CN114806389B - Fluorine-containing polyphosphazene visible light-cured aircraft anti-icing coating and preparation method thereof - Google Patents
Fluorine-containing polyphosphazene visible light-cured aircraft anti-icing coating and preparation method thereof Download PDFInfo
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- CN114806389B CN114806389B CN202210516704.9A CN202210516704A CN114806389B CN 114806389 B CN114806389 B CN 114806389B CN 202210516704 A CN202210516704 A CN 202210516704A CN 114806389 B CN114806389 B CN 114806389B
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
- C09D175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
- B05D3/06—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by exposure to radiation
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D5/00—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/14—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to metal, e.g. car bodies
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/24—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials for applying particular liquids or other fluent materials
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G79/00—Macromolecular compounds obtained by reactions forming a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon with or without the latter elements in the main chain of the macromolecule
- C08G79/02—Macromolecular compounds obtained by reactions forming a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon with or without the latter elements in the main chain of the macromolecule a linkage containing phosphorus
- C08G79/025—Polyphosphazenes
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- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/66—Additives characterised by particle size
- C09D7/67—Particle size smaller than 100 nm
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/70—Additives characterised by shape, e.g. fibres, flakes or microspheres
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D2202/00—Metallic substrate
- B05D2202/20—Metallic substrate based on light metals
- B05D2202/25—Metallic substrate based on light metals based on Al
Abstract
The invention discloses a fluorine-containing polyphosphazene visible light-cured aircraft anti-icing coating, which relates to the technical field of aviation coatings and is characterized in that the coating is prepared by adopting an ultrasonic atomization spraying technology and a visible light curing method, the coating comprises an oligomer, a reactive diluent, a photoinitiator and fluorine-containing polyphosphazene with a nanosheet shape, the thickness of the coating is 50-100 mu m, and the contact angle of the coating with water is more than 90 degrees. The invention also discloses a preparation method of the fluorine-containing polyphosphazene visible light-cured aircraft anti-icing coating. The anti-icing coating is cured under visible light, and has the advantages of economy, environmental protection, energy conservation, high efficiency and wide applicability. In addition, the fluorine-containing polyphosphazene with the nanosheet morphology is used as a functional auxiliary agent, so that the effective regulation and control of the wettability of the coating from hydrophilicity to hydrophobicity can be realized through a large-scale complex surface process widely applied to the windward side of an airplane, and the problem that the windward side of the airplane is frozen in the flying process is effectively solved.
Description
Technical Field
The invention relates to the technical field of aviation coatings, in particular to a fluorine-containing polyphosphazene visible light-cured aircraft anti-icing coating and a preparation method thereof.
Background
Flight safety is considered to be the most important requirement for modern aircraft design and operation, but suffers from a serious threat to the problem of aircraft wing icing — wing icing during aircraft flight is usually caused by supercooled water droplets impacting icing, and therefore is an abnormal (supercooled water droplets have abnormal structure and characteristics compared with water in a normal state), rapid (supercooled water droplet icing and subsequent ice growth process is usually in millisecond level), and complex (supercooled water droplet impacting icing process is influenced by a plurality of factors, accumulated ice shape and influence on ice parts are complex); the icing of the airplane can increase the roughness of the surface of the airplane, change the aerodynamic configuration and the quality of the airplane, further influence the surrounding flow field, and cause the increase of resistance, the reduction of lift force, the change of stall characteristics and the reduction of stability and controllability; the existing aircraft icing protection technology, whether a mechanical deicing technology, a liquid deicing technology or a thermal deicing technology, cannot completely meet the actual requirement for guaranteeing the flight safety of the aircraft, and crash events caused by the icing of the aircraft still occur, for example, 1, 4 days in 2001, two transport-8 aircrafts crash successively due to the icing of the empennage; in 2006, 6/3, the air police-200 early warning machine crashed in the eastern region of Anhui due to the icing of wings; in 2018, 1 month and 29 days, the Yun-8 airplane crashed in Guizhou due to icing at the horizontal tail. Therefore, in order to ensure the flight safety of the aircraft under the icing meteorological condition, a safer and more efficient aircraft icing protection technology is urgently needed.
Compared with the existing airplane icing protection technology, the anti-icing coating has the advantages of low cost, low energy consumption and wide application range, is expected to be combined with the existing airplane icing protection technology, improves the efficiency of the existing airplane icing protection technology, reduces the energy consumption required by the airplane icing protection, and reduces the pollution to the environment. However, although the solvent-based paint occupies the most significant market share of the aviation paint, the biggest problem is that the Organic solvent is inevitably used in a large amount, i.e. Volatile Organic Compounds (VOC) causes environmental pollution and resource waste after construction. In addition, the anti-icing coating which has been developed at present covers a plurality of different chemical functions and length scales, and shows a certain application prospect and value under corresponding application scenes, but has respective limitations: the super-hydrophobic surface is difficult to manufacture, high in cost, difficult to apply to the windward side of an airplane with a complex structure on a large scale and easy to lose effectiveness in a low-temperature and high-humidity environment; the smooth surface into which the fluid is injected gradually fails due to the loss of the lubricating fluid caused by ice/water shedding during the ice coating-deicing cycle, and the high porosity, low mechanical strength, additional increased weight of the lubricating fluid and reduced thermal conductivity of the smooth surface limit the practical application thereof in the field of aircraft icing protection; in contrast, the simplicity and ease of use of smooth surfaces combined with the relative robustness make them more suitable for use in harsh aircraft icing environments.
Accordingly, those skilled in the art have been devoted to developing a photocuring anti-icing coating based on smooth surface wettability modulation and a method for preparing the same.
Disclosure of Invention
In view of the above defects in the prior art, the technical problems to be solved by the present invention are the difficulties of high volatile organic compound content, high manufacturing difficulty, high cost, short service life, easy failure, etc. of the current anti-icing coating.
In order to realize the aim, the invention provides a preparation method of a fluorine-containing polyphosphazene visible light-cured aircraft anti-icing coating, which comprises the following steps:
step 1, reacting hexachlorocyclotriphosphazene and 4,4' - (hexafluoroisopropylidene) diphenol serving as monomers, acetonitrile serving as a solvent and triethylamine serving as an acid-binding agent under the assistance of ultrasonic water bath treatment and high-speed stirring, and then preparing fluorine-containing polyphosphazene with a nanosheet shape through a centrifugal process; the molar concentrations of the hexachlorocyclotriphosphazene, the 4,4' - (hexafluoroisopropylidene) diphenol and the triethylamine are respectively 0.05-0.15 mol.L -1 、0.15-0.45mol·L -1 And 0.30 to 0.90 mol. L -1 ；
Step 2, adding a reactive diluent, an oligomer and the fluorine-containing polyphosphazene into a preparation device, and uniformly mixing to obtain a first mixture;
step 3, adding a photoinitiator into the first mixture, and uniformly mixing to obtain a second mixture;
and 4, spraying the second mixture on the pretreated aluminum alloy plate, and curing under visible light to obtain the fluorine-containing polyphosphazene visible light-cured aircraft anti-icing coating.
Preferably, the ultrasonic water bath treatment condition in the step 1 is that the water temperature is 40-60 ℃, the ultrasonic frequency is 40kHz, the ultrasonic power is 300-1800W, the high-speed stirring condition in the step 1 is that the rotating speed of a high-speed dispersion disc is 500-2000rpm, the reaction time is 3-12h, the rotating speed of the centrifugal process is 10000rpm, and the time is 30min, and the fluorine-containing polyphosphazene with the nanosheet morphology has an irregular nanoscale lamellar structure, the size is 50-100nm, and the thickness is 10-100nm.
Preferably, the reactive diluent in the step 2 is cyclotrimethylolpropane formal acrylate, and the oligomer is one or more of aliphatic polyurethane diacrylate, aliphatic polyurethane tetraacrylate and aliphatic polyurethane hexaacrylate. And 2, the preparation device is a stirring tank.
Preferably, the photoinitiator in the step 3 is bis [2, 6-difluoro-3- (1H-pyrrolyl-1) phenyl ] titanocene.
Preferably, the mass ratio of the photoinitiator in the step 3 to the oligomer, the reactive diluent and the fluorine-containing polyphosphazene in the step 2 is 3-5.
Preferably, the mixing in the step 2 is physical mixing, the preparation device in the step 2 is a stirring tank, and the mixing in the step 3 is physical mixing under a light-shielding condition.
Preferably, the spraying in the step 4 is ultrasonic atomization spraying, the flow rate of the coating is 0.10-1.0mL/min, the ultrasonic frequency is 50kHz, and the ultrasonic power is 50W.
Preferably, the cured visible light in the step 4 is natural light or artificial simulated visible light,the illumination intensity is 1.0 × 10 4 -1.0×10 5 lx, light irradiation time 2.0-12.0 hours.
Preferably, in the step 4, the pretreatment process includes firstly grinding with 600# abrasive paper until the aluminum alloy substrate is completely exposed, and then cleaning the surface of the aluminum alloy plate with isopropanol, wherein the aluminum alloy plate is an aluminum alloy 2024-T42 plate.
The invention also provides a fluorine-containing polyphosphazene visible light-cured aircraft anti-icing coating prepared by using the method, the coating is prepared by adopting an ultrasonic atomization spraying technology and a visible light curing method, the coating comprises an oligomer, a reactive diluent, a photoinitiator and fluorine-containing polyphosphazene with a nanosheet shape, the thickness of the coating is 50-100 mu m, the coating is a hydrophobic coating, and the contact angle of the coating and a static water drop is greater than 90 degrees.
The invention is based on the shape regulation of the fluorine-containing polyphosphazene, the aircraft anti-icing coating is prepared by simply blending the fluorine-containing polyphosphazene, the oligomer, the reactive diluent and the visible light initiator according to a proper proportion and using a spraying process and a visible light curing process. Compared with the prior art, the method has the following technical effects:
(1) The preparation method of the anti-icing coating has the advantages of low energy consumption, low manufacturing cost, easy realization, wide application range and the like;
(2) Compared with the solvent-based paint occupying the main market share of the aviation paint at present, the visible light curing paint is used as the base material, so that the solvent-based paint with high volatile organic matter content and slow curing can be avoided, the visible light with energy occupying the main part in the natural environment can be fully utilized, and the advantages of economy, environmental protection, energy saving, high efficiency and wide applicability of the visible light curing paint are exerted;
(3) By using the fluorine-containing polyphosphazene with the nanosheet shape as the functional additive for modification, the effective regulation and control of the wettability of the coating from hydrophilicity to hydrophobicity can be realized through a large-scale complex surface process widely applied to the windward side of an airplane, so that the retention of supercooled water drops is reduced, the separation of the supercooled water drops is promoted, and the problem that the windward side of the airplane is frozen in the flying process is hopefully solved;
(4) Aiming at the limitation of the anti-icing coating which covers different chemical functions and length scales and is developed at present, the anti-icing coating which is formed by combining the visible light curing base material and the fluorine-containing polyphosphazene with the nanosheet shape is designed, so that the smooth surface which is simple in preparation process, low in cost, good in weather resistance and excellent in anti-icing performance and is more suitable for the aircraft icing environment can be obtained.
The conception, specific structure and technical effects of the present invention will be further described in conjunction with the accompanying drawings to fully understand the purpose, characteristics and effects of the present invention.
Drawings
FIG. 1 is a transmission electron microscope image of a fluorine-containing polyphosphazene used in a preferred embodiment of the present invention;
FIG. 2 is a graph of contact angle of a sample with water as a function of oligomer content in a preferred embodiment of the invention;
FIG. 3 shows the results of an anti-icing test performed in an icing wind tunnel according to a preferred embodiment of the present invention.
Detailed Description
The technical contents of the preferred embodiments of the present invention will be more clearly and easily understood by referring to the drawings attached to the specification. The present invention may be embodied in many different forms of embodiments and the scope of the invention is not limited to the embodiments set forth herein.
Example 1
Step one, dissolving 17.38g of hexachlorocyclotriphosphazene and 5.05g of 4,4' - (hexafluoroisopropylidene) diphenol by using 1L of acetonitrile, then, dropwise adding 80mL of triethylamine under the assistance of ultrasonic water bath treatment (ultrasonic frequency is 40kHz, ultrasonic power is 300W, water bath temperature is 40 ℃) and high-speed stirring (dispersion disc rotating speed is 500 rpm), continuing to react for 3 hours, and finally, separating a product by centrifugation (rotating speed is 10000rpm, and centrifugation time is 30 min) to obtain the fluorine-containing polyphosphazene with the nanosheet shape.
And step two, adding 40g of aliphatic polyurethane diacrylate, 60g of cyclotrimethylolpropane formal acrylate and 10g of fluorine-containing polyphosphazene into a stirring tank in sequence, and uniformly mixing.
And step three, adding 3g of bis [2, 6-difluoro-3- (1H-pyrrolyl-1) phenyl ] titanocene into the stirring tank under the condition of keeping out of the sun, and uniformly mixing.
And step four, uniformly spraying the mixed material onto an aluminum alloy 2024-T42 plate which is polished by 600-mesh sand paper and cleaned by isopropanol by using an ultrasonic atomization spraying machine, wherein the flow rate is 0.25mL/min, the ultrasonic frequency is 50kHz, the ultrasonic power is 50W, and then curing for 2 hours under natural illumination.
As shown in FIG. 1, the image of the field emission transmission electron microscope of the fluorine-containing polyphosphazene prepared by the above process steps is a transmission electron microscope image, and the fluorine-containing polyphosphazene has an irregular nanoscale lamellar structure with the size of 50-100nm and the thickness of 10-100nm.
Example 2
Step one, dissolving 34.76g of hexachlorocyclotriphosphazene and 10.09g of 4,4' - (hexafluoroisopropylidene) diphenol by using 1L of acetonitrile, then, dropwise adding 80mL of triethylamine under the assistance of ultrasonic water bath treatment (ultrasonic frequency is 40kHz, ultrasonic power is 900W, water bath temperature is 55 ℃) and high-speed stirring (dispersion disc rotating speed is 1000 rpm), continuing to react for 4.00 hours, and finally, separating the product by centrifugation (rotating speed is 10000rpm, and centrifugation time is 30 min) to obtain the fluorine-containing polyphosphazene with the nanosheet morphology.
And step two, sequentially adding 50g of aliphatic polyurethane diacrylate, 50g of cyclotrimethylolpropane methylal acrylate and 15g of fluorine-containing polyphosphazene into a stirring tank, and uniformly mixing.
And step three, adding 5g of bis [2, 6-difluoro-3- (1H-pyrrolyl-1) phenyl ] titanocene into the stirring tank under the condition of keeping out of the sun, and uniformly mixing.
Step four, uniformly spraying the mixed material on an aluminum alloy 2024-T42 plate which is polished by 600-mesh sand paper and cleaned by isopropanol by using an ultrasonic atomization spraying machine, wherein the flow rate is 0.50mL/min, the ultrasonic frequency is 50kHz, the ultrasonic power is 50W, and then, artificially simulating visible light (the illumination intensity is 6.0 multiplied by 10) is carried out 4 lx) was cured for 7h under irradiation.
Example 3
Step one, dissolving 52.14g of hexachlorocyclotriphosphazene and 15.14g4,4' - (hexafluoroisopropylidene) diphenol by using 1L of acetonitrile, then simultaneously dripping 80mL of triethylamine under the assistance of ultrasonic water bath treatment (ultrasonic frequency is 40kHz, ultrasonic power is 1500W, water bath temperature is 60 ℃) and high-speed stirring (rotating speed of a dispersion disc is 1500 rpm), continuing to react for 8 hours, and finally separating a product by centrifugation (rotating speed is 10000rpm, and centrifugation time is 30 min) to obtain the fluorine-containing polyphosphazene with the nanosheet morphology.
And step two, sequentially adding 60g of aliphatic polyurethane diacrylate, 40g of cyclotrimethylolpropane formal acrylate and 10g of fluorine-containing polyphosphazene into a stirring tank, and uniformly mixing.
And step three, adding 3g of bis [2, 6-difluoro-3- (1H-pyrrolyl-1) phenyl ] titanocene into the stirring tank under the condition of keeping out of the sun, and uniformly mixing.
And step four, uniformly spraying the mixed material on an aluminum alloy 2024-T42 plate which is polished by 600-mesh sand paper and cleaned by isopropanol by using an ultrasonic atomization spraying machine, wherein the flow rate is 0.75mL/min, the ultrasonic frequency is 50kHz, the ultrasonic power is 50W, and then curing is carried out for 12 hours under the irradiation of natural light.
Example 4
Step one, dissolving 17.38g of hexachlorocyclotriphosphazene and 5.05g of 4,4' - (hexafluoroisopropylidene) diphenol by using 1L of acetonitrile, then, dropwise adding 80mL of triethylamine under the assistance of ultrasonic water bath treatment (ultrasonic frequency is 40kHz, ultrasonic power is 1800W, water bath temperature is 50 ℃) and high-speed stirring (dispersion disc rotating speed is 2000 rpm), continuing to react for 12 hours, and finally, separating a product by centrifugation (rotating speed is 10000rpm, and centrifugation time is 30 min) to obtain the fluorine-containing polyphosphazene with the nanosheet shape.
And step two, sequentially adding 70g of aliphatic polyurethane diacrylate, 30g of cyclotrimethylolpropane methylal acrylate and 15g of fluorine-containing polyphosphazene into a stirring tank, and uniformly mixing.
And step three, adding 5g of bis [2, 6-difluoro-3- (1H-pyrrolyl-1) phenyl ] titanocene into the stirring tank under the condition of keeping out of the sun, and uniformly mixing.
And step four, uniformly spraying the mixed material on an aluminum alloy 2024-T42 plate which is polished by 600-mesh sand paper and cleaned by isopropanol by using an ultrasonic atomization spraying machine, wherein the flow rate is 1.00mL/min, the ultrasonic frequency is 50kHz, the ultrasonic power is 50W, and then curing is carried out for 12 hours under the irradiation of natural light.
As shown in FIG. 2, the contact angles of the blank group without the addition of the fluorine-containing polyphosphazene with water are respectively 49.24 degrees, 53.78 degrees, 54.12 degrees and 56.44 degrees; with the addition of the fluorine-containing polyphosphazene, the contact angles of the examples 1-4 with water are respectively increased to 91.99 degrees, 97.44 degrees, 100.68 degrees and 101.38 degrees; the addition of the fluorine-containing polyphosphazene as a functional auxiliary agent can obviously improve the hydrophobicity of the visible light cured coating.
As shown in fig. 3, which is the layer of ice accumulated under the same icing tunnel test conditions for example 4 and the blank set, it can be found that: compared with the blank group without adding the fluorine-containing polyphosphazene, the anti-icing coating in the embodiment 4 can obviously reduce the ice accumulation and the ice accumulation roughness, and can effectively improve the capability of the airplane to freeze under the icing meteorological condition.
On one hand, the invention can fully utilize visible light with energy in natural environment, and give play to the advantages of economy, environmental protection, energy saving, high efficiency and wide applicability of the visible light curing coating; on the other hand, the fluorine-containing polyphosphazene with the nanosheet morphology is used as a functional auxiliary agent, and the effective control of the wettability of the coating from hydrophilicity to hydrophobicity can be realized through a large-scale complex surface process widely applied to the windward side of an airplane, so that the separation of supercooled water drops is promoted, the retention time of the supercooled water drops is reduced, the ice accumulation is further reduced, the ice accumulation roughness is reduced, and the problem that the windward side of the airplane is iced in the flying process is hopefully solved.
The foregoing detailed description of the preferred embodiments of the invention has been presented. It should be understood that numerous modifications and variations could be devised by those skilled in the art in light of the present teachings without departing from the inventive concepts. Therefore, the technical solutions that can be obtained by a person skilled in the art through logical analysis, reasoning or limited experiments based on the prior art according to the concepts of the present invention should be within the scope of protection determined by the claims.
Claims (8)
1. A preparation method of a fluorine-containing polyphosphazene visible light-cured aircraft anti-icing coating is characterized by comprising the following steps:
step 1, reacting hexachlorocyclotriphosphazene and 4,4' - (hexafluoroisopropylidene) diphenol serving as monomers, acetonitrile serving as a solvent and triethylamine serving as an acid-binding agent under the assistance of ultrasonic water bath treatment and high-speed stirring, and then preparing fluorine-containing polyphosphazene with a nanosheet shape through a centrifugal process; the molar concentrations of the hexachlorocyclotriphosphazene, the 4,4' - (hexafluoroisopropylidene) diphenol and the triethylamine are respectively 0.05-0.15 mol.L -1 、0.15-0.45mol·L -1 And 0.30 to 0.90 mol. L -1 ；
Step 2, adding a reactive diluent, an oligomer and the fluorine-containing polyphosphazene into a preparation device, and uniformly mixing to obtain a first mixture;
step 3, adding a photoinitiator into the first mixture, and uniformly mixing to obtain a second mixture;
step 4, spraying the second mixture on a pretreated aluminum alloy plate, and curing under visible light to obtain a fluorine-containing polyphosphazene visible light-cured aircraft anti-icing coating;
the ultrasonic water bath treatment conditions in the step 1 are that the water temperature is 40-60 ℃, the ultrasonic frequency is 40kHz, and the ultrasonic power is 300-1800W, the high-speed stirring conditions in the step 1 are that the rotating speed of a high-speed dispersion disc is 500-2000rpm, the reaction time is 3-12h, the rotating speed of a centrifugal process is 10000rpm, and the time is 30min, and the fluorine-containing polyphosphazene with the nanosheet shape has an irregular nanoscale sheet layered structure, the size is 50-100nm, and the thickness is 10-100nm;
the mass ratio of the photoinitiator to the oligomer, the reactive diluent and the fluorine-containing polyphosphazene in the step 2 in the step 3 is 3-5.
2. The method for preparing the fluorine-containing polyphosphazene visible light-cured aircraft anti-icing coating according to claim 1, wherein the reactive diluent in the step 2 is cyclotrimethylolpropane formal acrylate, and the oligomer is one or more of aliphatic polyurethane diacrylate, aliphatic polyurethane tetraacrylate and aliphatic polyurethane hexaacrylate.
3. The method for preparing the fluorine-containing polyphosphazene visible light-curable aircraft anti-icing coating of claim 1, wherein the photoinitiator in the step 3 is bis [2, 6-difluoro-3- (1H-pyrrolyl-1) phenyl ] titanocene.
4. The method for preparing the fluorine-containing polyphosphazene visible light-cured aircraft anti-icing coating of claim 1, wherein the mixing in the step 2 is physical mixing, and the mixing in the step 3 is physical mixing under a condition of avoiding light.
5. The method for preparing the fluorine-containing polyphosphazene visible light-cured aircraft anti-icing coating according to claim 1, wherein the spraying in the step 4 is ultrasonic atomization spraying, the coating flow is 0.1-1.0mL/min, the ultrasonic frequency is 50kHz, and the ultrasonic power is 50W.
6. The method for preparing the fluorinated polyphosphazene visible light-curable aircraft anti-icing coating according to claim 1, wherein the visible light cured in the step 4 is natural light or artificial simulated visible light, and the illumination intensity is 1.0 x 10 4 -1.0×10 5 lx, light irradiation time 2.0-12.0 hours.
7. The method for preparing the fluorine-containing polyphosphazene visible light-cured aircraft anti-icing coating according to claim 1, wherein the pretreatment in the step 4 comprises the steps of firstly grinding with 600# abrasive paper until the aluminum alloy substrate is completely exposed, and then cleaning the surface of the aluminum alloy plate with isopropanol, wherein the aluminum alloy plate is an aluminum alloy 2024-T42 plate.
8. The fluorine-containing polyphosphazene visible light-cured aircraft anti-icing coating prepared by the method of any one of claims 1-7, wherein the coating is prepared by adopting an ultrasonic atomization spraying technology and a visible light curing method, the coating comprises an oligomer, a reactive diluent, a photoinitiator and fluorine-containing polyphosphazene with nanosheet morphology, the coating thickness is 50-100 μm, and the coating is a hydrophobic coating.
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| CN202210516704.9A CN114806389B (en) | 2022-05-12 | 2022-05-12 | Fluorine-containing polyphosphazene visible light-cured aircraft anti-icing coating and preparation method thereof |
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