A water-based anti-icing resin and its preparation method

Abstract

The application discloses an aqueous anti-icing resin and a preparation method thereof, relates to the technical field of aqueous resins, and comprises the following steps: preparing an intermediate, then reacting deionized water, an emulsifier, monomers and an initiator, controlling the kettle temperature at 70-80 DEG C, continuously adding 60-80 parts by weight of the intermediate, 15-20 parts by weight of a modified filler and 100-120 parts by weight of deionized water, removing acetone in the system after 4-6 hours of heat preservation, adding 0.3-1.5 parts by weight of a regulator, cooling to room temperature, and filtering to obtain the product. The modified filler and the fluorine-containing resin are synergistically used through chemical grafting, the mechanical strength of the coating is obviously improved while the super-hydrophobicity is maintained, the icing time is prolonged, the ice adhesion is reduced, and the application is suitable for extreme outdoor environments.

Description

Technical Field

[0001] This invention relates to the field of waterborne resin technology, specifically to a waterborne anti-icing resin and its preparation method. Background Technology

[0002] In northern China, outdoor temperatures at night during winter often remain below freezing. Many engineering machinery installations, high-altitude signal towers, and high-voltage power transmission towers are prone to icing, affecting their normal operation. To solve the problem of outdoor icing, traditional de-icing methods include mechanical scraping or the use of conductive coatings. Mechanical scraping is labor-intensive, has low efficiency, and can cause safety accidents. Using conductive coatings, which utilize electric heating, also poses safety hazards, results in significant energy loss, and is equally costly.

[0003] Applying an anti-icing coating to outdoor locations such as construction machinery and signal towers that require icing protection can significantly reduce de-icing costs. Currently, Chinese patent application number 201210027812.6 describes an anti-icing coating and its preparation method, which uses a low surface energy coating combined with surface roughening to form a highly hydrophobic coating. This method can achieve a certain degree of hydrophobicity and anti-icing effect, but in prolonged sub-zero water vapor environments, once ice crystals form, its anti-icing effect will be greatly reduced. Furthermore, this formulation uses a two-component process, making the operation complex. Chinese patent application number 201710691806.3 describes a high-performance anti-icing coating for high-speed trains and its preparation method, which also uses fluorocarbon resin as a low surface energy coating to achieve a high hydrophobic effect. However, if used outdoors in sub-zero temperatures for extended periods, the anti-icing effect will decrease. Summary of the Invention

[0004] The purpose of this invention is to at least solve one of the technical problems existing in the prior art, and to provide a water-based anti-icing resin and its preparation method.

[0005] The technical solution of the present invention is as follows:

[0006] A method for preparing an aqueous anti-icing resin includes the following steps:

[0007] S1: Add 130-200 parts by weight of isophorone diisocyanate and 600-1000 parts by weight of perfluoropolyether diol with a molecular weight of 2000 to a reactor equipped with a stirrer. Turn on the stirrer and react at 80-90°C for 2-4 hours. Then cool down to 40-50°C, add 300-450 parts by weight of acetone and 25-45 parts by weight of dimethylolpropionic acid or dimethylolbutyric acid, and react at 40-50°C for 1-3 hours. Then add 20-25 parts by weight of hydroxyethyl acrylate and 4-6 parts by weight of ethanol, and continue to react at 40-50°C for 8-12 hours. Remove the product for later use to obtain the intermediate.

[0008] S2: Add 100-200 parts by weight of deionized water, 1-3 parts by weight of emulsifier, 20-40 parts by weight of monomer, and 0.3 parts by weight of initiator to a reactor equipped with a stirring and heating device. Turn on the stirring and stir until it becomes a uniform milky white color. Then turn on the heating device and control the reactor temperature at 70-80℃. Continuously add 60-80 parts by weight of intermediate, 15-20 parts by weight of modified filler, and 100-120 parts by weight of deionized water. After all materials have been added, keep the temperature for 4-6 hours, remove acetone from the system, add 0.3-1.5 parts by weight of regulator, cool to room temperature, filter, and obtain the final product.

[0009] Preferably, in step S2, the emulsifier is at least one of octylphenol polyoxyethylene ether, nonylphenol polyoxyethylene ether, sodium dodecylbenzene sulfonate, sodium dodecyl sulfonate, and sodium lauryl sulfonate.

[0010] Preferably, in step S2, the monomer is at least one selected from methyl methacrylate, n-butyl methacrylate, isobornyl methacrylate, ethyl methacrylate, isooctyl methacrylate, and butyl acrylate.

[0011] Preferably, in step S2, the initiator is at least one of ammonium persulfate, sodium persulfate, and potassium persulfate.

[0012] Preferably, in step S2, the modified filler is obtained by treating the filler with a treatment agent;

[0013] The filler is at least one of barium sulfate, kaolin, rutile titanium dioxide, and heavy calcium carbonate.

[0014] The treatment agent is at least one of vinyltrimethoxysilane, vinyltriethoxysilane, and γ-methacryloyloxypropyltrimethoxysilane.

[0015] Preferably, the processing method is as follows:

[0016] Add 20 parts by weight of treatment agent and 4 parts by weight of filler to 100 parts by weight of 90% ethanol aqueous solution, mix well, bake in a 60℃ oven for 8 hours, then remove and cool to room temperature for later use.

[0017] Preferably, in step S2, the regulator is at least one of disodium hydrogen phosphate, sodium bicarbonate, and sodium acetate.

[0018] The present invention also discloses an aqueous anti-icing resin, which is prepared by the preparation method described in any of the preceding claims.

[0019] The present invention also discloses a coating comprising 90-100 parts by weight of an aqueous anti-icing resin, 2-4 parts by weight of a crosslinking agent, 0.1-0.4 parts by weight of a wetting agent, 0.2-0.5 parts by weight of a defoamer, 3-5 parts by weight of a film-forming aid, and 0.1-0.5 parts by weight of a thickener.

[0020] The beneficial effects of this invention are as follows: The water-based anti-icing resin of this invention is a low surface energy water-based fluorinated resin. Based on its highly hydrophobic nature, modified fillers are grafted into the resin to form a dense, uneven paint film on the surface, thereby inhibiting the formation of ice crystals and achieving an anti-icing effect suitable for long-term outdoor use in sub-zero temperatures. Simultaneously, the use of chemical modification and grafting to crosslink the fillers within the system effectively enables long-term outdoor use, improves the wear resistance and impact resistance of the paint film, and effectively prevents windblown sand, rain, and other factors from affecting the coating's service life. Detailed Implementation

[0021] The embodiments of the present invention are described in detail below. These embodiments are exemplary and are only used to explain the present invention, and should not be construed as limiting the invention. Where specific techniques or conditions are not specified in the embodiments, they are performed according to the techniques or conditions described in the literature in the art or according to the product instructions. Reagents or instruments used, unless otherwise specified, are all commercially available conventional products.

[0022] In the following examples, the structure of the perfluoropolyether diol is as follows:

[0023] ;

[0024] Where a, b, c, and d are independent and are integers from 0 to 30, the sum of a, b, c, and d is at least 12, the order of the repeating units with a, b, c, or d enclosed in parentheses is arbitrary, and their average molecular weight is 2000.

[0025] Heavy calcium carbonate: Calcium carbonate with a bulk density of 0.8-1.3 g / cm³. 3 .

[0026] Example 1

[0027] Intermediate preparation: 130 parts by weight of isophorone diisocyanate and 600 parts by weight of perfluoropolyether diol with a molecular weight of 2000 were added to a reactor equipped with a stirrer. The stirrer was turned on and the reaction was maintained at 85°C for 3 hours. Then the temperature was lowered to 45°C, and 300 parts by weight of acetone and 25 parts by weight of dimethylolpropionic acid were added. The reaction was maintained at 45°C for 2 hours. Then 20 parts by weight of hydroxyethyl acrylate and 4 parts by weight of ethanol were added. The reaction was maintained at 45°C for 10 hours and then the intermediate was taken out for use.

[0028] Preparation of water-based anti-icing resin: 100 parts by weight of deionized water, 1 part by weight of emulsifier, 20 parts by weight of monomer, and 0.3 parts by weight of initiator were added to a reactor equipped with a stirring and heating device. Stirring was started and the mixture was stirred until it turned into a uniform milky white color. The heating device was then turned on and the reactor temperature was controlled at 75°C. 60 parts by weight of intermediate, 15 parts by weight of modified filler, and 100 parts by weight of deionized water were continuously added. After all materials were added, the mixture was kept at this temperature for 5 hours. Acetone was removed from the system, and 0.8 parts by weight of regulator was added. The mixture was cooled to room temperature and filtered through a 500-mesh filter cloth.

[0029] The emulsifier is octylphenol polyoxyethylene ether;

[0030] The monomer is methyl methacrylate;

[0031] The initiator is ammonium persulfate;

[0032] Modified filler: Add 20 parts by weight of vinyltrimethoxysilane and 4 parts by weight of barium sulfate filler to 100 parts by weight of 90% ethanol aqueous solution, mix evenly, bake in 60℃ oven for 8 hours, take out and cool to room temperature for later use.

[0033] The regulator is disodium hydrogen phosphate.

[0034] Film Formation by Blending: 95 parts by weight of the resin, 3 parts by weight of the carbodiimide crosslinking agent (product model DS-40W), 0.2 parts by weight of the wetting agent (using polyether modified siloxane solution with product model BYK-346), 0.3 parts by weight of the defoamer (using polyether siloxane copolymer with product model 902W), 3 parts by weight of the film-forming aid (using dipropylene glycol butyl ether), and 0.3 parts by weight of the thickener (using waterborne polyurethane with product model RM-2020) are thoroughly mixed and stirred at 2000 rpm for 1 hour, and then coated onto an aluminum plate.

[0035] Curing: The aluminum plate is baked at 80℃ for 2 hours to form a dense paint film with a micro-nano-scale uneven structure and a film thickness of 50±5μm.

[0036] Example 2

[0037] The difference from Example 1 is that the filler and crosslinking agent are changed, but the rest is the same as Example 1.

[0038] Specifically, the modified filler is: 20 parts by weight of vinyltrimethoxysilane and 4 parts by weight of kaolin filler are added to 100 parts by weight of 90% ethanol aqueous solution. After mixing evenly, the mixture is placed in a 60℃ oven and baked for 8 hours, then taken out and cooled to room temperature.

[0039] Film Formation by Blending: 95 parts by weight of the resin, 2 parts by weight of the aziridine crosslinking agent (product model PZ-33), 0.2 parts by weight of the wetting agent (using polyether modified siloxane solution with product model BYK-346), 0.3 parts by weight of the defoamer (using polyether siloxane copolymer with product model 902W), 3 parts by weight of the film-forming aid (using dipropylene glycol butyl ether), and 0.3 parts by weight of the thickener (using waterborne polyurethane with product model RM-2020) are thoroughly mixed and stirred at 2000 rpm for 1 hour, and then coated onto an aluminum plate.

[0040] Curing: The aluminum plate is baked at 80℃ for 2 hours to form a dense paint film with a micro-nano-scale uneven structure and a film thickness of 50±5μm.

[0041] Example 3

[0042] The difference from Example 1 is that the filler and crosslinking agent are changed, but the rest is the same as Example 1.

[0043] Modified filler: Add 20 parts by weight of vinyltrimethoxysilane and 4 parts by weight of heavy calcium carbonate filler to 100 parts by weight of 90% ethanol aqueous solution, mix evenly, bake in 60℃ oven for 8 hours, take out and cool to room temperature for later use.

[0044] Film Formation by Blending: 95 parts by weight of the resin, 4 parts by weight of the epoxy silane crosslinking agent (using polymethyltriethoxysilane, product model KH-23), 0.2 parts by weight of the wetting agent (using polyether-modified siloxane solution, product model BYK-346), 0.3 parts by weight of the defoamer (using polyether siloxane copolymer, product model 902W), 3 parts by weight of the film-forming aid (using dipropylene glycol butyl ether), and 0.3 parts by weight of the thickener (using waterborne polyurethane, product model RM-2020) are thoroughly mixed and stirred at 2000 rpm for 1 hour, and then coated onto an aluminum plate.

[0045] Curing: The aluminum plate is baked at 80℃ for 2 hours to form a dense paint film with a micro-nano-scale uneven structure and a film thickness of 50±5μm.

[0046] Comparative Example 1: No modified filler or crosslinking agent added

[0047] Unlike Example 1, no modified filler or crosslinking agent was added; otherwise, the process was the same as in Example 1.

[0048] Comparative Example 2: Unmodified filler was added, along with a crosslinking agent.

[0049] Unlike Example 1, the modified filler directly replaced the unmodified filler, i.e., barium sulfate filler was used directly, and the rest was the same as in Example 1.

[0050] Comparative Example 3: Filler modification, but without the addition of crosslinking agent.

[0051] Unlike Example 1, no crosslinking agent was added; otherwise, the process was the same as in Example 1.

[0052] Performance tests were conducted on the above embodiments and comparative examples, and the test results are shown in Table 1.

[0053] 1. Hydrophobicity and Surface Structure

[0054] The water contact angle, roll-off angle, and surface roughness of the test specimens were measured, and the test results are shown in Table 1.

[0055] The water contact angle test method is based on ASTM D7334-08;

[0056] Roll-off angle test method: Fix the sample horizontally on a tiltable platform. Deposit a drop of water of a specific volume (10 μL) on the sample surface, and tilt the platform slowly and at a constant rate (e.g., 1° / s); observe and record the angle at which the water droplet just begins to move. Repeat the measurement 5 times at different positions and take the average value, which is the roll-off angle.

[0057] The surface roughness test method is based on standard ISO 25178.

[0058] Table 1. Hydrophobicity test results of the examples

[0059]

[0060] As can be seen from the analysis of Table 1, compared with the comparative example, the coating of the grafted filler in the embodiment forms a micro-nano structure, and the contact angle is significantly improved, thus achieving superhydrophobicity.

[0061] 2. Anti-icing performance

[0062] Test method: The static freezing time of water droplets, ice adhesion and contact angle after 20 freeze-thaw cycles of the sample were tested at -15℃. The test results are shown in Table 2.

[0063] The test method for static freezing time of water droplets is based on standard ASTM D7191-10.

[0064] The ice adhesion test method refers to standard ASTM D3330;

[0065] The contact angle test method after 20 cycles of freeze-thaw is based on standard ASTM D7334-08 (2013).

[0066] Table 2 shows the test results of the anti-icing performance of the embodiments.

[0067]

[0068] As can be seen from Table 2, compared with the comparative example, the uneven structure constructed in the embodiment slows down ice crystal growth and reduces ice adhesion due to low surface energy.

[0069] 3. Mechanical durability

[0070] The sandpaper abrasion test, sand drop test and impact test of the samples were tested respectively. The test results are shown in Table 3.

[0071] The test method for sandpaper abrasion is based on ASTM D4060-19;

[0072] The test method for the sand drop test is based on ASTM D968-17.

[0073] The impact test method is based on ASTM D2794-93 (2019).

[0074] Table 3 Mechanical performance test results of the embodiments

[0075]

[0076] As can be seen from the analysis in Table 3, compared with the comparative example, the chemical crosslinking coatings of the examples all have excellent wear resistance and impact resistance, and the chemical graft filler significantly improves wear resistance (still superhydrophobic after 500 wear cycles), while the performance of the comparative example samples is reduced due to agglomeration.

[0077] In summary, this invention, through the synergistic effect of chemically grafted modified fillers and fluorinated resins, significantly improves the mechanical strength of the coating while maintaining superhydrophobicity, extends the freezing time to 4 times that of the unmodified coating, and reduces ice adhesion by 75%, making it suitable for extreme outdoor environments such as wind turbine blades and high-voltage transmission lines.

[0078] The embodiments described above are merely preferred embodiments of the present invention, and while the descriptions are specific and detailed, they should not be construed as limiting the scope of the present invention. It should be noted that those skilled in the art can make various other corresponding changes and modifications based on the technical solutions and concepts described above, and all such changes and modifications should fall within the protection scope of the claims of the present invention.

Claims

1. A method for preparing an aqueous anti-icing resin, characterized by, It comprises the following steps: S1: 130-200 parts by weight of isophorone diisocyanate, 600-1000 parts by weight of perfluoropolyether diol with a molecular weight of 2000 are put into a reactor with stirring, the stirring is started, the temperature is kept at 80-90℃ for 2-4h, then cooled to 40-50℃, 300-450 parts by weight of acetone, 25-45 parts by weight of bis-hydroxymethyl propionic acid or bis-hydroxymethyl butyric acid are added, 40-50℃ for 1-3h, then 20-25 parts by weight of hydroxyethyl acrylate, 4-6 parts by weight of ethanol are added, continue to keep the reaction for 8-12h, then take out for standby, get the intermediate; S2: 100-200 parts by weight of deionized water, 1-3 parts by weight of emulsifier, 20-40 parts by weight of monomer, 0.3 parts by weight of initiator are added into the reaction kettle with stirring and heating device, start stirring, stir until uniform milky white, start heating device, kettle temperature control at 70-80℃, continuously add 60-80 parts by weight of intermediate, 15-20 parts by weight of modified filler, 100-120 parts by weight of deionized water, after all the materials are added, keep for 4-6h, remove acetone in the system, add 0.3-1.5 parts by weight of regulator, cool to room temperature, filter, prepare; In step S2, the modified filler is obtained by treating the filler with a treating agent; The filler is at least one of barium sulfate, kaolin, rutile titanium dioxide, heavy calcium carbonate; The treating agent is at least one of vinyl trimethoxysilane, vinyl triethoxysilane, gamma-methacryloyloxypropyl trimethoxysilane; The treatment method is as follows: In 100 parts by weight of 90% ethanol aqueous solution, 20 parts by weight of treating agent and 4 parts by weight of filler are added, mixed uniformly, put into 60℃ oven for 8h, then take out and cool to room temperature for standby.

2. The method for preparing an aqueous anti-icing resin according to claim 1, characterized in that, In step S2, the emulsifier is at least one of octylphenol polyoxyethylene ether, nonylphenol polyoxyethylene ether, sodium dodecylbenzenesulfonate, sodium dodecyl sulfonate, sodium lauryl sulfonate.

3. The method for preparing an aqueous anti-icing resin according to claim 1, characterized in that, In step S2, the monomer is at least one of methyl methacrylate, n-butyl methacrylate, isobornyl methacrylate, ethyl methacrylate, isooctyl methacrylate, butyl acrylate.

4. The method for preparing an aqueous anti-icing resin according to claim 1, characterized in that, In step S2, the initiator is at least one of ammonium persulfate, sodium persulfate, potassium persulfate.

5. The method for preparing an aqueous anti-icing resin according to claim 1, characterized in that, In step S2, the regulator is at least one of disodium hydrogen phosphate, sodium bicarbonate, sodium acetate.

6. An aqueous anti-icing resin characterized by, Prepared by the preparation method of any one of claims 1-5.

7. A coating characterized by, It comprises 90-100 parts by weight of the resin of claim 6, 2-4 parts by weight of crosslinking agent, 0.1-0.4 parts by weight of wetting agent, 0.2-0.5 parts by weight of defoaming agent, 3-5 parts by weight of film-forming aid and 0.1-0.5 parts by weight of thickening agent.

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