Anti-icing paint, preparation method thereof and anti-icing coating

Abstract

The invention relates to the technical field of coatings, and provides an anti-icing coating, a preparation method thereof and an anti-icing coating. The anti-icing coating comprises a first component and a second component, the first component contains fluorocarbon resin, a nano-scale filler I, a micron-scale filler II and a diluent; and the second component is prepared from polyisocyanate and isocyanate terminated silane. Fluorine and silicon resin are introduced into a coating system, the hydrophobicity of the coating can be improved, the surface roughness of the cured coating can be reduced through compounding of added micron filler and nano filler, the coating forms a lotus leaf effect, the contact area of water and a base material is reduced, and therefore the freezing speed of water on the base material at low temperature can be slowed down, and the service life of the coating is prolonged. And even if the ice is frozen, the ice adhesive force is greatly reduced, so that the ice layer is relatively easy to remove, and the influence of freezing on equipment is reduced.

Description

Technical Field

[0001] The present invention relates to the technical field of coatings, and in particular to an anti-icing coating and a preparation method thereof and an anti-icing coating. Background Art

[0002] Icing and frost problems have seriously affected people's daily lives and industrial production, and in serious cases, they will pose a huge threat to our lives and social security. For example, icing has become one of the main causes of plane crashes. In the past three decades alone, there have been as many as 803 flight accidents in the United States due to aircraft icing, and the probability of air crashes exceeds 15%; on coal freight trains, icing will cause water-containing coal to adhere to the wall panels of the truck and cannot be cleaned. It is difficult to clean it by manual knocking, which not only increases the labor intensity, but also damages the truck box structure and affects its use; fan blades are very easy to freeze in winter, affecting the power balance, and the fan blades have a high speed and a large centrifugal force. In the case of severe imbalance, the blades will break, causing heavy losses and even endangering personal safety.

[0003] In addition, surface ice has a huge impact on polar exploration, ocean development, long-distance power transmission and many other aspects. Therefore, delaying surface ice formation and removing ice accumulation is crucial. The commonly used deicing and anti-icing methods in engineering are mainly thermodynamic methods, mechanical methods and chemical methods, but these methods are often accompanied by a large amount of energy consumption and human and material resources consumption, and may even damage the surface of the equipment. Some methods cannot be modified to resist ice because the existing equipment has already been prepared. Summary of the invention

[0004] The present invention provides an anti-icing coating, a preparation method thereof and an anti-icing coating. By introducing fluorine and silicone resin into the coating system, the hydrophobicity of the coating can be improved. By adding a compound of micron fillers and nanometers, the surface roughness of the coating after curing can be reduced, so that the coating forms a "lotus leaf effect" and reduces the contact area between water and the substrate, thereby slowing down the freezing speed of water on the substrate at low temperatures. Even after freezing, the ice adhesion will be greatly reduced, making the ice layer easier to remove, thereby reducing the impact of freezing on the equipment.

[0005] In a first aspect, the present invention provides an anti-icing coating, comprising a first component and a second component; the first component contains a fluorocarbon resin, a nano-scale filler I, a micron-scale filler II and a diluent; the second component contains a polyisocyanate and an isocyanate-terminated silane.

[0006] As a preferred technical solution, the first component contains, by mass percentage: fluorocarbon resin: 65% to 85%; nano-scale filler I: 1% to 10%; micron-scale filler II: 1% to 10%; diluent: 10% to 25%.

[0007] As a preferred technical solution, the solid content of the fluorocarbon resin is ≥50%.

[0008] As a preferred technical solution, the number average molecular weight of the fluorocarbon resin is 20,000 to 30,000.

[0009] As a preferred technical solution, the fluorocarbon resin is selected from FEVE fluorocarbon resin; the FEVE fluorocarbon resin of the present invention is commercially available and is a copolymer of chlorotrifluoroethylene and vinyl ester arranged alternately.

[0010] As a preferred technical solution, based on the mass of FEVE fluorocarbon resin being 100%, the hydroxyl content in the FEVE fluorocarbon resin is 1.0% to 2.0%, and the fluorine content is 24.5 to 25.5.

[0011] As a preferred technical solution, the diluent is selected from at least one of ethyl acetate, butyl acetate, and propylene glycol methyl ether acetate.

[0012] As a preferred technical solution, the mass ratio of the nano-scale filler I to the micro-scale filler II is 1:10 to 10:1.

[0013] As a preferred technical solution, the particle size of the nanoscale filler I is in the range of 30 to 300 nm.

[0014] As a preferred technical solution, the nanoscale filler I is selected from any one of silicon oxide, zinc oxide and aluminum oxide.

[0015] As a preferred technical solution, the particle size of the micron-sized filler I is in the range of 5 to 50 μm.

[0016] As a preferred technical solution, the micron-sized filler II is stearic acid-modified titanium oxide powder.

[0017] The stearic acid-modified titanium oxide powder of the present invention is obtained by mixing titanium oxide and an ethanol solution of stearic acid. As a preferred embodiment, stearic acid and ethanol are mixed to obtain a mixed solution, the mass concentration of stearic acid in the mixed solution is 5% to 10%, and then titanium oxide powder is added at a mass ratio of 2:1 to 5:1 between the mixed solution and titanium oxide, and mechanical stirring is performed for 30 to 60 minutes at 30 to 35°C. After the reaction is completed, centrifugal filtration is performed, and the precipitate is rinsed with ethanol several times and then dried in an oven at 80°C to constant weight to obtain stearic acid-modified titanium oxide powder.

[0018] As a preferred technical solution, the first component further contains an auxiliary agent; preferably, the mass content of the auxiliary agent in the first component is 0.5% to 2%; preferably, the auxiliary agent is a dispersant, selected from at least one of BYK161 and BYK163.

[0019] As a preferred technical solution, the second component contains, by mass percentage: polyisocyanate: 85% to 95% isocyanate-terminated silane: 5% to 15%.

[0020] As a preferred technical solution, the polyisocyanate is at least one of a hexamethylene diisocyanate (HDI) trimer or an isophorone diisocyanate (IPDI) trimer.

[0021] As a preferred technical solution, the isocyanate-terminated silane has a structure shown in Formula III,

[0022]

[0023] In formula III, R is C 1-10 of alkyl.

[0024] As a preferred technical solution, the isocyanate-terminated silane is selected from at least one of isocyanate propyl trimethoxy silane and isocyanate propyl triethoxy silane.

[0025] In a second aspect, the present invention provides a method for preparing any one of the anti-icing coatings described in the first aspect, wherein the anti-icing coating is obtained by mixing the first component and the second component.

[0026] As a preferred technical solution, the mixing temperature is 20 to 40°C;

[0027] As a preferred technical solution, the mixing stirring speed is 1000-2000 rpm;

[0028] As a preferred technical solution, the mass ratio of the first component to the second component is (15-10):1.

[0029] In another aspect, the present invention provides an anti-icing coating, comprising any one of the anti-icing coatings described in the first aspect, or an anti-icing coating obtained by any one of the preparation methods described in the second aspect.

[0030] Generally, the anti-icing coating is applied on the surface of a substrate and dried to obtain the anti-icing coating. The substrate includes, but is not limited to, carbon steel material.

[0031] As a preferred technical solution, the water contact angle of the anti-icing coating is ≥132°, and the ice adhesion is ≤90 / KPa.

[0032] The ice adhesion of the anti-icing coating is selected from any value among 50 KPa, 51 KPa, 65 KPa, 85 KPa, 90 KPa, or any range value between any two of them.

[0033] The water contact angle of the anti-icing coating is selected from any value among 132°, 135°, 136°, 137°, 140°, or any range between the two.

[0034] Compared with existing anti-icing methods and coatings, the anti-icing coating and coating of the present invention have the following advantages:

[0035] (1) By spraying an anti-icing coating, the freezing speed of water on the substrate at low temperatures can be slowed down without making too many changes to the original material;

[0036] (2) By using isocyanate-terminated silane as a cross-linking component, the organosilicon group can be grafted into the coating through curing and cross-linking, forming a hydrophobic silane structure on the surface of the coating. Due to the combination of chemical bonds, it has a longer-lasting hydrophobic effect than general additives. The hydrophobic structure does not disappear after friction, and the hydrophobic state of the surface can be continuously maintained. At the same time, after curing, the organosilicon forms a "block structure" of alternating soft and hard with the fluorocarbon resin, which can further improve the surface roughness of the coating, reduce the contact area between water and the coating, and improve the anti-icing effect.

[0037] (3) The compounding of hydrophobically modified microfillers and nanofillers can further improve the microscopic roughness and hydrophobic effect of the coating, forming a "lotus leaf structure" and reducing ice adhesion. DETAILED DESCRIPTION

[0038] The present invention will be further described below in conjunction with specific embodiments, but they do not constitute any limitation to the present invention.

[0039] The instruments and materials used in the examples and comparative examples of the present invention are described as follows.

[0040] The number average molecular weight of FEVE fluorocarbon resin is about 25,000. Taking the mass of FEVE fluorocarbon resin as 100%, the hydroxyl content of FEVE fluorocarbon resin is 1.5%, the fluorine content is 25.0%, and the solid content is 51%.

[0041] The carbon steel is Q215 cold-rolled steel plate with the surface treated by sandblasting.

[0042] Dispersant BYK161 and dispersant BYK163 were purchased from BYK Chemical Company.

[0043] Isophorone diisocyanate trimer was purchased from Bayer AG with the brand name Z4470.

[0044] Hexamethylene diisocyanate trimer was purchased from Bayer, brand N3390.

[0045] Preparation method of anti-icing coating:

[0046] (1) using a diluent to dissolve the FEVE fluorocarbon resin, adding a dispersant to the dissolved fluorocarbon resin to disperse it evenly, and adding filler I and filler II to the system in sequence at a stirring speed of (2000-3000) rpm until the system is free of agglomeration, thereby obtaining a first component;

[0047] (2) mixing the polyisocyanate and the isocyanate-terminated silane uniformly with a mechanical stirring speed (1000 to 2000 rpm) to obtain a second component;

[0048] (3) The first component and the second component are mixed in a mass ratio of 10 to 15:1, coated on a substrate, and dried for 48 hours to obtain an anti-icing coating.

[0049] Preparation Example

[0050] Preparation of stearic acid modified titanium oxide powder: Stearic acid is added to ethanol and stirred evenly to form a mixed solution. The mass concentration of stearic acid in the mixed solution is 8%. Titanium oxide powder is added in a ratio of 2:1 between the mass ratio of the mixed solution and titanium oxide (particle size D90≈8 microns). The reaction is carried out by mechanical stirring at 30°C for 60 minutes. After the reaction is completed, centrifugal filtration is performed, and the precipitate is rinsed with ethanol several times, then dried in an oven at 80°C to constant weight and ground to obtain stearic acid modified titanium oxide powder (particle size D90≈8 microns).

[0051] Example 1

[0052] (1) 65 g of FEVE fluorocarbon resin was dissolved in 22 g of butyl acetate, and 2 g of dispersant BYK161 was added to the dissolved FEVE fluorocarbon resin to disperse evenly to obtain a mixed system. 1 g of nano silicon oxide (average particle size of 50 nm) and 10 g of stearic acid-modified titanium oxide powder were added to the mixed system in sequence at a stirring speed of 3000 rpm until the system was free of agglomerates to obtain a first component;

[0053] (2) 95 g of hexamethylene diisocyanate trimer and 5 g of isocyanate propyl trimethoxy silane were mixed to obtain a second component;

[0054] (3) mixing the first component and the second component in a high-speed mixer at a mass ratio of 12:1 at a temperature of about 25° C. and a stirring speed of 2000 rpm to obtain an anti-icing coating;

[0055] (4) The anti-icing coating is applied on carbon steel and dried for 48 hours to obtain an anti-icing substrate.

[0056] Example 2

[0057] (1) 75 g of FEVE fluorocarbon resin was dissolved in 22 g of butyl acetate, and 2 g of dispersant BYK161 was added to the dissolved FEVE fluorocarbon resin to disperse evenly to obtain a mixed system. 2 g of nano silicon oxide (average particle size of 50 nm) and 9 g of stearic acid-modified titanium oxide powder were added to the mixed system in sequence at a stirring speed of 3000 rpm until the system was free of agglomeration to obtain a first component;

[0058] (2) 95 g of hexamethylene diisocyanate trimer and 5 g of isocyanate propyl trimethoxy silane were mixed to obtain a second component;

[0059] (3) mixing the first component and the second component in a high-speed mixer at a mass ratio of 10:1 at a temperature of about 25° C. and a stirring speed of 2000 rpm to obtain an anti-icing coating;

[0060] (4) The anti-icing coating is applied on carbon steel and dried for 48 hours to obtain an anti-icing substrate.

[0061] Example 3

[0062] (1) 65 g of FEVE fluorocarbon resin was dissolved in 20 g of butyl acetate, and 1 g of dispersant BYK161 was added to the dissolved FEVE fluorocarbon resin to disperse evenly to obtain a mixed system. 9 g of nano zinc oxide (average particle size of 80 nm) and 5 g of stearic acid-modified titanium oxide powder were added to the mixed system in sequence at a stirring speed of 3000 rpm until the system was free of agglomerates to obtain a first component;

[0063] (2) 90 g of hexamethylene diisocyanate trimer and 10 g of isocyanate propyl trimethoxy silane were mixed to obtain a second component;

[0064] (3) mixing the first component and the second component in a high-speed mixer at a mass ratio of 13:1 at a temperature of about 25° C. and a stirring speed of 2000 rpm, and coating the mixture on carbon steel to obtain an anti-icing coating;

[0065] (4) The anti-icing coating is applied on carbon steel and dried for 48 hours to obtain an anti-icing substrate.

[0066] Example 4

[0067] (1) Use 14 g of ethyl acetate to dissolve 75 g of FEVE fluorocarbon resin, add 1 g of dispersant BYK163 to the dissolved fluorocarbon resin, and disperse evenly to obtain a mixed system. Add 9 g of nano silicon oxide (average particle size of 50 nm) and 5 g of stearic acid-modified titanium oxide powder to the system in sequence at a stirring speed of 2000 rpm until the system is free of agglomeration, to obtain a first component;

[0068] (2) 90 g of isophorone diisocyanate trimer and 10 g of isocyanate propyl triethoxy silane were mixed to obtain a second component;

[0069] (3) mixing the first component and the second component in a high-speed mixer at a mass ratio of 10:1 at a temperature of about 25° C. and a stirring speed of 2000 rpm to obtain an anti-icing coating;

[0070] (4) The anti-icing coating is applied on carbon steel and dried for 48 hours to obtain an anti-icing substrate.

[0071] Example 5

[0072] (1) 85 g of FEVE fluorocarbon resin was dissolved in 12 g of ethyl acetate, and 1 g of dispersant BYK163 was added to the dissolved FEVE fluorocarbon resin to disperse evenly to obtain a mixed system. 5 g of nano-alumina (average particle size of 80 nm) and 2 g of stearic acid-modified titanium oxide powder were added to the mixed system in sequence at a stirring speed of 2000 rpm until the system was free of agglomerates to obtain a first component;

[0073] (2) 85 g of isophorone diisocyanate trimer and 15 g of isocyanate propyl triethoxy silane were mixed to obtain a second component;

[0074] (3) mixing the first component and the second component in a high-speed mixer at a mass ratio of 10:1 at a temperature of about 25° C. and a stirring speed of 2000 rpm to obtain an anti-icing coating;

[0075] (4) The anti-icing coating is applied on carbon steel and dried for 48 hours to obtain an anti-icing substrate.

[0076] Comparative Example 1

[0077] The first component is the first component of Example 1, and the second component is pure hexamethylene diisocyanate trimer. The first component and the second component are mixed in a high-speed mixer at a mass ratio of 12:1, the temperature is about 25°C, the stirring speed is 2000rpm, and after mixing evenly, an anti-icing coating is obtained; the anti-icing coating is applied on carbon steel, and the anti-icing substrate is obtained after drying for 48 hours.

[0078] Comparative Example 2

[0079] Use 23g of butyl acetate to dissolve 70g of FEVE fluorocarbon resin, add 2g of dispersant BYK161 to the dissolved FEVE fluorocarbon resin, disperse evenly to obtain a mixed system. Add 5g of stearic acid-modified titanium oxide powder to the mixed system at a stirring speed of 3000rpm, without adding nanofiller, until the system is free of agglomeration to obtain the first component. The second component adopts the second component of Example 1. The first component and the second component are mixed in a high-speed mixer at a mass ratio of 12:1, the temperature is about 25°C, the stirring speed is 2000rpm, and after mixing evenly, an anti-icing coating is obtained; the anti-icing coating is applied to carbon steel, and the anti-icing substrate is obtained after drying for 48h.

[0080] Comparative Example 3

[0081] Use 23g of butyl acetate to dissolve 70g of FEVE fluorocarbon resin, add 2g of dispersant BYK161 to the dissolved FEVE fluorocarbon resin, disperse evenly to obtain a mixed system. Add 5g of nano-oxidation (average particle size of 80nm) to the mixed system at a stirring speed of 3000rpm, without adding stearic acid-modified titanium oxide powder, until the system is free of agglomeration to obtain the first component. The second component adopts the second component of Example 3. The first component and the second component are placed in a high-speed mixer at a mass ratio of 13:1, the temperature is about 25°C, the stirring speed is 2000rpm, and after mixing evenly, an anti-icing coating is obtained; the anti-icing coating is applied to carbon steel, and an anti-icing substrate is obtained after drying for 48h.

[0082] Comparative Example 4

[0083] Comparative Example 4 is a carbon steel substrate that is not coated with an anti-icing coating.

[0084] Test Case

[0085] The anti-icing substrates prepared in Examples 1 to 5, the anti-icing substrates prepared in Comparative Examples 1 to 3, and the carbon steel substrate of Comparative Example 4 were used as substrate samples and subjected to the following tests. The test results are shown in Tables 1 and 2.

[0086] Test substrate adhesion MPa / (steel): The test method is based on "GB / T 5210-2006 Paint and varnish adhesion test by pull-off method".

[0087] Test ice adhesion: The test method is to place 5 plastic rings of fixed size (inner diameter 31mm, wall thickness 3mm, height 25mm) horizontally on the surface of the substrate sample at -20℃, pour 6mL of 5℃ ice-water mixture, let it stand for 24h, and then use a tensile gauge to measure the minimum horizontal tension that causes the steel ring to move.

[0088] Test the water contact angle: The test method is to use the LSA100 contact angle meter produced by LAUDA Scientific of Germany.

[0089] Test the water contact angle after 50 frictions: The test method is to use an abrasion tester to abrade the substrate sample 50 times and then test the water contact angle again. The abrasion tester has a CS-10 roller model and a load of 250g.

[0090] Table 1

[0091]

[0092] Table 2

[0093]

[0094] The test results show that in Examples 1-5, the water contact angle is about 135°, there is an obvious hydrophobic effect, the ice adhesion is below 100 KPa, the formation of ice and the difficulty of removing ice can be reduced, and the hydrophobicity is still good after 50 times of abrasion.

[0095] In Comparative Example 1, no isocyanate-terminated silane was added, the hydrophobic effect was reduced, the anti-icing effect was weakened, and the contact angle decreased significantly after 50 abrasions.

[0096] In Comparative Examples 2 and 3, no nanofiller or microfiller coating was added, and the hydrophobic and anti-icing effects were significantly reduced.

[0097] The carbon steel substrate in Comparative Example 4 is a hydrophilic structure and has greater ice adhesion.

[0098] The above test data show that compared with comparative examples 1-4, embodiments 1-5 of the present invention have obvious anti-icing effects.

[0099] Any numerical value mentioned in the present invention includes all values ​​that increase by one unit each time from the lowest value to the highest value if there is only an interval of two units between any minimum value and any maximum value. For example, if the amount of a component, or the value of a process variable such as temperature, pressure, time, etc. is declared to be 50-90, in this specification it means that 51-89, 52-88... and 69-71 and 70-71 are specifically listed. For non-integer values, 0.1, 0.01, 0.001 or 0.0001 can be appropriately considered as a unit. These are just some specially specified examples. In this application, in a similar manner, all possible combinations of numerical values ​​between the listed lowest and highest values ​​are considered to have been disclosed.

[0100] It should be noted that the embodiments described above are only used to explain the present invention and do not constitute any limitation to the present invention. The present invention has been described with reference to typical embodiments, but it should be understood that the words used therein are descriptive and explanatory words, rather than restrictive words. The present invention may be modified as specified within the scope of the claims of the present invention, and the present invention may be revised without departing from the scope and spirit of the present invention. Although the present invention described therein relates to specific methods, materials and embodiments, it does not mean that the present invention is limited to the specific examples disclosed therein, on the contrary, the present invention can be extended to all other methods and applications with the same functions.

Claims

1. Anti-icing coating, characterized in that: comprising a first component and a second component; The first component contains fluorocarbon resin, nano-scale filler I, micro-scale filler II and diluent; The second component contains a polyisocyanate and an isocyanate-terminated silane.

2. The anti-icing coating according to claim 1, characterized in that: In terms of mass percentage, the first component comprises: Fluorocarbon resin: 65%~85%; Nano-scale filler I: 1% to 10%; Micron-sized filler II: 1% to 10%; Diluent: 10%~25%.

3. The anti-icing coating according to claim 1 or 2, characterized in that: The solid content of the fluorocarbon resin is ≥50%; And / or, the number average molecular weight of the fluorocarbon resin is 20,000 to 30,000; And / or, the fluorocarbon resin is selected from FEVE fluorocarbon resin; Preferably, based on the mass of the FEVE fluorocarbon resin being 100%, the hydroxyl content in the FEVE fluorocarbon resin is 1.0% to 2.0%, and the fluorine content is 24.5 to 25.5; And / or, the diluent is selected from at least one of ethyl acetate, butyl acetate, and propylene glycol methyl ether acetate.

4. The anti-icing coating according to claim 1, 2 or 3, characterized in that: The mass ratio of the nano-scale filler I to the micro-scale filler II is 1:10 to 10:1; And / or, the particle size of the nanoscale filler I is in the range of 30 to 300 nm; And / or, the nanoscale filler I is selected from any one of silicon oxide, zinc oxide and aluminum oxide; And / or, the particle size of the micron-sized filler I is in the range of 5 to 50 μm; And / or, the micron-sized filler II is stearic acid-modified titanium oxide powder; The stearic acid-modified titanium oxide powder is obtained by mixing titanium oxide with an ethanol solution of stearic acid; Preferably, the stearic acid-modified titanium oxide powder is prepared by mixing stearic acid with ethanol to obtain a mixed solution, wherein the mass concentration of stearic acid in the mixed solution is 5% to 10%; titanium oxide is then added in a mass ratio of 2:1 to 5:1 between the mixed solution and titanium oxide, and the mixture is reacted at 30 to 35° C. for 30 to 60 minutes.

5. The anti-icing coating according to any one of claims 1 to 4, characterized in that: The first component also contains an auxiliary agent; Preferably, the mass content of the auxiliary agent in the first component is 0.5% to 2%; Preferably, the auxiliary agent is a dispersant, selected from at least one of BYK161 and BYK163.

6. The anti-icing coating according to any one of claims 1 to 5, characterized in that: In terms of mass percentage, the second component comprises: Polyisocyanate: 85%~95% Isocyanate-terminated silane: 5% to 15%; Preferably, the polyisocyanate is selected from at least one of hexamethylene diisocyanate trimer and isophorone diisocyanate trimer; Preferably, the isocyanate-terminated silane has a structure shown in Formula III, In formula III, R is C 1-10 of alkyl.

7. The anti-icing coating according to claim 6, characterized in that: The isocyanate-terminated silane is selected from at least one of isocyanate propyl trimethoxy silane and isocyanate propyl triethoxy silane.

8. The method for preparing the anti-icing coating according to any one of claims 1 to 7, characterized in that: After the first component and the second component are mixed, the anti-icing coating is obtained; Preferably, the mixing temperature is 20 to 40°C; Preferably, the mixing stirring speed is 1000 to 2000 rpm; Preferably, the mass ratio of the first component to the second component is (15-10):

1.

9. An anti-icing coating, comprising the anti-icing coating according to any one of claims 1 to 7, or the anti-icing coating obtained by the preparation method according to claim 8.

10. The anti-icing coating according to claim 9, characterized in that: The anti-icing coating has a water contact angle of ≥132° and an ice adhesion of ≤90 / KPa.

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