Bi-component bionic super-hydrophobic ice and snow prevention coating and preparation method thereof

Abstract

The invention belongs to the technical field of coatings, and relates to a bi-component bionic super-hydrophobic ice and snow prevention coating and a preparation method thereof.The coating is prepared from a component A and a component B. The mass ratio of the component A to the component B is 1: (1-1.5), and the component A is prepared from 10-15 parts of modified hydroxyl-terminated polyurethane prepolymer, 20-30 parts of fluorosilicone resin, 2-5 parts of simethicone and 15-20 parts of graft modified inorganic particles; the modified hydroxyl-terminated polyurethane prepolymer is prepared by reacting diisocyanate, polymer dihydric alcohol and an alkyne-containing binary chain extender to prepare hydroxyl-terminated alkyne-containing polyurethane and then carrying out phenylacetylene in-situ graft polymerization; the grafted modified inorganic particles are prepared by in-situ grafting a mixture of phenylacetylene and phenylacetylene alcohol derivatives by taking alkynyl of an alkynyl silane coupling agent modified inorganic filler as an active site, and under the action of a component B polyisocyanate curing agent, a hydroxyl-terminated polyurethane prepolymer and active hydroxyl on the surfaces of the modified inorganic particles are subjected to a cross-linking reaction; and dense cross-linked networks are respectively formed, so that the coating has excellent hydrophobicity and durability.

Description

Technical Field

[0001] The present invention belongs to the technical field of coatings, and in particular relates to a two-component bionic super-hydrophobic anti-ice and snow coating and a preparation method thereof. Background Art

[0002] Ice brings many problems to industrial fields such as transportation, electricity, construction and agriculture: it can easily cause serious traffic accidents, make it difficult for wind turbine blades to operate and affect their energy output, damage power lines and crops, and cause aircraft engines, ships and air-conditioning systems to stop working, thus causing serious harm to social production and life.

[0003] Inspired by hydrophobic phenomena such as lotus leaves emerging from mud without getting stained and water striders crawling on the water surface, bionic super-hydrophobic materials have attracted widespread attention from researchers at home and abroad. Super-hydrophobic materials refer to surface materials with a static contact angle with water greater than 150° and a rolling angle less than 10°. They have high hydrophobicity and self-cleaning properties. In anti-icing technology, surface-coated bionic super-hydrophobic protective coatings stand out due to their simple process, wide applicability, and ability to be applied over large areas. By simulating the microscopic roughness and low surface energy characteristics of nature, bionic hydrophobic coatings can construct a protective layer with super-hydrophobic properties on the surface of objects, bringing new ideas and technical solutions to solving the problem of icing in various industries. For example, the anti-icing and anti-frosting polyurethane coating and its preparation method disclosed in patent CN102746782B are as follows: based on the weight of fluorine-containing silicone polyurethane resin, 20 to 45 parts by weight of fluorine-containing silicone polyurethane resin, 40 to 50 parts by weight of organic solvent, 0.2 to 1 part by weight of defoaming agent, 0.2 to 1 part by weight of anti-settling agent and 0.3 to 1 part by weight of leveling agent are stirred to prepare a mixed solution; 3 to 10 parts by weight of silane coupling agent, 1 to 10 parts by weight of nano inorganic oxide particles and 5 to 10 parts by weight of titanium dioxide are added to the above mixed solution and ball milled to obtain the anti-icing and anti-frosting polyurethane coating. CN115322612B discloses an inorganic filler dispersion, a super-hydrophobic insulating wear-resistant coating, and a preparation method thereof. The inorganic filler dispersion is first subjected to a primary modification of a mixture of nanometer and submicron inorganic fillers using a hydrophobic silane coupling agent, and then the primary modified micro-nano inorganic filler is reacted with a hydrophobic end hydroxyl blocking agent and a catalyst in an organic solvent to obtain a secondary modified inorganic filler dispersion. The secondary modified inorganic filler dispersion is ground with components such as hydroxyl-terminated polydimethylsiloxane to obtain a pre-coating pulp, and then uniformly mixed with components such as a latent curing agent and a solvent as a reinforcing component to obtain a single-component super-hydrophobic insulating wear-resistant coating.

[0004] The above are common biomimetic hydrophobic materials, which use micron or submicron inorganic fillers, nanoscale inorganic fillers, and low-surface-energy polymers as raw materials to form a "micro-nano multi-level structure" and "low-surface-energy chemistry" properties similar to a lotus leaf surface. The micron-level protrusions disrupt the continuous spreading of the liquid and increase the surface roughness. The nanoscale inorganic fillers form nanoscale secondary structures, achieving multi-scale graded roughness, further reducing the solid-liquid contact area. Combined with low-surface-energy polymer modification, the materials are endowed with super-hydrophobicity, delaying ice formation and significantly reducing the adhesion of ice to the surface. This allows freezing rain or snow, which are prone to ice formation, to fall off under the action of natural forces before freezing, exhibiting efficient anti-icing performance. However, durability issues in practical applications restrict the application of super-hydrophobic anti-icing materials: the inorganic fillers have poor interaction with the film-forming resin, and acidic and alkaline environments can cause the inorganic fillers to fall off, destroying the micro-nano multi-level structure of the super-hydrophobic surface, reducing the hydrophobicity, and reducing the anti-icing performance, or even completely losing the anti-icing performance.

[0005] Therefore, it is necessary to develop a superhydrophobic material with good durability. Summary of the Invention

[0006] To address the technical problem in the prior art that inorganic fillers in superhydrophobic materials are easily detached and hydrophobicity is reduced, resulting in insufficient hydrophobic durability, the coating of the present invention includes grafted modified inorganic particles, which are prepared by in-situ grafting a mixture of phenylacetylene and phenylacetylene alcohol derivatives using the acetylenic groups on the acetylenic modified particles as active sites. The phenylacetylene and phenylacetylene alcohol derivatives impart excellent hydrophobic properties and crosslinking activity to the inorganic particles. The modified hydroxyl-terminated polyurethane prepolymer in the coating is first prepared by reacting a diisocyanate, a polymer diol, and an acetylene-containing dibasic chain extender to obtain a hydroxyl-terminated acetylene-containing polyurethane, and then in-situ grafting polymerization of phenylacetylene onto the hydroxyl-terminated acetylene-containing polyurethane to obtain the coating. Under the action of a polyisocyanate curing agent, the hydroxyl-terminated polyurethane prepolymer undergoes a cross-linking reaction with the active hydroxyl groups on the surface of the modified inorganic particles to form a crosslinked network, which can effectively prevent the detachment of the inorganic filler and improve durability.

[0007] In order to achieve the above objectives, the following technical solutions are adopted:

[0008] A two-component bionic super-hydrophobic anti-ice and snow coating, comprising components A and B in a mass ratio of 1:1-1.5.

[0009] Component A comprises the following raw materials in parts by weight: 10-15 parts of a modified hydroxyl-terminated polyurethane prepolymer, 20-30 parts of a fluorosilicone resin, 2-5 parts of dimethyl silicone oil, 15-20 parts of graft-modified inorganic particles, and 30-70 parts of a first solvent; the modified hydroxyl-terminated polyurethane prepolymer is prepared by reacting a diisocyanate, a polymer diol, and an alkyne-containing dibasic chain extender to obtain an hydroxyl-terminated alkyne-containing polyurethane, and the obtained hydroxyl-terminated alkyne-containing polyurethane is subjected to in-situ graft polymerization of phenylacetylene in the presence of a rhodium catalyst; the graft-modified inorganic particles are prepared by modifying an inorganic filler with an alkynyl silane coupling agent to obtain alkynyl-modified particles, and then in-situ grafting a mixture of phenylacetylene and phenylacetylene alcohol derivatives with the alkynyl groups as active sites;

[0010] Component B includes the following raw materials in parts by weight: 1-3 parts of diluent, 3-5 parts of polyisocyanate, and 0.3-0.5 parts of catalyst.

[0011] The mass ratio of the alkynyl-modified particles, phenylacetylene, and phenylacetylene alcohol derivative is 1:5-7:0.2-2, preferably 1:5-7:0.5-1.5.

[0012] The phenylacetylene alcohol derivative is selected from one or a combination of two or more of 2-ethynylbenzyl alcohol, (3-ethynylphenyl)methanol, and 4-ethynylbenzyl alcohol.

[0013] The alkynyl silane coupling agent is selected from one or a combination of ethynyl triethoxysilane and [3-(triethoxysilyl)propyl] propargyl carbamate.

[0014] The inorganic filler has an average particle size of 30-150 nm. The inorganic filler is selected from a combination of one or two of an ultraviolet light shielding agent and a nanofiller. Preferably, the inorganic filler is a mixture of the ultraviolet light shielding agent and the nanofiller in a mass ratio of 1-3:1-3. The inorganic filler is compounded by the ultraviolet light shielding agent and the nanofiller, and while constructing the micro-nano hydrophobic structure of the coating, it imparts ultraviolet resistance, which helps the coating be applied in scenes such as outdoor weather resistance and marine corrosion protection.

[0015] The ultraviolet light shielding agent is selected from one or a combination of two or more of titanium dioxide, zinc oxide and carbon black.

[0016] The nanofiller is selected from one or a combination of two or more of calcium carbonate, kaolin, talc, and silicon dioxide.

[0017] The grafted modified inorganic particles are prepared by a method comprising the following steps:

[0018] 1) dispersing an inorganic filler in a second solvent containing an alkynyl silane coupling agent to react to obtain alkynyl-modified particles;

[0019] 2) Under an inert atmosphere, the alkynyl-modified particles are dispersed in a third solvent, phenylacetylene, phenylacetylene alcohol derivatives, and rhodium catalyst are added and mixed, and the resulting mixture is dropped into a polyvinyl alcohol aqueous solution, mixed, and reacted to obtain graft-modified inorganic particles.

[0020] In step 1), the mass ratio of the inorganic filler, the alkynyl silane coupling agent, and the second solvent is 1:1-1.5:40-50.

[0021] In step 1), the second solvent is selected from one or a combination of two or more of benzene, toluene, and xylene. The reaction is carried out under an inert atmosphere, heated to reflux, and reacted for 12-24 hours. After completion of the reaction, centrifugation, washing, and drying operations are also included.

[0022] In step 2), the mass ratio of the alkynyl-modified particles, solvent, rhodium catalyst, and polyvinyl alcohol aqueous solution is 1:50-80:0.1-0.3:300-500. The concentration of the polyvinyl alcohol aqueous solution is 1-3 wt%.

[0023] In step 2), the rhodium catalyst is selected from one or a combination of two of dirhodium dichloride and 2,5-norbornadiene tetraphenylborate rhodium.

[0024] In step 2), the mixing is carried out at 0-5°C with a stirring speed of 500-800 r / min for 10-30 minutes. The dripping is carried out at 0-5°C for 30-60 minutes. The reaction is first carried out at 0-5°C for 3-5 hours, and then heated to 20-30°C for 5-8 hours.

[0025] In step 2), the third solvent is selected from one or a combination of two or more of benzene, toluene, xylene, dichloromethane, and chloroform. After the reaction is completed, centrifugation, washing, and drying operations are also included.

[0026] The molar ratio of the polymer diol, alkyne-containing dibasic chain extender, diisocyanate, phenylacetylene and rhodium catalyst is 1.25-1.5:0.15-0.25:1:3-5:0.01-0.05.

[0027] The alkyne-containing dibasic chain extender is selected from one or a combination of two or more of 4-ethynyl-1,2-phenylenediamine, 1-propynyl glycerol ether, 3-ethynyl-1,2-phenylenediamine, dimethyloctyne diol, pent-4-yne 1,2-diol, 2-(2-propynyl) 1,3-propanediol, 5-hexyne-1,4-diamine, and 6-heptyne-2,5-diamine.

[0028] The diisocyanate is selected from one or a combination of MDI and TDI. The polymer diol is a polyester diol or a polyether diol with a number average molecular weight of 1000-2000.

[0029] Specifically, the modified hydroxyl-terminated polyurethane prepolymer is prepared by a method comprising the following steps:

[0030] Under an inert atmosphere, a polymer diol, an alkyne-containing dibasic chain extender, a diisocyanate, and an organic tin catalyst are added to a fourth solvent and mixed evenly. The temperature is raised to react to obtain a terminal hydroxyl-containing alkyne-containing polyurethane. The temperature is lowered to add phenylacetylene and a rhodium catalyst, and the mixture is mixed evenly. The temperature is controlled to react to obtain a modified terminal hydroxyl polyurethane prepolymer.

[0031] The temperature is lowered to 0-5°C, and the temperature-controlled reaction is carried out at 20-30°C for 12-24 hours.

[0032] After the temperature-controlled reaction is completed, the solvent is removed by distillation under reduced pressure at 20-60°C.

[0033] The organic tin catalyst is selected from one or a combination of dibutyltin dilaurate and stannous octoate. The amount of the catalyst is 0.05-0.2 wt% of the total weight of the diisocyanate, polymer diol and alkyne-containing chain extender.

[0034] The fourth solvent is selected from one or a combination of two or more of toluene, xylene, methyl ethyl ketone, dimethylformamide, butanone, and ethyl acetate. The temperature of the reaction is raised to 60-80° C. for 3-5 hours.

[0035] The fluorosilicone resin has a solid content of 50-70 wt%, a hydroxyl value of 40-60 mgKOH / g, an acid value of 0-10 mgKOH / g, and a fluorine content of ≥26%.

[0036] Furthermore, the fluorosilicone resin is selected from one or a combination of two or more of Dyke Technology DK-8050, Langbowan Biopharmaceutical LS-8722, Baiyi Chemical HLR-Si, and Kanglunxi Chemical Technology KX-501.

[0037] The viscosity of the dimethyl silicone oil is 500-1000 cst.

[0038] The polyisocyanate has an -NCO content of 15-25% and is selected from one or a combination of TDI trimer and HDI trimer. The polyisocyanate has a higher functional group density and, when reacting with a modified hydroxyl-terminated polyurethane prepolymer, forms a three-dimensional cross-linked network structure, improving the coating's density, hardness, and weather resistance.

[0039] The catalyst is selected from one or a combination of organic metal catalysts and tertiary amine catalysts.

[0040] The organometallic catalyst is selected from one or a combination of two or more of dibutyltin dilaurate and stannous octoate.

[0041] The tertiary amine catalyst is selected from one or a combination of two or more of triethylamine, dimethylbenzylamine and triethylenediamine.

[0042] The diluent is selected from one or a combination of two or more of an alkyl silane coupling agent, an amino silane coupling agent, an epoxy silane coupling agent, a hydroxy silane coupling agent, and an alkenyl silane coupling agent.

[0043] Furthermore, the diluent is selected from one or a combination of two or more of octyltrimethoxysilane, p-aminophenyltrimethoxysilane, 4-aminobutyltriethoxysilane, ethyltrimethoxysilane, allyltrimethoxysilane, 5,6-epoxyhexyltriethoxysilane, and hydroxymethyltriethoxysilane.

[0044] The first solvent is selected from one or a combination of two or more of toluene, xylene, ethanol, ethyl acetate, and butyl acetate.

[0045] The B component further comprises 0.5-5 parts of an auxiliary agent.

[0046] The auxiliary agent is selected from one or a combination of two or more of a defoamer, a leveling agent, a dispersant, and a light stabilizer.

[0047] The light stabilizer is selected from one or a combination of two or more of light stabilizer NBC, light stabilizer 1084, light stabilizer 2002, light stabilizer GW622, light stabilizer GW480, light stabilizer GW4807622, ​​light stabilizer GW944, and light stabilizer GW783.

[0048] The present invention also provides a method for preparing the above-mentioned two-component bionic super-hydrophobic anti-ice and snow coating, comprising the following steps:

[0049] Component A: Mix the modified hydroxyl-terminated polyurethane prepolymer, fluorosilicone resin, dimethyl silicone oil, grafted modified inorganic particles and the first solvent, vacuum dehydrate and package;

[0050] Component B: diluent, polyisocyanate curing agent, light stabilizer and auxiliary agents are vacuum dehydrated and packaged.

[0051] The vacuum dehydration conditions are as follows: vacuum degree -0.08 MPa to -0.1 MPa, and time 0.5-2.5 h.

[0052] Compared with the prior art, the present invention has the following beneficial effects:

[0053] 1. The coating of the present invention includes grafted modified inorganic particles, which are prepared by in-situ grafting a mixture of phenylacetylene and phenylacetylene alcohol derivatives onto the acetylene groups on the acetylene-modified particles as active sites. The phenylacetylene and phenylacetylene alcohol derivatives impart excellent hydrophobicity and crosslinking activity to the inorganic particles. The modified hydroxyl-terminated polyurethane prepolymer in the coating is first prepared by reacting a diisocyanate, a polymer diol, and an acetylene-containing dibasic chain extender to obtain a hydroxyl-terminated acetylene-containing polyurethane, and then in-situ grafting polymerization of phenylacetylene onto the hydroxyl-terminated acetylene-containing polyurethane. Under the curing action of a polyisocyanate curing agent, the hydroxyl-terminated polyurethane prepolymer undergoes a cross-linking reaction with the active hydroxyl groups on the surface of the modified inorganic particles to form a cross-linked network, which effectively prevents the shedding of the inorganic filler and improves durability.

[0054] 2. The dual grafting modification of phenylacetylene on the acetylenic modified particles and the terminal hydroxyl-containing acetylenic polyurethane in the present invention not only improves the dispersibility of the grafted modified inorganic particles in the coating, but also synergistically improves the hydrophobic properties of the coating. DETAILED DESCRIPTION

[0055] The present invention will be further described below in conjunction with specific embodiment, but is not limited to the content on the specification sheets. Unless otherwise specified, "parts" described in the embodiments of the present invention are all parts by weight. All reagents used are commercially available reagents in this area.

[0056] PEG2000 was purchased from Hai'an Petrochemical Plant, Jiangsu Province.

[0057] Dimethyl silicone oil with a viscosity of 1000 cst was purchased from Hubei Co-Formula Material Technology Co., Ltd.

[0058] 4-Ethynyl-1,2-phenylenediamine (CAS No. 58297-31-7) was purchased from Hubei Shixing Chemical Co., Ltd.

[0059] 1-Propynyl glycerol ether (CAS No. 13580-38-6) was purchased from Shenzhen Xinkairui New Material Technology Co., Ltd.

[0060] 4-Ethynylbenzyl alcohol (10602-04-7) was purchased from Shanghai Yaosen Biotechnology Co., Ltd.

[0061] Ethylene triethoxysilane (5700-28-7) was purchased from Shanghai Zhenneng Industrial Co., Ltd.

[0062] The polyisocyanate curing agent HDI trimer is Bayer N3900.

[0063] Rutile titanium dioxide VK-T60 with an average particle size of 60 nm was purchased from Hangzhou Wanjing New Materials Co., Ltd.

[0064] Silica with the product number Brofos-SiO2-150 and an average particle size of 150 nm was purchased from Bohuasi Nanotechnology (Ningbo) Co., Ltd.

[0065] Example 1

[0066] 1) Under a nitrogen atmosphere, 1 part by mass of an inorganic filler composed of titanium dioxide VK-T60 and silicon dioxide Brofos-SiO2-150 in a mass ratio of 3:1 was dispersed in 50 parts by mass of toluene containing 1 part by mass of ethynyltriethoxysilane using an ultrasonic wave at a power of 300 W for 45 minutes. The mixture was heated to reflux and reacted for 24 hours. The mixture was centrifuged, washed twice with ethanol, and dried in vacuo at 40°C to obtain alkynyl-modified particles.

[0067] 2) Under a nitrogen atmosphere, 1 part by mass of alkynyl-modified particles was dispersed in 80 parts by mass of toluene at a power of 300 W for 45 minutes, 7 parts by mass of phenylacetylene, 1.5 parts by mass of 4-ethynylbenzyl alcohol, and 0.3 parts by mass of 2,5-norbornadiene tetraphenylborate rhodium were added and stirred at a speed of 500 r / min for 10 minutes. The resulting mixture was added dropwise to 500 parts by mass of a 3 wt% aqueous solution of polyvinyl alcohol at 0°C over 30 minutes, stirred at 800 r / min at 0°C for 10 minutes, reacted at 0°C for 3 hours, then heated to 20°C for 8 hours, centrifuged, washed with ethanol, and dried in vacuo at 40°C to obtain grafted modified inorganic particles.

[0068] 3) Under a nitrogen atmosphere, 1.25 mol parts of PEG2000, 0.25 mol parts of chain extender 4-ethynyl-1,2-phenylenediamine, and 1 mol part of MDI were added to 35 mol parts of toluene and mixed. The mass of PEG2000, chain extender, and MDI and 0.1 wt% of dibutyltin dilaurate were added, and the temperature was raised to 80°C and reacted for 5 h to obtain a terminal hydroxyl-containing polyurethane. The temperature was lowered to 0°C, 5 mol parts of phenylacetylene and 0.03 mol parts of 2,5-norbornadiene tetraphenyl rhodium borate were added and mixed. The temperature was controlled at 20°C and the reaction was carried out for 24 h. The solvent toluene was removed by reduced pressure distillation at 60°C to obtain a modified terminal hydroxyl polyurethane prepolymer.

[0069] 4) Component A: 15 parts by mass of modified hydroxyl-terminated polyurethane prepolymer, 30 parts by mass of Dyke Technology DK-8050, 5 parts by mass of dimethyl silicone oil, 20 parts by mass of grafted modified inorganic particles, and 40 parts by mass of a 1:1 volume ratio of ethyl acetate and toluene mixed solvent, vacuum dehydrated at a vacuum degree of -0.08 MPa for 2.5 hours, and packaged;

[0070] Component B: 3 parts by mass of octyltrimethoxysilane, 5 parts by mass of HDI trimer Bayer N3900, 0.3 parts by mass of dibutyltin dilaurate, and 1 part by mass of light stabilizer 1084, dehydrate under vacuum at a vacuum degree of -0.08 MPa for 0.5 h, and package.

[0071] Example 2

[0072] The rest is the same as Example 1, except that in step 2), the amount of 4-ethynylbenzyl alcohol used is 0.5 parts by mass.

[0073] Example 3

[0074] The rest is the same as Example 1, except that in step 2), the amount of 4-ethynylbenzyl alcohol used is 0.2 parts by mass.

[0075] Example 4

[0076] The rest is the same as Example 1, except that in step 2), the amount of 4-ethynylbenzyl alcohol used is 2 parts by mass.

[0077] Example 5

[0078] The rest is the same as Example 1, except that in step 2), the amount of phenylacetylene used is 5 parts by mass.

[0079] Example 6

[0080] The rest is the same as Example 1, except that in step 3), the chain extender 4-ethynyl-1,2-phenylenediamine is replaced by an equimolar amount of 1-propynyl glycerol ether.

[0081] Example 7

[0082] The rest is the same as Example 1, except that in step 3), the amount of the chain extender 4-ethynyl-1,2-phenylenediamine used is 0.15 parts by mole.

[0083] Example 8

[0084] The rest is the same as Example 1, except that in step 3), the amount of phenylacetylene used is 3 parts by mole.

[0085] Example 9

[0086] The rest is the same as Example 1, except that in step 4), the amount of the graft-modified inorganic particles of component A is 15 parts by mass.

[0087] Example 10

[0088] 1) Under a nitrogen atmosphere, 1 part by mass of an inorganic filler composed of titanium dioxide VK-T60 and silicon dioxide Brofos-SiO2-150 in a mass ratio of 3:1 was dispersed in 50 parts by mass of toluene containing 1 part by mass of ethynyltriethoxysilane using an ultrasonic wave at a power of 300 W for 45 minutes. The mixture was heated to reflux and reacted for 24 hours. The mixture was centrifuged, washed twice with ethanol, and dried in vacuo at 40°C to obtain alkynyl-modified particles.

[0089] 2) Under a nitrogen atmosphere, 1 part by mass of alkynyl-modified particles was dispersed in 80 parts by mass of toluene at a power of 300 W for 45 minutes, 7 parts by mass of phenylacetylene, 1.5 parts by mass of 4-ethynylbenzyl alcohol, and 0.3 parts by mass of 2,5-norbornadiene tetraphenylborate rhodium were added and stirred at a speed of 500 r / min for 10 minutes. The resulting mixture was added dropwise to 500 parts by mass of a 3 wt% aqueous solution of polyvinyl alcohol at 0°C over 30 minutes, stirred at 800 r / min at 0°C for 10 minutes, reacted at 0°C for 3 hours, then heated to 20°C for 8 hours, centrifuged, washed with ethanol, and dried in vacuo at 40°C to obtain grafted modified inorganic particles.

[0090] 3) Under a nitrogen atmosphere, 1.25 mol of PEG2000, 0.25 mol of chain extender 4-ethynyl-1,2-phenylenediamine, 1 mol of MDI, PEG2000, chain extender, MDI and 0.1 wt% of dibutyltin dilaurate were added to 3500 mL of toluene and mixed. The mixture was heated to 80°C and reacted for 5 h to obtain a terminal hydroxyl-containing polyurethane. The mixture was cooled to 0°C and 5 mol of phenylacetylene and 0.03 mol of 2,5-norbornadiene tetraphenyl rhodium borate were added and mixed. The mixture was kept at 20°C and reacted for 24 h. The solvent toluene was removed by reduced pressure distillation at 60°C to obtain a modified terminal hydroxyl polyurethane prepolymer.

[0091] 4) Component A: 10 parts by mass of modified hydroxyl-terminated polyurethane prepolymer, 30 parts by mass of Dyke Technology DK-8050, 5 parts by mass of dimethyl silicone oil, 20 parts by mass of grafted modified inorganic particles, and 36 parts by mass of a 1:1 volume ratio of ethyl acetate and toluene mixed solvent, vacuum dehydrated at a vacuum degree of -0.08 MPa for 2.5 hours, and packaged;

[0092] Component B: 3 parts by mass of octyltrimethoxysilane, 3 parts by mass of HDI trimer Bayer N3900, 0.3 parts by mass of dibutyltin dilaurate, and 1 part by mass of light stabilizer 1084, dehydrate under vacuum at a vacuum degree of -0.08 MPa for 0.5 h, and package.

[0093] Comparative Example 1

[0094] The rest is the same as Example 1, except that, in step 2), phenylacetylene of equal mass is used to replace 4-ethynylbenzyl alcohol.

[0095] Comparative Example 2

[0096] The rest is the same as Example 1, except that in step 3), an equimolar amount of 1,2-phenylenediamine is used to replace the chain extender 4-ethynyl-1,2-phenylenediamine.

[0097] The coatings prepared in the above embodiment and comparative example were mixed at a mass ratio of 1:1, sprayed on the surface of the tinplate to a coating thickness of 30 μm, and dried naturally at room temperature for 24 hours. The following performance tests were performed:

[0098] Contact angle and rolling angle: The test was carried out in accordance with the standard GB / T45017-2024 test method for mechanical stability of superhydrophobic surfaces.

[0099] Flexibility: Refer to the standard GB / T1731-2020 Determination of flexibility of paint film and putty film for testing, and record the qualified shaft rod diameter, mm; the shaft rod diameters are 1mm, 2mm, 3mm, 4mm, 5mm, 10mm, and 15mm.

[0100] Acid resistance: Refer to standard GB / T9274-1988 Paints and varnishes - Determination of resistance to liquid media, immersion method, 50g / L sulfuric acid aqueous solution, immersion time 168h, re-measurement of contact angle and rolling angle.

[0101] Alkali resistance: Refer to standard GB / T9274-1988 Paints and varnishes - Determination of resistance to liquid media, immersion method, 50g / L sodium hydroxide solution, immersion time 168h, re-measure contact angle and rolling angle.

[0102] Table 1 Performance test results

[0103]

[0104] As can be seen from the Examples and Comparative Examples, under the curing action of a polyisocyanate curing agent, the hydroxyl-terminated polyurethane prepolymer undergoes a crosslinking reaction with the active hydroxyl groups on the surface of the modified inorganic particles, forming a crosslinked network that effectively prevents the inorganic filler from falling off and improves acid and alkali resistance. It is clearly evident from Example 1 and Comparative Example 1 that the absence of active hydroxyl groups on the particle surface significantly reduces acid resistance. The dual grafting modification of phenylacetylene onto both acetylenic-modified particles and hydroxyl-terminated acetylenic polyurethane not only improves the dispersibility of the grafted modified inorganic particles in the coating but also synergistically enhances the coating's hydrophobic properties.

[0105] Furthermore, the contact angle / sliding angle data from Examples 1-4 in Table 1 show that varying the amount of 4-ethynylbenzyl alcohol significantly alters the sliding angle of the coatings. This is presumably due to the amount of active groups in the grafted inorganic particles affecting their dispersion in the coating system, and uneven surface roughness in the coatings increasing the sliding angle. When the mass ratio of acetylenic-modified particles, phenylacetylene, and 4-ethynylbenzyl alcohol is 1:5-7:0.5-1.5, the coatings exhibit superhydrophobicity (contact angle >150°, sliding angle <10°).

[0106] The above detailed description is a specific description of one feasible embodiment of the present invention. This embodiment is not intended to limit the patent scope of the present invention. Any equivalent implementation or modification that does not depart from the present invention should be included in the scope of the technical solution of the present invention.

Claims

1. A two-component bionic super-hydrophobic anti-ice and snow coating, characterized in that: It includes components A and B with a mass ratio of 1:1-1.

5. Component A comprises the following raw materials in parts by weight: 10-15 parts of a modified hydroxyl-terminated polyurethane prepolymer, 20-30 parts of a fluorosilicone resin, 2-5 parts of dimethyl silicone oil, 15-20 parts of graft-modified inorganic particles, and 30-70 parts of a first solvent; the modified hydroxyl-terminated polyurethane prepolymer is prepared by reacting a diisocyanate, a polymer diol, and an alkyne-containing dibasic chain extender to obtain an hydroxyl-terminated alkyne-containing polyurethane, which is then subjected to in-situ graft polymerization of phenylacetylene on the obtained hydroxyl-terminated alkyne-containing polyurethane under the action of a rhodium catalyst; the graft-modified inorganic particles are prepared by modifying an inorganic filler with an alkynyl silane coupling agent to obtain alkynyl-modified particles, which are then subjected to in-situ graft polymerization of a mixture of phenylacetylene and phenylacetylene alcohol derivatives under the action of a rhodium catalyst; Component B includes the following raw materials in parts by weight: 1-3 parts of diluent, 3-5 parts of polyisocyanate, and 0.3-0.5 parts of catalyst.

2. The two-component bionic super-hydrophobic anti-ice and snow coating according to claim 1, characterized in that: The mass ratio of the alkynyl-modified particles, phenylacetylene, and phenylacetylene alcohol derivative is 1:5-7:0.2-2, preferably 1:5-7:0.5-1.

5.

3. The two-component bionic super-hydrophobic anti-ice and snow coating according to claim 1, characterized in that: The phenylacetylene alcohol derivative is selected from one or a combination of two or more of 2-ethynylbenzyl alcohol, (3-ethynylphenyl)methanol, and 4-ethynylbenzyl alcohol; the average particle size of the inorganic filler is 30-150 nm, and the inorganic filler is selected from one or a combination of two of an ultraviolet light shielding agent and a nanofiller; preferably, it is a mixture of an ultraviolet light shielding agent and a nanofiller in a mass ratio of 1-3:1-3; the alkynyl silane coupling agent is selected from one or a combination of two of ethynyltriethoxysilane and [3-(triethoxysilyl)propyl]propargylcarbamate.

4. The two-component bionic super-hydrophobic anti-ice and snow coating according to claim 1, characterized in that: The grafted modified inorganic particles are prepared by a method comprising the following steps: 1) dispersing an inorganic filler in a second solvent containing an alkynyl silane coupling agent to react to obtain alkynyl-modified particles; 2) Under an inert atmosphere, the alkynyl-modified particles are dispersed in a third solvent, phenylacetylene, phenylacetylene alcohol derivatives, and rhodium catalyst are added and mixed, and the resulting mixture is dropped into a polyvinyl alcohol aqueous solution, mixed, and reacted to obtain graft-modified inorganic particles.

5. The two-component bionic super-hydrophobic anti-ice and snow coating according to claim 4, characterized in that: In step 2), the mass ratio of the alkynyl-modified particles, solvent, rhodium catalyst, and polyvinyl alcohol aqueous solution is 1:50-80:0.1-0.3:300-500; the concentration of the polyvinyl alcohol aqueous solution is 1-3wt%; and the rhodium catalyst is selected from one or a combination of dirhodium dichloride and 2,5-norbornadiene tetraphenylborate rhodium.

6. The two-component bionic super-hydrophobic anti-ice and snow coating according to claim 1, characterized in that: The molar ratio of the polymer diol, alkyne-containing dibasic chain extender, diisocyanate, phenylacetylene, and rhodium catalyst is 1.25-1.5:0.15-0.25:1:3-5:0.01-0.05; the alkyne-containing dibasic chain extender is selected from one or a combination of two or more of 4-ethynyl-1,2-phenylenediamine, 1-propynyl glycerol ether, 3-ethynyl-1,2-phenylenediamine, dimethyloctyne diol, pent-4-yne-1,2-diol, 2-(2-propynyl)-1,3-propanediol, 5-hexyne-1,4-diamine, and 6-heptyne-2,5-diamine; the polymer diol is a polyester diol and / or a polyether diol with a number average molecular weight of 1000-2000; and the diisocyanate is selected from one or a combination of two of MDI and TDI.

7. The two-component bionic super-hydrophobic anti-ice and snow coating according to claim 1, characterized in that: The modified hydroxyl-terminated polyurethane prepolymer is prepared by a method comprising the following steps: Under an inert atmosphere, a polymer diol, an alkyne-containing dibasic chain extender, a diisocyanate, and an organic tin catalyst are added to a fourth solvent and mixed evenly. The temperature is raised to react to obtain a terminal hydroxyl-containing alkyne-containing polyurethane. The temperature is lowered to add phenylacetylene and a rhodium catalyst, and the mixture is mixed evenly. The temperature is controlled to react to obtain a modified terminal hydroxyl polyurethane prepolymer.

8. The two-component bionic super-hydrophobic anti-ice and snow coating according to claim 7, characterized in that: The temperature is lowered to 0-5°C, and the temperature-controlled reaction is carried out at 20-30°C for 12-24 hours.

9. The two-component bionic super-hydrophobic anti-ice and snow coating according to claim 1, characterized in that: The fluorosilicone resin has a solid content of 50-70wt%, a hydroxyl value of 40-60mgKOH / g, an acid value of 0-10mgKOH / g, and a fluorine content of ≥26%; the polyisocyanate has an -NCO content of 15-25% and is selected from one or a combination of TDI trimer and HDI trimer; and the catalyst is selected from one or a combination of organic metal catalysts and tertiary amine catalysts.

10. The method for preparing the two-component bionic super-hydrophobic anti-ice and snow coating according to any one of claims 1 to 9, characterized in that: The steps include: Component A: Mix the modified hydroxyl-terminated polyurethane prepolymer, fluorosilicone resin, dimethyl silicone oil, grafted modified inorganic particles and the first solvent, vacuum dehydrate and package; Component B: diluent, polyisocyanate curing agent, light stabilizer and auxiliary agents are vacuum dehydrated and packaged.

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