Epoxy-based solvent-free low-adhesion easy-deicing coating as well as preparation method and application thereof

Abstract

The invention belongs to the technical field of protective paint in the electric power industry, and discloses an epoxy-group solvent-free low-adhesion easy-deicing coating and a preparation method and application thereof, the coating comprises a first paint component and a second paint component; the first coating component is prepared from the following raw materials in parts by weight: 80 to 110 parts of modified epoxy-based glue, 40 to 60 parts of epoxy-terminated polydimethylsiloxane, 50 to 100 parts of a lubricating agent, 10 to 15 parts of a modified reinforcing material and 20 to 30 parts of modified functional filler; and the second coating component is prepared from the following raw materials in parts by weight: 75-95 parts of a curing agent and 5-10 parts of a lubricating agent. According to the invention, hydrophobic, tackifying, anti-aging, filler and other components are introduced, so that the low-adhesion and easy-deicing coating which is low in surface ice adhesion, stable in structure, excellent in adhesive force and capable of being recoated is designed, and the comprehensive performance of the coating is improved.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of protective coatings in the power industry, in particular to an epoxy-based solvent-free low-adhesion easy-ice-shedding coating layer, a preparation method and application thereof. BACKGROUND

[0002] Icing and snow are very common natural phenomena, and there are many types, such as: glaze icing, mixed rime icing, ice fog icing, frost, snow, etc. Severe icing and snow phenomena can pose a certain threat and harm to social life. As a basic industry of the national economy and people's livelihood, the rapid development of the power industry, the safe operation of the power grid is particularly important, and the environment of the power transmission line is complex and diverse, which will be affected by various environmental factors, especially in cold winter, the power transmission line in high humidity and low temperature environment is prone to icing.

[0003] Anti-icing coating technology has the advantages of low energy consumption, environmental protection, economic value, etc., and is increasingly important. At present, there are many coating anti-icing technologies, among which super-hydrophobic coating technology is a widely used technology, but its surface structure is fragile and easily damaged, affecting the icing effect. Super-lubricating coating technology is a kind of biomimetic material based on natural pitcher plant, with micro-nano porous structure as the structure lock, and by filling the pore structure with hydrophobic liquid material in different ways, a surface coating with low adhesion is formed. Compared with the super-hydrophobic coating structure, the liquid-liquid contact mode is replaced by the gas-liquid contact mode.

[0004] At present, there are relevant patents and papers and other materials researching on such anti-icing coating. For example, application number CN202510415449.2 discloses a kind of anti-icing super-hydrophobic super-smooth nano coating material and its preparation method and application, but its preparation method is complex, the production cost is low in economy, and the ice shedding capacity is not specified; for example, application number CN202311213376.6 discloses a kind of hydrophobic lubricating type anti-icing coating, but the hydrophobic lubricating type anti-icing coating has poor adhesion to the base material of the power transmission line, and the coating is easy to fall off during application.

[0005] Therefore, in order to solve the problems of fragile surface structure, easy damage of super-hydrophobic anti-icing coating, poor adhesion to the base material (<5MPa) of super-hydrophobic super-smooth coating, poor weather resistance (500h coating easy to crack, easy to powder and fall off), strong ice adhesion (>5N), and low static contact angle (100°-110°), how to provide an epoxy-based solvent-free low-adhesion easy-ice-shedding coating layer, a preparation method and application thereof is a problem to be solved at present. SUMMARY

[0006] The epoxy-based solvent-free low-adhesion ice-shedding coating, the preparation method and the application thereof provided by the embodiments of the present application solve the problems of high energy consumption, low ice-removing efficiency, environmental pollution, easy damage to the structure, poor durability, poor post-icing prevention ability and the like of the active ice-removing mode and the super-hydrophobic coating ice-removing mode in the prior art.

[0007] According to a first aspect of the embodiments of the present application, the epoxy-based solvent-free low-adhesion ice-shedding coating is provided.

[0008] In one embodiment, the epoxy-based solvent-free low-adhesion ice-shedding coating comprises a first coating component and a second coating component, and the mass ratio of the first component to the second component is 2.5-3:1.

[0009] The first coating component is composed of the following raw materials in parts by weight:

[0010] The modified epoxy-based adhesive is 80-110 parts, the epoxy-terminated polydimethylsiloxane is 40-60 parts, the lubricant is 50-100 parts, the modified reinforcing material is 10-15 parts, and the modified functional filler is 20-30 parts.

[0011] The second coating component is composed of the following raw materials in parts by weight:

[0012] The curing agent is 75-95 parts, and the lubricant is 5-10 parts.

[0013] The coating introduces hydrophobic, tackifying, anti-aging, filler and other components, and designs a low-adhesion ice-shedding coating with low ice adhesion, stable structure, excellent adhesion and recoatability, and improves the comprehensive performance of the coating.

[0014] In one embodiment, the modified epoxy-based adhesive is a mixture of one or both of silane coupling agent modified bisphenol A type epoxy resin E44 (20-50 parts) and silane coupling agent modified bisphenol A type epoxy resin E51 (30-50 parts) and bisphenol F type epoxy resin F170 (30-50 parts) (purpose: the addition of bisphenol F type epoxy resin aims to improve the aging resistance of the adhesive; the application of bisphenol A type epoxy resin E44 and E51 aims to improve the adhesion performance of the adhesive; the purpose of silane modification is to improve the aging resistance and adhesion of the adhesive).

[0015] Preferably, the modified epoxy-based adhesive is a mixture of silane coupling agent modified bisphenol A type epoxy resin E44, silane coupling agent modified bisphenol A type epoxy resin E51 and bisphenol F type epoxy resin F170.

[0016] Preferably, the modified epoxy-based adhesive comprises 25 parts of silane coupling agent modified bisphenol A type epoxy resin E44, 35 parts of silane coupling agent modified bisphenol A type epoxy resin E51, and 40 parts of bisphenol F type epoxy resin F170.

[0017] In one embodiment, the modified epoxy-based adhesive is prepared by adding at least one of silane coupling agent modified bisphenol A type epoxy resin E44 and silane coupling agent modified bisphenol A type epoxy resin E51, and bisphenol F type epoxy resin F170 into a mixing bottle, mechanically stirring for 0.5 h, and then vacuum processing at 75°C for 1 h by a banbury mixer to remove moisture contained in the adhesive and prevent affecting the performance in the later stage.

[0018] In one embodiment, the silane coupling agent is a mixture of one or more of KH550, KH560, and KH570, wherein the amount of silane coupling agent for modified bisphenol A type epoxy resin E44 is 3-10 parts, and the amount of silane coupling agent for modified bisphenol A type epoxy resin E51 is 5-8 parts.

[0019] Preferably, the silane coupling agent is KH550, the amount of silane coupling agent for modified bisphenol A type epoxy resin E44 is 7 parts, and the amount of silane coupling agent for modified bisphenol A type epoxy resin E51 is 6 parts.

[0020] In one embodiment, the modification method of bisphenol A type epoxy resin is to heat the bisphenol A type epoxy resin to 75°C in a flask, then stir and flow, and after the temperature is stable, drop the silane coupling agent (0.06 parts each time), and the interval time between each drop is not less than 10 s (to ensure that the previous drop is mixed uniformly to avoid local concentration of silane coupling agent, affecting the overall modification effect).

[0021] In one embodiment, the terminal epoxy-based polydimethylsiloxane has a viscosity of 50 mPa-500 mPa and an epoxy value of 0.44 or 0.51.

[0022] Preferably, the terminal epoxy-based polydimethylsiloxane has a viscosity of 200 mPa, an amount of 55 parts, and an epoxy value of 0.51 (easy to apply, beneficial to the adhesion of the coating to the substrate, and poor compatibility to form micropores to facilitate the migration of silicone oil).

[0023] In one embodiment, the lubricant in the first coating component is the same as the lubricant in the second coating component, and is made of a mixture of one or more of dimethyl silicone oil (viscosity 5 mPa-1500 mPa), perfluoropolyether silicone oil (viscosity 5 mPa-1500 mPa), and methyl fluorosilicone oil (viscosity 5 mPa-1500 mPa).

[0024] Preferably, the lubricant is dimethyl silicone oil with a viscosity of 50 mPa, and the amount is 60 parts (cost-effective and technically economical, and migration rate is controllable).

[0025] In one embodiment, the modified reinforcing material is mesoporous silica (particle size of 2-5 μm, porosity greater than 85%) and modified chopped glass fiber (diameter of 5-13 μm, length of 1-4 mm), and the mass ratio of mesoporous silica to modified chopped glass fiber is 1:1-3.

[0026] Preferably, the mesoporous silica has a D50 test particle size of 3 μm, the modified chopped glass fiber has a diameter of 7 μm and a length of 2 mm, and the mass ratio of the two is 1:1.5, and the amount is 12 parts (the chopped fiber can form pores).

[0027] In one embodiment, the modification process of the modified chopped glass fiber is as follows: first, the chopped glass fiber is mixed with 0.1 moL / L sodium hydroxide solution at a mass fraction of 1:10 at 25-35°C, and then the temperature is raised to 80-95°C for stirring treatment for 1.5 h; then the hydroxylated chopped glass fiber is obtained by centrifugal deionized water washing and drying treatment in an 80°C oven for 24 h; then 1 part of the hydroxylated chopped glass fiber is mixed with 10 parts of a mixture of ethanol and n-butanol (ethanol:n-butanol=3:7), and then 0.1-0.3 parts of silane coupling agent KH560 is added dropwise, and heated to 115-125°C for stirring reaction for 6 h; after the reaction, the modified chopped glass fiber is obtained by centrifugal washing with ethanol, and then the modified chopped glass fiber is treated by freeze-drying before use.

[0028] In one embodiment, the modified functional filler is at least one of modified flake graphite (particle size of 10-25 μm) and modified sheet iron oxide black (particle size of 10-25 μm).

[0029] Preferably, the amount of the modified functional filler is 25 parts, the D50 test particle size of the modified flake graphite is 15 μm, and the D50 test particle size of the modified sheet iron oxide black is 20 μm, and the addition amount ratio of the two is 1:1.

[0030] In one embodiment, the modification process of the modified flake graphite is: first, mixing and stirring the flake graphite with 0.1 moL / L sodium hydroxide solution at a mass fraction of 1:5 at 25-35℃, then stirring and treating at 70-85℃ for 2h; then centrifugal deionized water washing to obtain hydroxylated flake graphite, drying treatment in an 80℃ oven for 24h; then mixing 1 part of the hydroxylated flake graphite with 15 parts of a mixture of ethanol and n-butanol (ethanol:n-butanol = 3:7), then adding 0.3-0.5 parts of silane coupling agent KH560 dropwise, heating to 100-110℃, stirring for 7h; after the reaction is completed, washing by centrifugal ethanol, and the obtained modified flake graphite is treated by freeze-drying, ready for use.

[0031] In one embodiment, the modification process of the modified flake graphite is: first, mixing and stirring the flake graphite with 0.1 moL / L sodium hydroxide solution at a mass fraction of 1:5 at 25-35℃, then stirring and treating at 70-85℃ for 2h; then centrifugal deionized water washing to obtain hydroxylated flake graphite, drying treatment in an 80℃ oven for 24h; then mixing 1 part of the hydroxylated flake graphite with 15 parts of a mixture of ethanol and n-butanol (ethanol:n-butanol = 3:7), then adding 0.3-0.5 parts of silane coupling agent KH560 dropwise, heating to 100-110℃, stirring for 7h; after the reaction is completed, washing by centrifugal ethanol, and the obtained modified flake graphite is treated by freeze-drying, ready for use.

[0032] In one embodiment, the curing agent is cashew shell oil modified amine epoxy curing agent, and the amine value of the cashew shell oil modified amine epoxy curing agent is 240-280mmg KOH / g, and the viscosity is 300-600mPa.

[0033] According to a second aspect of the embodiments of the present application, a preparation method of an epoxy-based solvent-free low-adhesion easy-to-ice-release coating is provided.

[0034] In one embodiment, the preparation method of the epoxy-based solvent-free low-adhesion easy-to-ice-release coating comprises:

[0035] S1, mixing a predetermined number of parts of modified reinforcing materials, lubricants and epoxy-based polydimethylsiloxane by mechanical stirring method to obtain a preliminary mixture, and placing the preliminary mixture under a predetermined negative pressure condition for pressure holding treatment to obtain a secondary mixture;

[0036] S2, mixing the secondary mixture with a predetermined number of parts of modified reinforcing materials, modified epoxy-based glue and modified functional fillers by mechanical stirring method to obtain a tertiary mixture, and treating the tertiary mixture by a three-roll mill to obtain a first coating component, ready for use;

[0037] S3, the curing agent of the preset number of parts is placed in a stirring bottle and heated to a preset temperature, and a lubricant is added after stirring, and continues to stir after warming, and is emulsified and mixed by using a shearing stirrer to obtain a second coating component;

[0038] S4, the first coating component and the second coating component are mixed according to a preset ratio, and an epoxy-based solvent-free low-adhesion ice-release coating is obtained after uniform stirring.

[0039] In one embodiment, in step S1, the pressure under the preset negative pressure condition is 0.08-0.15mpa, and the pressure holding time is 4-6h;

[0040] In step S2, the grinding number of the three-roll grinding machine is 3-5 times;

[0041] In step S3, the preset temperature is 70-90℃, the stirring time is 0.5-1.5h, the temperature after warming is 80-100℃, the continuous stirring time is 0.5-1.5h, and the emulsification and mixing time is 0.5-1.5h.

[0042] According to a third aspect of the embodiment of the present application, an application of an epoxy-based solvent-free low-adhesion ice-release coating is provided.

[0043] In one embodiment, the application of the epoxy-based solvent-free low-adhesion ice-release coating comprises:

[0044] The surface of the substrate is polished by using 200 mesh sandpaper, and the polished substrate surface is cleaned by using non-woven fabric or a brush;

[0045] The first coating component and the second coating component are mixed according to a preset ratio, and an epoxy-based solvent-free low-adhesion ice-release coating is obtained after uniform stirring.

[0046] The epoxy-based solvent-free low-adhesion ice-release coating is coated on the cleaned substrate surface by brushing, spraying or rolling, and the coating thickness is 50-120μm.

[0047] Preferably, the coating method is brushing, and the coating thickness is 80μm. Brushing is convenient to operate, simple to operate, and saves materials; an 80μm coating is more conducive to the protection of silicone oil migration, and early migration is prone to loss, and late migration is difficult to achieve, which affects the performance of the coating.

[0048] The technical scheme provided by the embodiment of the present application can include the following beneficial effects:

[0049] 1) The present application improves the adhesion performance of the epoxy-based coating to the base protective material, and reduces the surface energy of the epoxy resin, improves the aging resistance, thereby improving the service life and anti-icing performance of the coating; the addition of cashew nut shell oil modified amine epoxy curing agent further improves the adhesion performance, aging resistance and waterproof performance of the coating to the base; the addition of mesoporous silica improves the storage amount of lubricant in the coating system, and the short-cut fiber provides a lubricant migration channel, which helps to form a super-smooth surface and further reduces the adhesion of ice on the coating surface; the sheet material has the functions of ultraviolet isolation and heat absorption, which improves the service life of the coating and melts the ice layer on the contact surface between the ice and the base, further forms a lubricating layer, and improves the ice-shedding performance of the coating.

[0050] 2) The formula provided by the present application ensures easy construction without solvent addition, and is environmentally friendly; the modified epoxy-based glue has low viscosity and is easy to prepare a solvent-free coating, and has excellent adhesion to metal wires, ceramics or glass insulators; in addition, under the synergistic action of various raw materials and the control of the preparation process, the coating surface has excellent super-smooth, hydrophobic, ice-shedding, and liquid droplet cleaning processes, which ensures the safe operation of the power transmission line in winter.

[0051] It should be understood that the above general description and the following detailed description are only exemplary and explanatory, and cannot limit the present application. BRIEF DESCRIPTION OF DRAWINGS

[0052] The drawings incorporated into the specification and forming a part thereof, illustrate embodiments in accordance with the present application, and together with the description, serve to explain the principles of the application.

[0053] Figure 1 is a flow chart of a preparation method of an epoxy-based solvent-free low-adhesion ice-shedding coating according to an exemplary embodiment;

[0054] Figure 2 is a schematic diagram of a preparation method of an epoxy-based solvent-free low-adhesion ice-shedding coating according to an exemplary embodiment;

[0055] Figure 3 is a column chart of the adhesion of each prepared coating to the substrate in Example 1 and Comparative Examples 1-8 according to an exemplary embodiment;

[0056] Figure 4 is a column chart of the adhesion of each prepared coating to ice in Example 1 and Comparative Examples 1-8 according to an exemplary embodiment;

[0057] Figure 5is a bar chart showing the ice delay time of each prepared coating in Example 1 and Comparative Examples 1-8 according to an exemplary embodiment;

[0058] Figure 6 is a bar chart showing the static contact angle of each prepared coating in Example 1 and Comparative Examples 1-8 according to an exemplary embodiment;

[0059] Figure 7 is a bar chart showing the adhesion of each prepared coating to the substrate in Example 1 and Comparative Examples 9-12 according to an exemplary embodiment;

[0060] Figure 8 is a bar chart showing the ice delay time of each prepared coating in Example 1 and Comparative Examples 9-12 according to an exemplary embodiment;

[0061] Figure 9 is a bar chart showing the static contact angle of each prepared coating in Example 1 and Comparative Examples 9-12 according to an exemplary embodiment;

[0062] Figure 10 is a bar chart showing the number of times of cycle ice accretion and de-icing of each prepared coating in Example 1 and Comparative Examples 9-12 according to an exemplary embodiment. DETAILED DESCRIPTION

[0063] The following description and drawings are illustrative of the specific embodiments herein and are sufficient to enable one skilled in the art to practice them. Portions and features of some embodiments can be included in, or substituted for, those of the other embodiments. The scope of the embodiments herein is inclusive of the entire range of claims, and is defined by the claims. Various embodiments are described in progression such that each subsequent embodiment builds upon previously described embodiments, but in no way requires the claimed subject matter of the previous embodiments. Throughout the drawings, identical or nearly identical components are typically labeled with the same reference numerals (leading dashes and the number being different between figures denote like components).

[0064] In the case of no conflict, the embodiments in the present application and the features in the embodiments can be combined with each other. And the raw materials used in the present application are all commercially available, unless otherwise specified.

[0065] According to a first aspect of the present application, an embodiment of an epoxy-based solvent-free low-adhesion easy-to-de-ice coating is provided.

[0066] In this alternative embodiment, the epoxy-based solvent-free low-adhesion easy-to-de-ice coating comprises a first coating component and a second coating component, and the mass ratio of the first component to the second component is 2.5-3:1;

[0067] wherein the first coating component is composed of the following raw materials in parts by weight:

[0068] Modified epoxy-based glue 80-110 parts, epoxy-based polydimethylsiloxane 40-60 parts, lubricant 50-100 parts, modified reinforcing material 10-15 parts and modified functional filler 20-30 parts;

[0069] The second coating component is composed of the following raw materials by weight fraction:

[0070] Curing agent 75-95 parts and lubricant 5-10 parts.

[0071] In this alternative embodiment, the modified epoxy-based glue is made by mixing at least one of silane coupling agent modified bisphenol A type epoxy resin E44 and silane coupling agent modified bisphenol A type epoxy resin E51 with bisphenol F type epoxy resin F170.

[0072] In this alternative embodiment, the modified epoxy-based glue is prepared by adding at least one of silane coupling agent modified bisphenol A type epoxy resin E44 and silane coupling agent modified bisphenol A type epoxy resin E51, and bisphenol F type epoxy resin F170 into a mixing bottle and mechanically stirring, and then vacuum treatment by a banbury mixer to remove the moisture contained in the glue.

[0073] In this alternative embodiment, the silane coupling agent is a mixture of one or more of KH550, KH560 and KH570, wherein the amount of silane coupling agent for modified bisphenol A type epoxy resin E44 is 3-10 parts, and the amount of silane coupling agent for modified bisphenol A type epoxy resin E51 is 5-8 parts.

[0074] In this alternative embodiment, the modification method of bisphenol A type epoxy resin is to heat the bisphenol A type epoxy resin in a flask to a preset temperature, then stir and flow, and after the temperature is stable, add silane coupling agent according to the preset time interval.

[0075] In this alternative embodiment, the lubricant in the first coating component is the same as the lubricant in the second coating component, which is made of a mixture of one or more of dimethyl silicone oil, perfluoropolyether silicone oil and methyl fluorosilicone oil.

[0076] In this alternative embodiment, the modified reinforcing material is mesoporous silica and modified chopped glass fiber, and the mass ratio of mesoporous silica to modified chopped glass fiber is 1:1-3.

[0077] In the optional embodiment, the modification process of the modified short-cut glass fiber is: mixing and stirring the short-cut glass fiber with a sodium hydroxide solution of a preset concentration at a preset first temperature, and stirring and treating at a preset second temperature after heating; obtaining hydroxylated short-cut glass fiber by washing with centrifugal deionized water, and drying in an oven at a preset temperature; mixing the hydroxylated short-cut glass fiber with a mixed solution of ethanol and n-butanol, and adding silane coupling agent dropwise, stirring and treating at a preset third temperature until the reaction is completed, and then washing by centrifugation with ethanol to obtain the modified short-cut glass fiber; and freezing and drying the modified short-cut glass fiber for later use.

[0078] In the optional embodiment, the modified functional filler is at least one of modified flake graphite and modified sheet-shaped iron oxide black.

[0079] In the optional embodiment, the modification process of the modified flake graphite is: mixing and stirring the flake graphite with a sodium hydroxide solution of a preset concentration at a preset first temperature, and stirring and treating at a preset fourth temperature after heating; obtaining hydroxylated flake graphite by washing with centrifugal deionized water, and drying in an oven at a preset temperature; mixing the hydroxylated flake graphite with a mixed solution of ethanol and n-butanol, and adding silane coupling agent dropwise, stirring and treating at a preset fifth temperature until the reaction is completed, and then washing by centrifugation with ethanol to obtain the modified flake graphite; and freezing and drying the modified flake graphite for later use.

[0080] In the optional embodiment, the modification process of the modified sheet-shaped iron oxide black is: mixing and stirring the sheet-shaped iron oxide black with a sodium hydroxide solution of a preset concentration at a preset first temperature, and stirring and treating at a preset fourth temperature after heating; obtaining hydroxylated iron oxide black by washing with centrifugal deionized water, and drying in an oven at a preset temperature; mixing the hydroxylated iron oxide black with a mixed solution of ethanol and n-butanol, and adding silane coupling agent dropwise, stirring and treating at a preset fifth temperature until the reaction is completed, and then washing by centrifugation with ethanol to obtain the modified sheet-shaped iron oxide black; and freezing and drying the modified sheet-shaped iron oxide black for later use.

[0081] In the optional embodiment, the preset first temperature is 25-35°C, the preset second temperature is 80-95°C, the preset third temperature is 115-125°C, the preset fourth temperature is 70-85°C, and the preset fifth temperature is 100-110°C.

[0082] In the optional embodiment, the curing agent is cashew shell oil modified amine epoxy curing agent, and the amine value of the cashew shell oil modified amine epoxy curing agent is 240-280 mmg KOH / g, the viscosity is 300-600 mPa.

[0083] 300-600 mPa.

[0084] According to a second aspect of the present application, as Figures 1-2 An embodiment of a method for preparing an epoxy-based solvent-free low-adhesion ice-release coating is shown.

[0085] In this alternative embodiment, the method for preparing an epoxy-based solvent-free low-adhesion ice-release coating comprises:

[0086] S1, uniformly mix a predetermined number of modified reinforcing materials, lubricants, and epoxy-based polydimethylsiloxane by mechanical stirring method to obtain a preliminary mixture, and place the preliminary mixture under a predetermined negative pressure condition for pressure holding treatment to obtain a secondary mixture;

[0087] S2, uniformly mix the secondary mixture with a predetermined number of modified reinforcing materials, modified epoxy-based glue, and modified functional fillers by mechanical stirring method to obtain a tertiary mixture, and pass the tertiary mixture through a three-roll mill to obtain a first coating component (i.e., coating component A), which is ready for use;

[0088] S3, place a predetermined number of curing agents in a stirring bottle and heat to a predetermined temperature, then add lubricants after stirring, continue stirring after warming, and use a shear stirrer for emulsification and mixing treatment to obtain a second coating component (i.e., coating component B);

[0089] S4, mix the first coating component and the second coating component according to a predetermined ratio, and obtain an epoxy-based solvent-free low-adhesion ice-release coating after uniform stirring.

[0090] In this alternative embodiment, in step S1, the pressure under the predetermined negative pressure condition is 0.08-0.15mpa, and the pressure holding treatment time is 4-6h;

[0091] In step S2, the grinding frequency of the three-roll mill during processing is 3-5 times;

[0092] In step S3, the predetermined temperature is 70℃-90℃, the stirring time is 0.5-1.5h, the temperature after warming is 80℃-100℃, the continuous stirring time is 0.5-1.5h, and the emulsification and mixing treatment time is 0.5-1.5h.

[0093] According to a second aspect of the present application, an embodiment of the application of an epoxy-based solvent-free low-adhesion ice-release coating is proposed.

[0094] In this alternative embodiment, the application of the epoxy-based solvent-free low-adhesion ice-release coating comprises:

[0095] Use sandpaper to polish the surface of the substrate, and use non-woven fabric or a brush to clean the polished surface of the substrate;

[0096] Mixing the first coating component and the second coating component according to a preset ratio, and obtaining an epoxy-based solvent-free low-adhesion easy-to-ice-release coating after uniform stirring;

[0097] The epoxy-based solvent-free low-adhesion easy-to-ice-release coating is coated on the surface of the cleaned substrate by brushing, spraying or rolling, and the coating thickness is 50-120 μm.

[0098] In order to facilitate the understanding of the above technical solutions of the present application, the above technical solutions of the present application are further described in the following specific examples, as follows:

[0099] Example 1

[0100] Coating formula:

[0101] Modified epoxy-based glue 100 parts (modified epoxy-based glue includes 25 parts of silane coupling agent modified bisphenol A type epoxy resin E44, 35 parts of silane coupling agent modified bisphenol A type epoxy resin E51, 40 parts of bisphenol F type epoxy resin F170); epoxy-terminated polydimethylsiloxane with a viscosity of 200 mPa, used in an amount of 55 parts; dimethyl silicone oil with a viscosity of 50 mPa, used in an amount of 60 parts; 4.8 parts of mesoporous silica with a diameter of 7 μm and a length of 2 mm; 12.5 parts of 15 μm flaky graphite D50 test particle size, 20 μm flaky iron oxide black 12.5 parts. The curing agent is cashew nut shell oil modified amine type epoxy curing agent 80 parts.

[0102] Coating preparation method:

[0103] Step 1: uniformly mechanically stirring a certain number of mesoporous silica reinforcing materials, lubricants, and epoxy-terminated polydimethylsiloxane to obtain a preliminary mixture;

[0104] Step 2: placing the preliminary mixture under negative pressure conditions (0.08 mpa) for 4 hours of pressure holding treatment to obtain a secondary mixture;

[0105] Step 3: uniformly mechanically stirring the secondary mixture obtained in step 2 with chopped fibers, modified epoxy-based glue, and functional fillers to obtain a tertiary mixture;

[0106] Step 4: processing the obtained tertiary mixture through a three-roll grinding machine, grinding the whole mixture for 3 times to obtain coating component A (i.e. the first coating component);

[0107] Step 5: placing a certain number of cashew nut shell oil modified amine type epoxy curing agents in a stirring bottle, heating to 85℃ and stirring for 1 hour, then slowly adding lubricants, heating to 93℃ and continuing to stir for 1 hour, then emulsifying and mixing with a shearing stirrer for 1 hour to obtain coating component B (i.e. the second coating component);

[0108] Step 6: Mix the paint A component with the paint B component according to the preset ratio, and obtain an epoxy-based solvent-free low-adhesion ice-release coating after uniform stirring.

[0109] Comparative Example 1: Compared with Example 1, the modified epoxy adhesive in the paint formulation is 100 parts (the modified epoxy adhesive includes 50 parts of silane coupling agent modified bisphenol A type epoxy resin E44 and 50 parts of bisphenol F type epoxy resin F170).

[0110] Comparative Example 2: Compared with Example 1, the modified epoxy adhesive in the paint formulation is 100 parts (the modified epoxy adhesive includes 50 parts of silane coupling agent modified bisphenol A type epoxy resin E51 and 50 parts of bisphenol F type epoxy resin F170).

[0111] Comparative Example 3: Compared with Example 1, the modified epoxy adhesive in the paint formulation is 100 parts (the modified epoxy adhesive includes 100 parts of silane coupling agent modified bisphenol A type epoxy resin E44.

[0112] Comparative Example 4: Compared with Example 1, the modified epoxy adhesive in the paint formulation is 100 parts (the modified epoxy adhesive includes 100 parts of silane coupling agent modified bisphenol A type epoxy resin E51).

[0113] Comparative Example 5: Compared with Example 1, the modified epoxy adhesive in the paint formulation is 100 parts (the modified epoxy adhesive includes 100 parts of silane coupling agent modified bisphenol F type epoxy resin F170).

[0114] Comparative Example 6: Compared with Example 1, the modified epoxy adhesive in the paint formulation is 100 parts of bisphenol A type epoxy resin E44.

[0115] Comparative Example 7: Compared with Example 1, the modified epoxy adhesive in the paint formulation is 100 parts of bisphenol A type epoxy resin E51.

[0116] Comparative Example 8: Compared with Example 1, the modified epoxy adhesive in the paint formulation is 100 parts of bisphenol F type epoxy resin F170.

[0117] Example 1 and the above eight comparative examples, except for the description of the difference, the rest of the components, content, preparation method, application method, are consistent.

[0118] The above paint is brushed on the surface of the treated aluminum plate, and after curing at 25°C for 24h, it is maintained for 7 days. Then, the coating performance is tested. See Table 1 and Figures 3-6 .

[0119] Table 1 Performance comparison of Example 1 and each comparative example

[0120]

[0121] It can be seen from the test data of Example 1 and Comparative Examples 1-8 that the coating performance of the three modified epoxy adhesives is better than that of the two modified epoxy adhesives, the coating performance of the two modified epoxy adhesives is better than that of the single modified epoxy adhesive, and the coating performance of the single modified epoxy adhesive is better than that of the ordinary epoxy adhesive; that is, by using the modified epoxy adhesive of the application, the adhesion of the coating to the substrate is enhanced, the aging resistance, the average ice adhesion, the relative ice delay time, and the static contact angle are all improved to different degrees.

[0122] Comparative Example 9: Compared with Example 1, no epoxy-terminated polydimethylsiloxane is added in the coating formulation;

[0123] Comparative Example 10: Compared with Example 1, no lubricant silicone oil component is added in the coating formulation;

[0124] Comparative Example 11: Compared with Example 1, no reinforcing material component is added in the coating formulation;

[0125] Comparative Example 12: Compared with Example 1, no functional material component is added in the coating formulation;

[0126] The above coating is brushed on the surface of the treated aluminum plate, and after curing at 25°C for 24h, it is maintained for 7 days. Then, the coating performance is tested. See Table 2 and Figures 7-10 .

[0127] Table 2 Performance comparison of Example 1 and each comparative example

[0128]

[0129] It can be seen from the test data of Example 1 and Comparative Examples 8-12 that epoxy-terminated polydimethylsiloxane, lubricant silicone oil, reinforcing material, and functional material all have different degrees of influence on the ice adhesion of the coating, especially the non-addition of the lubricant silicone oil component as a functional component of the coating structure, which increases the friction between the coating and the ice layer, shortens the ice delay time, and reduces the static water contact angle, directly leading to the inablity of the coating to remove ice; the non-addition of epoxy-terminated polydimethylsiloxane or reinforcing material or functional material leads to low porosity of the coating, reduced lubricant migration channels, reduced lubricity of the coating surface, and increased adhesion between the coating and the ice layer, resulting in reduced cycle ice removal performance of the coating; the non-addition of the functional flaky material increases the destructive effect of ultraviolet light on the coating, leading to the breakage of the molecular chain without shielding and protection, and the occurrence of deterioration.

[0130] The above coating is brushed on the surface of the treated aluminum plate, carbon steel plate, ceramic sheet, and glass sheet, and after curing at 25°C for 24h, it is maintained for 7 days. Then, the coating performance is tested. See Table 3.

[0131] Table 3 Performance comparison of Example 1 on different substrate surfaces

[0132]

[0133] The coating is tested by brushing on different substrate surfaces, and it is found that the performance stability of the coating is good, but there is a certain difference in the relative icing delay time, which is mainly due to the difference in the thermal conductivity coefficient of each substrate. The thermal conductivity coefficient of metal material is large, and the heat conduction efficiency is high. The thermal conductivity coefficient of ceramic glass material is small, and the heat conduction efficiency is low, so that the relative icing delay time of metal material is shorter than that of glass ceramic material. After each coating after the cycle icing is recoated and maintained again, each performance is not obviously changed. After the coating is polished by 400 mesh sandpaper with 200g load, the performance of each coating is not changed again.

[0134] The application is not limited to the structures described above and shown in the drawings, and various modifications and changes can be made without departing from the scope thereof. The scope of the application is only limited by the appended claims.

Claims

1. An epoxy-based solventless low-stick easy-to-deice coating characterized in that, The epoxy-based solvent-free low-adhesion easy-ice-release coating is composed of a first coating component and a second coating component, and the mass ratio of the first component to the second component is 2.5-3:1; The first coating component is composed of the following raw materials in parts by weight: 80-110 parts of modified epoxy-based glue, 40-60 parts of epoxy-based polydimethylsiloxane, 50-100 parts of lubricant, 10-15 parts of modified reinforcing material, and 20-30 parts of modified functional filler; The second coating component is composed of the following raw materials in parts by weight: 75-95 parts of curing agent and 5-10 parts of lubricant.

2. The epoxy-based solvent-free low-stick easy-to-deice coating of claim 1, wherein, The modified epoxy-based glue is made by mixing at least one of silane coupling agent modified bisphenol A type epoxy resin E44 and silane coupling agent modified bisphenol A type epoxy resin E51 with bisphenol F type epoxy resin F170.

3. The epoxy-based solvent-free low-stick easy-to-deice coating of claim 2, wherein, The preparation method of the modified epoxy-based glue is as follows: at least one of silane coupling agent modified bisphenol A type epoxy resin E44 and silane coupling agent modified bisphenol A type epoxy resin E51, and bisphenol F type epoxy resin F170 are added into a mixing bottle and mechanically stirred, and then vacuum treatment is performed by a banbury mixer to remove the moisture contained in the glue.

4. The epoxy-based, solventless, low-stick, easy-to-deice coating of claim 2, wherein, The silane coupling agent is a mixture of one or more of KH550, KH560, and KH570, wherein the amount of silane coupling agent for modified bisphenol A type epoxy resin E44 is 3-10 parts, and the amount of silane coupling agent for modified bisphenol A type epoxy resin E51 is 5-8 parts.

5. The epoxy-based, solvent-free, low-stick, easy-to-deice coating of claim 4, wherein, The modification method of bisphenol A type epoxy resin is as follows: the bisphenol A type epoxy resin is heated to a preset temperature in a flask, then stirred and flowed, and after the temperature is stable, the silane coupling agent is added dropwise according to the preset time interval.

6. The epoxy based solventless low adhesion ice-release coating of claim 1, wherein, The lubricant in the first coating component is the same as the lubricant in the second coating component, which is made of a mixture of one or more of dimethyl silicone oil, perfluoropolyether silicone oil, and methyl fluorosilicone oil.

7. The epoxy based solventless low adhesion ice-release coating of claim 1, wherein, The modified reinforcing material is mesoporous silica and modified short glass fiber, and the mass ratio of mesoporous silica to modified short glass fiber is 1:1-3.

8. The epoxy-based, solvent-free, low-stick, easy-to-deice coating of claim 7, wherein, The modification process of the modified short glass fiber is as follows: At a preset first temperature, the short glass fiber is mixed and stirred with a sodium hydroxide solution of a preset concentration, and then heated to a preset second temperature for stirring treatment; The hydroxylated short glass fiber is obtained by washing with centrifugal deionized water, and is dried in an oven at a preset temperature; The hydroxylated short glass fiber is mixed with a mixture of ethanol and n-butanol, and the silane coupling agent is added dropwise, heated to a preset third temperature for stirring treatment, until the reaction is completed, and then washed by centrifugation with ethanol to obtain the modified short glass fiber; The modified short glass fiber is freeze-dried and then used.

9. The epoxy-based, solventless, low-stick, easy-to-deice coating of claim 8, wherein, The modified functional filler is at least one of modified flake graphite and modified sheet iron oxide black.

10. The epoxy-based, solventless, low-stick, easy-to-deice coating of claim 9, wherein, The modification process of the modified flake graphite is as follows: At a preset first temperature, the flake graphite is mixed and stirred with a sodium hydroxide solution of a preset concentration, and then heated to a preset fourth temperature for stirring treatment; The hydroxylated flake graphite is obtained by washing with centrifugal deionized water, and is dried in an oven at a preset temperature; Mix the mixture of hydroxylated flake graphite ethanol and n-butanol, and drop the silane coupling agent, heat to the preset fifth temperature and stir until the reaction is complete, then wash with ethanol by centrifugation to obtain modified flake graphite; The modified flake graphite is freeze-dried and used after treatment.

11. The epoxy-based, solventless, low-stick, easy-to-deice coating of claim 10, wherein, The modification process of the modified sheet-shaped iron oxide black is: Mix the sheet-shaped iron oxide black with a sodium hydroxide solution of a preset concentration at a preset first temperature, and stir while warming to a fourth preset temperature; Wash the hydroxylated iron oxide black with centrifugal deionized water and dry in an oven at a preset temperature; Mix the hydroxylated iron oxide black with a mixture of ethanol and n-butanol, and drop the silane coupling agent, heat to the preset fifth temperature and stir until the reaction is complete, then wash with ethanol by centrifugation to obtain modified sheet-shaped iron oxide black; The modified sheet-shaped iron oxide black is freeze-dried and used after treatment.

12. The epoxy-based, solventless, low-stick, easy-to-deice coating of claim 11, wherein, The preset first temperature is 25-35°C, the preset second temperature is 80-95°C, the preset third temperature is 115-125°C, the preset fourth temperature is 70-85°C, and the preset fifth temperature is 100-110°C.

13. The epoxy based solventless low adhesion ice-release coating of claim 1, wherein, The curing agent is cashew nut shell oil modified amine epoxy curing agent, and the amine value of the cashew nut shell oil modified amine epoxy curing agent is 240-280 mmg KOH / g, and the viscosity is 300-600 mPa.

14. A process for the preparation of an epoxy based solventless low adhesion easy-to-ice-release coating characterized in that, It comprises: S1, mix the modified reinforcing material, lubricant and epoxy-terminated polydimethylsiloxane of a preset number of parts by mechanical stirring method to obtain a preliminary mixture, and place the preliminary mixture under a preset negative pressure condition for pressure retention treatment to obtain a secondary mixture; S2, mix the secondary mixture with the modified reinforcing material, modified epoxy-based glue and modified functional filler of a preset number of parts by mechanical stirring method to obtain a tertiary mixture, and pass the tertiary mixture through a three-roll mill to obtain a first coating component, which is ready for use; S3, place the curing agent of a preset number of parts in a stirring bottle and heat to a preset temperature, then add the lubricant after stirring, continue to stir after warming, and emulsify and mix by using a shear stirrer to obtain a second coating component; S4, mix the first coating component and the second coating component according to a preset ratio, and obtain an epoxy-based solvent-free low-adhesion easy-ice-release coating after stirring evenly.

15. The process for preparing an epoxy-based solvent-free low-stick easy-ice release coating of claim 14, wherein, In step S1, the pressure under the preset negative pressure condition is 0.08-0.15 MPa, and the pressure retention treatment time is 4-6 h; In step S2, the grinding frequency of the three-roll mill during treatment is 3-5 times; In step S3, the preset temperature is 70-90°C, the stirring time is 0.5-1.5 h, the temperature after warming is 80-100°C, the continuous stirring time is 0.5-1.5 h, and the emulsification and mixing treatment time is 0.5-1.5 h.

16. Use of an epoxy-based, solvent-free, low-adhesion, ice-shedding coating, characterized in that The application comprises: Use sandpaper to polish the surface of the substrate, and use non-woven fabric or a brush to clean the polished surface of the substrate; Mix the first coating component and the second coating component according to a preset ratio, and obtain an epoxy-based solvent-free low-adhesion easy-ice-release coating after stirring evenly. The epoxy-based solvent-free low-adhesion ice-release coating is coated on the surface of the cleaned substrate by brushing, spraying or rolling, and the coating thickness is 50-120 μm.

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