Intelligent anti-icing material and preparation method thereof

Abstract

The invention discloses a preparation method of an intelligent anti-icing material, which comprises the following steps: preparing a humidity response precursor of the intelligent anti-icing material by using quaternized chitosan and E44 epoxy resin as raw materials, and mixing a PDMS prepolymer A, porous SiO2 nanoparticles and silicone oil to prepare an oil storage functional precursor of the intelligent anti-icing material; mixing the intelligent anti-icing material humidity response precursor and the intelligent anti-icing material oil storage functional precursor, adding an amine curing agent T31, a PDMS curing agent B and a cross-linking agent, and performing cross-linking curing to obtain the intelligent anti-icing material. When the intelligent anti-icing material is sprayed on the power transmission line, continuity of liquid on the surface of the power transmission line can be destroyed, spreading of ice on the surface of the power transmission line can be inhibited, ice nucleation sites are greatly reduced, ice crystal nucleation is inhibited, release and recovery of a lubricating layer are controlled by utilizing humidity sensitivity of the intelligent anti-icing material, and in the freezing and thawing cycle, the anti-icing effect is good. The service life of the lubricating layer is prolonged, and the intelligent anti-icing effect under the complex environment change is achieved.

Description

Technical Field

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

[0002] Icing on transmission lines causes poles to fall, wires to break and trip, leading to power outages and causing serious obstacles and huge economic losses in various fields. In the north, the climate is dry, the temperature is low, and it is often accompanied by rain and snow. The environmental changes are complex, and higher anti-icing performance and durability requirements are placed on transmission lines erected at high altitudes.

[0003] The Chinese patent "A silicone resin anti-icing coating material and its preparation method" (application number: 202410215764.6, publication number: CN118325383A, publication date: 2024-07-12) discloses a silicone resin anti-icing coating material and its preparation method. Modified Al(OH)3 obtains hydrophobicity and combines silicone resin to prepare a hydrophobic anti-icing material, which can reduce the chance of water contact with the surface, but cannot completely prevent ice formation. The Chinese patent "A super-hydrophobic anti-icing coating for passive photothermal deicing, its preparation method and application" (application number: 202210799708.2, publication number: CN115160857A, publication date: 2022-10-11) discloses a super-hydrophobic anti-icing coating for passive photothermal deicing, its preparation method and application. In complex environmental changes and freeze-thaw cycles, the super-hydrophobic surface created by ethyl acetate and fluorinated silica has poor wear resistance and is easily damaged, and has a short service life. The Chinese patent "A method for preparing a fluorine-free, wear-resistant, super-hydrophobic anti-icing coating with photothermal effect" (application number: 202111436798.0, publication number: CN114058227A, publication date: 2022-02-18) discloses a method for preparing a fluorine-free, wear-resistant, super-hydrophobic anti-icing coating with photothermal effect. This type of material takes into account both hydrophobicity and photothermal deicing, but has a strong dependence on the absorption of solar energy. In continuous rainy, windy and snowy weather, especially at night, its anti-icing performance is severely limited.

[0004] Currently, most anti-icing materials on the market are hydrophobic anti-icing materials with micro-nano structures, which can reduce the chance of water contacting the surface but cannot completely prevent ice formation. The anti-icing effect will be lost after the micro-nano structure is worn and damaged during the freeze-thaw cycle. Summary of the invention

[0005] The purpose of the present invention is to provide a method for preparing an intelligent anti-icing coating, so as to solve the problem that the existing anti-icing coating is easily damaged and fails in freeze-thaw cycles under complex environmental changes.

[0006] In order to achieve the above object, the technical solution adopted by the present invention is:

[0007] A method for preparing an intelligent anti-icing material comprises the following steps:

[0008] Step 1: Preparation of humidity-responsive precursor of intelligent anti-icing material:

[0009] Step 1.1, adding quaternized chitosan to deionized water, heating in a water bath and stirring to dissolve, to obtain a quaternized chitosan solution;

[0010] Step 1.2, the quaternized chitosan solution obtained in step 1.1 is mixed and stirred evenly with E44 epoxy resin to obtain a humidity-responsive precursor of an intelligent anti-icing material;

[0011] Step 2: Preparation of intelligent anti-icing material oil storage functional precursor:

[0012] Add PDMS prepolymer A and porous SiO2 nanoparticles into silicone oil and stir evenly to obtain the smart anti-icing material oil storage functional precursor;

[0013] Step 3, constructing a hydrophilic-hydrophobic amphiphilic porous structure:

[0014] After evenly mixing the humidity-responsive precursor of the smart anti-icing material prepared in step 1 and the oil-storage functional precursor of the smart anti-icing material prepared in step 2, add amine curing agent T31, PDMS curing agent B and cross-linking agent, stir evenly, cross-link and cure, and obtain the smart anti-icing material.

[0015] Furthermore, in step 1.1, the mass ratio of the quaternized chitosan to deionized water is 4-7:100, the water bath heating temperature is 70-90° C., and the heating stirring time is 2-3 h.

[0016] Furthermore, the mass ratio of the quaternized chitosan solution to the E44 epoxy resin in step 1.2 is 30:50-70.

[0017] Furthermore, in step 2, the mass ratio of the PDMS prepolymer A, porous SiO2 nanoparticles and silicone oil is 10:2-5:50-80.

[0018] Furthermore, in step 3, the mass ratio of the PDMS curing agent B, the amine curing agent T31 and the cross-linking agent is 1:12-18:2-3.

[0019] Furthermore, the cross-linking agent in step 3 is one of isophorone diisocyanate and toluene diisocyanate.

[0020] Furthermore, in step 3, the cross-linking curing temperature is 50-80° C. and the time is 10-18 hours.

[0021] The intelligent anti-icing material is prepared according to the above-mentioned method for preparing an intelligent anti-icing material.

[0022] Compared with the prior art, the present invention has the following beneficial effects:

[0023] 1. The quaternized chitosan in the present invention retains some hydroxyl groups after cross-linking with the cross-linking agent, and has excellent water absorption. Before the arrival of rainy and snowy weather, as the environmental humidity increases, the material absorbs water and expands in volume to generate internal stress, squeeze the voids in the material, and release the silicone oil stored in the porous SiO2 and PDMS to form a uniform lubricating layer on the surface. The silicone oil lubricating layer isolates the liquid from the surface, and the smooth surface greatly reduces the ice nucleation sites, inhibits the nucleation of ice crystals, maintains excellent hydrophobicity under low temperature and high humidity conditions, and has excellent anti-icing ability. When the ambient temperature rises and the humidity decreases, the water in the coating evaporates, the material shrinks and the pores become larger, and the silicone oil refluxes and is stored inside the material under the adsorption of PDMS and porous SiO2. In the freeze-thaw cycle, the loss of silicone oil is reduced, the service life of the lubricating layer is extended, and the effect of intelligent anti-icing is achieved.

[0024] 2. In the present invention, component A contains quaternized chitosan as a hydrophilic group, and component B contains PDMS as a hydrophobic group. The two are combined to form an amphiphilic surface with alternating hydrophilic and hydrophobic properties, so that the coating has a high contact angle and high contact angle hysteresis. An energy barrier exists at the front of the droplet, which destroys the continuity of the liquid on the material surface and inhibits the spread of ice on the material surface.

[0025] 3. In the present invention, quaternized chitosan is used to undergo a cross-linking reaction with the amino group and the hydroxyl group in the isocyanate to generate a substituted urea, and E44 epoxy resin is added to improve the durability of the material. DETAILED DESCRIPTION

[0026] The present invention is further described in detail below in conjunction with specific implementation modes.

[0027] A method for preparing an intelligent anti-icing material comprises the following steps:

[0028] Step 1: Preparation of humidity-responsive precursor of intelligent anti-icing material:

[0029] Step 1.1, adding quaternized chitosan to deionized water, the mass ratio of quaternized chitosan to deionized water being 4-7:100, heating in a water bath at 70-90° C. with stirring for 2-3 h to obtain a quaternized chitosan solution;

[0030] Step 1.2, mixing the quaternized chitosan solution obtained in step 1.1 and the E44 epoxy resin in a mass ratio of 30:50-70 and stirring evenly to obtain a humidity-responsive precursor of an intelligent anti-icing material;

[0031] Step 2: Preparation of intelligent anti-icing material oil storage functional precursor:

[0032] Add PDMS prepolymer A and porous SiO2 nanoparticles into silicone oil and stir evenly to obtain a precursor of the intelligent anti-icing material with oil storage function, wherein the mass ratio of PDMS prepolymer A, porous SiO2 nanoparticles and silicone oil is 10:2-5:50-80;

[0033] Step 3, constructing a hydrophilic-hydrophobic amphiphilic porous structure:

[0034] After evenly mixing the humidity-responsive precursor of the smart anti-icing material prepared in step 1 and the oil-storage functional precursor of the smart anti-icing material prepared in step 2, add amine curing agent T31, PDMS curing agent B and cross-linking agent, stir evenly, cross-link and cure, and obtain the smart anti-icing material.

[0035] The mass ratio of PDMS curing agent B, amine curing agent T31 and isophorone diisocyanate is 1:12-18:2-3;

[0036] The cross-linking agent is one of isophorone diisocyanate and toluene diisocyanate;

[0037] The cross-linking curing temperature is 50-80°C and the time is 10-18h.

[0038] The present invention constructs an intelligent anti-icing material with a hydrophilic-hydrophobic amphiphilic porous structure, uses cross-linked quaternary ammonium chitosan as an intelligent humidity-responsive power driving material, and uses PDMS, porous SiO2 and silicone oil as oil storage functional materials. The two work synergistically to achieve controlled release of the silicone oil lubricating layer. The addition of E44 epoxy resin significantly improves the durability of the material, thereby solving the problem that the existing anti-icing coating is easily damaged and fails in freeze-thaw cycles under complex environmental changes.

[0039] Example 1

[0040] Add 1.15g of quaternized chitosan to 28.85ml of deionized water, heat in a water bath at 70℃ and stir for 2h, then add 50ml of E44 epoxy resin and mix well to obtain a humidity-responsive precursor of the intelligent anti-icing material; add 10g of PDMS prepolymer A and 2g of porous SiO2 nanoparticles to 50g of silicone oil and stir well to obtain an oil-storage functional precursor of the intelligent anti-icing material; mix the prepared humidity-responsive precursor of the intelligent anti-icing material and the oil-storage functional precursor of the intelligent anti-icing material evenly, then add 12g of amine curing agent T31, 1g of PDMS curing agent B and 2g of isophorone diisocyanate and stir well, cross-link and cure at 50℃ for 18h to obtain the intelligent anti-icing material.

[0041] Example 2

[0042] 1.96g of quaternized chitosan was added to 28.04ml of deionized water, heated in a water bath at 90°C and stirred for 3h, and then 70ml of E44 epoxy resin was added and mixed and stirred evenly to obtain a humidity-responsive precursor of the intelligent anti-icing material; 10g of PDMS prepolymer A and 5g of porous SiO2 nanoparticles were added to 80g of silicone oil and stirred evenly to obtain an oil-storage functional precursor of the intelligent anti-icing material; the humidity-responsive precursor of the intelligent anti-icing material and the oil-storage functional precursor of the intelligent anti-icing material were mixed evenly, and then 18g of amine curing agent T31, 1g of PDMS curing agent B and 3g of isophorone diisocyanate were added and stirred evenly, and cross-linked and cured at 80°C for 10h to obtain the intelligent anti-icing material.

[0043] Example 3

[0044] Add 1.4g of quaternized chitosan to 28.6ml of deionized water, heat in a water bath at 80℃ and stir for 2.5h, then add 60ml of E44 epoxy resin and mix well to obtain a humidity-responsive precursor of the intelligent anti-icing material; add 10g of PDMS prepolymer A and 3.5g of porous SiO2 nanoparticles to 65g of silicone oil and stir well to obtain an oil-storage functional precursor of the intelligent anti-icing material; mix the obtained humidity-responsive precursor of the intelligent anti-icing material and the oil-storage functional precursor of the intelligent anti-icing material, then add 15g of amine curing agent T31, 1g of PDMS curing agent B and 2.25g of isophorone diisocyanate and stir well, cross-link and cure at 65℃ for 14h to obtain the intelligent anti-icing material.

[0045] Example 4

[0046] Add 1.6g of quaternized chitosan to 28.4ml of deionized water, heat in a water bath at 75°C and stir for 2.7h, then add 65ml of E44 epoxy resin and mix well to obtain a humidity-responsive precursor of the intelligent anti-icing material; add 10g of PDMS prepolymer A and 3g of porous SiO2 nanoparticles to 60g of silicone oil and stir well to obtain an oil-storage functional precursor of the intelligent anti-icing material; mix the obtained humidity-responsive precursor of the intelligent anti-icing material and the oil-storage functional precursor of the intelligent anti-icing material evenly, then add 16g of amine curing agent T31, 1g of PDMS curing agent B and 2.5g of isophorone diisocyanate and stir well, cross-link and cure at 70°C for 13h to obtain the intelligent anti-icing material.

[0047] Example 5

[0048] Add 1.8g of quaternized chitosan to 28.2ml of deionized water, heat in a water bath at 85°C and stir for 2.4h, then add 55ml of E44 epoxy resin and mix well to obtain a humidity-responsive precursor of the intelligent anti-icing material; add 10g of PDMS prepolymer A and 4g of porous SiO2 nanoparticles to 70g of silicone oil and stir well to obtain an oil-storage functional precursor of the intelligent anti-icing material; mix the obtained humidity-responsive precursor of the intelligent anti-icing material and the oil-storage functional precursor of the intelligent anti-icing material, then add 14g of amine curing agent T31, 1g of PDMS curing agent B and 2.75g of isophorone diisocyanate and stir well, cross-link and cure at 55°C for 17h to obtain the intelligent anti-icing material.

[0049] Example 6

[0050] Add 1.3g of quaternized chitosan to 28.7ml of deionized water, heat in a water bath at 70℃ and stir for 3h, then add 67ml of E44 epoxy resin and mix well to obtain a humidity-responsive precursor of the intelligent anti-icing material; add 10g of PDMS prepolymer A and 2.5g of porous SiO2 nanoparticles to 55g of silicone oil and stir well to obtain an oil-storage functional precursor of the intelligent anti-icing material; mix the obtained humidity-responsive precursor of the intelligent anti-icing material and the oil-storage functional precursor of the intelligent anti-icing material, then add 17g of amine curing agent T31, 1g of PDMS curing agent B and 2.15g of toluene diisocyanate and stir well, cross-link and cure at 75℃ for 12h to obtain the intelligent anti-icing material.

[0051] Example 7

[0052] Add 1.9g of quaternized chitosan to 28.1ml of deionized water, heat in a water bath at 90℃ and stir for 2h, then add 52ml of E44 epoxy resin and mix well to obtain a humidity-responsive precursor of the intelligent anti-icing material; add 10g of PDMS prepolymer A and 4.5g of porous SiO2 nanoparticles to 75g of silicone oil and stir well to obtain an oil-storage functional precursor of the intelligent anti-icing material; mix the obtained humidity-responsive precursor of the intelligent anti-icing material and the oil-storage functional precursor of the intelligent anti-icing material evenly, then add 13g of amine curing agent T31, 1g of PDMS curing agent B and 2.9g of toluene diisocyanate and stir well, cross-link and cure at 60℃ for 15h to obtain the intelligent anti-icing material.

[0053] The above description of the present invention is only a partial embodiment, but the present invention is not limited to the above embodiment. The above embodiment is illustrative and not restrictive. All specific extensions of the materials and methods of the present invention, without departing from the scope of protection of the present invention and the claims, are within the scope of protection of the present invention.

Claims

1. A method for preparing an intelligent anti-icing material, characterized in that: The specific steps include: Step 1: Preparation of humidity-responsive precursor of intelligent anti-icing material: Step 1.1, adding quaternized chitosan to deionized water, heating in a water bath and stirring to dissolve, to obtain a quaternized chitosan solution; Step 1.2, the quaternized chitosan solution obtained in step 1.1 is mixed and stirred evenly with E44 epoxy resin to obtain a humidity-responsive precursor of an intelligent anti-icing material; Step 2: Preparation of intelligent anti-icing material oil storage functional precursor: PDMS prepolymer A and porous SiO2 nanoparticles are added into silicone oil and stirred evenly to obtain a precursor of the smart anti-icing material with oil storage function; Step 3, constructing a hydrophilic-hydrophobic amphiphilic porous structure: After evenly mixing the humidity-responsive precursor of the smart anti-icing material prepared in step 1 and the oil-storage functional precursor of the smart anti-icing material prepared in step 2, add amine curing agent T31, PDMS curing agent B and cross-linking agent, stir evenly, cross-link and cure, and obtain the smart anti-icing material.

2. The method for preparing an intelligent anti-icing material according to claim 1, characterized in that: The mass ratio of the quaternized chitosan and deionized water in step 1.1 is 4-7:100, the water bath heating temperature is 70-90° C., and the heating stirring time is 2-3 h.

3. The method for preparing an intelligent anti-icing material according to claim 1, characterized in that: The mass ratio of the quaternized chitosan solution to the E44 epoxy resin in step 1.2 is 30:50-70.

4. The method for preparing an intelligent anti-icing material according to claim 1, characterized in that: The mass ratio of the PDMS prepolymer A, porous SiO2 nanoparticles and silicone oil in step 2 is 10:2-5:50-80.

5. The method for preparing an intelligent anti-icing material according to claim 1, characterized in that: The mass ratio of the PDMS curing agent B, the amine curing agent T31 and the cross-linking agent in the step 3 is 1:12-18:2-3.

6. The method for preparing an intelligent anti-icing material according to claim 1, characterized in that: The cross-linking agent in step 3 is one of isophorone diisocyanate and toluene diisocyanate.

7. The method for preparing an intelligent anti-icing material according to claim 1, characterized in that: In step 3, the cross-linking curing temperature is 50-80°C and the time is 10-18h.

8. An intelligent anti-icing material prepared according to the method for preparing an intelligent anti-icing material according to claims 1-7.