstly uses 5-Hydroxymethylfurfural (HMF) and 1, 10-diaminodecane (DAD) as biomass raw materials, synthesizes a long alkyl chain Schiff base (HD) with two hydroxyl end caps without solvent, and then uses the HD to cure trifunctional epoxy resin TDE-85 to prepare a novel self-repairing epoxy resin coating HD-EP.
It is known that the key performance in passive anti-icing, namely super-hydrophobic performance, is derived from the synergistic effect of the surface structure of the coating material and low surface energy, however, in practical application, long-term abrasion of wind sand on the surface of the coating material is difficult to neglect, and particularly, the anti-icing coating of outdoor equipment which is exposed to wind sand erosion for a long time is used for wind turbine blades. The super-hydrophobic property of the coating can be continuously reduced due to the fact that the surface structure is continuously worn and damaged, and therefore the anti-icing property of the coating is greatly affected. In addition, for the photo-thermal deicing coating, in order to better absorb light energy, photo-thermal fillers are often distributed on the surface layer of the coating, and the photo-thermal fillers can fall off due to the accumulated abrasion of sand and wind, so that the photo-thermal performance is affected. In summary, the abrasion resistance is an important property determining whether the ice control coating can normally operate in practical applications. The prior art has the following problems: firstly, most photo-thermal anti-icing and anti-icing coatings are poor in wear resistance, the wear cycle can only be carried out about 50 times, the super-hydrophobic performance is lost, the self-repairing performance of the material is not involved, and the material is not subjected to the melting of beeswax at most, belongs to extrinsic self-repairing, is not self-repairing and has the limit of repairing times. In addition, sustainable green development is an important direction of development in the field of materials at present, and reports of using biomass raw materials as coating raw materials are not seen in the existing polishing-resistant heat control ice coating.
The invention discloses a photo-thermal super-hydrophobic control ice resin matrix composite coating with self-repairing performance and high wear resistance. The proposal is that mu TiN and nTiN are adopted to construct a surface micro-nano structure and are combined with fluorinated ADP, and the prepared self-repairing epoxy resin is used for reinforcing the adhesion between the filler and the substrate, so that the obtained coating has excellent structure and performance, super-hydrophobic performance, good wear resistance and ice prevention and removal performance.
1, 10-diaminodecane (DAD), petroleum ether was purchased from Shanghai Ala Biotechnology Co., ltd (China), 4, 5-epoxytetrahydrophthalic acid diglycidyl ester (TDE-85), 5-Hydroxymethylfurfural (HMF) was purchased from Shanghai Meilin Biotechnology Co., ltd (China), and absolute ethanol was purchased from Yonghai Chemie Co., ltd (China). Tridecafluorooctyl siloxane (FAS) was purchased from Shanghai Allatin Biotechnology Co., ltd (China), nano titanium nitride (nTiN, 20-100 nm), micro titanium nitride (μTiN, 2-10 μm) was purchased from Shanghai Yes Biotechnology Co., ltd (China), and Aluminum Dihydrogen Phosphate (ADP) was purchased from Shanghai Aldamas reagent Co., ltd (China). All reagents were not subjected to other treatments. The raw materials involved in the invention are existing products, and the specific preparation operation and the testing method are conventional technologies.
Recording nuclear magnetic resonance hydrogen spectrum with AVANCEIIIHD-400 nuclear magnetic resonance spectrometer (NMR) 1 H-NMR) and nuclear magnetic resonance carbon spectrum 13 C-NMR). With deuterated chloroform (CDCl) 3 ) As solvent, tetramethylsilane (TMS) was used as an internal standard.
Testing infrared spectrum (FTIR) by using Vertex 70 type intelligent Fourier transform infrared spectrometer, and scanning 600-4000cm -1 With a resolution of 4cm -1 。
High Resolution Mass Spectrum (HRMS) obtained by Ultimate 3000 high performance liquid chromatograph with ES modeI + 。
The reactivity of the resin prepolymer was measured by a Q200 Differential Scanning Calorimeter (DSC) under a nitrogen atmosphere (flow rate: 50 mLmin) -1 ) The temperature rising rate is 5 ℃ for min -1 、10℃min -1 、15℃min -1 20 ℃ min -1 . About 4mg of the sample was weighed and sealed in an aluminum crucible, and the scanning temperature was in the range of room temperature to 300 ℃.
Scratch pictures before and after the coating self-repair were recorded with a super depth camera (VHX-7000), with a magnification of 200.
The Water Contact Angle (WCA) and the roll angle (SA) of the coating were measured using a LSA60Pro type contact angle measuring instrument, the ambient temperature at the time of the test was 25 ℃, the volume of the droplet used for the WCA test was 4. Mu.L, and the volume of the droplet used for the SA test was 6. Mu.L.
The surface topography of the coating was analyzed using a cold field emission Scanning Electron Microscope (SEM) model hitachi s-4700.
The roughness and topography of the coating surface were analyzed using an Atomic Force Microscope (AFM) of Dimension Icon.
Recording an absorption spectrum of the coating in a wavelength range of 300-1000 nm by using an ultraviolet visible near infrared spectrophotometer (UV 3600), wherein the absorption spectrum is obtained by a formula A=1-T-R, T is projection, and R is reflection.
The photo-thermal conversion performance of the coating is measured and recorded by adopting a thermal infrared imager (PI 640 i), wherein 808nm near infrared light used in the measurement process is from an infrared laser (MDL-H-808-5W), and the energy density is 1W/cm 2 。
The anti-icing performance of the coating is tested on a freezing table, the tested environment temperature is 20 ℃, the humidity is 47%, and the temperature of the surface of the freezing table is-20 ℃. The testing method comprises the following steps: and (3) placing the coating sample to be tested on a freezing table, dripping 10 mu L of deionized water on the surface of the coating by using a liquid-transferring gun, and evaluating the passive anti-icing performance of the coating by measuring the time when the liquid drops start to appear at a solid-liquid interface and the time when the liquid drops are completely frozen. Under the same environmental conditions, the energy density is 1W/cm 2 Is coated by recording 10. Mu.L of completely frozenThe time for the droplet to reconvert to liquid was evaluated for photo-thermal deicing performance of the coating.
The mechanical durability of the coating was studied by sandpaper abrasion experiments. In the abrasion test, the coating was dragged at a constant speed for 10cm on 1200# sandpaper under a load of 100g as a test cycle, and the contact angle and the rolling angle after abrasion were measured, and the abrasion resistance of the coating was evaluated by recording the number of cycles the coating underwent before completely losing the superhydrophobic performance.
Example one synthesis of Schiff base ((decane-1, 10-diacyldi (azetidinylene)) bis (methylvinylidene) bis (furan-5, 2-diacyl)) dimethanol (HD).
The solvent-free method is adopted to synthesize the full bio-based Schiff base curing agent HD. 2.649g of HMF was charged into a round-bottomed flask, placed in a magnetically stirred oil bath with a water separator and a condensate reflux apparatus and magnetically stirred, after which 1.721g of DAD was uniformly added in 5 batches and reacted at 110℃for 1 hour. After the reaction is finished, washing by using 200mL of deionized water and 200mL of petroleum ether in sequence, then evaporating water and the rest reactants in vacuum at 80 ℃, and drying to obtain biomass Schiff base HD with the yield of 95%; the reaction scheme and the chemical structural formula of the product are shown in figure 1. In FIG. 2A is HD 1 H NMR (400 MHz, Chloroform-d) A figure; b in FIG. 2 is HD 13 C NMR (101 MHz, chlorine-d) chart. FIG. 2C is the FT-IR spectrum of HMF and HD of 1686cm -1 Is the stretching vibration peak of C=O in aldehyde group, and 1686cm after reaction -1 The peak at 1650cm disappeared -1 There appears a stretching vibration peak belonging to the imine bond c=n, indicating the reaction of aldehyde groups with amino groups. In mass spectrometry of HD, the molecular mass was measured as 411.2252, consistent with the theoretical value 411.2260 of HD.
Examples di HD-EP resin coatings.
0.304g of TDE-85, 0.396g of HD and 10mL of absolute ethanol were added to a beaker, and stirred at room temperature for 30 minutes to obtain a resin spray A. A 75 x 25 mm microscope slide was taken and cleaned using deionized water and ethanol as the substrate for the coating. Spray liquid a was sprayed onto clean glass slides using a spray parameter of 2bar, 15 cm. Every 2mL of spray solution A was sprayed, and the temperature was kept at 80℃for 2min to volatilize the solvent. And curing the sprayed coating according to the process of 180 ℃/2h+200 ℃/2h+220 ℃/2h to obtain the HD-EP resin coating, wherein the thickness of the coating is 30.84 mu m.
HD and TDE-85 are mixed according to the mol ratio of 1:1, and stirred for 30min at 180 ℃ to obtain the HD-EP prepolymer. DSC curves with different heating rates are adopted to study the curing behavior of the HD-EP prepolymer, and each curve has an obvious curing exothermic peak in the range of 200-250 ℃. The curing onset temperature (T) of each curve was known by tangential method for the curing exotherm i ) Peak temperature of solidification (T) p ) Cure termination temperature (T) f ) As shown in table 1. Then T under different heating rates is carried out by taking the heating rate as the abscissa and the temperature as the ordinate i 、T p 、T f Respectively performing linear fitting, and extrapolating straight lines obtained by the fitting to 0 ℃/min to obtain the T of the HD-EP resin i 、T p 、T f 180 ℃, 198 ℃ and 222 ℃ respectively.
Figure SMS_1
The WCA test was performed on the HD-EP resin coating using a contact angle meter with a water droplet at 95 WCA on the HD-EP surface, indicating that the coating was a hydrophobic surface. Since the wettability of the coating is closely related to the surface energy of the material, the surface energy of HD-EP was analyzed using the two-fluid method. The WCA of water and formamide on the HD-EP surface was first tested at 95℃and 86℃respectively, r for both liquids d L And r p L 51mN/m and 18.7mN/m, respectively. According to Owens-Wendt-Kaelble method, the surface energy r of the HD-EP resin coating can be obtained s =16.660mN/m。
Scratches were made on the HD-EP resin coating with a scalpel, 65.03 μm wide and 20.18 μm deep. Then the coating with scratches was kept at 180℃for 30min and observed again under a super depth microscope, which revealed a width reduction of the scratches to 28.93. Mu.m, and a depth of 5.65. Mu.m. Referring to FIG. 3, pictures before and after HD-EP self-repair, inMagnification under super depth microscope by 200 times. The repair efficiency (n) of the HD-EP coating under the condition is 55.5%, n= (W) 1 -W 2 ）/ W 1 X 100%, W in 1 To repair the width of the scratch, W 2 To repair the scratch width.
In the third embodiment, the photo-thermal coating is prepared by adopting a layer-by-layer spraying method.
The microscope slide with 75×25 mm substrate was cleaned with deionized water and ethanol in sequence before use.
(1) Preparation of a μTiN-based coating HD-EP@xTiNy/FADP.
0.304g TDE-85, 0.396g HD and 10mL absolute ethanol are added into a beaker, stirred at room temperature for 30min to obtain spraying liquid A, and part of the spraying liquid A is taken out for preparing spraying liquid B and spraying liquid C.
Mu TiN is added into a beaker, 5mL of absolute ethyl alcohol and 3mL of spraying liquid A are added, and the spraying liquid B is obtained after dispersion treatment for 30min in an ultrasonic instrument.
A spray solution C was obtained by mixing 0.05g of ADP, 0.25g of FAS, 2mL of spray solution A, and 3mL of absolute ethanol.
Spraying the spraying liquid A (the rest of spraying liquid A), the spraying liquid B and the spraying liquid C on the clean glass slide layer by layer sequentially by using spraying parameters of 2bar and 15 cm. After each layer was sprayed, the temperature was kept at 80℃for 2min to volatilize the solvent. Solidifying the sprayed coating according to the process of 180 ℃/2h+200 ℃/2h+220 ℃/2h to obtain a coating based on mu TiN, namely HD-EP@ mu TiN x /FADP 7 Wherein x is the mass percent of μTiN relative to the HD-EP resin (actually x%, omitted from the name for brevity), FADP 7 Refers to ADP in an amount of 7% by mass (omitted from the name for brevity) relative to the HD-EP resin, and is shown in Table 2, for example, the mass of the HD-EP resin is 0.7g, the mass of μTiN is 0.35g, and x is 50% and abbreviated as 50.
Figure SMS_2
(2) Coating HD-EP@yTiN containing two types of scale fillers x /FADP z Is prepared by the following steps.
0.304g TDE-85, 0.396g HD and 10mL absolute ethanol are added into a beaker, stirred at room temperature for 30min to obtain spraying liquid A, and part of the spraying liquid A is taken out for preparing spraying liquid C and spraying liquid D.
Mixing 0.05g ADP, 0.25g FAS, 2mL spraying liquid A and 3mL absolute ethyl alcohol to obtain spraying liquid C, namely biomass Schiff base-aluminum dihydrogen phosphate-fluorosilicone mixed liquid.
Adding mu TiN and nTiN into a beaker, adding 5mL of absolute ethyl alcohol and 3mL of spraying liquid A, and performing dispersion treatment in an ultrasonic instrument for 30min to obtain spraying liquid D, namely the biomass Schiff base-titanium nitride mixed liquid.
Spraying the spraying liquid A (the rest of spraying liquid A), the spraying liquid D and the spraying liquid C on the clean glass slide layer by layer sequentially by using spraying parameters of 2bar and 15 cm. After each layer was sprayed, the temperature was kept at 80℃for 2min to volatilize the solvent. And curing the sprayed coating according to the process of 180 ℃/2h+200 ℃/2h+220 ℃/2h. The coating obtained was designated as HD-EP@yTiN x /FADP z Where y represents the mass ratio of μTiN to nTiN (when μ: n is 1:1, y=a; when μ: n is 1:0.75, y=b; when μ: n is 1:0.5, y=c; when μ: n is 1:0.25, y=d), x represents the mass of both TiN fillers and the mass percentage relative to the HD-EP resin (actually x%, omitted from the name for brevity), and z represents the mass percentage of ADP relative to the HD-EP resin (actually z%, omitted from the name for brevity), see Table 3.
Figure SMS_3
HD-EP@μTiN x /FADP 7 In the coating, HD-EP@ mu TiN 75 /FADP 7 The WCA of (2) is maximum (125.2) and the SA is minimum (21.2), and the super-hydrophobic performance requirement is not satisfied, i.e., the coating surface has WCA of more than 150 ° and SA of less than 10 °. Coating HD-EP@nTiN containing nTiN only 75 /FADP 7 The surface structure of (a) is very fragile, liquid drops can easily penetrate into the coating, so that the coating does not have hydrophobic performance (WCA is smaller than 90 degrees), and obviously only mu is addedThe composite coating of TiN or nTiN does not have superhydrophobic performance.
FIG. 4 is a diagram of HD-EP@yTiN 0.75 /FADP 7 Is a WCA, SA of (A). It can be seen that the WCA of the coating showed a tendency to rise first and then fall when the micro-nano ratio was gradually decreased, while SA showed the opposite tendency. When the micro-nano ratio is 1:0.25, the WCA and SA of the coating are 153 degrees and 7.5 degrees respectively, and the coating has super-hydrophobic performance. When the micro-nano ratio reaches 1:0.5, the coating has optimal super-hydrophobic performance, the WCA reaches 165.5 degrees, and the SA also reaches 4 degrees. After the nTiN content is continuously increased and the micro-nano ratio reaches 1:0.75, WCA and SA respectively show the trend of decreasing and increasing, namely 151 DEG and 9 deg. And when the micro-nano ratio reaches 1:1, the WCA and SA of the coating were 128.2 ° and 26.4 °, respectively, when the coating had no superhydrophobic properties.
Surface SEM characterization of the coating was performed (fig. 5). At a magnification of 2.5K, it was found that the coating was HD-EP@. Mu. TiN 0.75 /FADP 7 The structure of (2) does not have super-hydrophobic condition, and the test contact angle is only 125.2 degrees. When the micro-nano ratio is changed from 1:0 to 1:0.25, a plurality of tiny nano-scale protrusions can be observed on the micro-scale protrusion structure, when the micro-nano ratio is up to 1:0.5, the structure of the surface of the coating further becomes more complex, a plurality of gully-shaped cracks appear, and the coating has optimal super-hydrophobic performance. And after the content of nTiN is continuously increased to enable the micro-nano ratio to reach 1:0.75 and 1:1, the superhydrophobic performance is continuously reduced along with the increase of the nTiN content, and even the superhydrophobic performance is lost. Whereas for coatings containing only nTiN, HD-EP@nTiN 0.75 /FADP 7 The surface structure of the coating is very fragile, and liquid drops can permeate into scratches after the repair of the coating, so that the coating does not have super-hydrophobic performance.
The traditional method for improving the wear resistance of the coating is mainly to add epoxy resin, polysiloxane and the like, strengthen the bonding effect of the filler and the substrate and construct a unique surface structure, such as an embedded structure; however, these methods only prevent the filler from falling off during wear, but do not avoid damage to the surface structure by wear. According to the invention, aluminum Dihydrogen Phosphate (ADP) is used as a protective shell of a surface structure, and the aim of improving the wear resistance of the coating is fulfilled through the synergistic effect of the ADP and a resin system.
The abrasion resistance of the coating is tested by adopting a sand paper polishing mode. FIG. 6 is a diagram of HD-EP@cTiN 75 /FADP z Schematic of the change in WCA and SA with increasing number of wear test cycles. It can be seen that the WCA of the coating gradually showed a decreasing trend and the SA increased with increasing cycle number. When the mass fraction of ADP reaches 7%, the coating HD-EP@cTiN is coated even if the abrasion cycle reaches 100 times 75 /FADP 7 Still 152.1 deg. and 7.6 deg. with the SA. This indicates that the coating has excellent wear resistance. After the ADP content was increased to 9 wt%, the degree of change in wettability before and after abrasion was smaller than that of other components, but the superhydrophobicity before abrasion was reduced, and WCA and SA were 155℃and 6.5℃respectively. For coating HD-EP@cTiN 75 When the number of wear reaches 30, SA is greater than 10 degrees; after more than 50 times, the WCA was also less than 150 °.
FIG. 7 is a diagram of HD-EP@cTiN 75 With HD-EP@cTiN 75 /FADP 7 SEM images before and after wear experiments. HD-EP@cTiN 75 The wear-resistant steel has obvious height fluctuation before wear, and is bright and dark, namely has high roughness; however, after 100 wear cycles, the micro-nano structure of the coating surface is severely damaged, and a large-scale flat area is displayed in the visual field. HD-EP@cTiN before wearing 75 /FADP 7 Has high-low and compact surface, and after 100 times of abrasion test, the surface structure composed of obvious protrusions and ravines can be observed, and the AFM is used for HD-EP@cTiN 75 With HD-EP@cTiN 75 /FADP 7 Roughness before and after the abrasion test was characterized, HD-EP@cTiN after 100 abrasion cycles 75 The structure of (C) is severely damaged, the roughness is greatly reduced from 539nm to 178nm, and the HD-EP@cTiN 75 /FADP 7 Roughness only decreases from 534nm to 467nm after being subjected to 100 wear cycles. This indicates that the coating has excellent wear resistance.
Compared with the prior art relating to the photo-thermal super-hydrophobic deicing coating with wear resistance, the coating of the inventionLayer HD-EP@cTiN 75 /FADP 7 The coating has relatively better wear resistance and comprehensive performance, has wear cycle times larger than most of the prior art, and solves the problems that the existing coating has good wear cycle performance, but has poor anti-icing performance and short stop-freezing time, and is difficult to be used as a surface coating of a fan blade.
Anti-icing and deicing properties of the coating. The passive anti-icing performance of the coating was studied by measuring the icing delay time. Slide glass, resin coating HD-EP and coating HD-EP@cTiN 75 /FADP 7 Three groups of samples to be tested are placed on a freezing table at the temperature of minus 20 ℃,10 mu L of deionized water is dripped on the surfaces of the samples, and then the freezing process of the liquid drops is observed and recorded. As shown in FIG. 8, the surface contact angle of the droplet is less than 90℃on both the slide and the resin coating, and is shown in HD-EP@cTiN 75 /FADP 7 The surface is larger than 150 degrees, and the surface presents a more complete sphere, which shows that the coating still has super-hydrophobic performance even under the low temperature environment of minus 20 ℃. In order to record the time of freezing the liquid drop on the surface of the sample, the time of obvious solid-liquid interface inside the liquid drop is selected as the initial freezing time of the liquid drop, and the time of completely freezing the liquid phase into the solid phase is selected as the freezing termination time. The results showed that the initial and final freezing times of the blank component slides were 4s and 37s, respectively, the HD-EP was 91s and 120s, and the HD-EP@cTiN 75 /FADP 7 289s and 446s and the droplets on the coating remain spherical in shape even if completely frozen. HD-EP@cTiN 75 /FADP 7 The icing time of the coating was prolonged to 12 times compared to the blank, indicating a good passive anti-icing capacity.
To study the photothermal deicing performance of the coating, 1W/cm was used 2 The 808nm laser with energy density simulates sunlight, irradiates the sunlight vertically to the frozen liquid drop on the surface of the coating, and observes and records the melting phenomenon of the liquid drop. As shown in FIG. 8, HD-EP@cTiN 75 /FADP 7 The ice on the surface of the coating melts rapidly within 10 seconds of irradiation, and the melted droplets remain in a spherical form, whereas the glass slide and the resin coating do not melt any even if irradiated for up to 100 secondsSigns of chemical conversion. The above results indicate that HD-EP@cTiN 75 /FADP 7 The coating has good photo-thermal deicing performance, and can completely melt the liquid drops frozen on the surface in a short time.
In addition, HD-EP@aTiN was also tested 75 /FADP 7 、HD-EP@bTiN 75 /FADP 7 、HD-EP@dTiN 75 /FADP 7 HD-EP@ mu TiN 75 /FADP 7 As shown in FIG. 9, the coating HD-EP@dTiN 75 /FADP 7 Is 285s and 375s, respectively, HD-EP@bTiN 75 / FADP 7 262s and 364s, respectively, and the coating HD-EP@aTiN 75 /FADP 7 、HD-EP@μTiN 75 /FADP 7 The super-hydrophobic performance is not possessed by the anti-icing agent, so that the anti-icing agent is poor in passive anti-icing performance, the anti-icing agent is 146s and 253s respectively, and the anti-icing agent is 116s and 194s respectively.
Thermal infrared imager is used for researching HD-EP@cTiN 75 /FADP 7 At 1W/cm 2 The photo-thermal conversion function under 808nm near infrared light. As shown in FIG. 10, when near infrared laser is irradiated on the sample surface, the temperature of the sample surface of all components is rapidly increased in a short time, HD-EP@cTiN 75 /FADP 7 The coating reaches 97.4 ℃; notably, the single-scale coating HD-EP@ mu TiN x /FADP 7 Even with a double-scale coating HD-EP@cTiN x /FADP 7 The same mass fraction was found, and the temperature after 50s of illumination was only 67.9 ℃.
FIG. 11 is a coating HD-EP@cTiN 75 /FADP 7 Super depth of field microscope pictures of the surface scratches before and after repair. The surface of the coating was scored by a scalpel with a width of 71.05 μm and a depth of 29.85 μm, after which an energy density of 2W/cm was used 2 The scratch area was irradiated with near infrared light of 808nm for 30min, and then a picture was taken after near infrared light repair. After 30min of repair of the coating, it was observed that scratches on the resin became no longer apparent, and healed again in the middle of the repaired scratches, not as continuous scratches. This is due to the fact that the resin on both sides of the scratch drives the migration of nTiN, μTiN and ADP bonded on the resin in the self-repairing process, so thatThe damaged surface structure is repaired to a certain extent. The width of the repaired scratch was 45.76 μm and the depth was 13.58. Mu.m. The calculated repair efficiency was 35.7%. Although HD-EP@cTiN 75 /FADP 7 Is reduced compared to HD-EP, but the coating HD-EP@cTiN 75 /FADP 7 The light-heat self-repairing device has a good light-heat conversion function, so that the heat self-repairing device with high energy consumption can be converted into energy-saving and area-controllable light self-repairing device.
Many surfaces in daily life eventually become contaminated by the accumulation of dust and dirt. For photo-thermal coatings, dust accumulation can greatly reduce the light absorption efficiency of the coating. During the cleaning process, a great deal of money, labor and energy is wasted. Self-cleaning superhydrophobic coatings are one of the best options for solving this problem, and droplets roll from the inclined coating and adsorb dust into the droplets, thereby realizing a self-cleaning function.
FIG. 12 is a coating HD-EP@cTiN 75 /FADP 7 Schematic diagram of self-cleaning function. 1g of sand was sprayed onto the surface of the coating and the coating was placed in a petri dish at an angle of inclination of around 10 °. Then 3mL of deionized water is dripped above the coating by a dropper, so that sand on the surface of the coating can be observed to be removed from the coating along with the rolling of the liquid drops, and finally the sand flows into a culture dish. After 3mL of deionized water was added dropwise, no substantial sand residue was found on the coating, indicating HD-EP@cTiN 75 /FADP 7 Has good self-cleaning function.
Compared with other anti-icing technologies, the photo-thermal anti-icing coating has the advantages of energy conservation, high efficiency and the like, is the most potential representative of anti-icing materials, and is applied to various fields such as aerospace, energy industry, civil traffic and the like. However, abrasion resistance has been one of the most important properties of the photothermal deicing coating material. Therefore, the development of the resin-based photo-thermal deicing coating with high wear resistance has important significance. The icing problem of wind power blades seriously hinders the development of wind power energy, and a photo-thermal super-hydrophobic ice-preventing and removing coating is an important strategy for solving the problem. However, the existing photo-thermal super-hydrophobic ice control coating has the problem of low wear resistance.
The invention synthesizes a biomass Schiff base by adopting a green biomass raw material and a solvent-free method, and reacts with epoxy resin TDE-85 to prepare the epoxy resin HD-EP with a self-repairing function; resin HD-EP is used as a coating adhesive, two-scale TiN (nTiN and mu TiN) is used as a filler and a surface micro-nano structure construction material, and fluorinated ADP is used, so that the photo-thermal super-hydrophobic ice control coating HD-EP@yTiN with high wear resistance and self-repairing performance is prepared by a layer-by-layer spraying method x /FADP z The coating has excellent superhydrophobic performance, the WCA is 165.5 degrees, the SA is 4 degrees, the wear resistance of the coating is good, and the superhydrophobic performance can be still maintained through 100 times of sand paper wear experiments; coating HD-EP@cTiN 75 /FADP 7 Has good ice preventing and removing performance, and the icing time at-20 ℃ is prolonged to 446s, and compared with a glass slide substrate, the icing delay time is 12 times. In addition, under the irradiation of a near infrared lamp, the accumulated ice can be completely melted within 10 seconds; in particular, the coating HD-EP@cTiN 75 /FADP 7 The light self-repairing capability is certain, and the repairing rate can reach 35.7% within 30min under the irradiation of 808nm near infrared light; in addition, the coating has excellent self-cleaning function, and 3mL of deionized water can be used for completing the self-cleaning function of 1g of sandy soil.

Claims (10)

1. A biomass schiff base is ((decane-1, 10-diacyldi (azetidinylene)) bis (methylvinylidene) bis (furan-5, 2-diacyl)) dimethanol.
2. The preparation method of the biomass Schiff base as claimed in claim 1, which is characterized by comprising the following steps of taking 5-hydroxymethylfurfural and 1, 10-diaminodecane as raw materials, and reacting for 0.5-3 h at 90-120 ℃ to obtain the biomass Schiff base.
3. A biomass schiff base polymer, characterized in that it is obtained from the biomass schiff base-cured epoxy resin according to claim 1.
4. The preparation method of the biomass Schiff base photo-thermal coating is characterized by comprising the following steps of 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 solidifying to obtain the biomass Schiff base photo-thermal coating; the biomass schiff base prepolymer is a mixture of the biomass schiff base and epoxy resin in claim 1.
5. The method for preparing a photo-thermal coating of biomass Schiff base according to claim 4, wherein the curing temperature is 180-220 ℃ and the curing time is 5-8 hours, and the curing adopts stepped heating; in the biomass Schiff base prepolymer-titanium nitride layer, titanium nitride consists of micro-titanium nitride and nano-titanium nitride with the mass ratio of 1:0.25-1; in the biomass Schiff base prepolymer-aluminum dihydrogen phosphate-fluorosilicone layer, the fluorosilicone is tridecafluorooctyl siloxane.
6. The method for preparing the biomass schiff base photo-thermal coating according to claim 4, which is characterized in that the biomass schiff base and the epoxy resin according to claim 1 are mixed in a solvent and then divided into three parts, namely mixed solution A, mixed solution B and mixed solution C; mixing the mixed solution B with titanium nitride in a solvent to obtain a biomass Schiff base-titanium nitride mixed solution; mixing the mixed solution C with aluminum dihydrogen phosphate and fluorosilicone in a solvent to obtain a biomass Schiff base-aluminum dihydrogen phosphate-fluorosilicone mixed solution; drying the mixed solution A to obtain a biomass Schiff base prepolymer film; drying the biomass Schiff base-titanium nitride mixed solution to obtain a biomass Schiff base prepolymer-titanium nitride layer; drying the biomass Schiff base-aluminum dihydrogen phosphate-fluorosilicone mixed solution to obtain a biomass Schiff base prepolymer-aluminum dihydrogen phosphate-fluorosilicone layer.
7. The preparation method of the biomass Schiff base photo-thermal coating according to claim 6, wherein the total volume of the mixed solution A, the mixed solution B and the mixed solution C is 100%, the volume of the mixed solution B is 20-40%, the volume of the mixed solution C is 15-30%, and the balance is the mixed solution A; the mass ratio of the biomass Schiff base to the epoxy resin is 100:55-80:3-9:30-40.
8. The biomass schiff base photo-thermal coating prepared by the preparation method of the biomass schiff base photo-thermal coating.
9. A photothermal deicing material comprising a substrate and a biomass schiff base photothermal coating on the surface of the substrate, wherein the biomass schiff base photothermal coating is the biomass schiff base photothermal coating of claim 8.
10. Use of the biomass schiff base of claim 1, the biomass schiff base polymer of claim 3 or the biomass schiff base photo-thermal coating of claim 8 for the preparation of an anti-icing coating; or the use of the photo-thermal deicing material according to claim 9 for preparing a fan blade coating material.
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