An epoxy resin material with long-term anti-icing performance and preparation method thereof

Abstract

The present invention relates to the technical field of electrical insulation materials for power transmission lines, and discloses an epoxy resin material with long-term anti-icing performance and a preparation method thereof. The raw material components, measured by weight, include 80-120 parts of alicyclic epoxy resin, 80-120 parts of curing agent, 0.5-2 parts of accelerator, and 5-10 parts of modified THV; the modified THV is obtained by electrospinning, heat treatment, and refinement of THV. The THV material used in this application has lower surface energy than silicone rubber, and the sponge structure can prevent water droplets from directly contacting the surface of the alicyclic epoxy resin, making it difficult for water droplets to adhere. Due to its lower surface energy, the THV material makes it easier for ice formed on the insulating material to fall off. Compared with silicone rubber, the THV material has better mechanical stability and better wear resistance, which ensures the long-term effectiveness of its anti-icing ability.

Description

Technical Field

[0001] The present invention relates to the technical field of electrical insulation materials for transmission lines, and in particular to an epoxy resin material with long-lasting anti-icing performance and a preparation method thereof. Background Art

[0002] High-voltage transmission line insulators are essential components in power systems, providing electrical isolation between high-voltage conductors and other structures such as towers and poles while also withstanding the mechanical stresses of the lines. Long-term exposure to the elements makes insulators susceptible to damage from various natural disasters, with ice disasters being one of the most serious threats. Uneven ice coverage on insulators can cause significant self-vibration in the wind, leading to collisions and breakage. Furthermore, during heavy snow (or sleet) or persistent fog, atmospheric contaminants can settle directly on the insulator surfaces or become trapped in the fog as condensation nuclei. This further increases the conductivity of the ice-water as the ice melts, distorting the voltage distribution across the insulator string (and even the surface voltage distribution of individual insulators). This reduces the flashover voltage across the ice-covered insulator string, potentially causing ice flashover accidents.

[0003] The surface of porcelain or glass insulators is hydrophilic and has a high surface energy. Water droplets are easily captured after hitting the surface of the insulator, and the ice layer formed is relatively dense. Silicone rubber composite insulation has good hydrophobicity and low initial surface energy, so water droplets are not easy to adhere to its surface.

[0004] At present, the main way to improve the anti-icing ability of the outer layer material of the insulator is to coat the surface with a hydrophobic coating (mostly RTV). However, due to its poor wear resistance, after being exposed to external sunlight and wind and sand erosion for a long time, the surface roughness will become larger, and functional groups such as hydroxyl and carboxyl will be produced on the surface, resulting in the loss of surface hydrophobicity, resulting in insufficient long-term anti-icing ability.

[0005] Therefore, how to ensure the long-term anti-icing ability of insulators under heavy snow (or sleet) in winter or continuous fog in mountainous areas is an urgent problem to be solved. Summary of the Invention

[0006] Technical problems solved by the present invention:

[0007] It is used to solve the current problem of insufficient long-term anti-icing ability of insulators.

[0008] The technical solution adopted in the present invention is:

[0009] The epoxy resin material provided in this application has long-term anti-icing performance. THV (a polymer of tetrafluoroethylene, hexafluoropropylene, and vinylidene fluoride) material is prepared into particles with a sponge structure. By filling THV particles in a cycloaliphatic epoxy resin, long-term anti-icing performance is achieved. The THV material used in this application has lower surface energy than silicone rubber, and the sponge structure can prevent water droplets from directly contacting the surface of the cycloaliphatic epoxy resin, making it difficult for water droplets to adhere (see Figure 1-Figure 3 THV material's lower surface energy makes ice buildup on insulation easier to remove. Furthermore, compared to silicone rubber, THV material offers greater mechanical stability and abrasion resistance, ensuring the long-term effectiveness of its anti-icing capabilities.

[0010] To expand on this, it means:

[0011] First, the present invention provides an epoxy resin material with long-lasting anti-icing performance. The raw material components, calculated by weight, include 80-120 parts of alicyclic epoxy resin, 80-120 parts of curing agent, 0.5-2 parts of accelerator, and 5-10 parts of modified THV.

[0012] The modified THV is obtained by electrospinning, heat treatment and refinement of THV.

[0013] According to some preferred embodiments, the raw material components, by weight, include 90-100 parts of alicyclic epoxy resin, 90-100 parts of curing agent, 0.8-1.2 parts of accelerator, and 7-9 parts of modified THV.

[0014] According to some preferred embodiments, the alicyclic epoxy resin includes at least one of 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexylcarboxylate, bis((3,4-epoxycyclohexyl)methyl)adipate, and vinylcyclohexene dioxide.

[0015] According to some preferred embodiments, the curing agent includes at least one of methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, and methylnadic anhydride.

[0016] According to some preferred embodiments, the accelerator includes at least one of N,N-dimethylbenzylamine, 2,4,6-tris(dimethylaminomethyl)phenol, and 2-ethyl-4-methylimidazole.

[0017] According to some preferred embodiments, the preparation method of modified THV is as follows: after dissolving THV, a single-layer membrane is obtained by electrospinning with a syringe, and the injection is repeated 8 to 10 times to obtain a treated material; the treated material is heat-treated at 60 to 90°C for 18 to 30 hours, and then crushed and ball-milled to obtain modified THV.

[0018] The particle size of the modified THV ranges from 5 to 15 μm.

[0019] According to some preferred embodiments, the syringe uses a 21 gauge blunt-tip needle.

[0020] According to some preferred embodiments, the electrospinning parameters are: a flow rate of 1.2 mL / h, a voltage of 17 kV, a working distance of 15 cm, and a spinning solution injection volume of 8.0 mL.

[0021] Second, the present invention provides a method for preparing the aforementioned epoxy resin material with long-lasting anti-icing performance, comprising the following steps:

[0022] The raw material components are mixed, placed in a mold, vacuum treated, and then heated and cured to obtain epoxy resin.

[0023] THV particle density (0.91g / cm 3 ) is less than the density of ester ring epoxy resin (1.0g / cm 3 During the resin casting process, the negative pressure formed by vacuuming will also accelerate the floating of THV particles. The structural diagram of the epoxy resin material formed is shown in Figure 3 .

[0024] According to some preferred embodiments, the vacuum treatment is performed by evacuating the air at -0.1 MPa for 20 to 60 minutes.

[0025] According to some preferred embodiments, the temperature is kept at 100-150° C. for 8-12 hours until the mixture is completely cured.

[0026] The technical mechanism and beneficial effects adopted by the present invention are:

[0027] (1) The epoxy resin material provided by the present invention has long-lasting anti-icing properties and superior hydrophobicity and anti-icing capabilities: THV material has a lower surface energy than silicone rubber, allowing it to inherit the excellent hydrophobicity of alicyclic epoxy resin materials when mixed with them. Furthermore, the sponge microstructure of the THV material creates an air barrier between the epoxy resin surface and water droplets, preventing direct contact between the water droplets and the epoxy resin surface, making it more difficult for the water droplets to adhere to the surface.

[0028] (2) The epoxy resin material with long-lasting anti-icing properties provided by the present invention has a longer-lasting anti-icing capability: THV material has better mechanical stability and superior wear resistance than silicone rubber. When subjected to wind and sand erosion in the natural environment, it is not easily worn and damaged, thereby ensuring the longer-lasting hydrophobic and anti-icing capability of the external insulation material. BRIEF DESCRIPTION OF THE DRAWINGS

[0029] Figure 1 Schematic diagram of the microstructure of modified THV particles (magnification 1000 times);

[0030] Figure 2 Schematic diagram of the microstructure of modified THV particles (magnification 10,000 times);

[0031] Figure 3 This is a schematic structural diagram of the epoxy resin material provided by the present invention. DETAILED DESCRIPTION

[0032] To make the purpose, technical solutions and advantages of the embodiments of the present invention clearer, 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 are used. Where the manufacturer of the reagents or instruments is not specified, all are conventional products that can be purchased commercially.

[0033] Example 1

[0034] An epoxy resin material with long-lasting anti-icing performance includes an alicyclic epoxy resin, an anhydride curing agent, an accelerator, and modified THV particles, wherein the alicyclic epoxy resin is 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexylcarboxylate, the anhydride curing agent is methylhexahydrophthalic anhydride, and the accelerator is N,N-dimethylbenzylamine. The THV particles are obtained by electrospinning, crushing, and ball milling, and have a particle size of 5 to 15 μm.

[0035] In this embodiment, the alicyclic epoxy resin is selected from Jiangsu Taitel New Materials Technology Co., Ltd., model TTA21P; the anhydride curing agent is selected from Puyang Huicheng Electronic Materials Co., Ltd., model B1012; the accelerator N,N-dimethylbenzylamine is selected from Shanghai Maclean Biochemical Technology Co., Ltd.; the N,N-dimethylformamide (DMF) solvent is selected from Maclean reagent; THV is selected from 3M Company of the United States, model THV 500GZ.

[0036] The epoxy resin material of this embodiment with long-term anti-icing performance includes the following steps:

[0037] Preparation and processing of HTV particles:

[0038] Step 1: Dissolve THV resin powder (8%) in DMF solvent and stir at room temperature for 4 hours under magnetic stirring to obtain a transparent liquid. A single-layer membrane was prepared on an aluminum foil receiver by electrospinning using a syringe (spinning parameters were set at a flow rate of 1.2 mL / h, a voltage of 17 kV, and a working distance of 15 cm, with a spinning solution injection volume of approximately 8.0 mL).

[0039] Step 2: Place the single-layer membrane on an aluminum foil receiver and repeat the above-mentioned injection process 8-10 times to obtain a THV material with a microporous sponge structure.

[0040] Step 3: Place the prepared THV material in a drying oven at 70°C for 24 hours to fully decompose the DMF solvent. The dried THV material is then placed in a crusher to initially crush it into smaller particles.

[0041] Step 4: The crushed particles are then placed in a ball mill for refinement until the particles reach the desired particle size;

[0042] Step 5: Use a sieving device to classify the ground THV particles and select microparticles that meet the size requirements. The sieving process needs to be repeated multiple times to ensure the uniformity and size consistency of the particles.

[0043] (2) Raw material mixing preparation

[0044] Mix 100 parts of cycloaliphatic epoxy resin, 90 parts of curing agent, 1 part of accelerator, and 8 parts of prepared HTV particles in a dispersing machine. Pour the mixture into a mold. Then, place it in a vacuum oven at 50-60°C and evacuate it at -0.1 MPa for 30 minutes to completely remove any remaining air.

[0045] (3) High temperature curing of the mixture

[0046] After vacuuming, the mold is placed in a constant temperature oven at 120° C. for 10 hours for complete curing; finally, the mold is demoulded after cooling to obtain the desired alicyclic epoxy material.

[0047] Example 2

[0048] The difference between this embodiment and embodiment 1 is that the addition amount of each component raw material is different, specifically: the mass parts of the alicyclic epoxy resin, acid anhydride curing agent, accelerator, and THV particle component are 100 parts, 90 parts, 1 part, and 5 parts respectively.

[0049] Example 3

[0050] The difference between this embodiment and embodiment 1 is that the addition amount of each component raw material is different, specifically: the mass parts of alicyclic epoxy resin, acid anhydride curing agent, accelerator, and THV particle component are 100 parts, 90 parts, 1 part, and 10 parts respectively.

[0051] Example 4

[0052] The difference between this embodiment and embodiment 1 is that the addition amount of each component raw material is the same, but the particle size of the THV particles is less than 5 μm, specifically: the mass parts of the alicyclic epoxy resin, anhydride curing agent, accelerator, and THV particle components are 100 parts, 90 parts, 1 part, and 8 parts respectively.

[0053] Example 5

[0054] The difference between this embodiment and embodiment 1 is that the addition amount of each component raw material is the same, but the particle size of the THV particles is greater than 15 μm, specifically: the mass parts of the alicyclic epoxy resin, anhydride curing agent, accelerator, and THV particle components are 100 parts, 90 parts, 1 part, and 8 parts respectively.

[0055] Comparative Example 1

[0056] The difference between this comparative example and Example 1 is that the raw materials added are different and the formula does not contain THV particles. Specifically, the alicyclic epoxy resin, the acid anhydride curing agent, and the accelerator are 100 parts, 90 parts, and 1 part, respectively.

[0057] Comparative Example 2

[0058] This comparative example differs from Example 1 in that the raw materials used are different. The THV particles in the formula are unmodified THV 500GZ with a particle size of 5-15 μm. Specifically, the alicyclic epoxy resin, anhydride curing agent, accelerator, and THV 500GZ are 100 parts, 90 parts, 1 part, and 8 parts, respectively.

[0059] Comparative Example 3

[0060] This comparative example differs from Example 1 in that the epoxy insulator raw materials consist of 100 parts alicyclic epoxy resin, 90 parts curing agent, and 1 part accelerator, and do not contain THV particles. After the epoxy insulator is cast, a layer of RTV coating (Shandong Xinheli Electric Power Technology Co., Ltd.) is applied to the outer layer of the epoxy insulator.

[0061] Test example

[0062] The performance tests of the samples of Examples 1-5 and Comparative Examples 1-3 were carried out as follows:

[0063] 1. Contact angle test: Use a contact angle meter to measure the contact angle between water droplets and different materials to determine the hydrophobicity of different materials.

[0064] 2. Wear resistance test: According to the national standard GB / T 1768-2006, the wear resistance of different materials was measured. The test wheel used was a CS-10, with a load of 500g and a rotation speed of 1000r.

[0065] 3. Anti-icing resistance test: Cylindrical icicles with a diameter of 1 cm and a height of 1 cm are frozen on the surfaces of different materials. A digital push-pull force gauge is used to measure the minimum force required for the icicles to slide on the surface of the material.

[0066] 4. Ice resistance test after abrasion: Freeze a cylindrical icicle with a diameter of 1 cm and a height of 1 cm on the surface of the abraded material. Use a digital push-pull force gauge to measure the minimum force required for the icicle to slide on the material surface.

[0067] The measurement results are shown in Table 1.

[0068] Table 1 Test results

[0069]

[0070] It can be seen from Examples 1, 2, and 3 that as the amount of modified THV in the epoxy resin increases, the contact angle becomes larger and larger, the initial anti-icing resistance becomes smaller and smaller, and water droplets are less likely to adhere to it; however, the wear resistance and anti-icing properties first decrease and then increase. The best comprehensive anti-icing performance is achieved when the addition amount is 8 parts.

[0071] It can be seen from Examples 1, 4, and 5 that when the modified THV particle size is 5-15 μm, the prepared epoxy resin material has good wear resistance and good anti-icing performance.

[0072] It can be seen from Example 1 and Comparative Example 1 that the hydrophobicity and wear resistance of the ester ring epoxy resin material prepared by adding modified THV particles are greatly improved, and the anti-icing ability is significantly improved.

[0073] It can be seen from Example 1 and Comparative Example 2 that the ester ring epoxy resin material prepared by adding modified HTV particles has greatly improved hydrophobicity and wear resistance compared to the unmodified material, and the anti-icing ability is also significantly improved.

[0074] It can be seen from Example 1 and Comparative Example 3 that the ester ring epoxy resin material prepared by adding THV particles has significantly improved wear resistance compared to the post-coated RTV coating, and still has excellent anti-icing effect after wear.

[0075] The foregoing description is merely a preferred embodiment of the present invention and is 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 are intended to be within the scope of protection of the present invention.

Claims

1. An epoxy resin material with long-lasting anti-icing performance, characterized in that: The raw material components are calculated by weight, including 80-120 parts of alicyclic epoxy resin, 80-120 parts of curing agent, 0.5-2 parts of accelerator, and 5-10 parts of modified THV; The preparation method of the modified THV is as follows: after dissolving THV, a single-layer membrane is obtained by electrospinning with a syringe, and the injection is repeated 8 to 10 times to obtain a treated material; the treated material is heat-treated at 60 to 90°C for 18 to 30 hours, and then crushed and ball-milled to obtain the modified THV.

2. The epoxy resin material with long-lasting anti-icing performance according to claim 1, wherein: The raw material components are calculated by weight and include 90-100 parts of alicyclic epoxy resin, 90-100 parts of curing agent, 0.8-1.2 parts of accelerator, and 7-9 parts of modified THV.

3. The epoxy resin material with long-lasting anti-icing performance according to claim 1, characterized in that: The alicyclic epoxy resin includes at least one of 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexylcarboxylate, bis((3,4-epoxycyclohexyl)methyl)adipate, and vinylcyclohexene dioxide.

4. The epoxy resin material with long-lasting anti-icing performance according to claim 1, characterized in that: The curing agent includes at least one of methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride and methylnadic anhydride.

5. The epoxy resin material with long-lasting anti-icing performance according to claim 1, characterized in that: The accelerator includes at least one of N,N-dimethylbenzylamine, 2,4,6-tris(dimethylaminomethyl)phenol, and 2-ethyl-4-methylimidazole.

6. The epoxy resin material with long-lasting anti-icing performance according to claim 1, characterized in that: The syringe used a 21-gauge flat-tip needle; and / or, electrospinning parameters: a flow rate of 1.2 mL / h, a voltage of 17 kV, a working distance of 15 cm, and a spinning solution injection volume of 8.0 mL.

7. A method for preparing an epoxy resin material with long-lasting anti-icing performance according to any one of claims 1 to 6, characterized in that: The steps include: The raw material components are mixed, placed in a mold, vacuum treated, and then heated and cured to obtain epoxy resin.

8. The method for preparing an epoxy resin material with long-lasting anti-icing performance according to claim 7, characterized in that: Vacuum treatment: vacuum at -0.1MPa atmospheric pressure for 20~60min.

9. The method for preparing an epoxy resin material with long-lasting anti-icing performance according to claim 8, characterized in that: Keep at 100~150℃ for 8~12h until completely solidified.

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