A cycloaliphatic epoxy resin material with sugar pollution self-degradation function and its preparation method

Abstract

The present invention relates to the field of insulating resin technology, for the application scenario containing a large amount of sugar organic matter pollution in the environment, the hydrophobicity of the external insulating material used for power equipment is seriously reduced, which easily leads to dangerous problems such as surface discharge, specifically discloses a kind of alicyclic epoxy resin material with sugar pollution self-degradation function and its preparation method, by mass fraction, the alicyclic epoxy resin material includes 90 120 parts of aliphatic epoxy resins, 70 90 parts of curing agents, 5 30 parts of photocatalytic microcapsules, 3 10 parts of polydimethylsiloxanes, 2 10 parts of POSS and 0.5 2 parts of curing accelerators. The present invention carries out structural modification treatment on epoxy resin matrix, and introduces therein a dimensionally stable free organosilicon dispersed phase and an inner core embedded with a microcapsule of a photocatalyst, which can simultaneously give the epoxy resin material excellent hydrophobicity and the ability to self-degrade sugar organic matter pollution.

Description

Technical Field

[0001] The present invention relates to the technical field of insulating resins, and in particular to an alicyclic epoxy resin material with a sugar contamination self-degradation function and a preparation method thereof. Background Art

[0002] Insulating materials, also known as dielectrics, are materials that are non-conductive or extremely conductive at the permissible voltage. Commonly found in electrical equipment, they isolate charged conductors of different potentials, allowing current to flow along a defined path. They also provide support, heat dissipation, energy storage, and moisture and mildew resistance. As power systems evolve toward higher voltages, larger capacities, and longer-distance transmission, the performance requirements for insulating materials in these systems are increasing. They must not only possess excellent electrical insulation and mechanical strength, but also maintain long-term, stable hydrophobicity and pollution flashover resistance in complex and changing environmental conditions.

[0003] Traditional power insulation materials are mostly silicone rubber, or elements such as fluorine are introduced into silicone rubber to improve and enhance the material's environmental adaptability. However, silicone rubber faces numerous challenges in specific application environments. For example, in sugarcane plantations and other similar environments, the surface of the insulation material outside the transmission line is susceptible to contamination containing large amounts of organic sugars. These organic sugars are not only highly hygroscopic but also hinder the migration of hydrophobic small molecules in the silicone rubber, causing a sharp decrease in its hydrophobic properties. This in turn triggers surface discharge, seriously threatening the safe operation of the transmission line.

[0004] In response to the problems existing in similar application scenarios, there is an urgent need for an insulating material that can effectively overcome the technical difficulty of the adverse effects of sugar substances attached to the surface of the material on the insulating material. Summary of the Invention

[0005] The purpose of the present invention is to address the problem that in application scenarios where the environment contains a large amount of sugar organic pollution, the hydrophobicity of the outer surface insulation material used for power equipment is seriously reduced, which easily leads to dangerous problems such as surface discharge.

[0006] The present invention is achieved through the following technical solutions:

[0007] The invention provides an alicyclic epoxy resin material with a sugar pollution self-degradation function. The material comprises, by mass, 90-120 parts of an aliphatic epoxy resin, 70-90 parts of a curing agent, 5-30 parts of a photocatalytic microcapsules, 3-10 parts of polydimethylsiloxane, 2-10 parts of POSS and 0.5-2 parts of a curing accelerator.

[0008] Preferably, the method for preparing the photocatalytic microcapsules comprises the following steps:

[0009] A1: Mix urea and formaldehyde, adjust the pH to 8.5-9.0, and heat to react to form a urea-formaldehyde prepolymer solution;

[0010] A2: Place the nanocatalyst in deionized water, add sodium lauryl sulfate, and disperse by ultrasonication to obtain a water-in-oil emulsion;

[0011] A3: adding the urea-formaldehyde prepolymer solution to the water-in-oil emulsion, adjusting the pH value to 3.5-4.5, stirring, then heating, and standing to solidify to obtain the photocatalytic microcapsules.

[0012] Preferably, in step A1, the mixture is heated to 75-95° C. and stirred for reaction for 15-35 minutes; in step A3, the mixture is heated to 50-60° C. and allowed to stand for curing for 1-1.5 hours.

[0013] Preferably, the nanocatalyst comprises any one or more of platinum, cobalt or titanium dioxide.

[0014] The above-mentioned photocatalytic microcapsules are introduced into epoxy resin. When sugar contaminants adhere to the surface of the alicyclic epoxy composite insulation material, the microcapsules inside the material release nanocatalysts. The nanocatalysts migrate to the surface to catalytically degrade the sugar organic contaminants, thereby realizing the self-cleaning function of the material surface, removing obstacles that inhibit the migration of hydrophobic small molecules, and maintaining long-term hydrophobic performance stability. In addition, the nanocatalysts released by the microcapsules inside the material have excellent UV aging resistance, can absorb UV light, neutralize photodegradation free radicals, and extend the outdoor service life of organic external insulation materials.

[0015] Preferably, the aliphatic epoxy resin includes one or more of 3,4-epoxycyclohexylcarboxylate, 3,4-epoxycyclohexylcarboxylate, bis((3,4-epoxycyclohexyl)methyl)adipate, tetrahydroindene diepoxide, 3,4-epoxycyclohexylcarboxylate acrylate, 3,4-epoxycyclohexylcarboxylate methacrylate, 3,4-epoxycyclohexylcarboxylate acrylate or vinylcyclohexene dioxide.

[0016] Preferably, the POSS comprises one or more of a hexasiloxane cage, an octasiloxane cage or a dodecasiloxane cage.

[0017] The present invention also provides a method for preparing the above-mentioned alicyclic epoxy resin material having the function of self-degradation of sugar pollution, comprising the following steps:

[0018] S1: firstly mix the aliphatic epoxy resin and POSS according to the amount, add peroxide, and heat to react; then add polydimethylsiloxane, a curing agent, and a curing accelerator, mix, and then place in a vacuum environment and stir to obtain an alicyclic epoxy resin intermediate emulsion;

[0019] S2 adds the photocatalytic microcapsules to the alicyclic epoxy resin intermediate emulsion, stirs and disperses the mixture, casts the mixture, heats and cures the mixture, and cools and demolds the mixture to obtain the alicyclic epoxy resin material with the self-degradation function for sugar contaminants. The microcapsule wall exhibits excellent interfacial bonding with the epoxy resin, thus avoiding problems such as reduced mechanical and insulating properties caused by poor microscopic interfacial properties between the directly added catalyst and the epoxy matrix.

[0020] In the present invention, a polydimethylsiloxane dispersed phase with stable micro-nano dimensions can be formed inside the alicyclic epoxy resin, and the free organic silicon small molecules inside the dispersed phase can migrate to the surface of the material, giving the material excellent hydrophobic and migration properties.

[0021] Preferably, in step S1, the temperature is heated to 60-100° C. and the reaction is carried out for 3-12 hours.

[0022] Preferably, when heating is started, peroxide is added at a uniform rate, and the addition time of peroxide is 40-60 minutes.

[0023] Preferably, in step S2, the temperature is heated to 100-120°C and the temperature is kept constant for curing for 5-8 hours.

[0024] The technical solution of the present invention has the following beneficial effects:

[0025] The present invention adopts an alicyclic epoxy resin with excellent leakage resistance, which can effectively resist surface discharge ablation and extend the service life of the epoxy resin insulating matrix in the above environment; and the epoxy resin matrix is ​​structurally modified, and then a dimensionally stable free silicone dispersed phase and microcapsules with a photocatalyst embedded in the inner core are introduced into it, which can simultaneously give the epoxy resin material excellent hydrophobicity and the ability to self-degrade sugar organic contaminants.

[0026] Among them, the microscopic interface of the microcapsule wall material and the epoxy resin matrix is ​​well bonded. Without adding other additives, problems such as interface incompatibility and uneven dispersion during mixing or application can be avoided, that is, the influence of external additives on the mechanical properties and insulation properties of the material can be avoided; in the photocatalytic microcapsules, TiO2 can not only serve as a photocatalytic substance, but also has excellent resistance to ultraviolet aging, which can further improve the service life of alicyclic epoxy resin insulation materials. In summary, the alicyclic epoxy resin material of the present invention can synergistically achieve the improvement of the hydrophobicity and mobility of epoxy resin insulation materials, the self-degradation ability of sugar organic contamination, weather resistance, etc., while reducing the cost of manual cleaning, and can effectively ensure the insulation and safety of power equipment whose surface is easily contaminated by sugar organic contamination. BRIEF DESCRIPTION OF THE DRAWINGS

[0027] Figure 1 This is a schematic diagram of the morphology of sugar pollution accumulation in Example 1;

[0028] Figure 2 This is a schematic diagram of the morphology of the photocatalytic microcapsules in Example 1 after release to degrade sugar pollution. DETAILED DESCRIPTION

[0029] To make the objectives, technical solutions, and advantages of the embodiments of the present invention more clear, the technical solutions in the embodiments of the present invention are described clearly and completely below. Where specific conditions are not specified in the embodiments, conventional conditions or conditions recommended by the manufacturer shall be followed; and where the manufacturers of the instruments, equipment, reagents, and raw materials used are not specified, they are all commercially available conventional products.

[0030] The present invention provides an alicyclic epoxy resin material having a sugar pollution self-degradation function, which comprises, by weight:

[0031] (1) 90-120 parts of an aliphatic epoxy resin, including but not limited to one or more of 3,4-epoxycyclohexylcarboxylate, 3,4-epoxycyclohexylcarboxylate, bis((3,4-epoxycyclohexyl)methyl)adipate, tetrahydroindene diepoxide, 3,4-epoxycyclohexylcarboxylate acrylate, 3,4-epoxycyclohexylcarboxylate methacrylate, 3,4-epoxycyclohexylcarboxylate acrylate, and vinylcyclohexene dioxide;

[0032] (2) 70-90 parts of curing agent;

[0033] (3) 0.5-2 parts of curing accelerator;

[0034] (4) 3-7 parts of polydimethylsiloxane, including but not limited to one or more of epoxy-terminated polydimethylsiloxane, hydroxyl-terminated polydimethylsiloxane, amino-terminated polydimethylsiloxane, and vinyl-terminated polydimethylsiloxane, and the molecular weight of the polydimethylsiloxane is 500-1000 g / mol, which can impart excellent hydrophobicity and migration properties to the material;

[0035] (5) 2-12 parts of POSS, POSS including but not limited to one or more of hexasiloxane cage, octasiloxane cage, and dodecasiloxane cage;

[0036] (6) 5-30 parts of photocatalytic microcapsules, which contain photocatalysts, including but not limited to one or more of platinum, cobalt and titanium dioxide, which have the ability to efficiently catalyze the degradation of organic matter and can decompose sugar organic pollutants, thereby removing surface hygroscopic pollutants and maintaining the hydrophobic properties of the material.

[0037] In the present invention, the above-mentioned photocatalytic microcapsules are embedding materials with urea-formaldehyde resin as the wall material and TiO2 as the core material, and can be prepared by an in-situ polymerization method, which specifically includes the following steps:

[0038] (1) Mixing urea and formaldehyde in a molar ratio of 1:1.5-3, adjusting the mixture to alkaline, preferably with a pH of 8.5-9.0, heating to 75-95° C., and stirring for 15-35 minutes to form a urea-formaldehyde prepolymer solution;

[0039] (2) The nanocatalyst is uniformly dispersed in deionized water, sodium lauryl sulfate is added, and a stable aqueous phase is obtained by ultrasonic treatment. The aqueous phase is then slowly injected into the oil phase and stirred to form a water-in-oil emulsion;

[0040] (3) The urea-formaldehyde prepolymer solution prepared above is added to the water-in-oil emulsion, and an acidic catalyst such as dilute hydrochloric acid is added to adjust the pH value of the material to 3.5-4.5, thereby promoting the polymerization of urea-formaldehyde at the emulsion interface and gradually forming tiny capsules with TiO2 as the core material; then the temperature is raised to 50-60°C, and the mixture is allowed to stand for 1-1.5 hours to allow the surface to solidify and form a capsule wall layer. The tiny capsules are separated by centrifugation or filtration, and the residual impurities are cleaned and dried to obtain photocatalytic microcapsules with stable morphology and structure.

[0041] In the present invention, the preparation method of the alicyclic epoxy resin material having the function of self-degradation of sugar pollution comprises the following steps:

[0042] (1) Preparation of alicyclic epoxy resin emulsion

[0043] The aliphatic epoxy resin and POSS are mixed in appropriate amounts, heated to 60-100° C., and reacted for 3-12 hours, during which peroxide is continuously added at a uniform speed for 40-60 minutes; a curing agent, a curing accelerator, and polydimethylsiloxane are then added, mixed, and stirred thoroughly until a uniform emulsion is formed; the uniformly mixed emulsion is placed in a vacuum environment and stirred to remove residual air in the mixed emulsion, thereby obtaining a hydrophobic alicyclic epoxy resin intermediate emulsion.

[0044] Among them, removing residual air in the emulsion through a vacuum environment can prevent bubbles from being generated after the material is solidified.

[0045] (2) Preparation of alicyclic epoxy resin materials with sugar pollution self-degradation function

[0046] The photocatalytic microcapsules are added to the alicyclic epoxy resin intermediate emulsion prepared above, and stirred evenly to uniformly disperse the photocatalytic microcapsules in the emulsion; the stirred mixture is then poured into a mold, and then placed in a constant temperature oven, heated to 100-120°C, and kept warm for 5-8 hours to fully carry out the curing reaction; after curing and molding, the mold is removed, cooled to room temperature, and then demolded to obtain an alicyclic epoxy resin material with the function of self-degradation of sugar pollution.

[0047] Example 1

[0048] Step 1: Take urea and formaldehyde in a molar ratio of 1:2 respectively, mix them, and add triethanolamine dropwise until the pH value of the mixture is adjusted to about 8.6, then heat it to about 80°C, continue stirring at 120rpm, and react for 20 minutes to obtain a urea-formaldehyde prepolymer solution; then take TiO2 nanoparticles, place them in an equal volume of deionized water, add 22wt% sodium lauryl sulfate, and ultrasonically disperse them for 45 minutes to obtain an oil-in-water emulsion; add the urea-formaldehyde prepolymer solution to the oil-in-water emulsion, add 1M hydrochloric acid solution dropwise until the pH value of the mixture is adjusted to about 4.0, then heat it to about 53°C, let it stand for 1.2 hours, separate the microcapsules by centrifugation, rinse them with deionized water, and dry them to obtain photocatalytic microcapsules.

[0049] Step 2: Take 3,4-epoxycyclohexylcarboxylate, methacrylic anhydride, 2,4,6-tris(dimethylaminomethyl)phenol, vinyl polydimethylsiloxane, dodecylsiloxane cage and the photocatalytic microcapsules prepared above in a mass ratio of 98:72:1.5:5.5:6.5:22 and set aside.

[0050] Step 3: First, mix 3,4-epoxycyclohexylcarboxylate with dodecylsiloxane cage, heat to 80°C, and react for 8 hours, during which hydrogen peroxide is added continuously at a uniform speed, and the addition time of hydrogen peroxide is 45 minutes; then add methacrylic anhydride, 2,4,6-tris(dimethylaminomethyl)phenol and vinyl polydimethylsiloxane, mix, and stir thoroughly until a uniform emulsion is formed; place the mixed emulsion in a vacuum environment and stir for 15 minutes to obtain a hydrophobic alicyclic epoxy resin intermediate emulsion; add photocatalytic microcapsules to the above-mentioned alicyclic epoxy resin intermediate emulsion, stir evenly, and then pour it into a mold, place it in an oven, heat to 105°C, and keep it at a constant temperature for 6.5 hours. After curing and molding, remove the mold, cool to room temperature, and demold to obtain an alicyclic epoxy resin material.

[0051] Example 2

[0052] Step 1: Take urea and formaldehyde in a molar ratio of 1:2 respectively, mix them, and add triethanolamine dropwise until the pH value of the mixture is adjusted to about 8.6, then heat it to about 80°C, continue stirring at 120rpm, and react for 20 minutes to obtain a urea-formaldehyde prepolymer solution; then take TiO2 nanoparticles, place them in an equal volume of deionized water, add 22wt% sodium lauryl sulfate, and ultrasonically disperse them for 45 minutes to obtain an oil-in-water emulsion; add the urea-formaldehyde prepolymer solution to the oil-in-water emulsion, add 1M hydrochloric acid solution dropwise until the pH value of the mixture is adjusted to about 4.0, then heat it to about 53°C, let it stand for 1.2 hours, separate the microcapsules by centrifugation, rinse them with deionized water, and dry them to obtain photocatalytic microcapsules.

[0053] Step 2: Take 3,4-epoxycyclohexylcarboxylate, methacrylic anhydride, 2,4,6-tris(dimethylaminomethyl)phenol, vinyl polydimethylsiloxane, dodecylsiloxane cage and the photocatalytic microcapsules prepared above in a mass ratio of 98:72:1.5:5.5:2.5:6 and set aside.

[0054] Step 3: First, mix 3,4-epoxycyclohexylcarboxylate with dodecylsiloxane cage, heat to 80°C, and react for 8 hours, during which hydrogen peroxide is added continuously at a uniform speed, and the addition time of hydrogen peroxide is 45 minutes; then add methacrylic anhydride, 2,4,6-tris(dimethylaminomethyl)phenol and vinyl polydimethylsiloxane, mix, and stir thoroughly until a uniform emulsion is formed; place the mixed emulsion in a vacuum environment and stir for 15 minutes to obtain a hydrophobic alicyclic epoxy resin intermediate emulsion; add photocatalytic microcapsules to the above-mentioned alicyclic epoxy resin intermediate emulsion, stir evenly, and then pour it into a mold, place it in an oven, heat to 105°C, and keep it at a constant temperature for 6.5 hours. After curing and molding, remove the mold, cool to room temperature, and demold to obtain an alicyclic epoxy resin material.

[0055] Example 3

[0056] Step 1: Take urea and formaldehyde in a molar ratio of 1:2 respectively, mix them, and add triethanolamine dropwise until the pH value of the mixture is adjusted to about 8.6, then heat it to about 80°C, continue stirring at 120rpm, and react for 20 minutes to obtain a urea-formaldehyde prepolymer solution; then take TiO2 nanoparticles, place them in an equal volume of deionized water, add 22wt% sodium lauryl sulfate, and ultrasonically disperse them for 45 minutes to obtain an oil-in-water emulsion; add the urea-formaldehyde prepolymer solution to the oil-in-water emulsion, add 1M hydrochloric acid solution dropwise until the pH value of the mixture is adjusted to about 4.0, then heat it to about 53°C, let it stand for 1.2 hours, separate the microcapsules by centrifugation, rinse them with deionized water, and dry them to obtain photocatalytic microcapsules.

[0057] Step 2: Take 3,4-epoxycyclohexylcarboxylate, methacrylic anhydride, 2,4,6-tris(dimethylaminomethyl)phenol, vinyl polydimethylsiloxane, dodecylsiloxane cage and the photocatalytic microcapsules prepared above in a mass ratio of 105:72:0.65:10:2.5:6.2 and set aside.

[0058] Step 3: First, mix 3,4-epoxycyclohexylcarboxylate with dodecylsiloxane cage, heat to 80°C, and react for 8 hours, during which hydrogen peroxide is added continuously at a uniform speed, and the addition time of hydrogen peroxide is 45 minutes; then add methacrylic anhydride, 2,4,6-tris(dimethylaminomethyl)phenol and vinyl polydimethylsiloxane, mix, and stir thoroughly until a uniform emulsion is formed; place the mixed emulsion in a vacuum environment and stir for 15 minutes to obtain a hydrophobic alicyclic epoxy resin intermediate emulsion; add photocatalytic microcapsules to the above-mentioned alicyclic epoxy resin intermediate emulsion, stir evenly, and then pour it into a mold, place it in an oven, heat to 105°C, and keep it at a constant temperature for 6.5 hours. After curing and molding, remove the mold, cool to room temperature, and demold to obtain an alicyclic epoxy resin material.

[0059] Example 4

[0060] Step 1: Take urea and formaldehyde in a molar ratio of 1:2, mix them, and add triethanolamine dropwise until the pH value of the mixture is adjusted to about 8.6, then heat it to about 80°C, stir it continuously at 120rpm, and react for 20 minutes to obtain a urea-formaldehyde prepolymer solution; then take cobalt powder, place it in an equal volume of deionized water, add 22wt% sodium lauryl sulfate, and ultrasonically disperse it for 45 minutes to obtain an oil-in-water emulsion; add the urea-formaldehyde prepolymer solution to the oil-in-water emulsion, add 1M hydrochloric acid solution dropwise until the pH value of the mixture is adjusted to about 4.0, then heat it to about 53°C, let it stand for 1.2 hours, separate the microcapsules by centrifugation, rinse with deionized water, and dry to obtain photocatalytic microcapsules.

[0061] Step 2: Take 3,4-epoxycyclohexylcarboxylate, methacrylic anhydride, 2,4,6-tris(dimethylaminomethyl)phenol, vinyl polydimethylsiloxane, dodecylsiloxane cage and the photocatalytic microcapsules prepared above in a mass ratio of 98:72:1.5:5.5:6.5:22 and set aside.

[0062] Step 3: First, mix 3,4-epoxycyclohexylcarboxylate with dodecylsiloxane cage, heat to 80°C, and react for 8 hours, during which hydrogen peroxide is added continuously at a uniform speed, and the addition time of hydrogen peroxide is 45 minutes; then add methacrylic anhydride, 2,4,6-tris(dimethylaminomethyl)phenol and vinyl polydimethylsiloxane, mix, and stir thoroughly until a uniform emulsion is formed; place the mixed emulsion in a vacuum environment and stir for 15 minutes to obtain a hydrophobic alicyclic epoxy resin intermediate emulsion; add photocatalytic microcapsules to the above-mentioned alicyclic epoxy resin intermediate emulsion, stir evenly, and then pour it into a mold, place it in an oven, heat to 105°C, and keep it at a constant temperature for 6.5 hours. After curing and molding, remove the mold, cool to room temperature, and demold to obtain an alicyclic epoxy resin material.

[0063] Example 5

[0064] Step 1: Take urea and formaldehyde in a molar ratio of 1:2 respectively, mix them, and add triethanolamine dropwise until the pH value of the mixture is adjusted to about 8.6, then heat it to about 80°C, continue stirring at 120rpm, and react for 20 minutes to obtain a urea-formaldehyde prepolymer solution; then take TiO2 nanoparticles, place them in an equal volume of deionized water, add 22wt% sodium lauryl sulfate, and ultrasonically disperse them for 45 minutes to obtain an oil-in-water emulsion; add the urea-formaldehyde prepolymer solution to the oil-in-water emulsion, add 1M hydrochloric acid solution dropwise until the pH value of the mixture is adjusted to about 4.0, then heat it to about 53°C, let it stand for 1.2 hours, separate the microcapsules by centrifugation, rinse them with deionized water, and dry them to obtain photocatalytic microcapsules.

[0065] Step 2: Take 3,4-epoxycyclohexylcarboxylate, methacrylic anhydride, 2,4,6-tris(dimethylaminomethyl)phenol, vinyl polydimethylsiloxane, dodecylsiloxane cage and the photocatalytic microcapsules prepared above in a mass ratio of 98:72:1.5:5.5:6.5:22 and set aside.

[0066] Step 3: First, mix 3,4-epoxycyclohexylcarboxylate with dodecylsiloxane cage, heat to 65°C, and react for 11.75 hours. During this period, hydrogen peroxide is added continuously at a uniform speed, and the addition time of hydrogen peroxide is 55 minutes; then, methacrylic anhydride, 2,4,6-tris(dimethylaminomethyl)phenol and vinyl polydimethylsiloxane are added, mixed, and stirred thoroughly until a uniform emulsion is formed; the uniformly mixed emulsion is placed in a vacuum environment and stirred for 15 minutes to obtain a hydrophobic alicyclic epoxy resin intermediate emulsion; photocatalytic microcapsules are added to the above-mentioned alicyclic epoxy resin intermediate emulsion, stirred evenly, and then poured into a mold, placed in an oven, heated to 105°C, and kept at a constant temperature for 6.5 hours. After curing and molding, the mold is removed, cooled to room temperature, and demolded to obtain an alicyclic epoxy resin material.

[0067] Comparative Example 1

[0068] Step 1: Take 3,4-epoxycyclohexylcarboxylate, methacrylic anhydride, 2,4,6-tris(dimethylaminomethyl)phenol and vinyl polydimethylsiloxane in a mass ratio of 98:72:1.5:12 respectively and set aside.

[0069] Step 2: First, mix 3,4-epoxycyclohexylcarboxylate with methacrylic anhydride, 2,4,6-tris(dimethylaminomethyl)phenol and vinyl polydimethylsiloxane, and stir thoroughly until a uniform emulsion is formed; place the uniformly mixed emulsion in a vacuum environment and stir for 15 minutes to obtain an epoxy resin intermediate emulsion; then pour it into a mold, place it in an oven, heat it to 105°C, and keep it at a constant temperature for 6.5 hours. After solidification and molding, remove the mold, cool it to room temperature, and demold it to obtain an epoxy resin material.

[0070] Comparative Example 2

[0071] Step 2: Take 3,4-epoxycyclohexylcarboxylate, methacrylic anhydride, 2,4,6-tris(dimethylaminomethyl)phenol, vinyl polydimethylsiloxane and TiO2 nanoparticles in a mass ratio of 98:72:1.5:12:22 respectively and set aside.

[0072] Step 3: First mix 3,4-epoxycyclohexylcarboxylate with methacrylic anhydride, 2,4,6-tris(dimethylaminomethyl)phenol and vinyl polydimethylsiloxane, and stir thoroughly until a uniform emulsion is formed; place the uniformly mixed emulsion in a vacuum environment and stir for 15 minutes to obtain an epoxy resin intermediate emulsion; add TiO2 nanoparticles to the above-mentioned epoxy resin intermediate emulsion, stir evenly, and then pour it into a mold, place it in an oven, heat to 105°C, and keep it at a constant temperature for 6.5 hours. After solidification and molding, take out the mold, cool to room temperature, and demold to obtain an alicyclic epoxy resin material.

[0073] Test example

[0074] (1) Figure 1 、 Figure 2 As shown, there are schematic diagrams of the morphology of the epoxy resin material when sugar contamination accumulates on the surface, and schematic diagrams of the morphology of the sugar contamination degraded after the release of photocatalytic microcapsules. It can be clearly seen from the figures that the alicyclic epoxy resin material in the present invention can realize the self-cleaning function of the material surface through the degradation effect of the photocatalytic microcapsules contained in itself, remove the obstacles that inhibit the migration of hydrophobic small molecules, and thus maintain the long-term stability of the hydrophobic performance.

[0075] (2) The epoxy resin materials prepared in Examples 1-5 and Comparative Examples 1-2 were used as samples to measure the hydrophobicity of the materials at the initial stage and after treatment. The results are summarized in Table 1 below:

[0076] Table 1 Material properties of different samples at different stages

[0077]

[0078] Among them, the water contact angle is measured by dropping a water drop on the surface of the epoxy resin material. The size of the contact angle can reflect the quality of the hydrophobicity; sugar treatment refers to the process of applying a 15% sucrose aqueous solution to the surface of the epoxy resin and leaving it at room temperature for 48 hours; the insulation performance is measured according to the requirements of GB / T1410-2006 "Test method for volume resistivity and surface resistivity of solid insulating materials".

[0079] The above measurement results demonstrate that, compared to Comparative Examples 1 and 2, the epoxy resin materials prepared using Examples 1 to 5 maintain longer-lasting hydrophobicity and stable insulation performance in environments with significant amounts of carbohydrate-containing organic contaminants. This demonstrates that the alicyclic epoxy resin material and its preparation method proposed in the present invention can address the issue of severely reduced hydrophobicity, which can easily lead to dangerous creeping discharge, in external surface insulation materials used in power equipment in applications where the environment contains significant amounts of carbohydrate-containing organic contaminants.

[0080] The above are merely preferred embodiments of the present invention and are not intended to limit the present invention. Those skilled in the art will readily appreciate that various modifications and variations of the present invention are possible. Any modifications, equivalent substitutions, or improvements made within the spirit and principles of the present invention shall be included within the scope of protection of the present invention.

Claims

1. An alicyclic epoxy resin material with a sugar pollution self-degradation function, characterized in that: The composition comprises, by weight, 90-120 parts of aliphatic epoxy resin, 70-90 parts of curing agent, 5-30 parts of photocatalytic microcapsules, 3-10 parts of polydimethylsiloxane, 2-10 parts of POSS and 0.5-2 parts of curing accelerator; The preparation method of the photocatalytic microcapsules comprises the following steps: A1: Mix urea and formaldehyde, adjust the pH to 8.5-9.0, and heat to react to form a urea-formaldehyde prepolymer solution; A2: Place the nanocatalyst in deionized water, add sodium lauryl sulfate, and disperse by ultrasonication to obtain a water-in-oil emulsion; A3: adding the urea-formaldehyde prepolymer solution to the water-in-oil emulsion, adjusting the pH value to 3.5-4.5, stirring, then heating, and standing to solidify to obtain the photocatalytic microcapsules; The preparation method of the alicyclic epoxy resin material comprises the following steps: S1: First, an aliphatic epoxy resin and POSS are mixed according to the amount, peroxide is added, and the mixture is heated for reaction; then, polydimethylsiloxane, a curing agent, and a curing accelerator are added, the mixture is mixed, and then placed in a vacuum environment and stirred to obtain an alicyclic epoxy resin intermediate emulsion; S2: adding the photocatalytic microcapsules to the alicyclic epoxy resin intermediate emulsion, stirring and dispersing, pouring, heating and curing, cooling and demoulding, to obtain the alicyclic epoxy resin material with the sugar pollution self-degradation function.

2. The alicyclic epoxy resin material having the function of self-degradation of sugar pollution according to claim 1, characterized in that: In step A1, heat to 75-95° C. and stir to react for 15-35 minutes; in step A3, heat to 50-60° C. and allow to stand and solidify for 1-1.5 hours.

3. The alicyclic epoxy resin material having the function of self-degradation of sugar pollution according to claim 1, characterized in that: The nanocatalyst includes any one or more of platinum, cobalt or titanium dioxide.

4. The alicyclic epoxy resin material having the function of self-degradation of sugar pollution according to claim 1, characterized in that: The aliphatic epoxy resin includes one or more of 3,4-epoxycyclohexylcarboxylate, 3,4-epoxycyclohexylcarboxylate, bis((3,4-epoxycyclohexyl)methyl)adipate, tetrahydroindene diepoxide, 3,4-epoxycyclohexylcarboxylate acrylate, 3,4-epoxycyclohexylcarboxylate methacrylate, 3,4-epoxycyclohexylcarboxylate acrylate or vinylcyclohexene dioxide.

5. The alicyclic epoxy resin material having the function of self-degradation of sugar pollution according to claim 1, characterized in that: The POSS includes one or more of a hexasiloxane cage, an octasiloxane cage or a dodecasiloxane cage.

6. The alicyclic epoxy resin material having the function of self-degradation of sugar pollution according to claim 1 is characterized in that: In step S1, the mixture is heated to 60-100° C. and reacted for 3-12 hours.

7. The alicyclic epoxy resin material having the function of self-degradation of sugar pollution according to claim 6, characterized in that: When heating begins, peroxide is added at a constant rate, and the peroxide addition time is 40-60 minutes.

8. The alicyclic epoxy resin material having the function of self-degradation of sugar pollution according to claim 1, characterized in that: In step S2, the temperature is heated to 100-120° C. and the temperature is kept to cure for 5-8 hours.

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