Biomass-based anti-icing coating with photothermal effect and preparation method thereof

Abstract

The application discloses a biomass-based anti-icing coating with a photo-thermal effect and a preparation method thereof. The coating is composed of A component and B component with a mass ratio of 1: (0.4-0.6). The A component is made of raw materials with the following mass fractions: 60-75% of hydrogenated bisphenol A type epoxy resin, 5-20% of carbonized nanocellulose, 5-20% of silane-modified nanocellulose and 2-10% of an additive. The B component is an amino polysiloxane resin. The coating has good artificial weathering resistance, a higher temperature rise range, a longer droplet freezing time and better hydrophobicity under the same conditions by adding the carbonized nanocellulose and the silane-modified nanocellulose.

Description

Technical Field

[0001] This invention belongs to the field of chemical materials technology, specifically relating to a biomass-based anti-icing coating with photothermal effect and its preparation method. Background Technology

[0002] Currently, researchers have developed many anti-icing coatings, most of which are based on principles such as micro / nano structures, superhydrophobic surfaces, photothermal effects, and electrothermal de-icing. However, several problems still exist. Under extreme conditions, superhydrophobic surfaces based on micro / nano structures are easily occupied by ice, causing the surface to lose its superhydrophobic properties and thus its protective performance. Anti-icing coatings based on photothermal effects are greatly affected by weather conditions and have poor sustained anti-icing effects. Anti-icing coatings based on the addition of hydrophobic fillers have fillers that are mostly inside the matrix, resulting in limited hydrophobic properties. Furthermore, many coatings use environmentally unfriendly raw materials, posing certain environmental hazards.

[0003] Patent document CN111019485A discloses a method for preparing a friction-resistant anti-icing coating, which uses fluorinated siloxane to hydrophobically modify nano-silica particles and uses epoxy resin as the matrix resin. However, this document only modifies the filler, resulting in limited hydrophobic properties and only delaying the icing process, with poor sustained anti-icing effect.

[0004] Patent document CN115595023A discloses an anti-icing coating for power transmission lines and its preparation method. An insulating-anti-corrosion inner coating and a photothermal-electrothermal-superhydrophobic outer coating are sequentially attached to the surface of the power transmission line substrate to achieve the anti-icing effect. However, the multi-layer structure in this document presents complex preparation processes and difficulties in application.

[0005] Patent document CN113667400A discloses an anti-icing and de-icing coating with both photothermal and self-cleaning properties, and its preparation method, which achieves photothermal synergy by adding hydrophobically modified carbon nanotubes. However, this document only modifies the filler, resulting in limited hydrophobic properties.

[0006] Patent document CN113528010A discloses the preparation and application of a super-slippery coating with long-lasting anti-icing properties. It employs a two-layer anti-icing structure: the upper layer is a cross-linked polymer containing anti-icing agent molecules with a smooth surface, and the lower layer is a porous structure storing the anti-icing agent. However, the multi-layer structure in this document presents complex preparation processes and difficulties in application.

[0007] Patent document CN111548730A discloses an anti-icing coating suitable for power grid equipment, its preparation method, and its application. It uses nanocomposite powder as pigment and leverages synergistic optical enhancement to prevent icing and facilitate de-icing. However, this document contains a high solvent content, which does not meet future environmental protection requirements.

[0008] Patent document CN110804395A discloses an anti-icing coating, an anti-icing material, and a method for preparing the same, introducing the photothermal effect of iodine into the field of anti-icing. However, this document requires the substrate to be placed in iodine vapor for adsorption treatment, which is a complex process and not suitable for the superstructure of polar ships.

[0009] Patent document CN117229713A discloses an anti-icing coating for the surface of a power transmission line and its preparation method, which utilizes a lubricant to form a super-slippery surface to delay the freezing of droplets. However, in this document, the power transmission line needs to be dipped in a base coat and then sprayed with a top coat, which is a relatively complex process and is not suitable for the superstructure of polar ships.

[0010] Patent document CN110204902A discloses a flexible, bendable, actively de-icing superhydrophobic anti-icing composite material, its preparation method, and its application, which is prepared from a room temperature vulcanizing liquid silicone rubber matrix and micro / nano materials. However, the silicone rubber in this document may suffer from embrittlement in polar environments and is prone to cracking.

[0011] Patent document CN109486269A discloses a superhydrophobic anti-icing coating, coating, and its preparation and application for active photothermal de-icing. It mainly consists of silicon carbide micropowder, carbon nanotubes, binder, hydrophobic agent, and solvent, which prolongs the freezing time of supercooled droplets and reduces surface adhesion to ice. However, the adhesion between the coating and the substrate in this document needs improvement, and the binder may experience embrittlement in polar environments.

[0012] Patent document CN112724830A discloses a superhydrophobic, antifouling, and anti-icing waterborne coating, mainly composed of surface-grafted fluoride nano-silica, perfluorodecyltrimethoxysilane, carbon microspheres, modified graphene, binder, and solvent, which prolongs the freezing time of water droplets on the coating surface. However, this document only modifies the filler, resulting in limited hydrophobic properties.

[0013] Patent document CN114231113A discloses a photothermal hydrophobic anti-icing and anti-dropping coating material, its preparation and application, comprising modified acrylic resin, hydrophobic particles and photothermal conversion particles, exhibiting good adhesion and anti-dropping properties, superhydrophobicity and photothermal characteristics. However, the coating in this document has a lower ability to cause droplets to detach on their own, and the photothermal conversion particles are mostly located inside the coating, resulting in a less pronounced photothermal effect.

[0014] Patent document CN114058227A discloses a method for preparing a fluorine-free, wear-resistant, superhydrophobic, and anti-icing coating with photothermal effect. The method involves spraying a nanoparticle composite suspension obtained by blending carbon nanotubes, hydrophobic nano-silica, a resin binder, a silane coupling agent, and a solvent onto the surface of a substrate. However, this document only modifies some of the fillers to be hydrophobic, resulting in limited hydrophobic properties.

[0015] Patent document CN114350259A discloses a biomass-based multifunctional photothermal protective coating and its preparation method, which involves calcining cellulose in a tube furnace to obtain carbonized hollow microtubes, then dispersing them in an organic solvent, adding a certain amount of thermosetting resin and curing agent, and then spraying or dipping them in. However, this document only carbonizes the cellulose without performing additional hydrophobic modification, resulting in limited hydrophobic properties.

[0016] Patent document CN115160857A discloses a passive photothermal de-icing superhydrophobic anti-icing coating, its preparation method, and its application. Ethyl cellulose, ZIF-8 derived hollow porous carbon fibers, and sodium chloride are sprayed as the base layer, and fluorinated silica is sprayed as the surface layer. Sodium chloride lowers the freezing point of water droplets, improving the anti-icing performance of the coating surface. However, the process in this document is relatively complex and not suitable for the superstructure of polar vessels.

[0017] Patent document CN114181614A discloses a MOF-based photothermal de-icing coating and its preparation method, which involves mixing crystalline powder with polydimethylsiloxane and then spraying it to extend the freezing time by utilizing the heat energy from photothermal conversion. However, the silicone rubber in this document may suffer from embrittlement in polar environments and is prone to cracking.

[0018] The literature [Lan Xijian, Zhang Xin, et al. Preparation and performance evaluation of high-strength, tough, and wear-resistant ice-breaking coating at low temperatures in polar regions [J]. Surface Technology, 2022, (6): 59-66.] uses hydrogenated epoxy resin and amino organosilicon curing agent as the base material. During the cross-linking and curing of the coating, the soft and hard block structure is formed by the action of Si=C and Si-O-Si bonds, which effectively improves the low-temperature brittleness of epoxy resin and reduces surface tension. High-hardness inorganic powders such as KH560 modified silicon carbide and basalt, and aggregates such as flexible drag-reducing polytetrafluoroethylene powder are fully and evenly dispersed in the base material to prepare a high-strength, tough, and wear-resistant ice-breaking coating at low temperatures in polar regions. The wear-resistant filler added in this literature can provide wear resistance when colliding with ice in the ice-breaking zone coating, but the hydrophobic properties provided by the base resin and polytetrafluoroethylene powder are limited (static contact angle of about 100°), which is not suitable for areas such as the superstructure of polar ships, where the requirements for hydrophobic and anti-icing properties are higher.

[0019] The literature [Sun Shibin, Shi Changwei, et al. Study on low-temperature wear and corrosion resistance of novel epoxy-based icebreaking coatings for polar ships [J]. Chinese Journal of Corrosion and Protection, 2024, 1-16.] uses modified basalt powder and mica powder as fillers, and hydrogenated epoxy resin and amino silicone curing agent as base materials. The hard fillers (mica powder and basalt powder) provide good wear resistance, but the static contact angle performance of the coating provided by polytetrafluoroethylene powder and matrix resin is very limited, and the hydrophobicity is insufficient, which cannot meet the requirements of anti-icing. Summary of the Invention

[0020] To address the need for anti-icing measures on exposed surfaces of polar vessels during navigation, this invention aims to provide a biomass-based anti-icing coating with photothermal effects and its preparation method. The prepared coating can be used on surfaces such as superstructures of polar vessels. The anti-icing coating is prepared by carbonization and hydrophobic modification of biomass biodegradable materials. In extreme environments, the superhydrophobic effect and photothermal effect work synergistically to prevent ice and snow adhesion. Furthermore, this invention is a solvent-free coating, and the raw material is biomass biodegradable material, meeting the requirements of green environmental protection and sustainable development.

[0021] To achieve the above objectives, the technical solution adopted by the present invention is as follows: The photothermal biomass-based anti-icing coating of the present invention comprises component A and component B in a mass ratio of 1:(0.4-0.6), characterized in that component A is made from raw materials comprising the following mass fractions: 60%-75% hydrogenated bisphenol A type epoxy resin, 5%-20% carbonized nanocellulose, 5%-20% silane-modified nanocellulose, and 2%-10% additives; component B is aminopolysiloxane resin; The hydrogenated bisphenol A type epoxy resin has a viscosity of 2000-5000 mPa·s and an epoxy equivalent of 200-240 g / eq, such as EPONEX1510 produced by Hexion Corporation of the United States, Sep-40E produced by Shanghai Bohuai Chemical Co., Ltd., TaiLuck-ST3000 produced by Toto Chemical Co., Ltd. of Japan, and CYDH3000 produced by Baling Petrochemical, etc. The additive is at least one of polyamide wax, polyethylene glycol, ethylene glycol butyl ether acetate, fluorinated polysiloxane, BYK306 leveling agent, BYK066 defoamer, BYK530 defoamer, and BYK054 defoamer. The aminopolysiloxane resin has a viscosity of 100-400 mPa·s and an amine hydrogen equivalent of 230-255 g / eq, such as SILRES HP2000 and HP2020 produced by Wacker Chemie GmbH in Germany, and LK-536 produced by Guangzhou Longkai Chemical Co., Ltd. The preparation method of the carbonized nanocellulose includes the following steps: placing nanocellulose powder into a tube furnace, heating it to 350°C at a certain heating rate, and holding it at that temperature for 0.5 to 2 hours; continuing to heat it to 700°C and holding it at that temperature for 0.5 to 3 hours; and naturally cooling it to room temperature to obtain carbonized nanocellulose. The nanocellulose has a diameter of 4–50 nm and a length of 0.2–5 μm.

[0022] Preferably, the heating rate is 2 to 5 °C / min.

[0023] The preparation method of the silane-modified nanocellulose includes the following steps: S1, placing nanocellulose powder into a sealable container, and then placing two open bottles containing methyltrimethoxysilane and deionized water respectively into the sealable container; sealing the sealable container, and then reacting at 70-105℃ for 2-10 hours; S2, taking out the solid powder and drying it in a vacuum drying oven to obtain silane-modified nanocellulose; The ratio of the mass of the nanocellulose, the volume of methyltrimethoxysilane, and the volume of deionized water is 3g:1mL:(1-3)mL.

[0024] Preferably, the nanocellulose has a diameter of 4–50 nm and a length of 0.2–5 μm; Preferably, in step S2, the drying temperature is 60-80°C and the drying time is 12-24 hours.

[0025] The preparation method of the biomass-based anti-icing coating with photothermal effect of the present invention includes the following steps: mixing the hydrogenated bisphenol A type epoxy resin, carbonized nanocellulose, silane-modified nanocellulose and additives, stirring at room temperature for 1 to 4 hours to obtain component A; then mixing component A and component B, stirring at room temperature for 0.2 to 0.5 hours to obtain the final product.

[0026] Compared with the prior art, the beneficial effects of the present invention are: This invention uses hydrogenated bisphenol A type epoxy resin, which has good weather resistance at low temperatures, as the base resin. It is cured with amino polysiloxane resin, improving the low-temperature toughness of the coating. Simultaneously, the low surface energy effect of the organosilicon resin effectively increases the contact angle and reduces ice and snow adhesion. Furthermore, it incorporates carbonized nanocellulose with photothermal effects and silane-modified nanocellulose fillers with superhydrophobic effects to construct a nanostructure with superhydrophobic properties. The synergistic effect of photothermal and superhydrophobic properties enhances anti-icing performance. Applied to the field of polar ship protection, this invention prepares a biomass-based anti-icing coating with photothermal effects, exhibiting excellent adhesion, abrasion resistance, and anti-icing properties. The preparation method is simple, and it is a solvent-free coating, making it more environmentally friendly. Detailed Implementation

[0027] Those skilled in the art should recognize that this embodiment is only used to illustrate the present invention and is not intended to limit the present invention. Any changes or modifications to the embodiment within the scope of the present invention are within the scope of the claims of the present invention.

[0028] Example 1 The preparation method of carbonized nanocellulose includes the following steps: 6g of nanocellulose powder (diameter of 10-30nm and length of 0.2-5μm) is placed in a tube furnace and heated to 350℃ at a heating rate of 2℃ / min and held for 1h; then heated to 700℃ at a heating rate of 5℃ / min and held for 1h; after the holding period, it is naturally cooled to room temperature to obtain carbonized nanocellulose.

[0029] Example 2 The preparation method of carbonized nanocellulose includes the following steps: 6g of nanocellulose powder (diameter of 10-30nm and length of 0.2-5μm) is placed in a tube furnace and heated to 350℃ at a heating rate of 5℃ / min, and held at that temperature for 0.5h; then heated to 700℃ at a heating rate of 3℃ / min, and held at that temperature for 1h; after the holding time is completed, it is naturally cooled to room temperature to obtain carbonized nanocellulose.

[0030] Example 3 The preparation method of silane-modified nanocellulose includes the following steps: S1, 6g of nanocellulose powder is placed in a wide-mouth glass bottle, and then two open-mouth glass vials containing 2mL of methyltrimethoxysilane and 2mL of deionized water are placed in the wide-mouth glass bottle respectively. The wide-mouth glass bottle is sealed and then placed at 75℃ for 6h to carry out silanization modification by gas phase precipitation; S2, after the reaction is completed, the solid powder is taken out and dried in a vacuum drying oven at 60℃ for 24h to obtain silane-modified nanocellulose.

[0031] Example 4 The preparation method of silane-modified nanocellulose includes the following steps: S1, 9g of nanocellulose powder is placed in a wide-mouth glass bottle, and then two open-mouth glass vials containing 3mL of methyltrimethoxysilane and 6mL of deionized water are placed in the wide-mouth glass bottle respectively. The wide-mouth glass bottle is sealed and then placed in an oven at 105℃ for 2h to carry out silanization modification by gas phase precipitation; S2, after the reaction is completed, the solid powder is taken out and dried in a vacuum drying oven at 60℃ for 24h to obtain silane-modified nanocellulose.

[0032] Example 5 The biomass-based anti-icing coating with photothermal effect is composed of component A and component B in a mass ratio of 1:0.5. Component A includes the following components in mass fractions: 65% hydrogenated bisphenol A type epoxy resin TaiLuck-ST3000, 15% carbonized nanocellulose prepared in Example 1, 15% silane-modified nanocellulose prepared in Example 3, and 5% additives (BYK306 leveling agent and BYK066 defoamer in a mass ratio of 1:1). Component B is aminopolysiloxane resin SILRES HP2000.

[0033] The preparation method of the anti-icing coating includes the following steps: (1) mixing hydrogenated bisphenol A type epoxy resin, carbonized nanocellulose, silane modified nanocellulose and additives in component A and stirring at room temperature for 2 hours; (2) mixing component A and component B in proportion and stirring at room temperature for 0.5 hours to obtain a biomass-based anti-icing coating with photothermal effect.

[0034] Example 6 The biomass-based anti-icing coating with photothermal effect is composed of component A and component B in a mass ratio of 1:0.4. Component A includes the following components by mass fraction: 65% hydrogenated bisphenol A type epoxy resin CYDH3000, 10% carbonized nanocellulose prepared in Example 1, 20% silane-modified nanocellulose prepared in Example 3, and 5% additives (organosilicon); component B is aminopolysiloxane resin LK-536.

[0035] The preparation method of the anti-icing coating includes the following steps: (1) mixing hydrogenated bisphenol A type epoxy resin, carbonized nanocellulose, silane modified nanocellulose and additives in component A and stirring at room temperature for 3 hours; (2) mixing component A and component B in proportion and stirring at room temperature for 0.5 hours to obtain a biomass-based anti-icing coating with photothermal effect.

[0036] Example 7 The biomass-based anti-icing coating with photothermal effect is composed of component A and component B in a mass ratio of 1:0.5. Component A includes the following components in mass fractions: 65% hydrogenated bisphenol A type epoxy resin 5001, 15% carbonized nanocellulose prepared in Example 1, 15% silane-modified nanocellulose prepared in Example 3, and 5% additives (BYK306 leveling agent and BYK066 defoamer in a mass ratio of 1:1). Component B is aminopolysiloxane resin SILRES HP 2020.

[0037] The preparation method of the anti-icing coating includes the following steps: (1) mixing hydrogenated bisphenol A type epoxy resin, carbonized nanocellulose, silane modified nanocellulose and additives in component A and stirring at room temperature for 3 hours; (2) mixing component A and component B in proportion and stirring at room temperature for 0.5 hours to obtain a biomass-based anti-icing coating with photothermal effect.

[0038] Comparative Example 1 Comparative Example 1 is a comparative example of Example 5. The formulation and preparation method are the same, except that carbonized nanocellulose is replaced with nanocellulose.

[0039] Comparative Example 2 Comparative Example 2 is a comparative example of Example 5. The formulation and preparation method are the same, except that the silane-modified nanocellulose is replaced with nanocellulose.

[0040] Experimental Example 1 The coatings prepared in Examples 5-7 and Comparative Examples 1-2 were subjected to performance tests.

[0041] Table 1 Performance test results of coatings in Examples 5-7 and Comparative Examples 1-2 The results shown in Table 1 indicate that the coatings prepared in Examples 5-7 possess excellent properties such as resistance to artificial weathering and delayed droplet freezing. Compared to Comparative Example 1, the carbonized nanocellulose in Example 5 exhibits a certain photothermal conversion effect, resulting in a higher temperature rise and a longer droplet freezing time under the same conditions. Compared to Comparative Example 2, the silane-modified nanocellulose demonstrates superhydrophobicity, giving Example 5 better hydrophobicity under the same conditions.

Claims

1. A biomass-based anti-icing coating with photothermal effect, comprising component A and component B in a mass ratio of 1:(0.4-0.6), characterized in that, Component A is made from the following raw materials in the indicated mass fractions: 60%–75% hydrogenated bisphenol A type epoxy resin, 5%–20% carbonized nanocellulose, 5%–20% silane-modified nanocellulose, and 2%–10% additives; Component B is an aminopolysiloxane resin. The hydrogenated bisphenol A type epoxy resin has a viscosity of 2000-5000 mPa·s and an epoxy equivalent of 200-240 g / eq; the amino polysiloxane resin has a viscosity of 100-400 mPa·s and an amine hydrogen equivalent of 230-255 g / eq. The preparation method of the biomass-based anti-icing coating includes the following steps: mixing the hydrogenated bisphenol A type epoxy resin, carbonized nanocellulose, silane-modified nanocellulose and additives, stirring at room temperature for 1 to 4 hours to obtain component A; then mixing component A and component B, stirring at room temperature for 0.2 to 0.5 hours to obtain the final product.

2. The biomass-based anti-icing coating according to claim 1, characterized in that, The additive is at least one of polyamide wax, polyethylene glycol, ethylene glycol butyl ether acetate, fluorinated polysiloxane, BYK306 leveling agent, BYK066 defoamer, BYK530 defoamer, and BYK054 defoamer.

3. The biomass-based anti-icing coating according to claim 1, characterized in that, The preparation method of the carbonized nanocellulose includes the following steps: placing nanocellulose powder into a tube furnace, heating it to 350°C at a certain heating rate, and holding it at that temperature for 0.5 to 2 hours; continuing to heat it to 700°C and holding it at that temperature for 0.5 to 3 hours; and naturally cooling it to room temperature to obtain carbonized nanocellulose.

4. The biomass-based anti-icing coating according to claim 3, characterized in that, The nanocellulose has a diameter of 4–50 nm and a length of 0.2–5 μm; the heating rate is 2–5 °C / min.

5. The biomass-based anti-icing coating according to claim 1, characterized in that, The preparation method of the silane-modified nanocellulose includes the following steps: S1, placing nanocellulose powder into a sealable container, and then placing two open bottles containing methyltrimethoxysilane and deionized water respectively into the sealable container; sealing the sealable container, and then reacting at 70-105℃ for 2-10 hours; S2, taking out the solid powder and drying it in a vacuum drying oven to obtain silane-modified nanocellulose.

6. The biomass-based anti-icing coating according to claim 5, characterized in that, The nanocellulose has a diameter of 4–50 nm and a length of 0.2–5 μm.

7. The biomass-based anti-icing coating according to claim 5, characterized in that, The ratio of the mass of the nanocellulose, the volume of methyltrimethoxysilane, and the volume of deionized water is 3g:1mL:(1-3)mL.

8. The biomass-based anti-icing coating according to claim 5, characterized in that, In step S2, the drying temperature is 60-80°C and the drying time is 12-24 hours.

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