A high-strength composite pole material and its preparation method

Abstract

The present invention provides a high-strength composite pole material and a preparation method thereof, belonging to the technical field of composite materials. It 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 high-strength composite pole material prepared by the present invention is synergistically modified by various modified carbon fibers, improving the compatibility and wettability between the carbon fiber and the epoxy resin substrate, and significantly enhancing the mechanical modification effect, thereby obtaining a high-strength composite pole material. At the same time, it has good heat resistance, aging resistance, solvent stability, good thermal conductivity, and broad application prospects.

Description

Technical Field

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

[0002] In the field of power transmission and distribution, as an important infrastructure, the performance of electric poles directly affects the safety and stability of the power grid. However, traditional steel and concrete electric poles have many deficiencies, such as large weight, difficult construction and transportation, poor corrosion resistance, etc. These problems are particularly prominent in areas with severe marine and salt spray corrosion. Epoxy resin, as a versatile, high-strength, and chemically resistant polymer, has become an ideal matrix for preparing composite electric pole materials. Its high strength and excellent adhesion enable epoxy resin to firmly bond with other materials after curing, forming 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 the composite electric pole material.

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

[0004] Carbon fiber (CF) reinforcing materials have many excellent properties such as high strength, high modulus, strong thermal stability, high electrical conductivity, and corrosion resistance. The resin matrix composite material made of CF as the reinforcing body has a density only 1 / 5 of that of steel, but its strength reaches 5 times that of steel. It is a commonly used reinforcing fiber for preparing high-performance resin matrix 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. Applying carbon fiber composite materials to the reinforcement of cement electric poles for power transmission and distribution lines can well solve safety problems such as cracks in cement poles, and does not increase the structural size and weight of the poles. It has characteristics such as increased tensile strength, corrosion resistance, and durability. However, in the use process, because pure epoxy resin and carbon fiber are mostly used in combination, although epoxy resin itself is a thermosetting resin with good heat resistance, high strength, and good adhesion to the substrate, it also has problems such as brittleness, poor impact resistance, anti-peeling, and vibration fatigue resistance, resulting in an unsatisfactory composite effect between the resin and carbon fiber. In addition, due to construction condition limitations, the indexes such as tensile effect and weather resistance after reinforcement are not stable enough. Therefore, the improvement of the preparation of carbon fiber / epoxy resin composite materials and the specific construction methods are urgently needed. Summary of the Invention

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

[0006] The technical solution of the present invention is realized as follows:

[0007] The present invention provides a high-strength composite pole material, which 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 modified by tannic acid and coupled with benzotriazole after being coated with titanium oxide / aluminum oxide / silicon oxide. The second modified carbon fiber is a carbon fiber prepared by modifying with polydopamine, coating with UiO-66-NH2, and reacting with octachloropropyl sesquisiloxane. The third modified carbon fiber is a carbon fiber with carbon fiber deposited on the surface of carbon nanotubes.

[0008] As a further improvement of the present invention, the preparation method of the first modified carbon fiber is as follows:

[0009] S1. Dissolve tetrabutyl titanate, aluminum isopropoxide, and tetraethyl orthosilicate in ethanol, add water and alkali, and stir and react to form a sol;

[0010] S2. Add carbon fiber to the sol, heat and stir to react, calcine, wash, dry, and grind to obtain ceramized carbon fiber;

[0011] S3. Add the ceramized carbon fiber to water, add tannic acid and a catalyst, heat and stir to react, centrifuge, wash, and dry to obtain modified ceramized carbon fiber;

[0012] S4. Add the modified ceramized carbon fiber to dichloromethane, add 1-chlorobenzotriazole and alkali, heat and reflux and stir to react, centrifuge, wash, and dry to obtain the first modified carbon fiber.

[0013] As a further improvement of the present invention, the mass ratio of tetrabutyl titanate, aluminum isopropoxide, tetraethyl orthosilicate and base in step S1 is 8-10:4-7:10-15:3-5, and the base is NaOH or KOH; in step S2, the mass ratio of carbon fiber to sol is 10-15:30-50, the temperature of the heating and stirring reaction is 50-70 °C, the time is 5-7 h, the calcination temperature is 500-600 °C, and the time is 2-4 h; in step S3, the mass ratio of ceramized carbon 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 3-5 h; in step S4, the mass ratio of modified ceramized carbon fiber, 1-chlorobenzotriazole and base is 10:2-3:1-2, the base is NaOH or KOH, and the time of the heating reflux stirring reaction is 2-4 h.

[0014] As a further improvement of the present invention, the preparation method of the second modified carbon fiber is as follows:

[0015] T1. Add carbon fiber into Tris-HCl solution, add dopamine hydrochloride, heat and stir for reaction, centrifuge, wash, and dry to obtain modified carbon fiber;

[0016] T2. Add modified carbon fiber, zirconium tetrachloride, and 2-aminoterephthalic acid into a mixed solution of N,N-dimethylformamide and acetic acid, ultrasonically disperse evenly, carry out hydrothermal reaction, centrifuge, wash, and dry to obtain UiO-66-NH2 modified carbon fiber;

[0017] T3. Add octachloropropyl sesquisiloxane and UiO-66-NH2 modified carbon fiber into dichloromethane, heat and reflux for reaction, centrifuge, wash, and dry to obtain the second modified carbon fiber.

[0018] As a further improvement of the present invention, in step T1, the mass ratio of carbon fiber to dopamine hydrochloride 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 3-5 h; in step T2, the mass ratio of modified carbon fiber, zirconium tetrachloride, and 2-aminoterephthalic acid is 10-14:3-4:2-3, the temperature of the hydrothermal reaction is 120-140 °C, and the time is 20-24 h; in step T3, the mass ratio of octachloropropyl sesquisiloxane and UiO-66-NH2 modified carbon fiber is 4-7:12-15, and the time of the heating reflux reaction is 2-4 h.

[0019] As a further improvement of the present invention, the preparation method of the third modified carbon fiber is as follows:

[0020] U1. Add carbon fiber into concentrated nitric acid, heat under reflux with stirring for reaction, centrifuge, wash, and dry to obtain acid-treated carbon fiber.

[0021] U2. Place the acid-treated carbon fiber in the center of a quartz porcelain boat and spread it evenly, dropwise add an iron solution, dry, heat to a first temperature under the protection of an inert gas, under the condition of replacing with hydrogen, heat to a second temperature, introduce n-hexane, react, and cool to room temperature under the protection of an inert gas to obtain a third modified carbon fiber.

[0022] As a further improvement of the present invention, in step U1, the solid-liquid ratio of the carbon fiber to the concentrated nitric acid is 1:3 - 5 g / mL, and the time for the heat reflux stirring reaction is 1 - 3 h; in step U2, the first temperature is 400 - 500 °C, the second temperature is 600 - 700 °C, the ventilation rate of the hydrogen is 100 - 120 mL / min, the ventilation rate of the n-hexane is 0.1 - 0.3 mL / min, the reaction time is 30 - 60 min, and the iron solution is a ferric chloride, ferric nitrate or ferric sulfate solution with a concentration of 1 - 3 wt%.

[0023] As a further improvement of the present invention, the curing agent is selected from at least one of diethylenetriamine, triethylenetetramine, m-phenylenediamine, and m-xylylenediamine, and the epoxy resin is E-51 or E-44.

[0024] The present invention further protects a preparation method of the above-mentioned high-strength composite electric pole material, which includes the following steps:

[0025] Mix epoxy resin, the first modified carbon fiber, the second modified carbon fiber, and the third modified carbon fiber evenly, add a curing agent, pour it into a mold, and cure by heating to obtain a high-strength composite electric pole material.

[0026] As a further improvement of the present invention, the temperature for heat curing is 100 - 120 °C, and the time is 1 - 3 h.

[0027] The present invention has the following beneficial effects:

[0028] The first modified carbon fiber prepared by the present invention is mixed with carbon fiber using an organic titanium-aluminum-silicate sol. After calcination, a titanium oxide / aluminum oxide / silicon oxide ceramic layer is coated on the surface, introducing oxygen-containing functional groups to increase the surface polarity of the composite material. At the same time, it can improve the fracture toughness of the composite material, significantly enhance the heat resistance of the carbon fiber. High-temperature treatment can improve the crystallinity and thermal stability of the carbon fiber, and the ceramic coating can provide good protection at high temperatures to prevent the carbon fiber from contacting 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 on 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. The surface is modified with reactive tannic acid, with conjugated groups and hydroxyl groups, etc. On the one hand, it can improve the compatibility with epoxy resin, and on the other hand, it can react with 1-chlorobenzotriazole to introduce free radical capture groups, thereby being able to capture free radicals generated during aging in the composite material and block the continuous reaction, so as to play a better aging resistance under synergistic action.

[0029] The second modified carbon fiber prepared by the present invention is modified with polydopamine on its surface, adsorbing 2-aminoterephthalic acid, and in-situ reacting to generate UiO-66-NH2 on the carbon fiber surface. It has advantages such as large porosity and specific surface area, diverse structures and functions, and containing unsaturated metal sites. To a great extent, it improves the interfacial bonding performance of the carbon fiber composite material. At the same time, due to the presence of amino groups and the amino groups on polydopamine, it promotes the curing reaction of the epoxy composite material, grafts onto the carbon fiber surface, forms a highly mechanically interlocked composite structure and releases interfacial residual stress, thereby obtaining a carbon fiber-reinforced composite material with excellent mechanical properties and tribological properties. Then it reacts with octachloropropylsilsesquioxane. There are many adjustable reactive functional groups on the POSS material. These reactive functional groups 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, it also improves the thermal conductivity of the material, and the heat energy quickly dissipates through the formed network, thereby improving the heat resistance of the material.

[0030] The third modified carbon fiber prepared by the present invention is first treated with strong acid. The carbon fiber is placed in a concentrated nitric acid solution. Using the corrosiveness of the strong acid, the surface of the carbon fiber is etched and enters the pores, generating pits and cracks on the fiber surface, expanding the micropores and defects, thereby improving the bonding property between the carbon fiber and the matrix. However, at the same time, its single fiber strength is reduced, so its mechanical modification is limited. Then, carbon nanotubes are further deposited on its surface by chemical vapor deposition. The deposited carbon nanotubes carry out a chemical reaction with the edge carbon atoms of the carbon fiber, and the grafting on its surface improves the specific surface roughness and capillary action of the third modified carbon fiber and the epoxy composite, improves the interfacial compatibility between the two, and at the same time, the carbon fiber after acid treatment is thickened, further improving its single fiber strength, and enhancing the mechanical modification effect on the resin material.

[0031] The high-strength composite electric pole material prepared by the present invention is synergistically modified by a variety of modified carbon fibers, improving the compatibility and wettability between the carbon fiber and the epoxy resin substrate, and significantly enhancing the mechanical modification effect, thereby preparing a high-strength composite electric pole material. At the same time, it has good heat resistance, aging resistance, solvent stability, good thermal conductivity, and has broad application prospects. Specific embodiments

[0032] The technical solutions in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all the embodiments. All other embodiments obtained by those of ordinary skill in the art based on the embodiments of the present invention without creative efforts shall fall within the protection scope of the present invention.

[0033] Carbon fiber, with a diameter of 7 μm, a length of 300 μm, and a 500-mesh black powder.

[0034] Preparation Example 1 Preparation of the first modified carbon fiber

[0035] The method is as follows:

[0036] S1. Dissolve 8 g of tetrabutyl titanate, 4 g of aluminum isopropoxide, and 10 g of tetraethyl orthosilicate in 200 mL of ethanol, add 100 mL of water and 3 g of NaOH, and stir and react for 1 h to form a sol;

[0037] S2. Add 10 g of carbon fiber to 30 g of the sol, heat to 50 °C, stir and react for 5 h, calcine at 500 °C for 2 h, wash, dry, and grind to obtain ceramicized carbon fiber;

[0038] S3. Add 10 g of ceramicized carbon fiber to 200 mL of water, add 3 g of tannic acid and 0.3 g of catalyst, heat to 50 °C, stir and react for 3 h, centrifuge, wash, and dry to obtain modified ceramicized carbon fiber;

[0039] The catalyst is a Tris-HCl solution with a pH of 8.5;

[0040] S4. Add 10 g of modified ceramized carbon fiber to 100 mL of dichloromethane, add 2 g of 1-chlorobenzotriazole and 1 g of NaOH, heat under reflux with stirring for 2 h, centrifuge, wash, and dry to obtain the first modified carbon fiber.

[0041] Preparation Example 2 Preparation of the First Modified Carbon Fiber

[0042] The method is as follows:

[0043] S1. Dissolve 10 g of tetrabutyl titanate, 7 g of aluminum isopropoxide, and 15 g of tetraethyl orthosilicate in 200 mL of ethanol, add 100 mL of water and 5 g of KOH, and stir and react for 1 h to form a sol;

[0044] S2. Add 15 g of carbon fiber to 50 g of the sol, heat to 70 °C, stir and react for 7 h, calcine at 600 °C for 4 h, wash, dry, and grind to obtain ceramized carbon fiber;

[0045] S3. Add 10 g of ceramized carbon fiber to 200 mL of water, add 5 g of tannic acid and 0.5 g of the catalyst, heat to 60 °C, stir and react for 5 h, centrifuge, wash, and dry to obtain modified ceramized carbon fiber;

[0046] The catalyst is a Tris-HCl solution with a pH of 9.5;

[0047] S4. Add 10 g of modified ceramized carbon fiber to 100 mL of dichloromethane, add 3 g of 1-chlorobenzotriazole and 2 g of KOH, heat under reflux with stirring for 4 h, centrifuge, wash, and dry to obtain the first modified carbon fiber.

[0048] Preparation Example 3 Preparation of the First Modified Carbon Fiber

[0049] The method is as follows:

[0050] S1. Dissolve 9 g of tetrabutyl titanate, 5.5 g of aluminum isopropoxide, and 12 g of tetraethyl orthosilicate in 200 mL of ethanol, add 100 mL of water and 4 g of KOH, and stir and react for 1 h to form a sol;

[0051] S2. Add 12 g of carbon fiber to 40 g of the sol, heat to 60 °C, stir and react for 6 h, calcine at 550 °C for 3 h, wash, dry, and grind to obtain ceramized carbon fiber;

[0052] S3. Add 10 g of ceramized carbon fiber to 200 mL of water, add 4 g of tannic acid and 0.4 g of the catalyst, heat to 55 °C, stir and react for 4 h, centrifuge, wash, and dry to obtain modified ceramized carbon fiber;

[0053] The catalyst is a Tris - HCl solution with pH = 9;

[0054] S4. Add 10 g of modified ceramized carbon fiber to 100 mL of dichloromethane, add 2.5 g of 1 - chlorobenzotriazole and 1.5 g of NaOH, heat under reflux with stirring for 3 h, centrifuge, wash, and dry to obtain the first modified carbon fiber.

[0055] Comparative Preparation Example 1

[0056] Compared with Preparation Example 3, the difference lies in that tetrabutyl titanate was not added in step S1.

[0057] Specifically as follows:

[0058] S1. Dissolve 5.5 g of aluminum isopropoxide and 21 g of tetraethyl orthosilicate in 200 mL of ethanol, add 100 mL of water and 4 g of KOH, stir and react for 1 h to form a sol.

[0059] Comparative Preparation Example 2

[0060] Compared with Preparation Example 3, the difference lies in that steps S1 and S2 were not carried out.

[0061] Specifically as follows:

[0062] S1. Add 10 g of carbon fiber to 200 mL of water, add 4 g of tannic acid and 0.4 g of the catalyst, heat to 55 °C, stir and react for 4 h, centrifuge, wash, and dry to obtain modified carbon fiber;

[0063] The catalyst is a Tris - HCl solution with pH = 9;

[0064] S4. Add 10 g of modified carbon fiber to 100 mL of dichloromethane, add 2.5 g of 1 - chlorobenzotriazole and 1.5 g of NaOH, heat under reflux with stirring for 3 h, centrifuge, wash, and dry to obtain the first modified carbon fiber.

[0065] Comparative Preparation Example 3

[0066] Compared with Preparation Example 3, the difference lies in that step S3 was not carried out.

[0067] Specifically as follows:

[0068] S1. Dissolve 9 g of tetrabutyl titanate, 5.5 g of aluminum isopropoxide and 12 g of tetraethyl orthosilicate in 200 mL of ethanol, add 100 mL of water and 4 g of KOH, stir and react for 1 h to form a sol;

[0069] S2. Add 12 g of carbon fiber to 40 g of sol, heat to 60 °C, stir and react for 6 h, calcine at 550 °C for 3 h, wash, dry, and grind to obtain ceramized carbon fiber;

[0070] S3. Add 10 g of ceramized carbon fiber to 100 mL of dichloromethane, add 2.5 g of 1-chlorobenzotriazole and 1.5 g of NaOH, heat under reflux and stir to react for 3 h, centrifuge, wash, and dry to obtain the first modified carbon fiber.

[0071] Comparative Preparation Example 4

[0072] Compared with Preparation Example 3, the difference is that step S4 is not carried out.

[0073] Specifically as follows:

[0074] S1. Dissolve 9 g of tetrabutyl titanate, 5.5 g of aluminum isopropoxide, and 12 g of tetraethyl orthosilicate in 200 mL of ethanol, add 100 mL of water and 4 g of KOH, stir and react for 1 h to form a sol;

[0075] S2. Add 12 g of carbon fiber to 40 g of sol, heat to 60 °C, stir and react for 6 h, calcine at 550 °C for 3 h, wash, dry, and grind to obtain ceramized carbon fiber;

[0076] S3. Add 10 g of ceramized 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 ceramized carbon fiber, which is the first modified carbon fiber;

[0077] The catalyst is a Tris-HCl solution with a pH of 9.

[0078] Preparation Example 4 Preparation of the second modified carbon fiber

[0079] The method is as follows:

[0080] T1. Add 12 g of carbon fiber to a Tris-HCl solution with a pH of 8.5, add 6 g of dopamine hydrochloride, heat to 50 °C, stir and react for 3 h, centrifuge, wash, and dry to obtain modified carbon fiber;

[0081] T2. Add 10 g of modified carbon fiber, 3 g of zirconium tetrachloride, and 2 g of 2-aminoterephthalic acid to a mixed solution of 400 mL of N,N-dimethylformamide and acetic acid (volume ratio 19:1), ultrasonically disperse for 20 min at 400 W, carry out hydrothermal reaction at 120 °C for 20 h, centrifuge, wash, and dry to obtain UiO-66-NH2 modified carbon fiber;

[0082] T3. Add 4 g of octachloropropylsilsesquioxane and 12 g of UiO-66-NH2 modified carbon fiber into 200 mL of dichloromethane, heat under reflux for 2 h, centrifuge, wash, and dry to obtain the second modified carbon fiber.

[0083] Preparation Example 5 Preparation of the Second Modified Carbon Fiber

[0084] The method is as follows:

[0085] T1. Add 15 g of carbon fiber into a Tris-HCl solution with a pH of 9.5, add 9 g of dopamine hydrochloride, heat to 60 °C, stir and react for 5 h, centrifuge, wash, and dry to obtain the modified carbon fiber;

[0086] T2. Add 14 g of modified carbon fiber, 4 g of zirconium tetrachloride, and 3 g of 2-aminoterephthalic acid into a mixed solution of 400 mL of N,N-dimethylformamide and acetic acid (volume ratio 19:1), ultrasonically disperse at 400 W for 20 min, carry out hydrothermal reaction at 140 °C for 24 h, centrifuge, wash, and dry to obtain UiO-66-NH2 modified carbon fiber;

[0087] T3. Add 7 g of octachloropropylsilsesquioxane and 15 g of UiO-66-NH2 modified carbon fiber into 200 mL of dichloromethane, heat under reflux for 4 h, centrifuge, wash, and dry to obtain the second modified carbon fiber.

[0088] Preparation Example 6 Preparation of the Second Modified Carbon Fiber

[0089] The method is as follows:

[0090] T1. Add 13 g of carbon fiber into a Tris-HCl solution with a pH of 9, add 7 g of dopamine hydrochloride, heat to 55 °C, stir and react for 4 h, centrifuge, wash, and dry to obtain the modified carbon fiber;

[0091] T2. Add 12 g of modified carbon fiber, 3.2 g of zirconium tetrachloride, and 2.6 g of 2-aminoterephthalic acid into a mixed solution of 400 mL of N,N-dimethylformamide and acetic acid (volume ratio 19:1), ultrasonically disperse at 400 W for 20 min, carry out hydrothermal reaction at 130 °C for 22 h, centrifuge, wash, and dry to obtain UiO-66-NH2 modified carbon fiber;

[0092] T3. Add 5.6 g of octachloropropylsilsesquioxane and 13 g of UiO-66-NH2 modified carbon fiber into 200 mL of dichloromethane, heat under reflux for 3 h, centrifuge, wash, and dry to obtain the second modified carbon fiber.

[0093] Comparative Preparation Example 5

[0094] Compared with Preparation Example 6, the difference lies in that step T1 was not carried out.

[0095] Specifically as follows:

[0096] T1. Add 12 g of carbon fiber, 3.2 g of zirconium tetrachloride, and 2.6 g of 2-aminoterephthalic acid to a mixed solution of 400 mL of N,N-dimethylformamide and acetic acid (volume ratio 19:1), ultrasonically disperse for 20 min at 400 W, carry out hydrothermal reaction at 130 °C for 22 h, centrifuge, wash, and dry to obtain UiO-66-NH2 modified carbon fiber;

[0097] T2. Add 5.6 g of octachloropropyl sesquisiloxane and 13 g of UiO-66-NH2 modified carbon fiber to 200 mL of dichloromethane, heat under reflux for 3 h, centrifuge, wash, and dry to obtain the second modified carbon fiber.

[0098] Comparative Preparation Example 6

[0099] Compared with Preparation Example 6, the difference lies in that step T2 was not carried out.

[0100] Specifically as follows:

[0101] T1. Add 13 g of carbon fiber to a Tris-HCl solution with a pH of 9, add 7 g of dopamine hydrochloride, heat to 55 °C, stir and react for 4 h, centrifuge, wash, and dry to obtain modified carbon fiber;

[0102] T2. Add 5.6 g of octachloropropyl sesquisiloxane and 13 g of modified carbon fiber to 200 mL of dichloromethane, heat under reflux for 3 h, centrifuge, wash, and dry to obtain the second modified carbon fiber.

[0103] Comparative Preparation Example 7

[0104] Compared with Preparation Example 6, the difference lies in that step T3 was not carried out.

[0105] Specifically as follows:

[0106] T1. Add 13 g of carbon fiber to a Tris-HCl solution with a pH of 9, add 7 g of dopamine hydrochloride, heat to 55 °C, stir and react for 4 h, centrifuge, wash, and dry to obtain modified carbon fiber;

[0107] T2. Add 12 g of modified carbon fiber, 3.2 g of zirconium tetrachloride, and 2.6 g of 2-aminoterephthalic acid to a mixed solution of 400 mL of N,N-dimethylformamide and acetic acid (volume ratio 19:1), ultrasonically disperse for 20 min at 400 W, carry out 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.

[0108] Preparation Example 7 Preparation of the Third Modified Carbon Fiber

[0109] The method is as follows:

[0110] U1. Add 10 g of carbon fiber to 30 mL of concentrated nitric acid, heat under reflux with stirring for 1 h, centrifuge, wash, and dry to obtain acid-treated carbon fiber;

[0111] U2. Place 10 g of acid-treated carbon fiber in the center of a quartz porcelain boat and spread it evenly, dropwise add 2 mL of 1 wt% iron chloride solution, dry, heat to 400 °C under Ar protection, replace with hydrogen, with the ventilation rate of hydrogen being 100 mL / min, heat to 600 °C, introduce n-hexane, with the ventilation rate of n-hexane being 0.1 mL / min, react for 30 min, and cool to room temperature under Ar protection to obtain the third modified carbon fiber.

[0112] Preparation Example 8 Preparation of the Third Modified Carbon Fiber

[0113] The method is as follows:

[0114] U1. Add 10 g of carbon fiber to 50 mL of concentrated nitric acid, heat under reflux with stirring for 3 h, centrifuge, wash, and dry to obtain acid-treated carbon fiber;

[0115] U2. Place 10 g of acid-treated carbon fiber in the center of a quartz porcelain boat and spread it evenly, dropwise add 2 mL of 3 wt% iron sulfate solution, dry, heat to 500 °C under Ar protection, replace with hydrogen, with the ventilation rate of hydrogen being 120 mL / min, heat to 700 °C, introduce n-hexane, with the ventilation rate of n-hexane being 0.3 mL / min, react for 60 min, and cool to room temperature under Ar protection to obtain the third modified carbon fiber.

[0116] Preparation Example 9 Preparation of the Third Modified Carbon Fiber

[0117] The method is as follows:

[0118] U1. Add 10 g of carbon fiber to 40 mL of concentrated nitric acid, heat under reflux with stirring for 2 h, centrifuge, wash, and dry to obtain acid-treated carbon fiber;

[0119] U2. Place 10 g of acid-treated carbon fiber in the center of a quartz porcelain boat and spread it evenly, dropwise add 2 mL of 2 wt% iron nitrate solution, dry, heat to 450 °C under Ar protection, replace with hydrogen, with the ventilation rate of hydrogen being 110 mL / min, heat to 650 °C, introduce n-hexane, with the ventilation rate of n-hexane being 0.2 mL / min, react for 45 min, and cool to room temperature under Ar protection to obtain the third modified carbon fiber.

[0120] Comparative Preparation Example 8

[0121] Compared with Preparation Example 6, the difference lies in that step U1 was not carried out.

[0122] Specifically as follows:

[0123] Place 10 g of carbon fiber in the center of a quartz porcelain boat and spread it evenly. Drop 2 mL of a 2 wt% iron nitrate solution, dry it, heat it to 450 °C under Ar protection, replace it with hydrogen, with the ventilation rate of hydrogen being 110 mL / min, heat it to 650 °C, introduce n-hexane, with the ventilation rate of n-hexane being 0.2 mL / min, react for 45 min, and cool it to room temperature under Ar protection to obtain the third modified carbon fiber.

[0124] Comparative Preparation Example 9

[0125] Compared with Preparation Example 6, the difference lies in that step U2 was not carried out.

[0126] Specifically as follows:

[0127] Add 10 g of carbon fiber to 40 mL of concentrated nitric acid, heat it under reflux and stir for 2 h, centrifuge, wash, and dry it to obtain the acid-treated carbon fiber, which is the third modified carbon fiber.

[0128] Example 1

[0129] This example provides a high-strength composite electric pole material.

[0130] 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.

[0131] The preparation method includes the following steps:

[0132] Mix E-51 epoxy resin, the first modified carbon fiber, the second modified carbon fiber, and the third modified carbon fiber, stir for 15 min, add diethylenetriamine, pour it into a mold, heat it to 100 °C, and cure for 3 h to obtain the high-strength composite electric pole material.

[0133] Example 2

[0134] This example provides a high-strength composite electric pole material.

[0135] 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.

[0136] The preparation method comprises the following steps:

[0137] Mix E-51 epoxy resin, the first modified carbon fiber, the second modified carbon fiber, and the third modified carbon fiber, stir for 15 min, add triethylenetetramine, pour into a mold, heat to 120 °C, and cure for 1 h to obtain a high-strength composite pole material.

[0138] Example 3

[0139] This example provides a high-strength composite pole material.

[0140] 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.

[0141] The preparation method comprises the following steps:

[0142] Mix E-51 epoxy resin, the first modified carbon fiber, the second modified carbon fiber, and the third modified carbon fiber, stir for 15 min, add triethylenetetramine, pour into a mold, heat to 110 °C, and cure for 2 h to obtain a high-strength composite pole material.

[0143] Comparative Example 1

[0144] Compared with Example 3, the difference lies in that the first modified carbon fiber is prepared from Comparative Preparation Example 1.

[0145] Comparative Example 2

[0146] Compared with Example 3, the difference lies in that the first modified carbon fiber is prepared from Comparative Preparation Example 2.

[0147] Comparative Example 3

[0148] Compared with Example 3, the difference lies in that the first modified carbon fiber is prepared from Comparative Preparation Example 3.

[0149] Comparative Example 4

[0150] Compared with Example 3, the difference lies in that the first modified carbon fiber is prepared from Comparative Preparation Example 4.

[0151] Comparative Example 5

[0152] Compared with Example 3, the difference lies in that the second modified carbon fiber is prepared from Comparative Preparation Example 5.

[0153] Comparative Example 6

[0154] Compared with Example 3, the difference lies in that the second modified carbon fiber is prepared from Comparative Preparation Example 6.

[0155] Comparative Example 7

[0156] Compared with Example 3, the difference lies in that the second modified carbon fiber is prepared from Comparative Preparation Example 7.

[0157] Comparative Example 8

[0158] Compared with Example 3, the difference lies in that the third modified carbon fiber is prepared from Comparative Preparation Example 8.

[0159] Comparative Example 9

[0160] Compared with Example 3, the difference lies in that the third modified carbon fiber is prepared from Comparative Preparation Example 9.

[0161] Comparative Example 10

[0162] Compared with Example 3, the difference lies in that the first modified carbon fiber is not added.

[0163] Raw material composition (parts by weight): 110 parts of E-51 epoxy resin, 10 parts of the second modified carbon fiber prepared from Preparation Example 6, 4 parts of the third modified carbon fiber prepared from Preparation Example 9, 40 parts of triethylenetetramine.

[0164] Comparative Example 11

[0165] Compared with Example 3, the difference lies in that the second modified carbon fiber is not added.

[0166] Raw material composition (parts by weight): 110 parts of E-51 epoxy resin, 12 parts of the first modified carbon fiber prepared from Preparation Example 3, 4 parts of the third modified carbon fiber prepared from Preparation Example 9, 40 parts of triethylenetetramine.

[0167] Comparative Example 12

[0168] Compared with Example 3, the difference lies in that the second modified carbon fiber is not added.

[0169] Raw material composition (parts by weight): 110 parts of E-51 epoxy resin, 12 parts of the first modified carbon fiber prepared from Preparation Example 3, 10 parts of the second modified carbon fiber prepared from Preparation Example 6, 40 parts of triethylenetetramine.

[0170] Test Example 1

[0171] The mechanical properties of the high-strength composite pole materials prepared in Examples 1-3 and Comparative Examples 1-12 were tested, and the results are shown in Table 1.

[0172] According to the mechanical test standards of GB / T 1040-2006 and GB / T 9341-2008, the flexural strength and tensile strength were detected; according to the standard of GB / T 1043-2008, the impact strength was detected.

[0173] Table 1

[0174]

[0175] As can be seen from the above table, the high-strength composite pole materials prepared in Examples 1-3 of the present invention have good mechanical properties.

[0176] Test Example 2

[0177] 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.

[0178] Salt spray resistance: Salt spray resistance detection was carried out according to the standard test of GB / T 1771-1991.

[0179] Aging resistance: After the specimen was heat-aged at 180 °C for 10 h, according to the mechanical test standard of GB / T 1040-2006, the tensile strength of the specimen was tested, and the tensile strength retention rate (%) was calculated. Calculation method: Tensile strength retention rate (%) = tensile strength after aging / tensile strength before aging × 100%.

[0180] Heat resistance: After the specimen was continuously heated at 120 °C for 5 days, it was taken out and its weight loss rate (%) was tested.

[0181] Thermal conductivity: The thermal conductivity of the material was tested using a thermal conductivity tester.

[0182] Table 2

[0183]

[0184] As can be seen from the above table, the high-strength composite pole materials prepared in Examples 1-3 of the present invention have good salt spray, heat resistance and aging resistance, and a relatively high thermal conductivity.

[0185] The above are only the preferred embodiments of the present invention and are not intended to limit the present invention. Any modifications, equivalent replacements, improvements, etc. made within the spirit and principle of the present invention shall be included in the protection scope of the present invention.

Claims

1. A high-strength composite pole material, characterized in that, It is prepared from the following raw materials in parts by weight: 90 - 120 parts of epoxy resin, 10 - 15 parts of the first modified carbon fiber, 8 - 12 parts of the second modified carbon fiber, 3 - 5 parts of the third modified carbon fiber, and 30 - 50 parts of a curing agent. The first modified carbon fiber is a carbon fiber modified by tannic acid and coupled with benzotriazole after being coated with titanium oxide / aluminum oxide / silicon oxide. The second modified carbon fiber is a carbon fiber prepared by coating UiO-66-NH2 after being modified with polydopamine and reacting with octachloropropyl sesquisiloxane. The third modified carbon fiber is a carbon fiber obtained by depositing carbon fibers on the surface of carbon nanotubes. The preparation method of the third modified carbon fiber is as follows: U1. Add carbon fibers to concentrated nitric acid, heat under reflux with stirring, centrifuge, wash, and dry to obtain acid-treated carbon fibers. U2. Place the acid-treated carbon fibers in the center of a quartz porcelain boat and spread them evenly, dropwise add an iron solution, dry, heat to a first temperature under inert gas protection, change to a hydrogen atmosphere, heat to a second temperature, introduce n-hexane, react, and cool to room temperature under inert gas protection to obtain the third modified carbon fiber.

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. Dissolve tetrabutyl titanate, aluminum isopropoxide, and tetraethyl orthosilicate in ethanol, add water and a base, and stir to react to form a sol. S2. Add carbon fibers to the sol, heat with stirring, calcine, wash, dry, and grind to obtain ceramized carbon fibers. S3. Add the ceramized carbon fibers to water, add tannic acid and a catalyst, heat with stirring, centrifuge, wash, and dry to obtain modified ceramized carbon fibers. S4. Add the modified ceramized carbon fibers to dichloromethane, add 1-chlorobenzotriazole and a base, heat under reflux with stirring, centrifuge, wash, and dry to obtain the first modified carbon fiber.

3. The high-strength composite pole material according to claim 2, characterized in that, In step S1, the mass ratio of tetrabutyl titanate, aluminum isopropoxide, tetraethyl orthosilicate, and the base is 8 - 10:4 - 7:10 - 15:3 - 5, and the base is NaOH or KOH. In step S2, the mass ratio of the carbon fibers to the sol is 10 - 15:30 - 50, the temperature of the heating and stirring reaction is 50 - 70 °C, the time is 5 - 7 h, the calcination temperature is 500 - 600 °C, and the time is 2 - 4 h. In step S3, the mass ratio of the ceramized carbon fibers, tannic acid, and the 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 - 5 h. In step S4, the mass ratio of the modified ceramized carbon fibers, 1-chlorobenzotriazole, and the base is 10:2 - 3:1 - 2, the base is NaOH or KOH, and the time of the heating under reflux with stirring is 2 - 4 h.

4. The high-strength composite pole material according to claim 1, wherein The preparation method of the second modified carbon fiber is as follows: T1. Add carbon fibers to a Tris-HCl solution, add dopamine hydrochloride, heat with stirring, centrifuge, wash, and dry to obtain modified carbon fibers. T2. Add modified carbon fiber, zirconium tetrachloride, and 2-aminoterephthalic acid into a mixed solution of N,N-dimethylformamide and acetic acid, ultrasonically disperse them evenly, conduct a hydrothermal reaction, centrifuge, wash, and dry to obtain UiO-66-NH2 modified carbon fiber; T3. Add octachloropropyl sesquisiloxane and UiO-66-NH2 modified carbon fiber into dichloromethane, heat and reflux for reaction, centrifuge, wash, and dry to obtain the second modified carbon fiber.

5. The high-strength composite pole material according to claim 4, characterized in that, In step T1, the mass ratio of the carbon fiber to dopamine hydrochloride 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 - 5 h; in step T2, the mass ratio of the modified carbon fiber, zirconium tetrachloride, and 2-aminoterephthalic acid is 10 - 14:3 - 4:2 - 3, the temperature of the hydrothermal reaction is 120 - 140 °C, and the time is 20 - 24 h; in step T3, the mass ratio of octachloropropyl sesquisiloxane and UiO-66-NH2 modified carbon fiber is 4 - 7:12 - 15, and the time of the heating and reflux reaction is 2 - 4 h.

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

7. The high-strength composite pole material according to claim 1, wherein The curing agent is selected from at least one of diethylenetriamine, triethylenetetramine, m-phenylenediamine, and m-xylylenediamine, and the epoxy resin is E-51 or E-44.

8. A method for preparing a high-strength composite pole material according to any one of claims 1-7, characterized in that, It includes the following steps: Mix epoxy resin, the first modified carbon fiber, the second modified carbon fiber, and the third modified carbon fiber evenly, add a curing agent, pour it into a mold, and heat and cure to obtain a high-strength composite pole material.

9. The preparation method according to claim 8, wherein The temperature of the heating and curing is 100 - 120 °C, and the time is 1 - 3 h.

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