Bio-based anti-icing material with multi-scale synergistic effect and preparation method thereof

Abstract

The invention discloses a bio-based multi-scale synergistic effect anti-icing material and a preparation method thereof, and belongs to the technical field of anti-icing materials, the preparation method comprises the following steps: S1, preparing a component A; and S2, mixing the component A and the component B to prepare the anti-icing material. According to the bio-based anti-icing material with the multi-scale synergistic effect and the preparation method of the bio-based anti-icing material, a nano-micron-macroscopic cross-scale structural design is coupled with multiple anti-icing mechanisms, so that hydrophobic coatings can be formed on the surfaces of bridge cables, electric wires, wind power blades and the like in a severe cold environment in the north and at a high altitude; the anti-icing coating still has good anti-icing performance at-20 to-8 DEG C, can reduce the adhesive force of water and ice to the greatest extent, automatically falls off when icing has certain self weight, prevents equipment from being damaged and damaged by icing, and reduces the maintenance cost of facilities and equipment.

Description

Technical Field

[0001] The present invention relates to the technical field of anti-icing materials, and in particular to a bio-based multi-scale synergistic anti-icing material and a preparation method thereof. Background Art

[0002] In the extremely cold regions and high altitude environments in the north, key infrastructure such as bridge cables, transmission lines, and wind turbine blades face serious icing problems. Ice loads cause structural deformation and fracture, power outages, and wind turbine shutdowns, with annual economic losses exceeding 10 billion yuan. Current deicing technologies focus on melting ice by heating or chemical methods and preventing the formation of ice layers with the properties of superhydrophobic or self-cleaning coatings. In traditional deicing technologies, electric heating deicing consumes a lot of energy, mechanical deicing damages the surface, and chemical deicing agents pollute the soil. Superhydrophobic coatings are gradually being widely used due to their excellent properties such as water repellency, self-cleaning, corrosion resistance, anti-icing, and oil-water separation.

[0003] Superhydrophobic coatings usually require special preparation processes to create appropriate micro- and nanoscale surface structures, which are technically demanding and expensive to prepare. Moreover, many superhydrophobic materials may degrade or lose their superhydrophobicity under harsh environmental conditions, such as high temperature, strong ultraviolet radiation, high humidity, acid-base environment, and mechanical wear. Therefore, it is urgent to develop a new type of material that is environmentally friendly, adaptable to extreme environments, and has long-lasting ice-repellent properties. Summary of the invention

[0004] The purpose of the present invention is to provide a bio-based anti-icing material with multi-scale synergistic effects and a preparation method thereof. Through the nano-micro-macro cross-scale structural design and the coupling of multiple anti-icing mechanisms, a hydrophobic coating can be formed on the surfaces of bridge cables, wires, wind turbine blades, etc. in the severe cold environment of the north and at high altitudes. It still has good anti-icing performance at -20~-8℃, and can minimize the adhesion of water and ice. When the ice has a certain weight, it will fall off by itself, preventing ice from damaging and harming the equipment and reducing the maintenance cost of facilities and equipment.

[0005] To achieve the above objectives, the present invention provides a bio-based multi-scale synergistic anti-icing material, comprising a component A and a component B, wherein the weight ratio of component A to component B is 10-15:1.

[0006] Preferably, component A includes the following raw materials, by weight: 40-55 parts of bio-based modified polyester resin, 20-30 parts of polytrifluoropropylmethylsiloxane, 10-20 parts of hydrophobically modified nano-silica, 1-3 parts of nano-titanium dioxide, 0.5-1 parts of graphene, 0.5-1 parts of modified attapulgite, 1-3 parts of nano-glass beads, 1-8 parts of additives, 7-13 parts of solvents, and 10-20 parts of pigments.

[0007] Preferably, component B includes the following raw materials in parts by weight: 10-15 parts of curing agent.

[0008] Preferably, the auxiliary agent includes a dispersant, a leveling agent, an anti-settling agent and a defoaming agent, and the solvent is dimethylformamide.

[0009] Preferably, the pigment includes one or more of titanium dioxide, iron oxide, carbon black, and copper oxide.

[0010] Preferably, the curing agent is methyl ethyl ketone peroxide.

[0011] The present invention provides a method for preparing a bio-based multi-scale synergistic anti-icing material, comprising the following steps: S1, preparing component A; S2. Mix component A and component B to prepare an anti-icing material.

[0012] Preferably, the specific steps of S1 are: adding bio-based modified polyester resin, polytrifluoropropylmethylsiloxane, hydrophobically modified nano-silica, nano-titanium dioxide, graphene, modified attapulgite, nano-glass beads, additives, solvents and pigments into a reaction kettle according to weight and stirring for 20-24 hours, first reacting at room temperature for 1-2 hours, then heating to 60-80°C and reacting for 2-3 hours, then cooling to room temperature, and using an automatic monitoring viscometer to monitor the viscosity to obtain component A.

[0013] Preferably, the specific operation of S2 is: uniformly stirring component A and component B according to a weight ratio at room temperature to obtain an anti-icing material.

[0014] Preferably, in S2, the stirring time is 5-10 min.

[0015] Therefore, the present invention adopts the above-mentioned bio-based multi-scale synergistic anti-icing material and its preparation method, through the nano-micro-macro cross-scale structure design and the coupling of multiple anti-icing mechanisms, and has the following beneficial effects: (1) At the nanoscale, biomass is introduced into polyester resin to modify it to increase the hydroxyl and hydrogen bond molecular structure, and then materials such as polytrifluoropropylmethylsiloxane are added to limit the disordered growth of ice crystals and delay the formation of ice crystals; (2) At the micrometer scale, graphene materials are used to form a porous skeleton with a honeycomb pore structure with bio-based modified polyester resin, which reduces the contact area between ice and the substrate and reduces the ice adhesion strength; (3) At the macroscopic scale, hydrophobic materials such as hydrophobic modified nano-silica are used to increase the surface hydrophobic angle, inhibit the freezing of water droplets, form a dynamic sliding interface, and the ice layer will fall off by itself when it has a certain weight; (4) Bio-based resins are renewable raw materials that can reduce dependence on petroleum. After disposal, they can be recycled through biodegradation or pyrolysis, which can effectively avoid microplastic pollution.

[0016] The technical solution of the present invention is further described in detail below through embodiments. DETAILED DESCRIPTION

[0017] The technical solution of the present invention is further illustrated by the following examples.

[0018] Unless otherwise defined, technical or scientific terms used in the present invention shall have the common meanings understood by one having ordinary skills in the field to which the present invention belongs.

[0019] A bio-based multi-scale synergistic anti-icing material, the preparation method of which comprises the following steps: S1. Prepare component A: add 40-55 parts of bio-based modified polyester resin, 20-30 parts of polytrifluoropropylmethylsiloxane, 10-20 parts of hydrophobically modified nano-silica, 1-3 parts of nano-titanium dioxide, 0.5-1 parts of graphene, 0.5-1 parts of modified attapulgite, 1-3 parts of nano-glass beads, 1-8 parts of additives including dispersants, leveling agents, anti-settling agents and defoaming agents, 7-13 parts of solvent dimethylformamide, and 10-20 parts of pigments including titanium dioxide, iron oxide, carbon black and copper oxide into a reactor and stir for 20-24 hours. First react at room temperature for 1-2 hours, then heat to 60-80°C for reaction for 2-3 hours, then cool to room temperature, monitor the viscosity with an automatic monitoring viscometer to obtain component A.

[0020] Among them, bio-based modified polyester resin serves as the main film-forming matrix of the material, providing structural support and bonding properties. Bio-based groups are introduced into polyester resin for modification to increase hydrophobic molecular structures such as hydroxyl groups and hydrogen bonds. The hydrophobic groups on the polyester chain interfere with the orderly arrangement of water molecules, inhibit the spreading and freezing of water droplets, reduce the surface energy of the material, form a hydrophobic interface, and prolong the nucleation time of ice crystals. Since the molecular chain flexibility of bio-based polyester resin is better than that of petroleum-based resin and it remains elastic at -50°C, it has stronger toughness at low temperatures. In addition, bio-based resin is a renewable raw material that can reduce dependence on petroleum. After disposal, it can be recycled through biodegradation or pyrolysis, which can effectively avoid microplastic pollution.‌

[0021] Polytrifluoropropylmethylsiloxane introduces fluorine-containing silicon segments, which significantly reduce the surface energy of anti-icing materials, and has the functions of forming a hydrophobic surface, reducing the attachment of water molecules, inhibiting ice crystal nucleation, and delaying the freezing process. Hydrophobically modified nano-silica constructs a "lotus effect" surface through a nano-scale rough structure, increases the surface micro-nano structure, and enhances hydrophobicity. Nano-titanium dioxide decomposes organic matter under ultraviolet light to keep the surface clean, and can also assist in delaying freezing through photothermal effects. The high thermal conductivity of graphene promotes uniform distribution of heat on the surfaces of beams, cables, wires, wind turbine blades, etc., inhibits local freezing, and reduces ice adhesion through layer stacking. Modified attapulgite is a natural porous mineral filler that absorbs residual moisture through a porous structure, reduces the formation of surface ice, and improves the cohesion and wear resistance of the coating.

[0022] S2. Component B is 10-15 parts of curing agent methyl ethyl ketone peroxide. Component A and component B are stirred at room temperature for 5-10 minutes in a weight ratio of 10-15:1 to obtain an anti-icing material.

[0023] After the bio-based modified polyester resin is combined with nanoparticles, during the curing process, the hydrophobic segments and particles are oriented on the surface to form micron-scale protrusions and construct a multi-scale rough surface, which can reduce the contact between ice crystals and the substrate and reduce the adhesion of ice.

[0024] Example 1 A bio-based multi-scale synergistic anti-icing material, the preparation method of which comprises the following steps: S1. Preparation of component A: add 40 parts of bio-based modified polyester resin, 30 parts of polytrifluoropropylmethylsiloxane, 15 parts of hydrophobically modified nano-silica, 2 parts of nano-titanium dioxide, 1 part of graphene, 0.5 parts of modified attapulgite, 3 parts of nano-glass beads, 8 parts of additives including dispersants, leveling agents, anti-settling agents and defoaming agents, 7 parts of solvent dimethylformamide, and 15 parts of pigments including titanium dioxide, iron oxide, carbon black and copper oxide into a reactor and stir for 24 hours. First react at room temperature for 2 hours, then heat to 80°C for 3 hours, then cool to room temperature, monitor the viscosity with an automatic monitoring viscometer, and obtain component A.

[0025] S2, component B is 10 parts of curing agent methyl ethyl ketone peroxide, and component A and component B are stirred at room temperature for 10 minutes in a weight ratio of 10:1 to obtain an anti-icing material.

[0026] Example 2 A bio-based multi-scale synergistic anti-icing material, the preparation method of which comprises the following steps: S1. Prepare component A: add 50 parts of bio-based modified polyester resin, 25 parts of polytrifluoropropylmethylsiloxane, 10 parts of hydrophobically modified nano-silica, 1 part of nano-titanium dioxide, 0.8 parts of graphene, 1 part of modified attapulgite, 2 parts of nano-glass beads, 6 parts of additives including dispersants, leveling agents, anti-settling agents and defoaming agents, 10 parts of solvent dimethylformamide, and 10 parts of pigments including titanium dioxide, iron oxide, carbon black and copper oxide into a reactor and stir for 24 hours. First react at room temperature for 1 hour, then heat to 80°C for 3 hours, then cool to room temperature, monitor the viscosity with an automatic monitoring viscometer, and obtain component A.

[0027] S2, component B is 10 parts of curing agent methyl ethyl ketone peroxide, and component A and component B are stirred at room temperature for 10 minutes in a weight ratio of 10:1 to obtain an anti-icing material.

[0028] Example 3 A bio-based multi-scale synergistic anti-icing material, the preparation method of which comprises the following steps: S1. Preparation of component A: add 55 parts of bio-based modified polyester resin, 30 parts of polytrifluoropropylmethylsiloxane, 20 parts of hydrophobically modified nano-silica, 3 parts of nano-titanium dioxide, 0.5 parts of graphene, 1.5 parts of modified attapulgite, 1 part of nano-glass beads, 4 parts of additives including dispersants, leveling agents, anti-settling agents and defoaming agents, 13 parts of solvent dimethylformamide, and 20 parts of pigments including titanium dioxide, iron oxide, carbon black and copper oxide into a reactor and stir for 24 hours. First react at room temperature for 1 hour, then heat to 80°C for 3 hours, then cool to room temperature, monitor the viscosity with an automatic monitoring viscometer, and obtain component A.

[0029] S2, component B is 10 parts of curing agent methyl ethyl ketone peroxide, and component A and component B are stirred at room temperature for 10 minutes in a weight ratio of 10:1 to obtain an anti-icing material.

[0030] Experimental Testing The anti-icing material prepared in Examples 1-3 was applied to the surface of the construction member to form a coating. The adhesion of the coating was tested by the cross-hatch method, the hardness of the coating was tested by the pencil method, and the contact angle of a water drop on the coating surface was measured by a contact angle tester. The results are shown in Table 1.

[0031] Table 1 Anti-icing material performance test results

[0032] As can be seen from Table 1, the adhesion grades between the coatings formed on the surface of the construction components by the anti-icing materials prepared in Examples 1-3 and the construction components are all Grade 1. The hardness of the coatings reaches 5H, 4H, and 5H respectively, all showing relatively high hardness. The contact angles of the coatings are 117°, 116°, and 118° respectively, showing good non-wetting properties.

[0033] The anti-icing materials prepared in Examples 1-3 were respectively applied to the surface of the construction components, and then the construction components were respectively immersed in 5% sulfuric acid solution, 5% sodium chloride solution, and saturated calcium hydroxide solution for 48 h. The construction components were taken out and the surface coatings were observed, and no abnormal phenomena were found, indicating that the coatings have excellent acid and alkali corrosion resistance.

[0034] The anti-icing materials prepared in Examples 1-3 were respectively applied to the surface of the construction components, and the anti-icing effect on the surface of the construction components was continuously observed at -20~-8°C in the northern outdoors. Within 6 h, no ice was formed on the surface of the construction components. As the test time increased, ice gradually formed on the surface of the construction components. When reaching a certain weight, the ice cubes automatically fell off, indicating that the coating still has good anti-icing performance at -20~-8°C.

[0035] Therefore, the present invention adopts the above-mentioned anti-icing material with a bio-based multi-scale synergistic effect and its preparation method. Through the nano-micro-macro cross-scale structure design and the coupling of multiple anti-icing mechanisms, it can form a hydrophobic coating on the surfaces of bridge cables, wires, wind turbine blades, etc. in the harsh northern environment and high altitude. It still has good anti-icing performance at -20~-8°C, and can minimize the adhesion of water and ice, and automatically fall off when the ice has a certain self-weight, preventing ice from causing damage and harm to equipment, and reducing the maintenance cost of facilities and equipment.

[0036] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention and are not intended to limit them. Although the present invention has been described in detail with reference to the preferred embodiments, those of ordinary skill in the art should understand that they can still modify or equivalently replace the technical solutions of the present invention, and these modifications or equivalent replacements cannot make the modified technical solutions deviate from the spirit and scope of the technical solutions of the present invention.

Claims

1. A bio-based multi-scale synergistic anti-icing material, characterized in that: The invention comprises component A and component B, wherein the weight ratio of component A to component B is 10-15:

1.

2. The anti-icing material according to claim 1, characterized in that: Measured by weight, component A includes raw materials: 40-55 parts of bio-based modified polyester resin, 20-30 parts of polytrifluoropropylmethylsiloxane, 10-20 parts of hydrophobically modified nano-silica, 1-3 parts of nano-titanium dioxide, 0.5-1 parts of graphene, 0.5-1.5 parts of modified attapulgite, 1-3 parts of nano-glass beads, 1-8 parts of additives, 7-13 parts of solvents, and 10-20 parts of pigments.

3. The anti-icing material according to claim 1, characterized in that: Calculated by weight, component B includes the following raw materials: 10-15 parts of curing agent.

4. The anti-icing material according to claim 2, characterized in that: The additives include dispersants, leveling agents, anti-settling agents and defoaming agents, and the solvent is dimethylformamide.

5. The anti-icing material according to claim 2, characterized in that: The pigment includes one or more of titanium dioxide, iron oxide, carbon black, and copper oxide.

6. The anti-icing material according to claim 3, characterized in that: The curing agent is methyl ethyl ketone peroxide.

7. The method for preparing a bio-based multi-scale synergistic anti-icing material according to any one of claims 1 to 6, characterized in that: The following steps are involved: S1, preparing component A; S2. Mix component A and component B to prepare an anti-icing material.

8. The preparation method according to claim 7, characterized in that: The specific steps of S1 are: adding bio-based modified polyester resin, polytrifluoropropylmethylsiloxane, hydrophobically modified nano-silica, nano-titanium dioxide, graphene, modified attapulgite, nano-glass beads, additives, solvents and pigments into a reactor according to weight proportions and stirring for 20-24 hours, first reacting at room temperature for 1-2 hours, then heating to 60-80°C to react for 2-3 hours, then cooling to room temperature, monitoring the viscosity with an automatic monitoring viscometer, and obtaining component A.

9. The preparation method according to claim 7, characterized in that: The specific operation of S2 is: mixing component A and component B uniformly according to the weight ratio at room temperature to obtain the anti-icing material.

10. The preparation method according to claim 9, characterized in that: In S2, the stirring time is 5-10 min.

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