Epoxy resin material with long-acting anti-icing performance and preparation method thereof

Abstract

The invention relates to the technical field of electric transmission line electrical insulating materials, and discloses an epoxy resin material with long-acting icing resistance and a preparation method thereof.The epoxy resin material is prepared from, by weight, 80-120 parts of alicyclic epoxy resin, 80-120 parts of curing agent, 0.5-2 parts of accelerant and 5-10 parts of modified THV; the modified THV is obtained by carrying out electrostatic spinning, heat treatment and refining on THV. Compared with silicone rubber, the THV material adopted by the invention has lower surface energy, and the sponge structure can prevent water drops from being in direct contact with the surface of the alicyclic epoxy resin, so that the water drops are difficult to attach. The THV material enables ice formed by the insulating material to fall off more easily due to the low surface energy of the THV material. Compared with silicone rubber, the THV material has better mechanical stability and better wear resistance, so that the long-term effect of the anti-icing capability is ensured.

Description

Technical Field

[0001] The present invention relates to the technical field of electrical insulation materials for power 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 an indispensable and important component in the power system. They are responsible for electrically isolating high-voltage conductors from other structures such as towers and poles, and also bear the mechanical stress of the line. Insulators are exposed to the natural environment for a long time and are easily damaged by various natural disasters, among which ice disasters are one of the most serious threats. On the one hand, uneven ice coating on insulators will produce large-scale self-vibration under the action of wind, causing insulators to collide with each other, resulting in breakage and falling; on the other hand, under heavy snow (or sleet) or continuous fog weather conditions, dirty particles in the atmosphere directly settle on the surface of the insulator or are contained in the fog as condensation nuclei, so that the ice water conductivity further increases when the ice on the insulator melts, causing distortion of the voltage distribution of the insulator string (and also distortion of the voltage distribution on the surface of a single insulator), thereby reducing the flashover voltage of the ice-covered insulator string, resulting in ice flash 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 formed ice layer 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 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 increase, 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 by the present invention is:

[0009] The epoxy resin material with long-term anti-icing performance provided in the present application is prepared from THV (polymer of tetrafluoroethylene, hexafluoropropylene and vinylidene fluoride) material into particles with a sponge structure, and the THV particles are filled in the alicyclic epoxy resin to achieve long-term anti-icing performance. The THV material used in the present application has a 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 (see Figure 1-Figure 3 ). THV materials have a lower surface energy, which makes it easier for ice formed on insulating materials to fall off. In addition, THV materials have better mechanical stability and wear resistance than silicone rubber, ensuring the long-term effectiveness of their anti-icing ability.

[0010] To expand on this, that is to say:

[0011] First, the present invention provides an epoxy resin material with long-term anti-icing performance, wherein the raw material components, 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, electrospinning is performed using a syringe to obtain a single-layer membrane, 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 various components of the raw materials 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 schematic diagram of the epoxy resin material formed is shown in Figure 3 .

[0024] According to some preferred embodiments, vacuum treatment: vacuuming at -0.1 MPa atmospheric pressure for 20 to 60 min.

[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 as follows:

[0027] (1) The epoxy resin material with long-term anti-icing performance provided by the present invention has a more excellent hydrophobic and anti-icing ability: THV material has a lower surface energy than silicone rubber, so it can inherit its excellent hydrophobicity after being mixed with alicyclic epoxy resin material. In addition, the sponge microstructure of THV material creates an air barrier between the epoxy resin surface and water droplets, so that water droplets will not directly contact the epoxy resin surface, making it more difficult for water droplets to adhere to the surface.

[0028] (2) The epoxy resin material with long-term anti-icing performance provided by the present invention has a longer-term anti-icing ability: THV material has better mechanical stability and better wear resistance than silicone rubber. When eroded by wind and sand in the external natural environment, it is not easy to be worn and damaged, thereby ensuring the longer-term hydrophobic and anti-icing ability 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 10000 times);

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

[0032] In order to make the purpose, technical scheme and advantages of the embodiments of the present invention clearer, the technical scheme in the embodiments of the present invention will be described clearly and completely below. If the specific conditions are not specified in the embodiments, they are carried out according to conventional conditions or conditions recommended by the manufacturer. If the manufacturer of the reagents or instruments used is not specified, they are all conventional products that can be purchased commercially.

[0033] Example 1

[0034] An epoxy resin material with long-lasting anti-icing performance comprises an alicyclic epoxy resin, an anhydride curing agent, an accelerator, and modified THV particles, wherein the alicyclic epoxy resin is 3,4-epoxycyclohexylcarboxylic acid-3,4-epoxycyclohexyl methyl ester, the anhydride curing agent is methyl hexahydrophthalic anhydride, the accelerator is N,N-dimethylbenzylamine, and the THV particles are obtained by electrostatic spinning, crushing, and ball milling, and the particle size is 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 McLean Biochemical Technology Co., Ltd.; the N,N-dimethylformamide (DMF) solvent is selected from McLean reagent; THV is selected from 3M Company of the United States, model THV 500GZ.

[0036] An epoxy resin material with long-term anti-icing performance in this embodiment 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 h under magnetic stirring to obtain a transparent liquid. The syringe was prepared into a single-layer membrane on an aluminum foil receiver by electrospinning (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, and the spinning solution injection volume was about 8.0 mL).

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

[0040] Step 3: Place the prepared THV material in a heat drying oven and bake at 70°C for 24 hours to fully utilize the DMF solvent. Then place the dried THV material into a crusher and initially crush it into smaller particles.

[0041] Step 4: Put the crushed particles into a ball mill for refining until the particles reach the required particle size;

[0042] Step 5: Use screening equipment to classify the ground THV particles and screen out microparticles that meet the size requirements. The screening process needs to be performed multiple times to ensure the uniformity and size consistency of the particles.

[0043] (2) Raw material mixing preparation

[0044] 100 parts of alicyclic epoxy resin, 90 parts of curing agent, 1 part of accelerator and 8 parts of prepared HTV particles were mixed together and fully stirred in a stirring disperser, and the stirred mixture was introduced into a mold. Then, it was placed in a 50-60°C vacuum oven and vacuumed for 30 minutes at an atmospheric pressure of -0.1MPa to ensure that the residual air in the mixture was completely extracted.

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

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

[0047] Example 2

[0048] The difference between this embodiment and embodiment 1 is that the added amount of each component raw material is different, specifically, the mass parts of alicyclic epoxy resin, 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 added amount of each component raw material is different, specifically, the mass parts of alicyclic epoxy resin, 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 types of 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] The difference between this comparative example and Example 1 is that the types of raw materials added are different, and 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] The difference between this comparative example and Example 1 is that the raw material components of the epoxy insulator are 100 parts of alicyclic epoxy resin, 90 parts of curing agent, and 1 part of accelerator, and no THV particles are contained. After the epoxy insulator is cast, a layer of RTV coating (Shandong Xinheli Electric Power Technology Co., Ltd.) is coated on the outer layer of the epoxy insulator.

[0061] Test example

[0062] The performance tests were performed on samples of Examples 1-5 and Comparative Examples 1-3, and the specific methods are 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 is measured. The test grinding wheel is CS-10, with a load of 500g and a rotation speed of 1000r.

[0065] 3. Anti-icing resistance test: Freeze cylindrical icicles with a diameter of 1 cm and a height of 1 cm on the surface of different materials. Use a digital push-pull force gauge to measure the minimum force required for the icicles to slide on the surface of the material.

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

[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 not easy to adhere to it; however, the wear resistance and anti-icing properties first decrease and then increase, and the anti-icing comprehensive performance is best when the addition amount is 8 parts.

[0071] It can be seen from Examples 1, 4 and 5 that when the particle size of the modified THV 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 hydrophobicity and wear resistance of the ester ring epoxy resin material prepared by adding the modified HTV particles are greatly improved compared with the unmodified ones, 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 above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. For those skilled in the art, the present invention may have various modifications and variations. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention shall be included in the protection scope of the present invention.

Claims

1. An epoxy resin material with long-term 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 modified THV is obtained by electrospinning, heat treatment and refinement of THV.

2. The epoxy resin material with long-term anti-icing performance according to claim 1, characterized in that: 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-term 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-term 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-term 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-term anti-icing performance according to any one of claims 1 to 5, characterized in that: The preparation method of modified THV is as follows: after dissolving THV, a single-layer membrane is obtained by electrostatic spinning 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 the modified THV is obtained by crushing and ball milling.

7. The epoxy resin material with long-term anti-icing performance according to claim 6, 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.

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

9. The method for preparing the epoxy resin material with long-term anti-icing performance according to claim 8, characterized in that: Vacuum treatment: Vacuum for 20 to 60 minutes at -0.1MPa atmospheric pressure.

10. The method for preparing the epoxy resin material with long-term anti-icing performance according to claim 9, characterized in that: Keep at 100-150℃ for 8-12 hours until completely cured.

Images