High-strength composite electric pole material and preparation method thereof

Abstract

The invention provides a high-strength composite electric pole material and a preparation method thereof, and belongs to the technical field of composite materials. The composite material is prepared from the following raw materials in parts by weight: 90-120 parts of epoxy resin, 10-15 parts of first modified carbon fibers, 8-12 parts of second modified carbon fibers, 3-5 parts of third modified carbon fibers and 30-50 parts of a curing agent. According to the prepared high-strength composite electric pole material, through synergistic modification of multiple kinds of modified carbon fibers, the compatibility and wettability of the carbon fibers and the epoxy resin base material are improved, the mechanical modification effect is obviously enhanced, and therefore the prepared high-strength composite electric pole material has the good heat resistance, aging resistance, solvent resistance stability and heat conductivity and can be widely applied to the field of electric pole materials. Wide application prospects are realized.

Description

Technical Field

[0001] The invention relates to the technical field of composite materials, and in particular to a high-strength composite pole material and a preparation method thereof. Background Art

[0002] In the field of power transmission and distribution, utility poles are important infrastructure, and their performance directly affects the safety and stability of the power grid. However, traditional steel and concrete utility poles have many shortcomings, such as heavy weight, difficult construction and transportation, and poor corrosion resistance, especially in areas with severe marine and salt spray corrosion. These problems are particularly prominent. Epoxy resin, as a multi-purpose, high-strength, and chemically resistant polymer, has become an ideal matrix for preparing composite pole materials. Its high strength and excellent adhesion enable epoxy resin to firmly combine with other materials after curing to form a composite material with excellent overall performance. At the same time, the chemical resistance, heat resistance, electrical insulation, low shrinkage, and low volatility of epoxy resin further enhance the corrosion resistance and stability of composite pole materials.

[0003] In order to further improve the mechanical properties of composite poles, modified fibers are selected as reinforcing materials. Modified fibers improve certain properties of conventional chemical fibers through chemical or physical methods. These modified fibers not only have excellent mechanical properties, but also can effectively resist corrosion and salt spray erosion, thereby extending the service life of the poles.

[0004] Carbon fiber (CF) reinforced materials have many excellent properties such as high strength, high modulus, strong thermal stability, high conductivity and corrosion resistance. The density of resin-based composite materials made of CF as reinforcement is only 1 / 5 of that of steel, but the strength is 5 times that of steel. It is a commonly used reinforcing fiber for preparing high-performance resin-based composite materials. Among them, carbon fiber / epoxy resin composite materials are the most well-known and are widely used in aircraft manufacturing, construction industry, etc. The application of carbon fiber composite materials in the reinforcement of cement poles for power transmission and distribution lines can well solve the safety problems such as cracks in cement poles, and does not increase the structural size and weight of the poles. It has the characteristics of increased tensile strength, corrosion resistance, and durability. However, in the process of use, because pure epoxy resin and carbon fiber are mostly used for composite, epoxy resin itself is a thermosetting resin. Although it has good heat resistance, high strength and good adhesion to the substrate, it also has the problems of brittleness, impact resistance, peeling resistance and vibration fatigue resistance, which makes the resin and carbon fiber composite effect unsatisfactory. In addition, due to the limitations of construction conditions, the tensile effect and weather resistance of the reinforced cement poles are not stable enough. Therefore, the use of carbon fiber / epoxy resin composite materials to reinforce cement poles is in urgent need of improvement from the preparation of composite materials to the specific construction methods. Summary of the invention

[0005] The purpose of the present invention is to propose a high-strength composite electric pole material and a preparation method thereof. Through the synergistic modification of multiple modified carbon fibers, the compatibility and wettability of carbon fibers with epoxy resin substrates are improved, and the mechanical modification effect is significantly enhanced, thereby obtaining a high-strength composite electric pole material. At the same time, the material has good heat resistance, aging resistance, solvent resistance, stability, good thermal conductivity, and broad application prospects.

[0006] The technical solution of the present invention is achieved in this way: The invention provides a high-strength composite electric pole material, which is prepared from the following raw materials by weight: 90-120 parts of epoxy resin, 10-15 parts of first modified carbon fiber, 8-12 parts of second modified carbon fiber, 3-5 parts of third modified carbon fiber, and 30-50 parts of curing agent, wherein the first modified carbon fiber is a carbon fiber that is coated with titanium oxide / aluminum oxide / silicon oxide, modified with tannic acid and coupled with benzotriazole, the second modified carbon fiber is a carbon fiber that is modified with polydopamine, coated with UiO-66-NH2, and prepared with octachloropropylsilsesquioxane, and the third modified carbon fiber is a carbon fiber deposited on the surface of a carbon nanotube.

[0007] As a further improvement of the present invention, the preparation method of the first modified carbon fiber is as follows: S1. Tetrabutyl titanate, aluminum isopropoxide and tetraethyl orthosilicate are dissolved in ethanol, water and alkali are added, and the reaction is stirred to form a sol; S2. adding carbon fiber to the sol, heating and stirring the reaction, calcining, washing, drying, and grinding to obtain ceramic carbon fiber; S3. The ceramic carbon fiber is added to water, tannic acid and a catalyst are added, heated and stirred for reaction, centrifuged, washed, and dried to obtain a modified ceramic carbon fiber; S4. Add the modified ceramic carbon fiber into dichloromethane, add 1-chlorobenzotriazole and a base, heat under reflux and stir to react, centrifuge, wash, and dry to obtain a first modified carbon fiber.

[0008] As a further improvement of the present invention, the mass ratio of tetrabutyl titanate, aluminum isopropoxide, tetraethyl orthosilicate and alkali in step S1 is 8-10:4-7:10-15:3-5, and the alkali is NaOH or KOH; the mass ratio of carbon fiber and sol in step S2 is 10-15:30-50, the temperature of the heating and stirring reaction is 50-70°C, the time is 5-7h, the calcination temperature is 500-600°C, and the time is 2-4h; the The mass ratio of the ceramic carbon fiber, tannic acid and catalyst is 10:3-5:0.3-0.5, the catalyst is a Tris-HCl solution with a pH of 8.5-9.5, the temperature of the heating and stirring reaction is 50-60°C, and the time is 3-5h; the mass ratio of the modified ceramic carbon fiber, 1-chlorobenzotriazole and alkali in step S4 is 10:2-3:1-2, the alkali is NaOH or KOH, and the time of the heating reflux stirring reaction is 2-4h.

[0009] As a further improvement of the present invention, the preparation method of the second modified carbon fiber is as follows: T1. Adding carbon fiber to Tris-HCl solution, adding dopamine hydrochloride, heating and stirring to react, centrifuging, washing, and drying to obtain modified carbon fiber; T2. The modified carbon fiber, zirconium tetrachloride, and 2-aminoterephthalic acid were added to a mixed solution of N,N-dimethylformamide and acetic acid, ultrasonically dispersed, hydrothermally reacted, centrifuged, washed, and dried to obtain UiO-66-NH2 modified carbon fiber; T3. Add octachloropropylsilsesquioxane and UiO-66-NH2 modified carbon fiber into dichloromethane, heat to reflux reaction, centrifuge, wash, and dry to obtain a second modified carbon fiber.

[0010] As a further improvement of the present invention, the mass ratio of the carbon fiber and dopamine hydrochloride in step T1 is 12-15:6-9, the pH value of the Tris-HCl solution is 8.5-9.5, the temperature of the heating and stirring reaction is 50-60°C, and the time is 3-5h; the mass ratio of the modified carbon fiber, zirconium tetrachloride, and 2-aminoterephthalic acid in step T2 is 10-14:3-4:2-3, the temperature of the hydrothermal reaction is 120-140°C, and the time is 20-24h; the mass ratio of octachloropropyl silsesquioxane and UiO-66-NH2 modified carbon fiber in step T3 is 4-7:12-15, and the heating reflux reaction time is 2-4h.

[0011] As a further improvement of the present invention, the preparation method of the third modified carbon fiber is as follows: U1. Adding carbon fiber to concentrated nitric acid, heating to reflux with stirring, centrifuging, washing, and drying to obtain acid-treated carbon fiber; U2. Place the acid-treated carbon fiber in the center of a quartz boat and spread it evenly, drop an iron solution, dry, heat to a first temperature under inert gas protection, replace with hydrogen, heat to a second temperature, introduce n-hexane, react, cool to room temperature under inert gas protection, and obtain a third modified carbon fiber.

[0012] As a further improvement of the present invention, the solid-to-liquid ratio of the carbon fiber and concentrated nitric acid in step U1 is 1:3-5g / mL, and the heating reflux stirring reaction time is 1-3h; in step U2, the first temperature is 400-500°C, the second temperature is 600-700°C, the hydrogen ventilation volume is 100-120mL / min, the n-hexane ventilation volume is 0.1-0.3mL / min, the reaction time is 30-60min, and the iron solution is ferric chloride, ferric nitrate or ferric sulfate solution, and the concentration is 1-3wt%.

[0013] As a further improvement of the present invention, the curing agent is selected from at least one of diethylenetriamine, triethylenetetramine, meta-phenylenediamine and meta-phenylenediamine, and the epoxy resin is E-51 or E-44.

[0014] The present invention further protects a method for preparing the above-mentioned high-strength composite pole material, comprising the following steps: The epoxy resin, the first modified carbon fiber, the second modified carbon fiber and the third modified carbon fiber are evenly mixed, a curing agent is added, poured into a mold, heated and cured, and a high-strength composite pole material is obtained.

[0015] As a further improvement of the present invention, the temperature of the heating curing is 100-120° C. and the time is 1-3 hours.

[0016] The present invention has the following beneficial effects: The first modified carbon fiber prepared by the present invention adopts organic titanium-aluminum-silicon alkoxide sol to mix with carbon fiber, and after calcination, a layer of titanium oxide / aluminum oxide / silicon oxide ceramic layer is coated on the surface, oxygen-containing functional groups are introduced to increase the surface polarity of the composite material, and the fracture toughness of the composite material can be improved at the same time, and the heat resistance of the carbon fiber can be significantly improved. High temperature treatment can improve the crystallinity and thermal stability of the carbon fiber, and the ceramic coating can provide good protection at high temperature to prevent the carbon fiber from contacting with oxygen and oxidizing. The dense ceramic layer can effectively block the erosion of harmful factors such as oxygen, moisture, and ultraviolet rays in the external environment to the carbon fiber, thereby improving the aging resistance of the composite material. At the same time, titanium oxide also has good effects such as absorbing ultraviolet rays, further improving the ultraviolet aging resistance, and the surface is modified by reactive tannic acid, with conjugated groups and hydroxyl groups, etc., which can improve the compatibility with epoxy resin on the one hand, and can react with 1-chlorobenzotriazole on the other hand, introduce free radical capture groups, thereby capturing free radicals generated by aging in the composite material, blocking continued reaction, thereby playing a better aging resistance under synergistic effect.

[0017] The second modified carbon fiber prepared by the present invention is modified by polydopamine on its surface, adsorbs 2-aminoterephthalic acid, and reacts in situ on the surface of the carbon fiber to generate UiO-66-NH2, which has the advantages of large porosity and specific surface area, diversified structure and function, and contains unsaturated metal sites, which greatly improves the interface bonding performance of the carbon fiber composite material. At the same time, due to the presence of amino groups and amino groups on polydopamine, the curing reaction of the epoxy composite material is promoted, and it is grafted onto the surface of the carbon fiber to form a highly mechanically interlocked composite structure and release the interface residual stress, thereby obtaining a carbon fiber reinforced composite material with excellent mechanical properties and tribological properties. Then react with octachloropropylsilsesquioxane, and there are many adjustable active functional groups on the POSS material, which can react with epoxy resin and support the formation of a cross-linked network in the system. In addition, the POSS component can be more evenly distributed throughout the system, improving its compatibility and wettability with epoxy resin, and increasing the surface roughness of the carbon fiber. The surface stress is effectively transmitted, dispersed and absorbed by the uniform transition interface, greatly enhancing the mechanical properties. At the same time, the thermal conductivity of the material is also improved, and heat energy is dissipated extremely quickly through the formed network, thereby improving the heat resistance of the material.

[0018] The third modified carbon fiber prepared by the present invention is first treated with a strong acid, and the carbon fiber is placed in a concentrated nitric acid solution. The corrosiveness of the strong acid is used to etch the surface of the carbon fiber and enter the holes, so that pits and cracks are generated on the fiber surface, and micropores and defects are enlarged, thereby improving the bonding between the carbon fiber and the matrix, but at the same time, the single fiber strength is also reduced, so that the mechanical modification is limited. Therefore, carbon nanotubes are further deposited on the surface by chemical vapor deposition, and the deposited carbon nanotubes react with the edge carbon atoms of the carbon fiber. The surface grafting improves the specific surface roughness and capillary action of the third modified carbon fiber and the epoxy composite material, improves the interface compatibility between the two, and at the same time, the carbon fiber treated with acid is thickened, the single fiber strength is further improved, and the mechanical modification effect on the resin material is enhanced.

[0019] The high-strength composite electric pole material prepared by the present invention is synergistically modified by multiple modified carbon fibers, thereby improving the compatibility and wettability of the carbon fibers with the epoxy resin matrix, and the mechanical modification effect is significantly enhanced, thereby preparing a high-strength composite electric pole material. At the same time, the material has good heat resistance, aging resistance, solvent resistance stability, good thermal conductivity, and broad application prospects. DETAILED DESCRIPTION

[0020] The technical solutions in the embodiments of the present invention are described clearly and completely below. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of them. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0021] Carbon fiber, 7μm diameter, 300μm length, 500 mesh black powder.

[0022] Preparation Example 1 Preparation of the first modified carbon fiber Here’s how: S1. 8 g of tetrabutyl titanate, 4 g of aluminum isopropoxide and 10 g of ethyl orthosilicate were dissolved in 200 mL of ethanol, 100 mL of water and 3 g of NaOH were added, and the reaction was stirred for 1 h to form a sol; S2. 10 g of carbon fiber was added to 30 g of sol, heated to 50 ° C, stirred for 5 h, calcined at 500 ° C for 2 h, washed, dried, and ground to obtain ceramic carbon fiber; S3. 10 g of ceramic carbon fiber was added to 200 mL of water, 3 g of tannic acid and 0.3 g of catalyst were added, heated to 50° C., stirred for reaction for 3 h, centrifuged, washed, and dried to obtain modified ceramic carbon fiber; The catalyst is a Tris-HCl solution with a pH of 8.5; S4. 10 g of the modified ceramic carbon fiber was added to 100 mL of dichloromethane, and 2 g of 1-chlorobenzotriazole and 1 g of NaOH were added. The mixture was heated under reflux and stirred for 2 h. The mixture was centrifuged, washed, and dried to obtain a first modified carbon fiber.

[0023] Preparation Example 2 Preparation of the First Modified Carbon Fiber Here’s how: S1. 10 g of tetrabutyl titanate, 7 g of aluminum isopropoxide and 15 g of tetraethyl orthosilicate were dissolved in 200 mL of ethanol, 100 mL of water and 5 g of KOH were added, and the reaction was stirred for 1 h to form a sol; S2. 15 g of carbon fiber was added to 50 g of sol, heated to 70 ° C, stirred for 7 h, calcined at 600 ° C for 4 h, washed, dried, and ground to obtain ceramic carbon fiber; S3. 10 g of ceramic carbon fiber was added to 200 mL of water, 5 g of tannic acid and 0.5 g of catalyst were added, heated to 60° C., stirred for reaction for 5 h, centrifuged, washed, and dried to obtain modified ceramic carbon fiber; The catalyst is a Tris-HCl solution with a pH of 9.5; S4. 10 g of the modified ceramic carbon fiber was added to 100 mL of dichloromethane, 3 g of 1-chlorobenzotriazole and 2 g of KOH were added, and the mixture was heated under reflux and stirred for 4 h, centrifuged, washed, and dried to obtain a first modified carbon fiber.

[0024] Preparation Example 3 Preparation of the first modified carbon fiber Here’s how: S1. 9 g of tetrabutyl titanate, 5.5 g of aluminum isopropoxide and 12 g of ethyl orthosilicate were dissolved in 200 mL of ethanol, 100 mL of water and 4 g of KOH were added, and the reaction was stirred for 1 h to form a sol; S2. 12 g of carbon fiber was added to 40 g of sol, heated to 60 ° C, stirred for 6 h, calcined at 550 ° C for 3 h, washed, dried, and ground to obtain ceramic carbon fiber; S3. 10 g of ceramic carbon fiber was added to 200 mL of water, 4 g of tannic acid and 0.4 g of catalyst were added, heated to 55° C., stirred for 4 h, centrifuged, washed, and dried to obtain modified ceramic carbon fiber; The catalyst is a Tris-HCl solution with a pH of 9; S4. 10 g of the modified ceramic carbon fiber was added to 100 mL of dichloromethane, and 2.5 g of 1-chlorobenzotriazole and 1.5 g of NaOH were added. The mixture was heated under reflux and stirred for 3 h. The mixture was centrifuged, washed, and dried to obtain a first modified carbon fiber.

[0025] Comparative Preparation Example 1 Compared with Preparation Example 3, the difference is that tetrabutyl titanate is not added in step S1.

[0026] The details are as follows: S1. Dissolve 5.5 g aluminum isopropoxide and 21 g ethyl orthosilicate in 200 mL ethanol, add 100 mL water and 4 g KOH, and stir to react for 1 h to form a sol.

[0027] Comparative Preparation Example 2 Compared with Preparation Example 3, the difference is that steps S1 and S2 are not performed.

[0028] The details are as follows: S1. Add 10 g of carbon fiber to 200 mL of water, add 4 g of tannic acid and 0.4 g of catalyst, heat to 55 ° C, stir and react for 4 h, centrifuge, wash, and dry to obtain modified carbon fiber; The catalyst is a Tris-HCl solution with a pH of 9; S4. 10 g of the modified carbon fiber was added to 100 mL of dichloromethane, and 2.5 g of 1-chlorobenzotriazole and 1.5 g of NaOH were added. The mixture was heated under reflux and stirred for 3 h. The mixture was centrifuged, washed, and dried to obtain a first modified carbon fiber.

[0029] Comparative Preparation Example 3 Compared with Preparation Example 3, the difference is that step S3 is not performed.

[0030] The details are as follows: S1. 9 g of tetrabutyl titanate, 5.5 g of aluminum isopropoxide and 12 g of ethyl orthosilicate were dissolved in 200 mL of ethanol, 100 mL of water and 4 g of KOH were added, and the reaction was stirred for 1 h to form a sol; S2. 12 g of carbon fiber was added to 40 g of sol, heated to 60 ° C, stirred for 6 h, calcined at 550 ° C for 3 h, washed, dried, and ground to obtain ceramic carbon fiber; S3. 10 g of ceramic carbon fiber was added to 100 mL of dichloromethane, and 2.5 g of 1-chlorobenzotriazole and 1.5 g of NaOH were added. The mixture was heated under reflux and stirred for 3 h. The mixture was centrifuged, washed, and dried to obtain a first modified carbon fiber.

[0031] Comparative Preparation Example 4 Compared with Preparation Example 3, the difference is that step S4 is not performed.

[0032] The details are as follows: S1. 9 g of tetrabutyl titanate, 5.5 g of aluminum isopropoxide and 12 g of ethyl orthosilicate were dissolved in 200 mL of ethanol, 100 mL of water and 4 g of KOH were added, and the reaction was stirred for 1 h to form a sol; S2. 12 g of carbon fiber was added to 40 g of sol, heated to 60 ° C, stirred for 6 h, calcined at 550 ° C for 3 h, washed, dried, and ground to obtain ceramic carbon fiber; S3. Add 10 g of ceramic carbon fiber to 200 mL of water, add 4 g of tannic acid and 0.4 g of catalyst, heat to 55° C., stir and react for 4 h, centrifuge, wash, and dry to obtain a modified ceramic carbon fiber, which is the first modified carbon fiber; The catalyst is a Tris-HCl solution with a pH of 9.

[0033] Preparation Example 4 Preparation of the Second Modified Carbon Fiber Here’s how: T1. Add 12 g of carbon fiber to a Tris-HCl solution with a pH value of 8.5, add 6 g of dopamine hydrochloride, heat to 50°C, stir to react for 3 h, centrifuge, wash, and dry to obtain modified carbon fiber; T2. 10 g of modified carbon fiber, 3 g of zirconium tetrachloride, and 2 g of 2-aminoterephthalic acid were added to 400 mL of a mixed solution of N, N-dimethylformamide and acetic acid (volume ratio of 19:1), ultrasonically dispersed at 400 W for 20 min, hydrothermally reacted at 120 ° C for 20 h, centrifuged, washed, and dried to obtain UiO-66-NH2 modified carbon fiber; T3. 4 g of octachloropropyl silsesquioxane and 12 g of UiO-66-NH2 modified carbon fiber were added to 200 mL of dichloromethane, heated under reflux for 2 h, centrifuged, washed, and dried to obtain a second modified carbon fiber.

[0034] Preparation Example 5 Preparation of the Second Modified Carbon Fiber Here’s how: T1. Add 15 g of carbon fiber to a Tris-HCl solution with a pH value of 9.5, add 9 g of dopamine hydrochloride, heat to 60°C, stir and react for 5 hours, centrifuge, wash, and dry to obtain modified carbon fiber; T2. 14 g of modified carbon fiber, 4 g of zirconium tetrachloride, and 3 g of 2-aminoterephthalic acid were added to 400 mL of a mixed solution of N,N-dimethylformamide and acetic acid (volume ratio of 19:1), ultrasonically dispersed at 400 W for 20 min, hydrothermally reacted at 140 ° C for 24 h, centrifuged, washed, and dried to obtain UiO-66-NH2 modified carbon fiber; T3. 7 g of octachloropropyl silsesquioxane and 15 g of UiO-66-NH2 modified carbon fiber were added to 200 mL of dichloromethane, heated under reflux for 4 h, centrifuged, washed, and dried to obtain a second modified carbon fiber.

[0035] Preparation Example 6 Preparation of the Second Modified Carbon Fiber Here’s how: T1. Add 13 g of carbon fiber to a Tris-HCl solution with a pH value of 9, add 7 g of dopamine hydrochloride, heat to 55°C, stir to react for 4 hours, centrifuge, wash, and dry to obtain modified carbon fiber; T2. 12 g of modified carbon fiber, 3.2 g of zirconium tetrachloride, and 2.6 g of 2-aminoterephthalic acid were added to 400 mL of a mixed solution of N, N-dimethylformamide and acetic acid (volume ratio of 19:1), ultrasonically dispersed at 400 W for 20 min, hydrothermally reacted at 130 ° C for 22 h, centrifuged, washed, and dried to obtain UiO-66-NH2 modified carbon fiber; T3. 5.6 g of octachloropropyl silsesquioxane and 13 g of UiO-66-NH2 modified carbon fiber were added to 200 mL of dichloromethane, heated under reflux for 3 h, centrifuged, washed, and dried to obtain a second modified carbon fiber.

[0036] Comparative Preparation Example 5 Compared with Preparation Example 6, the difference is that step T1 is not performed.

[0037] The details are as follows: T1. 12g carbon fiber, 3.2g zirconium tetrachloride, and 2.6g 2-aminoterephthalic acid were added to 400mL of a mixed solution of N,N-dimethylformamide and acetic acid (volume ratio of 19:1), ultrasonically dispersed at 400W for 20min, hydrothermally reacted at 130℃ for 22h, centrifuged, washed, and dried to obtain UiO-66-NH2 modified carbon fiber; T2. 5.6 g of octachloropropyl silsesquioxane and 13 g of UiO-66-NH2 modified carbon fiber were added to 200 mL of dichloromethane, heated under reflux for 3 h, centrifuged, washed, and dried to obtain a second modified carbon fiber.

[0038] Comparative Preparation Example 6 Compared with Preparation Example 6, the difference is that step T2 is not performed.

[0039] The details are as follows: T1. Add 13 g of carbon fiber to a Tris-HCl solution with a pH value of 9, add 7 g of dopamine hydrochloride, heat to 55°C, stir to react for 4 hours, centrifuge, wash, and dry to obtain modified carbon fiber; T2. 5.6 g of octachloropropylsilsesquioxane and 13 g of modified carbon fiber were added to 200 mL of dichloromethane, heated to reflux for reaction for 3 h, centrifuged, washed, and dried to obtain a second modified carbon fiber.

[0040] Comparative Preparation Example 7 Compared with Preparation Example 6, the difference is that step T3 is not performed.

[0041] The details are as follows: T1. Add 13 g of carbon fiber to a Tris-HCl solution with a pH value of 9, add 7 g of dopamine hydrochloride, heat to 55°C, stir to react for 4 hours, centrifuge, wash, and dry to obtain modified carbon fiber; T2. Add 12 g of modified carbon fiber, 3.2 g of zirconium tetrachloride, and 2.6 g of 2-aminoterephthalic acid into 400 mL of a mixed solution of N,N-dimethylformamide and acetic acid (volume ratio of 19:1), perform ultrasonic dispersion at 400 W for 20 min, perform hydrothermal reaction at 130 ° C for 22 h, centrifuge, wash, and dry to obtain UiO-66-NH2 modified carbon fiber, which is the second modified carbon fiber.

[0042] Preparation Example 7 Preparation of the Third Modified Carbon Fiber Here’s how: U1. 10 g of carbon fiber was added to 30 mL of concentrated nitric acid, heated to reflux and stirred for 1 h, centrifuged, washed, and dried to obtain acid-treated carbon fiber; U2. Place 10g of acid-treated carbon fiber in the center of a quartz porcelain boat and spread it evenly, add 2mL of 1wt% ferric chloride solution, dry, heat to 400°C under Ar gas protection, replace with hydrogen at a rate of 100mL / min, heat to 600°C, introduce n-hexane at a rate of 0.1mL / min, react for 30min, cool to room temperature under Ar gas protection, and obtain a third modified carbon fiber.

[0043] Preparation Example 8 Preparation of the Third Modified Carbon Fiber Here’s how: U1. 10 g of carbon fiber was added to 50 mL of concentrated nitric acid, heated to reflux with stirring for 3 h, centrifuged, washed, and dried to obtain acid-treated carbon fiber; U2. Place 10g of acid-treated carbon fiber in the center of a quartz porcelain boat and spread it evenly, add 2mL of 3wt% ferric sulfate solution, dry, heat to 500°C under Ar gas protection, replace with hydrogen at a rate of 120mL / min, heat to 700°C, introduce n-hexane at a rate of 0.3mL / min, react for 60min, cool to room temperature under Ar gas protection, and obtain a third modified carbon fiber.

[0044] Preparation Example 9 Preparation of the Third Modified Carbon Fiber Here’s how: U1. 10 g of carbon fiber was added to 40 mL of concentrated nitric acid, heated to reflux and stirred for 2 h, centrifuged, washed, and dried to obtain acid-treated carbon fiber; U2. Place 10g of acid-treated carbon fiber in the center of a quartz porcelain boat and spread it evenly, add 2mL of 2wt% ferric nitrate solution, dry, heat to 450°C under Ar gas protection, replace with hydrogen at a flow rate of 110mL / min, heat to 650°C, introduce n-hexane at a flow rate of 0.2mL / min, react for 45min, cool to room temperature under Ar gas protection, and obtain the third modified carbon fiber.

[0045] Comparative Preparation Example 8 Compared with Preparation Example 6, the difference is that step U1 is not performed.

[0046] The details are as follows: Place 10g of carbon fiber in the center of a quartz porcelain boat and spread it evenly, add 2mL of 2wt% ferric nitrate solution, dry, heat to 450°C under Ar gas protection, replace with hydrogen at a hydrogen flow rate of 110mL / min, heat to 650°C, introduce n-hexane at a flow rate of 0.2mL / min, react for 45min, cool to room temperature under Ar gas protection, and obtain a third modified carbon fiber.

[0047] Comparative Preparation Example 9 Compared with Preparation Example 6, the difference is that step U2 is not performed.

[0048] The details are as follows: 10 g of carbon fiber was added into 40 mL of concentrated nitric acid, heated under reflux and stirred for reaction for 2 h, centrifuged, washed, and dried to obtain acid-treated carbon fiber, which is the third modified carbon fiber.

[0049] Example 1

[0050] This embodiment provides a high-strength composite pole material.

[0051] Raw material composition (parts by weight): 90 parts of E-51 epoxy resin, 10 parts of the first modified carbon fiber prepared in Preparation Example 1, 8 parts of the second modified carbon fiber prepared in Preparation Example 4, 3 parts of the third modified carbon fiber prepared in Preparation Example 7, and 30 parts of diethylenetriamine.

[0052] The preparation method comprises the following steps: E-51 epoxy resin, the first modified carbon fiber, the second modified carbon fiber, and the third modified carbon fiber were mixed, stirred for 15 minutes, diethylenetriamine was added, poured into a mold, heated to 100°C, and cured for 3 hours to obtain a high-strength composite pole material.

[0053] Example 2

[0054] This embodiment provides a high-strength composite pole material.

[0055] Raw material composition (parts by weight): 120 parts of E-51 epoxy resin, 15 parts of the first modified carbon fiber prepared in Preparation Example 2, 12 parts of the second modified carbon fiber prepared in Preparation Example 5, 5 parts of the third modified carbon fiber prepared in Preparation Example 8, and 50 parts of triethylenetetramine.

[0056] The preparation method comprises the following steps: E-51 epoxy resin, the first modified carbon fiber, the second modified carbon fiber, and the third modified carbon fiber were mixed, stirred for 15 minutes, triethylenetetramine was added, poured into a mold, heated to 120°C, and cured for 1 hour to obtain a high-strength composite pole material.

[0057] Example 3

[0058] This embodiment provides a high-strength composite pole material.

[0059] Raw material composition (parts by weight): 110 parts of E-51 epoxy resin, 12 parts of the first modified carbon fiber prepared in Preparation Example 3, 10 parts of the second modified carbon fiber prepared in Preparation Example 6, 4 parts of the third modified carbon fiber prepared in Preparation Example 9, and 40 parts of triethylenetetramine.

[0060] The preparation method comprises the following steps: E-51 epoxy resin, the first modified carbon fiber, the second modified carbon fiber, and the third modified carbon fiber were mixed, stirred for 15 minutes, triethylenetetramine was added, poured into a mold, heated to 110°C, and cured for 2 hours to obtain a high-strength composite pole material.

[0061] Comparative Example 1 Compared with Example 3, the difference is that the first modified carbon fiber is prepared by Comparative Preparation Example 1.

[0062] Comparative Example 2 Compared with Example 3, the difference is that the first modified carbon fiber is prepared by Comparative Preparation Example 2.

[0063] Comparative Example 3 Compared with Example 3, the difference is that the first modified carbon fiber is prepared by Comparative Preparation Example 3.

[0064] Comparative Example 4 Compared with Example 3, the difference is that the first modified carbon fiber is prepared by Comparative Preparation Example 4.

[0065] Comparative Example 5 Compared with Example 3, the difference is that the second modified carbon fiber is prepared by Comparative Preparation Example 5.

[0066] Comparative Example 6 Compared with Example 3, the difference is that the second modified carbon fiber is prepared by Comparative Preparation Example 6.

[0067] Comparative Example 7 Compared with Example 3, the difference is that the second modified carbon fiber is prepared by Comparative Preparation Example 7.

[0068] Comparative Example 8 Compared with Example 3, the difference is that the third modified carbon fiber is prepared by Comparative Preparation Example 8.

[0069] Comparative Example 9 Compared with Example 3, the difference is that the third modified carbon fiber is prepared by Comparative Preparation Example 9.

[0070] Comparative Example 10 The difference compared with Example 3 is that the first modified carbon fiber is not added.

[0071] Raw material composition (parts by weight): 110 parts of E-51 epoxy resin, 10 parts of the second modified carbon fiber prepared in Preparation Example 6, 4 parts of the third modified carbon fiber prepared in Preparation Example 9, and 40 parts of triethylenetetramine.

[0072] Comparative Example 11 The difference compared with Example 3 is that the second modified carbon fiber is not added.

[0073] Raw material composition (parts by weight): 110 parts of E-51 epoxy resin, 12 parts of the first modified carbon fiber prepared in Preparation Example 3, 4 parts of the third modified carbon fiber prepared in Preparation Example 9, and 40 parts of triethylenetetramine.

[0074] Comparative Example 12 The difference compared with Example 3 is that the second modified carbon fiber is not added.

[0075] Raw material composition (parts by weight): 110 parts of E-51 epoxy resin, 12 parts of the first modified carbon fiber prepared in Preparation Example 3, 10 parts of the second modified carbon fiber prepared in Preparation Example 6, and 40 parts of triethylenetetramine.

[0076] Test Example 1 The high-strength composite pole materials prepared in Examples 1-3 and Comparative Examples 1-12 were subjected to mechanical property tests, and the results are shown in Table 1.

[0077] The bending strength and tensile strength tests are carried out according to the mechanical testing standards of GB / T 1040-2006 and GB / T 9341-2008; the impact strength test is carried out according to the standard of GB / T 1043-2008.

[0078] Table 1

[0079] It can be seen from the above table that the high-strength composite pole materials prepared in Examples 1-3 of the present invention have good mechanical properties.

[0080] Test Example 2 The high-strength composite pole materials prepared in Examples 1-3 and Comparative Examples 1-12 were subjected to performance tests, and the results are shown in Table 2.

[0081] Salt spray resistance: Salt spray resistance test is carried out according to the standard test of GB / T 1771-1991.

[0082] Aging resistance: After the sample is aged at 180℃ for 10h, the tensile strength of the sample is tested according to the mechanical test standard of GB / T 1040-2006, and the tensile strength retention rate (%) is calculated. The calculation method is: tensile strength retention rate (%) = tensile strength after aging / tensile strength before aging × 100%.

[0083] Heat resistance: After heating the sample at 120℃ for 5 days, take it out and test its weight loss rate (%).

[0084] Thermal conductivity: Use thermal conductivity tester to test the thermal conductivity of the material.

[0085] Table 2

[0086] It can be seen from the above table that the high-strength composite pole materials prepared in Examples 1-3 of the present invention have good salt spray resistance, heat resistance, aging resistance, and high thermal conductivity.

[0087] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims

1. A high-strength composite pole material, characterized in that: The invention is prepared from the following raw materials in parts by weight: 90-120 parts of epoxy resin, 10-15 parts of first modified carbon fiber, 8-12 parts of second modified carbon fiber, 3-5 parts of third modified carbon fiber and 30-50 parts of curing agent. The first modified carbon fiber is a carbon fiber which is coated with titanium oxide / aluminum oxide / silicon oxide, modified with tannic acid and coupled with benzotriazole. The second modified carbon fiber is a carbon fiber which is modified with polydopamine, coated with UiO-66-NH2 and prepared with octachloropropylsilsesquioxane. The third modified carbon fiber is a carbon fiber deposited on the surface of carbon nanotubes.

2. The high-strength composite pole material according to claim 1, characterized in that: The preparation method of the first modified carbon fiber is as follows: S1. Tetrabutyl titanate, aluminum isopropoxide and tetraethyl orthosilicate are dissolved in ethanol, water and alkali are added, and the reaction is stirred to form a sol; S2. adding carbon fiber to the sol, heating and stirring the reaction, calcining, washing, drying, and grinding to obtain ceramic carbon fiber; S3. The ceramic carbon fiber is added to water, tannic acid and a catalyst are added, heated and stirred for reaction, centrifuged, washed, and dried to obtain a modified ceramic carbon fiber; S4. Add the modified ceramic carbon fiber into dichloromethane, add 1-chlorobenzotriazole and a base, heat under reflux and stir to react, centrifuge, wash, and dry to obtain a first modified carbon fiber.

3. The high-strength composite pole material according to claim 2, characterized in that: The mass ratio of tetrabutyl titanate, aluminum isopropoxide, tetraethyl orthosilicate and alkali in step S1 is 8-10:4-7:10-15:3-5, and the alkali is NaOH or KOH; the mass ratio of carbon fiber and sol in step S2 is 10-15:30-50, the temperature of the heating and stirring reaction is 50-70°C, the time is 5-7h, the temperature of the calcination is 500-600°C, and the time is 2-4h; the ceramic carbon fiber in step S3 The mass ratio of fiber, tannic acid and catalyst is 10:3-5:0.3-0.5, the catalyst is Tris-HCl solution with pH=8.5-9.5, the temperature of the heating and stirring reaction is 50-60°C, and the time is 3-5h; the mass ratio of the modified ceramic carbon fiber, 1-chlorobenzotriazole and alkali in step S4 is 10:2-3:1-2, the alkali is NaOH or KOH, and the time of the heating reflux stirring reaction is 2-4h.

4. The high-strength composite pole material according to claim 1, characterized in that: The preparation method of the second modified carbon fiber is as follows: T1. Adding carbon fiber to Tris-HCl solution, adding dopamine hydrochloride, heating and stirring to react, centrifuging, washing, and drying to obtain modified carbon fiber; T2. The modified carbon fiber, zirconium tetrachloride, and 2-aminoterephthalic acid were added to a mixed solution of N,N-dimethylformamide and acetic acid, ultrasonically dispersed, hydrothermally reacted, centrifuged, washed, and dried to obtain UiO-66-NH2 modified carbon fiber; T3. Add octachloropropylsilsesquioxane and UiO-66-NH2 modified carbon fiber into dichloromethane, heat to reflux reaction, centrifuge, wash, and dry to obtain a second modified carbon fiber.

5. The high-strength composite pole material according to claim 4, characterized in that: The mass ratio of the carbon fiber and dopamine hydrochloride in step T1 is 12-15:6-9, the pH value of the Tris-HCl solution is 8.5-9.5, the temperature of the heating and stirring reaction is 50-60°C, and the time is 3-5h; the mass ratio of the modified carbon fiber, zirconium tetrachloride, and 2-aminoterephthalic acid in step T2 is 10-14:3-4:2-3, the temperature of the hydrothermal reaction is 120-140°C, and the time is 20-24h; the mass ratio of octachloropropylsilsesquioxane and UiO-66-NH2 modified carbon fiber in step T3 is 4-7:12-15, and the time of the heating reflux reaction is 2-4h.

6. The high-strength composite pole material according to claim 1, characterized in that: The preparation method of the third modified carbon fiber is as follows: U1. Adding carbon fiber to concentrated nitric acid, heating to reflux with stirring, centrifuging, washing, and drying to obtain acid-treated carbon fiber; U2. Place the acid-treated carbon fiber in the center of a quartz boat and spread it evenly, drop an iron solution, dry, heat to a first temperature under inert gas protection, replace with hydrogen, heat to a second temperature, introduce n-hexane, react, cool to room temperature under inert gas protection, and obtain a third modified carbon fiber.

7. The high-strength composite pole material according to claim 6, characterized in that: In step U1, the solid-liquid ratio of the carbon fiber and concentrated nitric acid is 1:3-5g / mL, and the heating reflux stirring reaction time is 1-3h; in step U2, the first temperature is 400-500°C, the second temperature is 600-700°C, the hydrogen ventilation volume is 100-120mL / min, the n-hexane ventilation volume is 0.1-0.3mL / min, the reaction time is 30-60min, and the iron solution is ferric chloride, ferric nitrate or ferric sulfate solution with a concentration of 1-3wt%.

8. The high-strength composite pole material according to claim 1, characterized in that: The curing agent is selected from at least one of diethylenetriamine, triethylenetetramine, meta-phenylenediamine and meta-xylylenediamine, and the epoxy resin is E-51 or E-44.

9. A method for preparing the high-strength composite pole material according to any one of claims 1 to 8, characterized in that: The following steps are involved: The epoxy resin, the first modified carbon fiber, the second modified carbon fiber and the third modified carbon fiber are evenly mixed, a curing agent is added, poured into a mold, heated and cured, and a high-strength composite pole material is obtained.

10. The preparation method according to claim 9, characterized in that: The temperature of the heating curing is 100-120° C. and the time is 1-3 hours.

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