Radiation heat dissipation coating resistant to high concentration ozone and method of making and using same

Abstract

The application discloses a kind of radiation heat dissipation coating of high-concentration ozone resistance and preparation and use method thereof.The radiation heat dissipation coating of high-concentration ozone resistance includes A component and B component;With mass parts, the A component includes fluorocarbon resin 60-80 parts, chromium spinel 8-10 parts, carbon nanotube 0.1-0.3 parts, carbon black 0.4-1 part, SiC 3-6 parts, Al2O3 3-6 parts, solvent 40-60 parts, ultraviolet light absorber 0.3-1 part, antioxidant 0.3-1 part, antifungal agent 0.5-3 parts, anti-sediment agent 1-3 parts, adhesion promoter 0.3-1 part, dispersing agent 0.5-2 parts, defoaming agent 0.5-1 part, leveling agent 0.5-1 part;The B component is fluorine-containing modified isocyanate curing agent;The mass ratio of A component and B component is 100:(12.5-25).The radiation heat dissipation coating of high-concentration ozone resistance provided by the application has good ozone resistance, ultraviolet resistance, low-temperature resistance and radiation heat dissipation performance, and can meet the protection needs of airport equipment.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of industrial coating technology, in particular to a radiation heat dissipation coating resistant to high concentration ozone and a preparation and use method thereof. BACKGROUND

[0002] The ozone concentration in near space environment is high, according to GJB 1172.18-1991 Military Equipment Climate Extreme Value Ozone, the ozone concentration at 22km-28km can reach 0.76mg / m 3 , which can cause quality loss, mechanical, surface morphology and other parameters to deteriorate, seriously affecting the performance and life of the equipment, so the near space equipment needs to be protected against corrosion.

[0003] The base material is affected by factors such as the physical and chemical properties of the material itself, the structure part of the equipment, the characteristics of the deployment environment, etc., and the protection method adopted is also different. The near space equipment outside the carrying platform is more prone to corrosion because the external structure is exposed to a high concentration of ozone environment, and needs to be protected.

[0004] The common protection methods for equipment include coating protection, external wrapping protection of corrosion-resistant materials, etc. Wrapping protection with corrosion-resistant materials can affect the heat dissipation of the equipment, and thus affect the performance of the equipment, and the conventional coating protection method is difficult to meet the requirements of ozone resistance, ultraviolet resistance, low temperature resistance and radiation heat dissipation in near space. SUMMARY

[0005] In view of the above problems, the present application provides a radiation heat dissipation coating resistant to high concentration ozone and a preparation and use method thereof. The coating provided by the present application has good ozone resistance, ultraviolet resistance, low temperature resistance and radiation heat dissipation performance, which can guarantee the service performance and life of the near space equipment.

[0006] To achieve the above-mentioned purpose, the present application realizes the following technical scheme:

[0007] On the one hand, the present application provides a radiation heat dissipation coating resistant to high concentration ozone, which comprises A component and B component;

[0008] The A component comprises fluorocarbon resin 60-80 parts, chromium spinel 8-10 parts, carbon nanotube 0.1-0.3 parts, carbon black 0.4-1 parts, SiC 3-6 parts, Al2O3 3-6 parts, solvent 40-60 parts, ultraviolet light absorber 0.3-1 parts, antioxidant 0.3-1 parts, mildew-proof agent 0.5-3 parts, anti-settling agent 1-3 parts, adhesion promoter 0.3-1 parts, dispersing agent 0.5-2 parts, defoaming agent 0.5-1 parts, leveling agent 0.5-1 parts, all by mass fraction;

[0009] The B component is a fluorine-containing modified isocyanate curing agent;

[0010] The mass ratio of the A component and the B component is 100:(12.5-25).

[0011] The coating component of the present application uses long-acting weather-resistant fluorocarbon resin as a base material, the C-F bond has high bond energy and good stability, and can remain stable in a high-concentration ozone environment. The coating component contains chromite, carbon nanotubes and carbon black, which can improve the radiation heat dissipation performance of the coating; SiC and Al2O3 as functional fillers can improve the mechanical strength and hardness of the system; the solvent can reduce the viscosity of the system, facilitating dispersion and construction; the antioxidant and the ultraviolet light absorber can further improve the ozone resistance and aging resistance of the coating; the mildewcide can effectively kill the mold on the surface of the coating; the anti-settling agent can change the rheological properties of the resin, preventing the settling of the fillers; the adhesion promoter can form a chemical bond with the substrate or primer, improving the adhesion; the dispersant can effectively wet the surface of the fillers, adsorbing on the surface of the particles for a long time and keeping the particles uniformly dispersed; the defoaming agent can eliminate or inhibit bubbles in the system, avoiding defects such as bubbles or pinholes; the leveling agent can reduce the surface tension of the system, improving the permeability of the coating, reducing the spot and stain defects in the construction process, and promoting uniform film formation.

[0012] Preferably, the solvent is one or more of xylene, butyl acetate, acetone, butanone and toluene.

[0013] Preferably, the ultraviolet light absorber is a benzotriazole compound, the antioxidant is a phenolic substance, the mildewcide is a quaternary ammonium salt substance, the anti-settling agent is fumed silica, the adhesion promoter is a silane coupling agent, the dispersant is a modified polyester substance, the defoaming agent is a polysiloxane substance, and the leveling agent is an organic modified polysiloxane substance.

[0014] Preferably, the preparation method of the fluorine-containing modified isocyanate curing agent comprises: heating and refluxing graphene, isocyanate monomer and catalyst at 90-95℃ for 8-10h, adding perfluoro long-chain monol after cooling to 80-85℃ and continuing to react for 3-4h to obtain the fluorine-containing modified isocyanate curing agent.

[0015] Preferably, the mass ratio of graphene, isocyanate monomer, catalyst and perfluoro long-chain monol is (0.8-1.8):90:(0.1-0.2):(8-9).

[0016] Preferably, the isocyanate monomer is a trifunctional aliphatic isocyanate.

[0017] Preferably, the trifunctional aliphatic isocyanate is hexamethylene diisocyanate trimer, and the perfluoro long-chain monol is 2-perfluorooctyl ethanol.

[0018] On the other hand, the present application also provides a preparation method of the above-mentioned radiation heat dissipation coating resistant to high-concentration ozone, comprising the following steps:

[0019] Fluorocarbon resin, chromic spinel, carbon nanotube, carbon black, SiC, Al2O3, solvent, ultraviolet light absorber, antioxidant, mildewcide, anti-settling agent, adhesion promoter, dispersant, defoamer, leveling agent are mixed and stirred at a certain speed to disperse uniformly, and then grinded to a fineness of less than 25 μm to obtain component A;

[0020] A fluorine-containing modified isocyanate curing agent is added to component A, and after being mixed uniformly, a radiation heat dissipation coating resistant to high-concentration ozone is obtained.

[0021] In a third aspect, the present application provides a use method of the radiation heat dissipation coating resistant to high-concentration ozone, which comprises coating the radiation heat dissipation coating resistant to high-concentration ozone in the above technical solution on a surface of a substrate, and obtaining a radiation heat dissipation coating layer resistant to high-concentration ozone after room temperature curing.

[0022] Preferably, the coating method comprises blade coating, brush coating, roller coating or spraying, and the substrate comprises an air equipment substrate or a primer.

[0023] Preferably, the room temperature curing time is 1-2 days, and the thickness of the coating layer is 90-130 μm.

[0024] The present application has the following advantages:

[0025] The radiation heat dissipation coating resistant to high-concentration ozone has good ozone resistance, ultraviolet resistance, low-temperature resistance and radiation heat dissipation performance, and can meet the protection requirements of air equipment. In the near space environment, the air is thin and cannot be dissipated by convection, and the addition of chromic spinel, carbon nanotube and carbon black can improve the radiation heat dissipation coefficient of the coating layer, thereby effectively reducing the heat generated by the electronic components of the air equipment during operation. The long-acting weather-resistant fluorocarbon resin is used as the film-forming resin material, and the fluorine-containing modified isocyanate curing agent provides a crosslinked structure node when reacting with the fluorocarbon resin in the coating component, thereby further improving the mechanical strength, adhesion and weather resistance of the coating layer.

[0026] In the present application, graphene is used to toughen and modify isocyanate under the action of a catalyst, and then a fluorine-containing modified isocyanate is prepared by partially capping the toughened and modified isocyanate with a perfluoro long-chain monoalcohol. The toughening and modification of graphene and the introduction of a perfluoro long-chain group increase the molecular flexibility, thereby improving the low-temperature resistance and toughness of the coating layer.

[0027] The preparation method of the radiation heat dissipation coating resistant to high-concentration ozone comprises separately preparing a coating component and a curing agent component, and then mixing the coating component and the curing agent component at a certain ratio for coating, which is simple in process and conducive to popularization.

[0028] The method for using the anti-high-concentration-ozone radiation heat dissipation paint of the present application can adopt various coating methods, such as blade coating, brush coating, roller coating and spray coating, and can be dried and cured under natural conditions after coating, without the need for other drying equipment, and is convenient to operate. BRIEF DESCRIPTION OF DRAWINGS

[0029] In order to more clearly illustrate the technical solutions of the embodiments of the present application, the drawings of the embodiments will be briefly introduced below.

[0030] Figure 1 Micro-morphology of the coating prepared for the embodiment 3 and the comparative example 1 after 1000h ozone (1607pphm) resistance. DETAILED DESCRIPTION

[0031] The technical solutions in the embodiments of the present application will be described clearly and completely below in combination with the embodiments of the present application. Obviously, the described embodiments are only a part of the embodiments of the present application, rather than all the embodiments of the present application. Based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without creative labor fall within the scope of protection of the present application.

[0032] Embodiment 1

[0033] An anti-high-concentration-ozone radiation heat dissipation paint, comprising, by mass fraction, 100 parts of a paint component and 12.5 parts of a curing agent component;

[0034] The paint component comprises the following raw materials by mass fraction:

[0035]

[0036]

[0037] The curing agent component comprises the following raw materials by mass fraction:

[0038]

[0039] The preparation method of the anti-high-concentration-ozone radiation heat dissipation paint is as follows:

[0040] (B1) 60 parts of long-acting weather-resistant fluorocarbon resin, 8 parts of chromium spinel, 0.1 part of carbon nanotube, 0.4 part of carbon black, 3 parts of SiC, 3 parts of Al2O3, 40 parts of solvent, 0.3 part of ultraviolet light absorber, 0.3 part of antioxidant, 0.5 part of mildew preventive, 1 part of anti-settling agent, 0.3 part of adhesion promoter, 0.5 part of dispersant, 0.5 part of defoaming agent, 0.5 part of leveling agent are added into a dispersion tank, and are uniformly dispersed by high-speed (800r / min) stirring, and are grinded to a fineness of less than 25μm to obtain the paint component;

[0041] (B2) 0.9 parts of graphene was dispersed in 100 mL of xylene, after ultrasonic dispersion for 1 h, slowly added into 90 parts of trifunctional aliphatic isocyanate, continuously stirred, 0.1 parts of organic bismuth catalyst was added, heated to 95℃, and kept refluxing for 8 h, cooled to 85℃, then 9 parts of perfluoro long-chain monol was slowly added through a constant pressure dropping funnel, after the dropping was completed, the reaction was continued for 4 h, and a fluorine-containing modified isocyanate curing agent was obtained after cooling;

[0042] (B3) The paint component obtained in step (B1) and the curing agent component obtained in step (B2) were mixed uniformly at a mass ratio of 100:12.5 to obtain a high-concentration ozone-resistant radiation heat dissipation paint.

[0043] In use, the high-concentration ozone-resistant radiation heat dissipation paint was coated on the surface of a tinplate substrate by using a doctor blade method, the coating thickness was 100±10 μm, and the paint was dried and cured at room temperature for 48 h to obtain a high-concentration ozone-resistant radiation heat dissipation coating with good ozone resistance, ultraviolet resistance, low-temperature resistance, and radiation heat dissipation performance.

[0044] The obtained high-concentration ozone-resistant radiation heat dissipation coating had the following properties: ozone resistance (1607 pphm) for 1000 h, powdering 0 grade, cracking 0 grade, and color difference ΔE=0.28; low-pressure storage for 1.8 kPa, coating macroscopic morphology rating 0 grade, and color difference rating 0 grade; low-temperature storage at -95℃ for 96 h, coating macroscopic morphology rating 0 grade, and color difference rating 0 grade; temperature shock at high temperature -25℃ and low temperature -85℃, coating macroscopic morphology rating 0 grade, and color difference rating 0 grade; ultraviolet resistance for 1000 h, powdering 0 grade, cracking 0 grade, and color difference ΔE=0.23; infrared emissivity 0.96 (0.5-13.5 μm); adhesion 1 grade, flexibility 1 mm; mold resistance for 28 d, 0 grade.

[0045] Example 2

[0046] A high-concentration ozone-resistant radiation heat dissipation paint, comprising 100 parts of a paint component and 25 parts of a curing agent component by mass fraction;

[0047] The paint component comprises the following raw materials by mass fraction:

[0048]

[0049] The curing agent component comprises the following raw materials by mass fraction:

[0050]

[0051] The preparation method of the high-concentration ozone-resistant radiation heat dissipation paint is as follows:

[0052] (B1) 80 parts of long-acting weather-resistant fluorocarbon resin, 10 parts of chromium spinel, 0.3 parts of carbon nanotubes, 1 part of carbon black, 6 parts of SiC, 6 parts of Al2O3, 60 parts of butyl acetate, 1 part of ultraviolet light absorber, 1 part of antioxidant, 3 parts of mildewcide, 3 parts of anti-settling agent, 1 part of adhesion promoter, 2 parts of dispersant, 1 part of defoamer, 1 part of leveling agent are added into a dispersion tank, stirred and dispersed uniformly at high speed (1000 r / min), and grinded to a fineness of less than 25 μm to obtain a coating component;

[0053] (B2) 0.8 parts of graphene are dispersed in 100 mL of xylene, ultrasonic dispersion for 1 h, then slowly added into 90 parts of trifunctional aliphatic isocyanate, continuously stirred, 0.2 parts of organic bismuth catalyst is added, heated to 95℃, and kept at reflux for 8 h, then 9 parts of perfluoro long-chain monol is slowly added through a constant pressure dropping funnel at 85℃, after the addition is completed, the reaction is continued for 4 h, and then cooled to obtain a fluorine-containing modified isocyanate curing agent;

[0054] (B3) the coating component obtained in step (B1) and the curing agent component obtained in step (B2) are mixed uniformly at a mass ratio of 100:25 to obtain a radiation heat dissipation coating resistant to high concentration ozone.

[0055] In use, the radiation heat dissipation coating resistant to high concentration ozone is coated on the surface of a base by using a tinplate as the base and adopting a scraping coating method, the coating thickness is 120±10 μm, and the coating is dried and cured at room temperature for 24 h to obtain a radiation heat dissipation coating layer resistant to high concentration ozone, which has good ozone resistance, ultraviolet resistance, low-temperature resistance and radiation heat dissipation performance.

[0056] The obtained radiation heat dissipation coating layer resistant to high concentration ozone has the following properties: ozone resistance (1607 pphm) for 1200 h, 0-level chalking, 0-level cracking, and color difference ΔE=0.25; low-pressure storage for 1.8 kPa, 0-level coating macro-morphology rating and 0-level color difference rating; low-temperature storage at-95℃ for 96 h, 0-level coating macro-morphology rating and 0-level color difference rating; temperature shock at high temperature-25℃ and low temperature-85℃, 0-level coating macro-morphology rating and 0-level color difference rating; ultraviolet resistance for 1000 h, 0-level chalking, 0-level cracking, and color difference ΔE=0.20; infrared emissivity 0.98 (0.5-13.5 μm); adhesion 1 level, flexibility 1 mm; mold resistance for 28 d, 0 level.

[0057] Example 3

[0058] A radiation heat dissipation coating resistant to high concentration ozone comprises 100 parts of a coating component and 20 parts of a curing agent component by mass fraction.

[0059]

[0060]

[0061] The curing agent component comprises the following raw materials by mass fraction:

[0062]

[0063] The preparation method is as follows:

[0064] (B1) 64 parts of long-acting weather-resistant fluorocarbon resin, 7.5 parts of chromium spinel, 0.2 parts of carbon nanotubes, 0.75 parts of carbon black, 5 parts of SiC, 5 parts of Al2O3, 50 parts of butyl acetate, 0.8 parts of ultraviolet light absorber, 0.8 parts of antioxidant, 2 parts of mildewcide, 2 parts of anti-settling agent, 1 part of adhesion promoter, 1 part of dispersant, 1 part of defoaming agent, 1 part of leveling agent are added into a dispersion tank, and stirred and dispersed uniformly at high speed (1000 r / min), and then ground to a fineness of less than 25 μm to obtain a paint component;

[0065] (B2) 1.8 parts of graphene are dispersed in 100 mL of xylene, ultrasonic dispersion is performed for 1 h, then slowly added into 90 parts of trifunctional aliphatic isocyanate, continuously stirred, 0.2 parts of organic bismuth catalyst is added, heated to 95℃, and kept at reflux for 8 h, then cooled to 85℃, and 8 parts of perfluoro long-chain monol is slowly added through a constant-pressure dropping funnel, after the addition is completed, the reaction is continued for 4 h, and then cooled to obtain a fluorine-containing modified isocyanate curing agent;

[0066] (B3) The paint component obtained in step (B1) and the curing agent component obtained in step (B2) are stirred and mixed uniformly at a mass ratio of 100:20 to obtain a high-concentration ozone-resistant radiation heat dissipation paint.

[0067] In use, the high-concentration ozone-resistant radiation heat dissipation paint is coated on the surface of a base by roll coating method, taking tinplate as the base, the coating thickness is 110±10 μm, and the paint is dried and cured at room temperature for 36 h to obtain a high-concentration ozone-resistant radiation heat dissipation coating layer with good ozone resistance, ultraviolet resistance, low-temperature resistance and radiation heat dissipation performance.

[0068] The obtained high-concentration ozone-resistant radiation heat dissipation coating layer has the following properties: ozone resistance (1607 pphm) for 1000 h, powdering 0 level, cracking 0 level, color difference ΔE = 0.3; low-pressure storage for 1.8 kPa, coating macroscopic morphology rating 0 level, color difference rating 0 level. Low-temperature storage for 96 h at-95℃, coating macroscopic morphology rating 0 level, color difference rating 0 level; temperature shock, high temperature-25℃; low temperature-85℃, coating macroscopic morphology rating 0 level, color difference rating 0 level; ultraviolet resistance for 1000 h, powdering 0 level, cracking 0 level, color difference ΔE = 0.25; infrared emissivity 0.97 (0.5-13.5 μm); adhesion 1 level, flexibility 1 mm; mold resistance for 28 d, 0 level.

[0069] Comparative Example 1

[0070] 100 parts of the same coating component as in Example 3 were selected, with 20 parts of 3390 used as the curing agent component; the preparation method is as follows:

[0071] (B1) Add 64 parts of long-lasting weather-resistant fluorocarbon resin, 7.5 parts of chromium spinel, 0.2 parts of carbon nanotubes, 0.75 parts of carbon black, 5 parts of SiC, 5 parts of Al2O3, 50 parts of butyl acetate, 0.8 parts of ultraviolet absorber, 0.8 parts of antioxidant, 2 parts of mildew inhibitor, 2 parts of anti-settling agent, 1 part of adhesion promoter, 1 part of dispersant, 1 part of defoamer, and 1 part of leveling agent to a dispersion tank, stir and disperse evenly at high speed (1000 r / min), and grind until the fineness is less than 25 μm to obtain the coating components;

[0072] (B2) 0.2 parts of organic bismuth catalyst were added to 99.8 parts of 3390 curing agent, and the mixture was stirred and dispersed at high speed (500 r / min) for 10 min to obtain the curing agent component;

[0073] (B3) Mix the coating component obtained in step (B1) and the curing agent component obtained in step (B2) at a mass ratio of 100:20 to obtain a comparative coating.

[0074] In use, tinplate is used as the substrate, and the coating is applied to the substrate surface by roller coating method. The coating thickness is 110±10μm, and the coating is dried and cured at room temperature for 36 hours to obtain the comparison coating.

[0075] The obtained comparative coating, after 1000 hours of ozone (1607 pphm), showed microcracks (e.g.) Figure 1 As shown), color difference ΔE = 1.8; low-pressure storage 1.8 kPa, coating macroscopic morphology rating 0, color difference rating 0. Low-temperature storage -95℃, 96h, microcracks appear in the coating; temperature shock, high temperature -25℃, low temperature -85℃, microcracks appear in the coating; UV resistance 1000h, chalking grade 0, cracking grade 0, color difference ΔE = 0.7; infrared emissivity 0.92 (0.5~13.5μm); adhesion grade 2, flexibility 2mm; mildew resistance, 28d, grade 0.

[0076] It can be seen that the radiation heat dissipation coating with high concentration ozone resistance in Example 3 has significantly improved performance compared with the comparative coating, and its ozone resistance, low temperature resistance, thermal radiation performance, adhesion and flexibility are all superior.

[0077] In summary, this invention uses long-lasting weather-resistant fluorocarbon resin as the film-forming resin material and fluorinated modified isocyanate as the curing agent, which enables the prepared coating to have good mechanical strength, adhesion, temperature resistance, radiative heat dissipation and weather resistance.

[0078] It should be noted that the above embodiments all belong to the same inventive concept, and the description of each embodiment has its own emphasis. If the description in an individual embodiment is not exhaustive, the description in other embodiments can be referred to.

[0079] The above-described embodiments only express the implementation of the present application, and the description is more specific and detailed, but it should not be understood as limiting the scope of the patent. It should be noted that for ordinary skilled persons in the art, without departing from the inventive concept, a number of modifications and improvements can be made, which are within the scope of the present application. Therefore, the protection scope of the present application patent should be subject to the appended claims.

Claims

1. A radiation heat sink coating resistant to high concentrations of ozone, characterized in that, The A component and the B component are included; The A component includes fluorocarbon resin 60-80 parts by mass, chromium spinel 8-10 parts, carbon nanotubes 0.1-0.3 parts, carbon black 0.4-1 part, SiC 3-6 parts, Al2O3 3-6 parts, solvent 40-60 parts, ultraviolet light absorber 0.3-1 part, antioxidant 0.3-1 part, mildewcide 0.5-3 parts, anti-settling agent 1-3 parts, adhesion promoter 0.3-1 part, dispersant 0.5-2 parts, defoamer 0.5-1 part, leveling agent 0.5-1 part; The B component is a fluorine-containing modified isocyanate curing agent; The mass ratio of the A component and the B component is 100:(12.5-25); The preparation method of the fluorine-containing modified isocyanate curing agent includes: heating and refluxing graphene, isocyanate monomer and catalyst at 90-95°C for 8-10h, adding perfluoro long-chain monoalcohol after cooling to 80-85°C and continuing to react for 3-4h to obtain the fluorine-containing modified isocyanate curing agent; The mass ratio of the graphene, the isocyanate monomer, the catalyst and the perfluoro long-chain monoalcohol is (0.8-1.8):90:(0.1-0.2):(8-9); The isocyanate monomer is trifunctional aliphatic isocyanate; The trifunctional aliphatic isocyanate is hexamethylene diisocyanate trimer, and the perfluoro long-chain monoalcohol is 2-perfluorooctyl ethanol.

2. The radiation heat dissipation coating against high concentration ozone according to claim 1, characterized by, The solvent is one or more of dimethylbenzene, butyl acetate, acetone, butanone and toluene.

3. The preparation method of the radiation heat dissipation coating resistant to high-concentration ozone according to any one of claims 1-2, comprising the following steps: Mixing fluorocarbon resin, chromium spinel, carbon nanotubes, carbon black, SiC, Al2O3, solvent, ultraviolet light absorber, antioxidant, mildewcide, anti-settling agent, adhesion promoter, dispersant, defoamer and leveling agent, uniformly dispersing, and grinding to a fineness of less than 25μm to obtain the A component; Adding the fluorine-containing modified isocyanate curing agent to the A component, uniformly mixing to obtain the radiation heat dissipation coating resistant to high-concentration ozone.

4. A method of using a radiation heat sink coating resistant to high concentrations of ozone, characterized by, Coating the radiation heat dissipation coating resistant to high-concentration ozone according to any one of claims 1-2 on the surface of a substrate, and curing at room temperature to obtain a radiation heat dissipation coating layer resistant to high-concentration ozone.

5. The method of use of claim 4, wherein, The coating method includes blade coating, brush coating, roller coating or spraying, and the substrate includes an air equipment substrate or a primer.

6. The method of use of claim 4, wherein, The curing time at room temperature is 1-2d, and the thickness of the coating layer is 90-130μm.

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