CN116102513A

CN116102513A - Benzoxazine monomer, composite material and preparation method

Info

Publication number: CN116102513A
Application number: CN202310387380.8A
Authority: CN
Inventors: 顾嫒娟; 张晓剑; 梁国正; 袁莉
Original assignee: Suzhou University
Current assignee: Suzhou University
Priority date: 2023-04-12
Filing date: 2023-04-12
Publication date: 2023-05-12
Anticipated expiration: 2043-04-12
Also published as: CN116102513B

Abstract

The invention discloses a benzoxazine monomer, a composite material and a preparation method thereof. The four-layer structure composite coating formed by the C-d, HSi, P@mAlN and P@nAlN effectively solves the problems of poor wear resistance and liquid puncture resistance of the traditional superhydrophobic coating, and the anti-icing coating which has good wear resistance, good liquid puncture resistance and excellent anti-icing performance is obtained and is more suitable for the icing environment of wind power blades. The coating exhibits remarkable mechanical and chemical durability, which greatly prolongs the service life of the coating and widens its practical application.

Description

Benzoxazine monomer, composite material and preparation method

Technical Field

The invention belongs to a high molecular material and an ice preventing and removing technology thereof, relates to a preparation method of a high molecular thermosetting material, and in particular relates to a benzoxazine monomer, a composite material and a preparation method, which are applied to a wind power blade ice preventing and removing coating with photo-thermal performance.

Background

Wind power is used as a novel renewable clean energy source and becomes a third largest power source after thermal power and hydroelectric power. The wind turbine blade is mainly distributed in cold areas with high air density and coastal areas with low temperature and high humidity in China, so that the surface of the wind turbine blade is easy to freeze, the wind turbine blade is frozen to seriously influence a wind power generation system, the ice on the blade breaks the aerodynamic shape, the efficiency and the service life of wind power generation equipment are reduced, and the safety of maintenance personnel is threatened to a certain extent.

Currently, there are two main methods for reducing and eliminating surface icing, namely, an anti-icing method and an icephobic method. The former is used for relieving or resisting the freezing of surface water and mainly comprises a super-hydrophobic coating method and a porous oiling smooth surface method; the latter refers to the removal of the ice formed by suitable means, mainly including mechanical, thermal and chemical deicing. Among them, electrothermal coating represents a typical contact deicing method, i.e. adding conductive filler to the coating to generate heat; while photothermal coatings represent a non-contact deicing method, i.e., absorbing light to generate heat. Unlike the two coatings described above, superhydrophobic coatings having a high water contact angle (WCA >150 °) and a low slip angle (SA <10 °) are considered to be a very promising anti-icing coating. Although the superhydrophobic coating has good anti-icing properties, water droplets eventually freeze at lower temperatures. Considering the limitation of electrothermal and ice-melting coatings in deicing, combining photo-thermal and super-hydrophobic properties is expected to realize a composite coating with excellent anti-icing and deicing properties.

At present, methods for artificially constructing the superhydrophobic surface mainly comprise a chemical etching method, a sol-gel method, a modified micro-nano particle coating method, a chemical vapor deposition method, an electrodeposition method, a laser etching method and the like. Among them, the coating method is simple in operation process and low in cost, and most importantly, it can produce an effective super-hydrophobic film. However, the micro-nano structure is susceptible to external force to cause failure, and the micro-nano structure is mainly characterized in that the wear resistance and the liquid puncture resistance of the super-hydrophobic surface are poor, so that the super-hydrophobic property is lost. Accordingly, those skilled in the art have been working to develop a stable superhydrophobic deicing coating having excellent abrasion resistance and liquid penetration resistance, which can be deicing by photo-thermal, and a method of preparing the same.

Disclosure of Invention

The main problem facing the superhydrophobic surface at present is the problem of low service life caused by poor wear resistance and liquid penetration resistance, which greatly limits the wide application of the superhydrophobic surface in the fields of deicing and the like. Only if the structure of the superhydrophobic surface is known, the above problems can be solved by using proper raw materials, filler and surface modifier to cooperate from the preparation of the superhydrophobic surface. The invention aims to provide an ice prevention and removal coating with photo-thermal performance and a preparation method thereof, so that the coating has excellent wear resistance and liquid puncture resistance.

In order to achieve the aim of the invention, the invention adopts the following technical scheme:

a benzoxazine monomer having the chemical structural formula:

。

the invention discloses a preparation method of the benzoxazine monomer, which takes cardanol, paraformaldehyde and dehydroabietylamine as raw materials to prepare the benzoxazine monomer through reaction. Preferably, the mole ratio of the dehydroabietylamine to the paraformaldehyde to the cardanol is 1:2-2.2:1; the reaction temperature is 100-120 ℃ and the reaction time is 1-3 h. The novel benzoxazine (C-d) containing long fatty chains is designed and synthesized by using biomass raw material cardanol as a phenol source and dehydrogenated rosin amine as an amine source through a solvent-free method, the biomass content is high, the yield is good, the synthesis process is environment-friendly, a catalyst is not needed, and the coating has excellent thermal stability.

The invention discloses a benzoxazine composite material and a preparation method thereof, comprising the following steps: sequentially preparing a hyperbranched polysiloxane film layer and a dopamine-coated aluminum nitride film layer on the film layer of the benzoxazine monomer; then curing to obtain a benzoxazine composite material; the preparation method of the hyperbranched polysiloxane comprises the steps of dropwise adding hydrochloric acid into a silane coupling agent aqueous solution, and then reacting for 5-8 hours at 50-60 ℃ to obtain transparent liquid; the transparent liquid is then dried to give the hyperbranched polysiloxane.

Preferably, the dopamine-coated aluminum nitride film layer consists of a dopamine-coated micrometer aluminum nitride film layer and a dopamine-coated nanometer aluminum nitride film layer; the grain size of the micrometer aluminum nitride is 1-20 mu m, and the grain size of the nanometer aluminum nitride is 10-100 nm.

In the invention, the mass ratio of the benzoxazine monomer to the hyperbranched polysiloxane to the dopamine coated micron aluminum nitride to the dopamine coated nanometer aluminum nitride is 1:0.3-0.5:0.2-0.3:0.1-0.15.

In the method, corresponding functional layers are prepared by drying solutions of materials of all layers, specifically, benzoxazine monomer solutions are dried, and a benzoxazine monomer film is obtained; drying the hyperbranched polysiloxane solution to obtain a hyperbranched polysiloxane film layer; and drying the dopamine-coated aluminum nitride solution to obtain the dopamine-coated aluminum nitride membrane layer. Tetrahydrofuran is used as a solvent to respectively prepare a benzoxazine monomer solution, a hyperbranched polysiloxane solution and a dopamine-coated aluminum nitride solution.

In the invention, the solidification is step heating, the temperature is 160-220 ℃ and the time is 3-6 hours. The step heating is a conventional method for curing resin, for example, the resin is heated for 1-2 hours by taking 20 ℃ as a gradient.

The invention discloses a deicing material, which comprises a base material and a coating on the surface of the base material, wherein the coating is the benzoxazine composite material.

The invention discloses application of a benzoxazine composite material in preparation of a deicing coating or a deicing material with photo-thermal properties, such as a wind power blade with the photo-thermal properties coating.

The micro-nano structure of the superhydrophobic surface is easy to fail due to the action of external force, so that the abrasion resistance is poor, the coating with high abrasion resistance in the prior art adopts a fluorination technology, and the abrasion resistance of the coating without carrying out the surface fluorination treatment of the filler is poor. Therefore, developing a fluorine-free green photo-thermal/super-hydrophobic ice control composite coating with excellent wear resistance is a challenge with important application value. The wind power blade is inevitably impacted by rainwater in the service process, if the coating is impacted by liquid, gaps of the micro-nano structure on the surface are not infiltrated by the liquid, peak pressure generated when the liquid drops impact the surface can be borne, even if the surface is frozen, the surface is not damaged, the aim of deicing can be achieved under the action of light and heat, but unfortunately, the traditional photo-thermal/super-hydrophobic anti-deicing composite coating does not study the liquid penetration resistance or the performance deviation, and limits the feasibility of application of the coating on the wind power blade. Therefore, the research of developing a novel fluoride-free photo-thermal/super-hydrophobic ice-preventing and removing composite coating with wear resistance and liquid puncture resistance has very important significance. The invention provides a four-layer structure composite coating (C-d/yHSi/0.4P@2bAlN, y is the weight ratio of HSi to C-d) composed of C-d, HSi, P@mAlN and P@nAlN, and the coating with very good structure and performance is obtained through composition proportion, so that the problems of poor wear resistance and liquid puncture resistance of the existing super-hydrophobic coating are effectively solved, and the anti-icing coating with good wear resistance, good liquid puncture resistance and excellent anti-icing performance is obtained, and is more suitable for the icing environment of wind power blades.

Compared with the prior art, the invention has the following beneficial effects:

(1) The invention designs and synthesizes the flexible bio-based benzoxazine monomer with long fatty chain and fatty ring, the synthesis process has no byproducts and no catalyst ring-opening solidification, and the natural raw materials are all renewable biomass resources, so the invention has environmental friendliness;

(2) The dopamine is used for coating the same aluminum nitride with different sizes as the filler, so that the micro-nano structure surface is constructed, the problems of aggregation defects and the like caused by different fillers are effectively avoided, the effective lifting of the coating from hydrophobic to super-hydrophobic is realized, the stay of water drops is reduced, the separation of supercooled water drops is promoted, and the problem of icing of the wind power blade in a cold environment can be solved;

(3) The aluminum nitride filler is firstly used for constructing a super-hydrophobic surface, is combined with resin, brings unexpected performance, and can play an important role in the field of photo-thermal deicing;

(4) The novel bio-based benzoxazine monomer and hyperbranched polysiloxane synthesized by design are combined with multi-size aluminum nitride, so that the problems of poor wear resistance and liquid puncture resistance of the existing super-hydrophobic coating are effectively solved, and the anti-icing coating which has good wear resistance, good liquid puncture resistance and excellent anti-icing performance and is more suitable for the icing environment of the wind power blade is obtained.

Drawings

In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are required to be used in the embodiments or the description of the prior art will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments described in the present invention, and other drawings may be obtained according to the drawings without inventive effort to those skilled in the art.

FIG. 1 is an IR chart of all bio-based benzoxazine monomer and cardanol, dehydroabietylamine prepared in example 1 of the present invention.

FIG. 2 is a schematic illustration of the whole bio-based benzoxazine monomer prepared in example 1 of the present invention ¹ H NMR chart.

FIG. 3 is a diagram of the whole bio-based benzoxazine monomer prepared in example 1 of the present invention 1 ¹ C NMR chart.

FIG. 4 is a graph showing the phenomenon of silver mirror when the ice control coating obtained in example 1 of the present invention is immersed in water.

FIG. 5 is an IDT of a C-d/yHSi/0.4P@2bAlN coating before and after 100 cycles of sandpaper abrasion.

FIG. 6 is WCA and SA of different coatings after 100 cycles of sandpaper wear, where a is C-d/0.3HSi/0.4P@2bAlN, b is C-d/0.4HSi/0.4P@2bAlN, and C is C-d/0.5 HSi/0.4P@2AlN.

FIG. 7 is a photograph of a cross section of different layers during preparation of a C-d/0.5HSi/0.4P@2bAlN coating under a super depth of field microscope, wherein a is a C-d layer, b is a C-d/0.5HSi layer, C is a C-d/0.5HSi/0.4P@mAlN layer, and d is a C-d/0.5HSi/0.4P@2bAlN layer.

FIG. 8 shows the impact of water droplets on the surface of different coatings, where a is C-d/0.4P@mAlN layer, b is C-d/0.4P@2bAlN C layer, and C is C-d/0.5 HSi/0.4P@2AlN layer.

FIG. 9 is a photo-thermal deicing of 100. Mu.L of water at-20℃on different surfaces, where a is the slide, b is the C-d coating, C is the C-d/0.5HSi/0.4P@2bAlN coating.

FIG. 10 is a graph of the coating of each component in IR (1W/cm ² 808 nm) of the surface after irradiation.

FIG. 11 is a variation of the C-d/xP@mAlN coating after 10 cycles of sandpaper wear, where a is WCA and b is IDT.

Fig. 12 is IDT of each coating layer.

FIG. 13 is a variation of the C-d/0.4P@zbAlN coating after 10 cycles of sandpaper wear, where a is WCA and b is IDT.

FIG. 14 is a graph showing the change of the C-d/0.5HSi/0.4P@2bAlN coating after soaking in solutions of different pH for 24 hours, wherein a is WCA and b is SA.

FIG. 15 is the self-cleaning performance of a C-d/0.5HSi/0.4P@2bAlN coating, where a is the scattering of 0.01g of the selected silt on the surface of the C-d/0.5HSi/0.4P@2bAlN coating at an inclination angle of about 15 ℃, b is the rinsing with 1mL of deionized water, and C is the departure of silt from the surface of the coating with water.

FIG. 16 is a WCA photograph of water droplets on the surface of a C-d/HSi coating.

Detailed Description

The invention takes cardanol as a phenol source, reacts with biomass formaldehyde and dehydroabietylamine for a period of time under the condition of heating, condensing and refluxing, dissolves the biomass formaldehyde and dehydroabietylamine into chloroform after the reaction is finished, and obtains a novel bio-based benzoxazine monomer after purification processes such as washing, drying, suction filtration, rotary evaporation and the like are sequentially carried out; then tetrahydrofuran is used as a solvent to prepare a benzoxazine monomer solution.

Pouring KH-560 and water into a three-neck flask for mixing; dropwise adding hydrochloric acid while stirring at room temperature to keep the pH of the solution between 1 and 2, and stirring for 10 to 20 minutes; then stirring for 5-8 h at 50-60 ℃ to obtain light colorless transparent liquid; the liquid was dried in vacuo at 60 ℃ for 7h to give a colorless transparent viscous liquid, designated HSi, and then hyperbranched polysiloxane solution was prepared using tetrahydrofuran as solvent.

Placing Tris buffer solution (pH 8.5), ethanol, water and AlN into a round bottom flask, performing ultrasonic dispersion, adding dopamine, and stirring at room temperature to observe that the solution turns from white to black; and washing the reaction solution with ethanol and deionized water respectively, filtering, and drying in a drying oven at 65 ℃ to obtain the polydopamine coated aluminum nitride. The mass ratio of the ethanol to the water to the Tris buffer solution is 1:1-5:0.1-0.3. And dispersing polydopamine coated aluminum nitride by using tetrahydrofuran as a solvent to prepare polydopamine coated aluminum nitride solution.

Removing pollutants on the surface of a substrate conventionally, firstly, uniformly spraying a benzoxazine monomer solution on the surface of the substrate, and placing the substrate on a hot table for a period of time to volatilize the solvent to prepare a benzoxazine monomer film layer; then spraying hyperbranched polysiloxane solution, and placing the hyperbranched polysiloxane solution on a hot table for a period of time to volatilize the solvent to prepare a hyperbranched polysiloxane film layer; then spraying polydopamine coated micron aluminum nitride solution, and placing a period of volatile solvent on a hot table to prepare a polydopamine coated micron aluminum nitride film layer; then spraying polydopamine coated nano aluminum nitride solution, and placing a period of volatile solvent on a hot table to prepare a polydopamine coated nano aluminum nitride film layer; finally, the step heating and curing are carried out to obtain the anti-icing coating with photo-thermal performance, which can be used as the anti-icing coating of the wind power blade with photo-thermal performance. The substrate is a conventional material such as glass slide, aluminum plate, steel plate, epoxy resin plate, etc., and cleaning is a conventional method such as ultrasonic treatment with deionized water, ethanol, acetone, respectively, and then drying in an oven to remove oil stains and pollutants on the surface. The spraying is a conventional method, a spray gun is adopted, the pressure of the spray gun during spraying is 1-3 bar, and the distance between the spray gun and the substrate is 5-20 cm. When the solvent is volatilized on the hot stage, the temperature of the hot stage is 50-100 ℃ and the standing time is 1-10 min.

In order to make the technical solution of the present invention better understood by those skilled in the art, the technical solution of the present invention will be further and clearly described by the following detailed description and the accompanying drawings, and it is obvious that the described embodiments are some, but not all, embodiments of the present invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention. Furthermore, unless otherwise defined, all scientific and technical terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The experimental methods, in which specific conditions are not noted in the following examples, are generally conducted under conventional conditions or under conditions recommended by the manufacturer.

The raw materials and sources used in the invention are respectively as follows: cardanol (> 90%) was purchased from sigma aldrich limited in Shanghai, china; dehydroabietylamine (> 90%), alN (50 nm) was purchased from Shanghai microphone Biochemical technologies Co., ltd; paraformaldehyde (analytically pure), alN (2 μm), sodium hydroxide (analytically pure), sodium chloride (analytically pure), tris buffer (Tris buffer) were purchased from shanghai ala Ding Shenghua technologies, inc; gamma- (2, 3-glycidoxy) propyltrimethoxysilane (KH-560) was purchased from shanghai source leaf biotechnology limited; ethanol (analytically pure), hydrochloric acid (analytically pure), chloroform (analytically pure) were purchased from Jiangsu Qiangsheng functional chemical Co., ltd; tetrahydrofuran (analytically pure) was purchased from adult westernia chemical company limited.

Performance testing

The coating was tested at 300-1200cm using a UV3600 ultraviolet visible near infrared spectrophotometer (UV-vis-NIR) ^-1 Absorption rate in the inner part. The morphology and roughness of the coating were observed using a Dimension Icon Atomic Force Microscope (AFM). The surface morphology of the coating before and after abrasion was observed using a Hitachi S-4700 Scanning Electron Microscope (SEM). Test the coatingThe sample was inverted over the 2000# sandpaper surface and the coating was brought into contact with the sandpaper. A weight of 100g was pressed against the sample surface and the sample was moved laterally 10cm as a wear cycle. The contact angle and sliding angle of the coating were measured after every ten wear cycles. Impact of water drops (diameter: 3 mm) released from a height of 4cm on the superhydrophobic surface was evaluated for the liquid penetration resistance of the coating. The drop impingement process was recorded using a high speed camera. At least three different locations on each surface and three different samples of the same composition were subjected to puncture resistance testing. The freezer is lowered to-10 ℃ and the coating is placed on top for 10 minutes to ensure that the surface temperature of the coating is reduced to the target temperature. 10 mu L of deionized water is dripped on the surface of the coating, the freezing process of the water drops is observed through a camera, and the time required for the water drops to be completely frozen is recorded. The patterned coating is irradiated by an MDL-H-808-5W type infrared laser with the irradiation density of 1W/cm ² The 808nm infrared irradiation surface of the (B) is recorded by using a Pl640i thermal infrared imager, the temperature change of the surface of the coating under the irradiation of infrared light is recorded, and the photo-thermal property of the coating is studied. The coatings were immersed in HCl or NaOH solutions of different pH values for 24 hours, and contact angles and sliding angles of the coatings were measured to analyze chemical durability of the coatings. The adhesion properties of the coating were evaluated using a grid method. The coating surface was scored with 1mm spacing in a cross-hatch method, and the coating adhesion rating was assessed by analyzing the area lost by the coating surface after tape stripping. 0.1mL of water was dropped onto the coating and slide and allowed to freeze completely at-20 ℃. The illumination density was 1W/cm ² The frozen water was irradiated with infrared light of 808nm, and the melting of ice was observed with a camera and the melting time was recorded.

Example 1

Cardanol (10 mmol,3.0451 g), dehydroabietylamine (10 mmol,2.8547 g) and paraformaldehyde (20 mmol,0.6 g) were placed in a round bottom flask under reflux conditions; heating and stirring at 70 ℃ for 0.5h, and then heating to 110 ℃ for 2h. After the reaction was completed, a yellow liquid was obtained. After cooling to room temperature, the yellow liquid is dissolved in 50mL of chloroform, 400mL of 4% NaOH aqueous solution is used for washing to remove unreacted substances, deionized water is used for washing to be neutral, and the emulsification phenomenon is broken through adding saturated saline in the liquid separation process; drying with anhydrous magnesium sulfate, removing the anhydrous magnesium sulfate by suction filtration, and finally removing chloroform by rotary evaporation to obtain yellow viscous liquid which is novel benzoxazine monomer and is marked as C-d, wherein the yield is 67.5%.

The IR diagram of the novel bio-based benzoxazine monomer, cardanol and dehydroabietylamine is shown in figure 1, and can be seen that the symmetrical telescopic vibration peak of oxazine ring C-O-C group (1239 cm ^-1 ) And an antisymmetric telescopic vibration peak (1029 cm) ^-1 ) Symmetrical stretching vibration peak of C-N-C (1116 cm) ^-1 ) In-plane extension vibration of C-H on oxazine ring and oxazine ring skeleton vibration peak (964 cm ^-1 ). 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. And (3) carrying out characterization on a nuclear magnetic hydrogen spectrum and a nuclear magnetic carbon spectrum of the prepared novel bio-based benzoxazine monomer, wherein the nuclear magnetic hydrogen spectrum is shown in a figure 2, and the nuclear magnetic carbon spectrum is shown in a figure 3. Based on the above spectra, it was confirmed that C-d had been successfully synthesized.

The slide glass is taken as a substrate, treated by deionized water, ethanol and acetone respectively for 5min, and then dried at 80 ℃ to remove oil stains and pollutants on the surface. Tetrahydrofuran (THF) is used as a solvent to prepare a C-d solution with the concentration of 10wt percent, and the solution is dispersed for 0.5h for standby. The C-d solution was removed and sprayed onto a glass slide by a spray gun and placed on a hot stand at 80℃for 5min to evaporate the solvent. The resulting coating was cured according to the 180 ℃/1h+200 ℃/1h+220 ℃/1h+240 ℃/2h process, and the resulting coating was designated as a C-d coating.

Static contact angle (WCA) and Sliding Angle (SA) were measured using a contact angle measuring instrument (LSA 60 Pro) with 10 μl deionized water as a test drop, and each sample was measured five times at different points, and the average value was taken as a test result. The WCA of the water drop on the surface of the C-d coating is 102+/-3 degrees and is larger than 90 degrees, which indicates that the C-d coating is a hydrophobic surface; SA is greater than 60. According to Owens-Wendt-Kaelble method, conventionally calculatedγ _s Surface free energy of C-d coating was lower than that of Polytetrafluoroethylene (PTFE) (18.5 mN/m) and PDMS =15.7 mN/mFree energy (25 mN/m).

Thermogravimetric analysis of materials using a TGA55 thermogravimetric analyzer (TGA), at N ₂ At 10 ℃ for min under atmosphere ^-1 T of the C-d coating from 30 ℃ to 800 DEG C _di The C-d coating has excellent heat stability at 317 ℃ which is higher than 269 ℃ of cardanol-based benzoxazine resin in the prior literature.

The hardness of the C-d coating was measured to be 2H according to the national Standard-determination of paint film hardness by the paint and varnish Pencil method (GB/T6739-2006).

The impact strength of the material was tested using a digital display type simple beam pendulum impact tester (XCJD-5, underwire and instruments manufacturing limited) with a test standard of GB/T8809-2015. The results show that the impact strength of the C-d film is 6.48kJ/m ² Impact strength (5.09 kJ/m) higher than that of the conventional benzoxazine resin (MDA-BOZ) ² ) The C-d film can be bent into a U-shape without breaking.

Example two

20g KH-560 and 2g deionized water were poured into a three-necked flask and mixed; dropwise adding hydrochloric acid under stirring at 25 ℃ to keep the pH of the solution between 1 and 2, and stirring for 15min; then stirred in an oil bath at 55 ℃ for 7 hours to obtain a light colorless transparent liquid. The liquid is dried for 7 hours in vacuum at 60 ℃ to obtain colorless transparent viscous liquid which is named HSi and is filled into a sample bottle for sealing and preservation.

2.5mL Tris buffer (pH-8.5), 20mL ethanol, 50mL deionized water, 2g AlN (micron-sized) were placed in a round bottom flask and dispersed by conventional sonication for 1h. 1g of dopamine was added to the mixed solution and stirred at room temperature for 12h, and the solution was observed to change from white to black. Washing the P@mAlN reaction solution with ethanol and deionized water respectively, filtering, and drying in a 65 ℃ oven to obtain polydopamine coated micro aluminum nitride (P@mAlN).

Polydopamine coated nanoaluminum nitride (p@naln) was prepared by reference to the procedure described above.

THF is used as a solvent to prepare a C-d solution, a P@mAlN solution and an HSi solution with the concentration of 10wt% respectively, and the solution is uniformly dispersed for 0.5 hour by ultrasound for later use. The slide glass is taken as a substrate, and is sequentially treated by deionized water, ethanol and acetone for 5min respectively, and then is put into an oven at 80 ℃ for drying, so as to remove oil stains and pollutants on the surface.

Example III

According to the coating composition shown in Table 1, the C-d solution was removed and sprayed onto a glass slide by a spray gun, and the solvent was evaporated by placing it on a 80℃hot plate for 5 minutes to form a C-d coating. Spraying the HSi solution onto the surface of the C-d, and placing the C-d on a hot table at 80 ℃ for 5min to volatilize the solvent to form the C-d/HSi coating. And spraying the P@mAlN solution onto the surface of the C-d/HSi coating, placing the C-d/HSi coating on a hot table at 80 ℃ for 5min to volatilize the solvent, then continuously spraying the P@nAlN solution, and drying the C-d/HSi coating on the hot table at 80 ℃ for 2h. Finally, the coating obtained is cured according to the process of 160 ℃/1h+180 ℃/1h+200 ℃/1h+220 ℃/2h, and the obtained coating is marked as C-d/yHSi/0.4P@2bAlN, wherein y is the weight ratio of HSi to C-d. The prepared ice control coating is soaked in deionized water, so that the silver mirror phenomenon shown in fig. 4 can be observed, and the coating has excellent hydrophobicity.

FIG. 5 shows the Icing Delay Time (IDT) of the C-d/yHSi/0.4P@2bAlN coating, and it can be seen that the IDT of the water drop on the C-d/0.5HSi/0.4P@2bAlN coating reaches 627s, which shows that chemical bonds such as Si-O-C and the like or intermolecular hydrogen bonds formed by dehydration can strengthen the action between the filler and the matrix. In the icing process of the coating, the acting force between the filler and the matrix is enhanced, so that the micro-nano structure on the surface is not easily damaged by freezing of water partially permeated into the micro-nano structure. FIG. 5 also shows the IDT of a C-d/yHSi/0.4P@2bAlN coating after 100 cycles of sandpaper abrasion. After 100 cycles of wear, the IDTs for C-d/0.3HSi/0.4P@2bAlN and C-d/0.4HSi/0.4P@2bAlN were 60% and 62% of the initial values, respectively. The IDT reduction amplitude is obviously smaller than that of the C-d/0.4P@zbAlN coating. The C-d/0.5HSi/0.4P@2bAlN coating has basically no change in IDT after 100 abrasion cycles, and shows very strong abrasion resistance. However, as the HSi content increases from 30% to 50%, the coating surface WCA decreases from 162.9 ° to 154.7 °.

By superhydrophobic properties is meant WCA >150 °, SA <10 °. FIG. 6 shows the WCA and SA of three C-d/yHSi/0.4P@2bAlN coatings after different times of abrasion cycles, wherein the C-d/0.5HSi/0.4P@2bAlN still maintains the superhydrophobic performance (WCA= 150.98 °, RA=8.2°), and the subsequent comprehensive performance is all studied by taking the C-d/0.5HSi/0.4P@2bAlN coating as a study object.

In the preparation of the C-d/0.5HSi/0.4P@2bAlN coating, the cross section of the coating sample was photographed every time after spraying one layer, and the preparation of four layers of coating each having a thickness of 15 μm, 7 μm, 11 μm and 9 μm by spraying the C-d solution, the HSi solution, the P@mAlN solution and the P@nAlN solution in this order was obtained (FIG. 7).

Comparative example one

According to the composition of the coating (Table 2), the removed C-d solution was sprayed onto a glass slide by a spray gun, and the solvent was volatilized on a hot stand at 80℃for 5 minutes to form a C-d coating. P@mAlN solutions in different proportions were sprayed onto the C-d surface and dried for 2h on a hot bench at 80 ℃. The resulting coating was cured according to the 180 ℃/1h+200 ℃/1h+220 ℃/1h+240 ℃/2h process, and the resulting coating was designated as C-d/xP@mAlN, where x is the weight ratio of P@mAlN to C-d.

According to the coating composition shown in Table 3, the C-d solution was removed and sprayed onto a glass slide by a spray gun, and the solvent was evaporated by placing it on a 80℃hot plate for 5 minutes to form a C-d coating. Spraying the P@mAlN solution onto the surface of the C-d, and placing the C-d on a hot table at 80 ℃ for 5min to volatilize the solvent; spraying P@nAlN solution, and drying for 2h on a hot bench at 80 ℃. Curing according to the process of 180 ℃/1h+200 ℃/1h+220 ℃/1h+240 ℃/2h, wherein the obtained coating is marked as C-d/0.4P@zbAlN, and z is the weight ratio of P@mAlN to P@nAlN; the SA of the coating is less than 10 DEG only when P@mAlN: P@nAlN is 1:0.25 and 1:0.5.

The resistance of a coating to penetration by liquids is generally evaluated by a water droplet impingement on the surface of the coating. There are typically three consequences after a water droplet hits a surface: firstly, the water drops do not bounce and are completely adsorbed on the coating surfaceA noodle; secondly, although the water drops bounce, part of the water drops still remain on the surface; thirdly, the surface is not penetrated by water drops, and the water drops can automatically roll off on the surface with a slightly inclined angle. In the former two cases, the water droplets cannot be separated from the surface in time, so that the probability of icing is greatly increased, and in the last case, the probability of icing on the surface is greatly reduced. As shown in FIG. 8, the water drops cannot bounce after the surface of the C-d/0.4P@mAlN coating is impacted, which means that the water drops cannot be separated from the surface in time in a low-temperature environment below zero, and the water drops are easy to freeze. On the other hand, on the surfaces of the C-d/0.4P@2bAlN and C-d/0.5HSi/0.4P@2bAlN coatings, water drops are diffused and contracted to achieve rebound, but the C-d/0.4P@2bAlN surfaces still have water drops remained, which indicates that the surfaces are penetrated by the water drops, and the C-d/0.5HSi/0.4P@2bAlN surfaces have no water drops remained, so that the excellent liquid penetration resistance is shown. As a comparison, the coating material used by the existing fan blade has water droplets remaining on the surface through the same test, which indicates that the surface has been pierced by the water droplets; the prior disclosure of the subject group has durable super-hydrophobic E-51/ACNTB-SiO with micro/nano structure surface ₂ After carrying out an experiment that water drops strike the surface of the coating, the abrasion-resistant super-hydrophobic composite material of the KH570 composite material coating has water drops remained on the surface of the coating, which indicates that the surface is pierced by the water drops; surface-functionalized SiO under investigation in the subject group ₂ Coating Fe ₃ O ₄ Nanoparticle (FSK)/bio-based benzoxazine (C-dd) composite coating takes cardanol and decanediamine as raw materials, and after water drops impact the surface of the coating in various filler ratios, water drops remain on the surface of the coating, which indicates that the surface is pierced by the water drops.

Freezing 100 μl of water on the surface of the frozen table at-20deg.C, and adopting light intensity of 1W/cm ² And (3) observing the melting time of ice by infrared light irradiation. FIG. 9 is a photo-thermal deicing of 100. Mu.L of water at-20deg.C on the surfaces of glass slide, C-d coating and C-d/0.5HSi/0.4P@2bAlN coating, and it can be seen that neither glass slide nor C-d coating surface was melted by ice irradiation for 1000 seconds; and after 343s of infrared light irradiation, the ice on the surface of the C-d/0.5HSi/0.4P@2bAlN coating is basically completely melted, which proves that the C-d/0.5 HSi/0.4P@2AlN coating has excellent propertiesPhoto-thermal deicing performance.

The illumination density is 1W/cm ² The surface temperature was recorded by irradiating each surface with 808nm infrared light. As shown in FIG. 10, after 60s of irradiation, the surface temperature of all the coatings had increased, but to a different extent. The surface temperature of the C-d/yHSi/0.4P@2bAlN coating rises from 28 ℃ to 59.8-63.8 ℃, which shows that the construction of the micro-nano structure and the existence of HSi are helpful for improving the photo-thermal property of the coating.

Furthermore, for a bilayer C-d/xp@maln coating, x=30wt% with WCA less than 145 °, x=50wt% with WCA less than 152 °; the abrasion test result of the sand paper shows that the abrasion resistance of the C-d/xP@mAlN coating (figure 11) is poor, the WCA of all the coatings is reduced to be less than 150 degrees, and the superhydrophobic performance is lost; the IDT of the C-d/xP@mAlN coating is reduced from 213-361s to 103-164s before abrasion. Fig. 12 is an Icing Delay Time (IDT) for each coating. As can be seen, the C-d/0.4P@zbAlN IDT (458-600 s) served as a control, the slide glass (52 s), the C-d coating (104 s) and the C-d/xP@mAlN (213-361 s).

It is well known that improving wear resistance is an important point and difficulty in developing an ice coating, and sand paper wear experiments can well simulate the external force wear behavior of the coating in use. FIG. 13 shows the change in WCA and IDT of a C-d/0.4P@zbAlN coating after 10 cycles of sandpaper wear. The results show that after 10 cycles of abrasion of the sand paper, the WCA of all coatings is reduced to less than 150 degrees, and the super-hydrophobic performance is lost; meanwhile, the IDT is shortened, and the IDT of the C-d/0.4P@zbAlN coating is reduced to 132-206s from 376-600s before abrasion, so that the super-hydrophobicity can be optimized, but the abrasion resistance cannot be effectively improved by constructing a micro-nano structure.

FIG. 14 is a graph of WCA and SA after soaking the C-d/0.5HSi/0.4P@2bAlN coating in solutions of different pH values for 24 h. After 24 hours of soaking in a solution with a pH value between 1 and 10, the WCA of the coating is still higher than 150 degrees, and SA is smaller than 10 degrees; whereas when the pH is >10, the WCA is less than 150 DEG, the SA is greater than 10 DEG, and the superhydrophobic characteristic is lost. These data indicate that the superhydrophobic properties of the coating have good chemical stability in solutions at ph=1-10.

The grid method is widely used to evaluate the adhesion properties of the coating, and the adhesion test results show that the coating shows the highest adhesion rating of 0. In everyday life, the coating is often covered with solid or liquid contaminants (such as dust), which can seriously affect the absorption of light by the coating, reducing deicing efficiency. FIG. 15 shows the self-cleaning performance of a C-d/0.5HSi/0.4P@2bAlN coating, wherein sediment in a greening pond is screened by a 100-mesh screen, 0.01g of the screened sediment is scattered on the surface of the C-d/0.5HSi/0.4P@2bAlN coating with an inclination angle of about 15 ℃, and then the sediment on the surface of the coating can be seen to leave the surface of the coating along with water by washing with 1mL of deionized water, and the coating shows excellent self-cleaning performance. The excellent self-cleaning ability can effectively remove contaminants from the coating surface, thereby maintaining long-term photo-thermal stability of the coating surface.

Comparative example Tribenzoxazine/hyperbranched polysiloxane coating

And C-d solution is removed and sprayed on a glass slide through a spray gun, and the glass slide is placed on a hot table at 80 ℃ for 5min to volatilize the solvent, so that a C-d coating is formed. Spraying the HSi solution onto the surface of the C-d, and placing the C-d on a hot table at 80 ℃ for 5min to volatilize the solvent to form the C-d/HSi coating. Finally, the resulting coating was cured according to the 160 ℃/1h+180 ℃/1h+200 ℃/1h+220 ℃/2h process, denoted C-d/yHSi, where y is the weight ratio of HSi to C-d, and 50%, the WCA of the C-d/0.5HSi coating was reduced to 87.5℃compared to the C-d coating (WCA 102.+ -. 3 ℃) (FIG. 16).

Summarizing:

the invention adopts a spraying method to prepare a four-layer structure coating (C-d/yHSi/0.4P@2bAlN), and has the following technical progress:

(1) All the C-d/xP@mAlN coatings do not meet the requirement of a super-hydrophobic surface; in the C-d/0.4P@zbAlN coating, only when P@mAlN: P@nAlN is 1:0.25 and 1: when the SA of the coating is smaller than 10 degrees and the rest of the coating does not reach super-hydrophobic property at 0.5, and after the sand paper is worn for 10 cycles, all the coating loses the super-hydrophobic property, so that the wear resistance cannot be effectively improved by constructing the micro-nano structure.

(2) The IDT of the C-d/yHSi/0.4P@2bAlN coating is improved along with the increase of the HSi content, and the IDT of the water drop on the C-d/0.5HSi/0.4P@2bAlN coating reaches 627s; after 100 cycles of abrasion, the IDTs of C-d/0.3HSi/0.4P@2bAlN and C-d/0.4HSi/0.4P@2bAlN were 60% and 62% of the initial values, respectively, while the IDTs (627 s) of the C-d/0.5HSi/0.4P@2bAlN coating were substantially unchanged, and the superhydrophobic properties (WCA= 150.98 °, RA=8.2°) were maintained, exhibiting excellent abrasion resistance.

(3) On the surfaces of the C-d/0.4P@2bAlN and C-d/0.5HSi/0.4P@2bAlN coatings, water drops are diffused and contracted to achieve rebound, but the C-d/0.4P@2bAlN surfaces still have water drops remained, which shows that the surfaces are penetrated by the water drops, and on the surfaces of the C-d/0.5HSi/0.4P@2bAlN surfaces, the water drops are diffused and contracted to achieve rebound, no water drops remain, and excellent liquid penetration resistance is shown.

(4) At an illumination density of 1W/cm ² Under 808nm infrared radiation, the surface temperature of the C-d/yHSi/0.4P@2bAlN coating rises from 28 ℃ to 59.8-63.8 ℃, the C-d/0.5HSi/0.4P@2bAlN coating has optimal photo-thermal deicing performance, under 808nm infrared radiation, the surface temperature rises to 63.8 ℃ rapidly, and 100 mu L of water is frozen to form ice which is melted in 343 s.

(5) The C-d/0.5HSi/0.4p@2baln coating has excellent chemical stability (ph=1-10), effectively prevents adhesion of contaminants, and has excellent adhesion.

In summary, the C-d/HSi/0.4P@2bAlN has super-hydrophobic property, reduces the curing temperature, and overcomes the two bottleneck problems of poor wear resistance, poor liquid resistance and the like in the prior art.

Claims

1. The benzoxazine monomer is characterized by having the following chemical structural formula:

。

2. the method for preparing the benzoxazine monomer according to claim 1, wherein cardanol, paraformaldehyde and dehydroabietylamine are used as raw materials for preparing the benzoxazine monomer through reaction.

3. The method for preparing benzoxazine monomer according to claim 2, wherein the molar ratio of dehydroabietylamine, paraformaldehyde and cardanol is 1: (2-2.2):1; the reaction temperature is 100-120 ℃ and the reaction time is 1-3 h.

4. The preparation method of the benzoxazine composite material is characterized by comprising the following steps of: sequentially preparing a hyperbranched polysiloxane film layer and a dopamine-coated aluminum nitride film layer on the film layer of the benzoxazine monomer according to claim 1; then curing to obtain a benzoxazine composite material; the preparation method of the hyperbranched polysiloxane comprises the steps of dropwise adding hydrochloric acid into a silane coupling agent aqueous solution, and then reacting for 5-8 hours at 50-60 ℃ to obtain transparent liquid; the transparent liquid is then dried to give the hyperbranched polysiloxane.

5. The method for preparing the benzoxazine composite material according to claim 4, wherein the dopamine-coated aluminum nitride film layer consists of a dopamine-coated micrometer aluminum nitride film layer and a dopamine-coated nanometer aluminum nitride film layer; the grain size of the micrometer aluminum nitride is 1-20 mu m, and the grain size of the nanometer aluminum nitride is 10-100 nm.

6. The method for preparing the benzoxazine composite material according to claim 5, wherein the mass ratio of the benzoxazine monomer to the hyperbranched polysiloxane to the dopamine-coated micro aluminum nitride to the dopamine-coated nano aluminum nitride is 1:0.3-0.5:0.2-0.3:0.1-0.15.

7. The method for preparing the benzoxazine composite material according to claim 4, wherein the benzoxazine monomer solution is dried to obtain a film layer of the benzoxazine monomer; drying the hyperbranched polysiloxane solution to obtain a hyperbranched polysiloxane film layer; and drying the dopamine-coated aluminum nitride solution to obtain the dopamine-coated aluminum nitride membrane layer.

8. The benzoxazine composite prepared by the method of preparing a benzoxazine composite according to claim 4.

9. An icebreaking material comprising a substrate and a coating on the surface of the substrate, wherein the coating is the benzoxazine composite according to claim 8.

10. Use of the benzoxazine monomer according to claim 1 and the benzoxazine composite according to claim 8 for preparing an anti-icing coating or anti-icing material with photo-thermal properties.