CN113136141A - Polyphosphazene rain erosion resistant coating for airborne radar antenna housing and preparation method thereof - Google Patents
Polyphosphazene rain erosion resistant coating for airborne radar antenna housing and preparation method thereof Download PDFInfo
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- C09D185/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon; Coating compositions based on derivatives of such polymers
- C09D185/02—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon; Coating compositions based on derivatives of such polymers containing phosphorus
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- 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
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- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
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- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
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Abstract
Polyphosphazene rain erosion resistant coating for airborne radar antenna housing and preparation method thereof, belonging to the technical field of airborne radar antenna housing coating. The wave-transparent coating material which is easy to coat, suitable for high-altitude (low-temperature) flying environment, rain erosion resistant, hydrophobic and not easy to freeze is developed by introducing a cross-linking agent capable of adapting to thermal or photo curing and combining with the formula design of a coating mainly depending on the excellent flexibility, good high-temperature stability, extremely low glass transition temperature, excellent insulating property and chemical medium resistance of a fluorinated polyphosphazene main chain.
Description
Technical Field
The invention relates to a special protective coating for an airborne radar antenna housing, which is a high-performance coating taking fluorine-containing polyphosphazene as a matrix film-forming material and has more excellent rain erosion resistance, scouring resistance and anti-icing property in a high-altitude environment compared with a conventional protective coating for an airborne radar antenna housing.
Background
An airborne radome (radome) is made of a glass fiber reinforced plastic having a honeycomb structure. In the flight process, due to the scouring of high-speed airflow and sand and the high-speed impact of raindrops and ice particles under various complex meteorological conditions, the surface of the radome is damaged, the thickness of the radome is reduced, and the mechanical strength of the radome is influenced; when the cover body thickness changes and is not uniform, wave transmittance can be reduced, signal errors are increased, and even the honeycomb structure is damaged in serious conditions, so that the whole radar antenna cover is scrapped. Therefore, protective measures are required to be introduced into the radome, and the radome coating designed for the environment is adopted, so that the radome protective measures are the most effective radome protective measures at present.
An airborne radome coating is a composite coating system in which a rain erosion resistant coating provides the most critical protection. The rain erosion resistant coating is divided into a resin type and a rubber type, and the rubber type is mainly adopted at present because the shock resistance of the resin type coating is not ideal. Specifically, the coating is divided into chlorinated rubber, polyurethane, silicone rubber and fluororubber coatings. The chlorinated rubber type coating has the characteristics of water resistance, wear resistance, sun resistance and the like, but has low temperature resistance and insulating property. The polyurethane-based coating is excellent in wear resistance and rain erosion resistance, but gradually loses elasticity and rain erosion resistance when used over a wide temperature range for a long time, and is also low in flame retardancy (lightning stroke resistance). The silicone rubber coating has excellent heat resistance, cold resistance and insulativity, but has poor mechanical property and chemical medium resistance (deicing fluid, hydraulic oil and the like); fluororubbers are excellent in heat resistance, but insufficient in cold resistance. Because various types of rain erosion resistant coatings have a series of problems at present, the use efficiency of the radome is directly influenced, and the development of the rain erosion resistant coating with more excellent comprehensive performance has very important application value.
From the patent database, the number of patents (granted or published) related to the radome coating is limited, and at present, the main focus is on "a radome rain erosion prevention elastic protection coating and a preparation method thereof" in patent CN201711283745.3 (granted by the invention), "the radome rain erosion prevention elastic protection coating has relatively good wear resistance and elasticity by adopting a polyaspartic ester polyurea system, and the service life of the radome can be prolonged. Patent CN201710585354.0 (disclosure of the invention) "preparation method of rain erosion prevention and antistatic function integrated coating material for radome", a rain erosion prevention coating is prepared by physical blending of fluorocarbon, polyurethane and organosilicon modified polyurethane (antistatic function is realized by introducing conductive filler), obviously, it is difficult to obtain significant improvement in performance by combining several different elastic materials only through physical blending. Patent CN201811197032.X (invention discloses) "organic-inorganic coating for ceramic radome moisture-proof and preparation method thereof", adopts polysilicon system coating, and is mainly used for sealing micropores on the surface of ceramic radome material to avoid water vapor adsorption from influencing the wave-transmitting performance of the radome. Patent CN201510405868.4 (disclosure of the invention) "coating, antenna and antenna housing", introduces styrene copolymerized thermoplastic elastomer to prepare antenna housing coating, and has good electromagnetic property, wave-transmitting property and weather resistance. Patent CN201110420517.2 "a method for preparing a high-wave-transparent super-hydrophobic moisture-proof coating for radome material", which adopts micron-scale silica and fluoropolymer to realize a high-wave-transparent super-hydrophobic moisture-proof function. Patent CN201810691245.1 "a flame-retardant wear-resistant coating material for radar covers and a preparation method thereof", adopts EVA resin and thermosetting liquid polyimide pure resin to endow the coating with flame-retardant wear-resistant function. Patent CN201811497755.1 "an antistatic coating for radome and its preparation method", which uses polyaspartic acid ester polyurea system as the coating base material, and realizes integration of antistatic and rain erosion resistant functions by adding various fillers. In addition to the requirement of the rain erosion resistant coating on the airborne radome, the rain erosion resistant function of the wind turbine blade coating is also required (with some differences in the severity), for example, patent CN201580005331.7, "coating composition for forming coating film with impact resistance", introduces polyol, isocyanurate and urea-based polyisocyanate compound and curing catalyst, provides a wind turbine blade coating film forming method with rain erosion resistant and chipping resistant functions, and belongs to a modified polyurea system material from the description. Patent CN201010546141.5 "a method for preparing polyurethane finish for wind blades", a polyurethane system is used to prepare a coating with wind sand resistance and rain erosion resistance.
In conclusion, the prior patents related to the radar antenna cover rain erosion resistant coating mainly focus on the modified layer of the conventional rain erosion resistant coating material such as polyurethane, organic silicon and polyurea material system (the polyurea system is equivalent to the polyurethane in high and low temperature performances), and no application report of introducing a newer generation of material is seen.
The polyphosphazene serving as a new-generation organic-inorganic polymer has excellent fireproof flame retardant property, hydrophobicity, high and low temperature resistance, corrosion resistance, chemical resistance, high insulativity and radiation resistance, and completely meets the technical requirements of the protective material of the airborne radome.
Disclosure of Invention
Aiming at the technical problems existing in the radar antenna housing rain erosion resistant coating background technology, the invention provides a preparation method of a polyphosphazene airborne radar antenna housing rain erosion resistant coating.
The invention mainly relies on the excellent flexibility and good high-temperature stability of polyphosphazene main chain, extremely low glass transition temperature, excellent insulating property and chemical medium resistance, develops a wave-transparent coating material which is easy to coat, suitable for high-altitude (low-temperature) flying environment, rain erosion resistant, hydrophobic and difficult to freeze by introducing a cross-linking agent capable of adapting to thermal or light curing and combining with the formula design of a coating.
Wherein the fluorinated polyphosphazene structure is:
wherein R1 is a fluorine-containing or fluorine-free aryloxy group (including a phenoxy group, an alkylphenoxy group, a cyclic alkenyl-substituted phenoxy group, a linear alkenyl-substituted phenoxy group, etc.), a fluorine-containing or fluorine-free alkoxy group, or an anilino group.
Wherein R2 is a fluorine-containing or non-fluorine-containing aryloxy group (including phenoxy, alkylphenoxy, cyclic alkenylphenoxy, and chain alkenylphenoxy), a fluorine-containing or non-fluorine-containing alkoxy group, or a fluorine-containing or non-fluorine-containing amine group.
The anilino group is an anilino group, a substituted anilino group (e.g., an anilino group substituted with a chain alkyl group), or the like.
R1 and R2 are selected from trifluoroethanol, octafluoropentanol, hexafluoroisopropanol, 4-fluorophenol, oxygen group corresponding to hexafluorobisphenol A, p-trifluoromethylanilino, 2,3,5, 6-tetrafluoroterephthalamide and the like.
In the formula, R1 and R2 on a single nitrogen and phosphorus segment in a polymer molecule can be the same or different, R1 on different nitrogen and phosphorus segments in the same polymer molecule can be the same or different, and R2 on different nitrogen and phosphorus segments in the same polymer molecule can be the same or different; and the R1 or R2 group in the same polymer molecule at least contains fluorine-containing substituent groups, namely fluorine-containing aryloxy groups or/and fluorine-containing alkoxy groups or/and fluorine-containing amino groups, and the molar content of the fluorine-containing substituent groups is not less than 20%. 100. gtoreq.n.gtoreq.20, preferably. gtoreq.30.
Polyphosphazene structures such as;
the preparation method of the polyphosphazene rain erosion resistant coating of the airborne radar radome comprises the following steps:
the method comprises the following steps: preparing polydichlorophosphazene by a bulk or solution polymerization method, dripping sodium salt or lithium salt of a nucleophilic reagent corresponding to side group groups R1 and R2 required by the product fluorinated polyphosphazene into a polydichlorophosphazene organic solution, reacting at room temperature, precipitating a polymer from a reaction mixed solution, and drying in vacuum to obtain a fluorinated polyphosphazene pre-crosslinked material containing different substituents;
step two: and (2) adding the fluorinated polyphosphazene pre-crosslinked material obtained in the step (1) into an organic solvent, after fully dissolving, sequentially adding a wetting dispersant, a leveling agent, a defoaming agent, an adhesion promoter and other surface auxiliaries and various pigments and fillers, fully stirring and uniformly dispersing, grinding and adjusting viscosity to prepare a coating A component, and canning for later use.
Step three: and uniformly stirring the curing agent, the coupling agent and the organic solvent to prepare a coating component B, and canning for later use.
Step four: during coating, firstly, surface treatment is carried out on a primer coating of the radome, then the prepared coating A and the prepared coating B are mixed according to a ratio (such as a mass ratio of 10:1), after the components are fully and uniformly stirred, the coating is uniformly sprayed on the surface of the cover body in an air spraying mode, then the coating is crosslinked into a film in a heating or photocuring mode, and the spraying → curing is repeated according to the design thickness requirement of the coating, so that the radome rain erosion resistant coating with the required thickness is finally formed.
The nucleophilic reagent is sodium salt or lithium salt of R1 and R2 groups; for example, the sodium or lithium salt of the nucleophile fluoroalcohol is selected from: sodium or lithium salts of trifluoroethanol, octafluoropentanol, hexafluoroisopropanol, etc., sodium or lithium salts of fluorophenol selected from: sodium salts or lithium salts of 4-fluorophenol, hexafluorobisphenol a and the like; the sodium or lithium salt of the fluoroamine is selected from: sodium salts or lithium salts of p-trifluoromethylaniline, 2,3,5, 6-tetrafluoroterephthalamide, and the like.
The solvent used for preparing the polydichlorophosphazene organic solution in the first step is one or more of tetrahydrofuran, dioxane, pyridine, ethanol, acetone and the like; the precipitating agent selected in step one is selected from: one or more of water, n-heptane, cyclohexane, petroleum ether, ethyl acetate, diethyl ether, dichloromethane, chloroform, acetone, acetonitrile, benzene and xylene.
The solvent used in the second step is one or more of methyl pyrrolidone, tetrahydrofuran, dioxane, pyridine, ethanol and acetone.
The wetting dispersant used in the second step is one or more of BYK111, BYK2152, BYK118, BYK110, BYK2200, Anti-terra-u and BYK 3950. The leveling agent is one or more of BYK358, BYK361, Efka3570, BYK3902, BYK360, BYK368 and BYK 3535; the defoaming agent is one or more of BYK077, BYK1791, BYK054 and BYK 066; the adhesion promoter is one or more of BYK 306, irco2000, BYK333 and BYK 4510.
The filler obtained in the second step is R960, BT-34, chopped quartz fiber, wet sericite, chopped polyimide fiber, BT-SD2, P0086, chopped aramid fiber,
812. One or more of L0084, TICO655, quartz powder, phthalocyanine blue, benzimidazolone yellow and the like.
Wherein, the fluorinated polyphosphazene pre-crosslinked material in the second step accounts for 5-15% of the A component by weight, 65-80% of the solvent by weight, 0.5-1.5% of the wetting dispersant by weight, 0.5-1.2% of the flatting agent by weight, 0.5-1% of the defoaming agent by weight, 0.5-1% of the adhesion promoter by weight and 5-15% of the pigment and filler by weight.
Step three, the curing agent is one or more of acetophenone, benzophenone, alpha-hydroxy ketone, dicumyl peroxide and the like and derivatives thereof; the coupling agent is BYK346, KH550, BYK028, Ceratix8461, Ceraflour925, KH560, IR1010, BYK-A555, Anti-terra-u100, or a mixture thereof,
1770 and (b) one or more of.
Wherein in the third step, the curing agent accounts for 1-5 percent, the coupling agent accounts for 1-5 percent, and the organic solvent accounts for 90-98 percent
Compared with the prior art, the invention has the main advantages that:
the invention introduces polyphosphazene material as film forming material, and the low temperature elasticity characteristic of the material is combined with the technique of pigment and filler, thus being beneficial to improving the rain erosion resistance of the cover body in high-altitude flight environment; the polyphosphazene has the characteristic of low dielectric constant, and combines the low dielectric constant pigment and filler compounding technology to endow the coating with excellent electromagnetic wave transmission performance; the fluorine content is adjusted by selecting the side group in the synthesis process, so that the coating is endowed with excellent hydrophobicity, the aggregation and icing probability of a water film on the surface of the cover body is favorably reduced, and the transmission loss of electromagnetic waves is reduced; the cross-linking agent is introduced, so that the coating can be formed into a film by ultraviolet light curing, the convenience of field construction of the coating is given, and the maintainability is improved.
Drawings
Fig. 1 is a graph showing the transmission loss of a radar wave according to the embodiment.
Detailed Description
Embodiments of the invention are described further below.
Example 1:
preparing 15g of polydichlorophosphazene according to a bulk or solution polymerization method, dripping 43.13g of sodium octafluoropentoxy and 18.59g of sodium trifluoroethoxysulfate into a tetrahydrofuran solution of the polydichlorophosphazene, reacting at room temperature for 24 hours, then precipitating a polymer from the reaction mixed solution by using petroleum ether and xylene, and drying in vacuum to obtain the octafluoropentoxy, trifluoroethoxy substituted fluorinated polyphosphazene elastic material.
Adding 30g of the prepared fluorinated polyphosphazene elastic material into 180g of methyl pyrrolidone solvent, adding 3g of BYK110, 2.2g of BYK361, 2g of BYK077, 1.8g of BYK4510, 12g R960, 4g of BT-SD2 and 5g of chopped aramid fiber in sequence under stirring, fully stirring and dispersing, grinding for 24 hours, and then adding 20g of methyl pyrrolidone solvent to prepare the fluorinated polyphosphazene rain erosion resistant coating A component.
0.5g of acetophenone, 0.3g of alpha-hydroxy ketone, 1.2g of BYK028 and 24g of methyl pyrrolidone solvent are mixed uniformly to prepare the fluorinated polyphosphazene rain erosion resistant coating component B.
And (4) polishing the glass fiber reinforced plastic test piece by using sand paper, wiping by using ethanol, and airing for later use.
Coating A component: component B is 10: mixing the components according to the weight ratio of 1, stirring the mixture evenly, and spraying the mixture on the surface of a glass fiber reinforced plastic test piece by using an air spray gun under the room temperature condition → standing the mixture for 30 minutes under the room temperature condition → placing the mixture under a 313nm ultraviolet lamp for irradiating for 60 minutes → finishing the preparation of the polyphosphazene rain erosion resistant coating.
Example 2:
preparing 15g of polydichlorophosphazene according to a bulk or solution polymerization method, dripping 43.13g of sodium octafluoropentoxide and 18.59g of sodium trifluoroethoxysulfate into a dioxane solution of the polydichlorophosphazene, reacting at room temperature for 24 hours, then precipitating a polymer from the reaction mixed solution by using petroleum ether and xylene, and drying in vacuum to obtain the octafluoropentoxy, trifluoroethoxy substituted fluorinated polyphosphazene elastic material.
Adding 30g of the prepared fluorinated polyphosphazene elastic material into 180g of methyl pyrrolidone solvent, adding 3g of BYK2152, 2g of Efka3570, 2g of BYK1791, 2g of irco2000, 5g R960, 4g of chopped aramid fiber and 12g of quartz powder in sequence under stirring, fully stirring and dispersing, grinding for 24 hours, and then adding 20g of methyl pyrrolidone solvent to prepare the fluorinated polyphosphazene rain erosion resistant coating A component.
0.5g of acetophenone, 0.3g of alpha-hydroxy ketone, 1.2g of IR1010 and 24g of methyl pyrrolidone solvent are mixed uniformly to prepare the fluorinated polyphosphazene rain erosion resistant coating component B.
And (4) polishing the glass fiber reinforced plastic test piece by using sand paper, wiping by using ethanol, and airing for later use.
Coating A component: component B is 10: mixing the components according to the weight ratio of 1, stirring the mixture evenly, and spraying the mixture on the surface of a glass fiber reinforced plastic test piece by using an air spray gun under the room temperature condition → standing the mixture for 30 minutes under the room temperature condition → placing the mixture under a 313nm ultraviolet lamp for irradiating for 60 minutes → finishing the preparation of the polyphosphazene rain erosion resistant coating.
Example 3:
preparing 15g of polydichlorophosphazene according to a bulk or solution polymerization method, dripping 42.65g of sodium hexafluorodiphenol, 17.36g of sodium trifluoroethoxy and 5g of double-bond sodium into a pyridine solution of the polydichlorophosphazene, reacting at room temperature for 24 hours, then using n-heptane and water to precipitate a polymer from the reaction mixed solution, and drying in vacuum to obtain the hexafluorobisphenol A group, the trifluoroethoxy group and the fluorinated polyphosphazene elastic material containing double bonds.
Adding 30g of the prepared fluorinated polyphosphazene elastic material into 180g of methyl pyrrolidone solvent, adding 2.8g of Anti-terra-u, 2.2g of BYK3902, 2.2g of BYK054, 1.8g of BYK333, 7g of quartz powder, 4g of short aramid fiber and 10g of wet sericite in turn under stirring, fully stirring and dispersing, grinding for 24 hours, and then adding 20g of methyl pyrrolidone solvent to prepare the fluorinated polyphosphazene rain erosion resistant coating component A.
0.5g of acetophenone, 0.3g of alpha-hydroxy ketone, 1.2g of KH560 and 24g of methyl pyrrolidone are mixed uniformly to prepare the fluorinated polyphosphazene rain erosion resistant coating component B.
And (4) polishing the glass fiber reinforced plastic test piece by using sand paper, wiping by using ethanol, and airing for later use.
Coating A component: component B is 10: mixing the components according to the weight ratio of 1, stirring the mixture evenly, and spraying the mixture on the surface of a glass fiber reinforced plastic test piece by using an air spray gun under the room temperature condition → standing the mixture for 30 minutes under the room temperature condition → placing the mixture under a 313nm ultraviolet lamp for irradiating for 60 minutes → finishing the preparation of the polyphosphazene rain erosion resistant coating.
Example 4:
preparing 15g of polydichlorophosphazene according to a bulk or solution polymerization method, dripping 43.13g of sodium octafluoropentoxide and 18.59g of sodium trifluoroethoxysulfate into a tetrahydrofuran solution of the polydichlorophosphazene, reacting at room temperature for 24 hours, then precipitating a polymer from the reaction mixed solution by using petroleum ether and n-heptane, and drying in vacuum to obtain the octafluoropentoxy, trifluoroethoxy substituted fluorinated polyphosphazene elastic material.
Adding 30g of the prepared fluorinated polyphosphazene elastic material into 180g of methyl pyrrolidone solvent, adding 3g of Anti-terra-u, 2.2g of BYK3902, 2g of BYK054, 1.8g of BYK333, 6g of quartz powder, 5g of chopped polyimide fiber, 7g R960 and 3g L0084 in sequence under stirring, fully stirring and dispersing, grinding for 24 hours, and then adding 20g of methyl pyrrolidone solvent to prepare the fluorinated polyphosphazene rain erosion resistant coating A component.
0.5g of acetophenone, 0.3g of alpha-hydroxy ketone, 1.2g of Anti-terra-u100 and 24-methyl pyrrolidone are uniformly mixed to prepare the fluorinated polyphosphazene rain erosion resistant coating component B.
And (4) polishing the glass fiber reinforced plastic test piece by using sand paper, wiping by using ethanol, and airing for later use.
Coating A component: component B is 10: mixing the components according to the weight ratio of 1, stirring the mixture evenly, and spraying the mixture on the surface of a glass fiber reinforced plastic test piece by using an air spray gun under the room temperature condition → standing the mixture for 30 minutes under the room temperature condition → placing the mixture under a 313nm ultraviolet lamp for irradiating for 60 minutes → finishing the preparation of the polyphosphazene rain erosion resistant coating.
Example 5:
preparing 15g of polydichlorophosphazene according to a bulk or solution polymerization method, dripping 43.13g of sodium octafluoropentoxide and 18.59g of sodium trifluoroethoxysulfate into a mixed solution of tetrahydrofuran and pyridine of the polydichlorophosphazene, reacting at room temperature for 24 hours, then precipitating a polymer from the reaction mixed solution by using petroleum ether and xylene, and drying in vacuum to obtain the octafluoropentoxy, trifluoroethoxy substituted fluorinated polyphosphazene elastic material.
Adding 30g of the prepared fluorinated polyphosphazene elastic material into 180g of methyl pyrrolidone solvent, adding 2.5g of Anti-terra-u, 2.3g of BYK3902, 2.2g of BYK054, 2g of BYK333, 5g of wet sericite, 6g of short-cut quartz fiber, 0.7g R960, 4.3g of phthalocyanine blue and 5g of benzimidazolone yellow in sequence under stirring, fully stirring and dispersing, grinding for 24 hours, and then adding 20g of methyl pyrrolidone solvent to prepare the fluorinated polyphosphazene rain erosion resistant coating A component.
0.5g of acetophenone, 0.3g of alpha-hydroxy ketone, 1.2g of BYK028 and 24g of methyl pyrrolidone solvent are mixed uniformly to prepare the fluorinated polyphosphazene rain erosion resistant coating component B.
And (4) polishing the glass fiber reinforced plastic test piece by using sand paper, wiping by using ethanol, and airing for later use.
Coating A component: component B is 10: mixing the components according to the weight ratio of 1, stirring the mixture evenly, and spraying the mixture on the surface of a glass fiber reinforced plastic test piece by using an air spray gun under the room temperature condition → standing the mixture for 30 minutes under the room temperature condition → placing the mixture under a 313nm ultraviolet lamp for irradiating for 60 minutes → finishing the preparation of the polyphosphazene rain erosion resistant coating.
Example 6:
preparing 15g of polydichlorophosphazene according to a bulk or solution polymerization method, dripping 43.13g of sodium octafluoropentoxide and 18.59g of sodium trifluoroethoxysulfate into a dioxane solution of the polydichlorophosphazene, reacting at room temperature for 24 hours, then precipitating a polymer from the reaction mixed solution by using dichloromethane and n-heptane, and drying in vacuum to obtain the octafluoropentoxy, trifluoroethoxy substituted fluorinated polyphosphazene elastic material.
30g of the prepared fluorinated polyphosphazene elastomer was added to 180g of methyl pyrrolidone solvent2.9g of Anti-terra-u, 2.2g of BYK3902, 2.1g of BYK054, 1.8g of BYK333, 1g R960, 5g of chopped quartz fiber and 2g of chopped quartz fiber are added in turn with stirring
812. And (3) fully stirring and dispersing 6g of phthalocyanine blue and 7g of benzimidazolone yellow, grinding for 24 hours, and then adding 20g of methyl pyrrolidone solvent to prepare the fluorinated polyphosphazene rain erosion resistant coating component A.
0.5g of acetophenone, 0.3g of alpha-hydroxy ketone, 1.2g of Ceraflur 925 and 24g of methyl pyrrolidone are mixed uniformly to prepare the component B of the fluorinated polyphosphazene rain erosion resistant coating.
And (4) polishing the glass fiber reinforced plastic test piece by using sand paper, wiping by using ethanol, and airing for later use.
Coating A component: component B is 10: mixing the components according to the weight ratio of 1, stirring the mixture evenly, and spraying the mixture on the surface of a glass fiber reinforced plastic test piece by using an air spray gun under the room temperature condition → standing the mixture for 30 minutes under the room temperature condition → placing the mixture under a 313nm ultraviolet lamp for irradiating for 60 minutes → finishing the preparation of the polyphosphazene rain erosion resistant coating.
Neutral salt spray resistance: GB/T1771-2007 determination of neutral salt spray resistance of colored paint and varnish
Moisture and heat resistance: GB/T1740-2007 determination of humidity and heat resistance of paint film
Artificial weather aging resistance: GB/T14522 & 2008 & lt & ltArtificial climate aging test method for plastics, coatings and rubber materials for mechanical industry products & gt fluorescent ultraviolet lamp & lt & gt
Soaking gasoline: GB/T1734 & lt determination of gasoline resistance of paint film & gt.
Finally, it should be noted that the above-mentioned embodiments illustrate only preferred embodiments of the invention and do not limit the invention.
Claims (9)
1. The preparation method of the polyphosphazene rain erosion resistant coating for the airborne radar radome is characterized by comprising the following steps:
the method comprises the following steps: preparing polydichlorophosphazene by a bulk or solution polymerization method, dripping sodium salt or lithium salt of a nucleophilic reagent corresponding to side group groups R1 and R2 required by the product fluorinated polyphosphazene into a polydichlorophosphazene organic solution, reacting at room temperature, precipitating a polymer from a reaction mixed solution, and drying in vacuum to obtain a fluorinated polyphosphazene pre-crosslinked material containing different substituents;
step two: and (2) adding the fluorinated polyphosphazene pre-crosslinked material obtained in the step (1) into an organic solvent, after fully dissolving, sequentially adding a wetting dispersant, a leveling agent, a defoaming agent, an adhesion promoter and other surface auxiliaries and various pigments and fillers, fully stirring and uniformly dispersing, grinding and adjusting viscosity to prepare a coating A component, and canning for later use.
Step three: and uniformly stirring the curing agent, the coupling agent and the organic solvent to prepare a coating component B, and canning for later use.
Step four: during coating, firstly, carrying out surface treatment on a primer coating of the radome, then mixing the prepared coating A and the prepared coating B according to a ratio (such as a mass ratio of 10:1), after fully and uniformly stirring, uniformly spraying the coating on the surface of the radome in an air spraying manner, then crosslinking and forming a film by the coating in a heating or photocuring manner, repeating the spraying → curing according to the design thickness requirement of the coating, and finally forming the radome rain erosion resistant coating with the required thickness;
the fluorinated polyphosphazene structure is:
wherein R1 is a fluorine-containing or fluorine-free aryloxy group (including a phenoxy group, an alkylphenoxy group, a cyclic alkenyl-substituted phenoxy group, a linear alkenyl-substituted phenoxy group, etc.), a fluorine-containing or fluorine-free alkoxy group, or an anilino group.
Wherein R2 is a fluorine-containing or non-fluorine-containing aryloxy group (including phenoxy, alkylphenoxy, cyclic alkenylphenoxy, and chain alkenylphenoxy), a fluorine-containing or non-fluorine-containing alkoxy group, or a fluorine-containing or non-fluorine-containing amine group.
The anilino group is an anilino group, a substituted anilino group (e.g., an anilino group substituted with a chain alkyl group), or the like.
2. The method for preparing the rain erosion resistant coating of the polyphosphazene for the airborne radar radome of claim 1, wherein the nucleophilic reagent is sodium salt or lithium salt of R1 or R2 group; for example, the sodium or lithium salt of the nucleophile fluoroalcohol is selected from: sodium or lithium salts of trifluoroethanol, octafluoropentanol, hexafluoroisopropanol, etc., sodium or lithium salts of fluorophenol selected from: sodium salts or lithium salts of 4-fluorophenol, hexafluorobisphenol a and the like; the sodium or lithium salt of the fluoroamine is selected from: sodium salts or lithium salts of p-trifluoromethylaniline, 2,3,5, 6-tetrafluoroterephthalamide, and the like.
3. The method for preparing the rain erosion resistant coating of the polyphosphazene of the airborne radome according to the claim 1, wherein the solvent used for preparing the organic solution of the polydichlorophosphazene in the step one is one or more of tetrahydrofuran, dioxane, pyridine, ethanol, acetone and the like; the precipitating agent selected in step one is selected from: one or more of water, n-heptane, cyclohexane, petroleum ether, ethyl acetate, diethyl ether, dichloromethane, chloroform, acetone, acetonitrile, benzene and xylene.
4. The method for preparing the rain erosion resistant coating of the radome polyphosphazene of the airborne radar according to the claim 1, wherein the solvent used in the second step is one or more of methyl pyrrolidone, tetrahydrofuran, dioxane, pyridine, ethanol and acetone.
5. The method for preparing the rain erosion resistant coating of the polyphosphazene of the airborne radome of claim 1, wherein the wetting dispersant used in the second step is one or more of BYK111, BYK2152, BYK118, BYK110, BYK2200, Anti-terra-u and BYK 3950. The leveling agent is one or more of BYK358, BYK361, Efka3570, BYK3902, BYK360, BYK368 and BYK 3535; the defoaming agent is one or more of BYK077, BYK1791, BYK054 and BYK 066; the adhesion promoter is one or more of BYK 306, irco2000, BYK333 and BYK 4510.
6. The method for preparing the polyphosphazene rain erosion resistant coating of the airborne radome of claim 1, wherein the filler obtained in the second step is R960, BT-34, chopped quartz fiber, wet sericite, chopped polyimide fiber, BT-SD2, P0086, chopped aramid fiber, or polyester fiber,
812. One or more of L0084, TICO655, quartz powder, phthalocyanine blue, benzimidazolone yellow and the like.
7. The preparation method of the polyphosphazene rain erosion resistant coating of the airborne radar antenna cover according to claim 1, wherein the fluorinated polyphosphazene pre-crosslinked material in the step two comprises 5-15 wt% of the first component, 65-80 wt% of the solvent, 0.5-1.5 wt% of the wetting dispersant, 0.5-1.2 wt% of the leveling agent, 0.5-1 wt% of the defoaming agent, 0.5-1 wt% of the adhesion promoter, and 5-15 wt% of the pigment and filler.
8. The preparation method of the rain erosion resistant coating of the polyphosphazene of the airborne radome as claimed in claim 1, wherein the curing agent in the third step is one or more of acetophenone, benzophenone, alpha-hydroxy ketone, dicumyl peroxide and the like and derivatives thereof; the coupling agent is BYK346, KH550, BYK028, Ceratix8461, Ceraflour925, KH560, IR1010, BYK-A555, Anti-terra-u100, or a mixture thereof,
1770;
in the third step, the curing agent accounts for 1-5%, the coupling agent accounts for 1-5%, and the organic solvent accounts for 90-98%.
9. The rain erosion resistant coating of the polyphosphazene for airborne radomes prepared by the method of any of claims 1 to 8.
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