Anti-oxidation long-life photovoltaic frame and preparation method thereof

Abstract

The invention relates to the technical field of photovoltaic modules, and particularly discloses an anti-oxidation long-life photovoltaic frame and a preparation method thereof.The anti-oxidation long-life photovoltaic frame takes grafted hindered phenol type polyurethane as a resin matrix and is filled with basalt fiber cloth modified by KH-550 activated kaolin, and a silica sol coating containing nano titanium dioxide is attached to the surface of the anti-oxidation long-life photovoltaic frame; the prepared anti-oxidation long-service-life photovoltaic frame is high in strength and good in aging resistance, and can still keep certain strength after aging.

Description

Technical Field

[0001] The invention relates to the technical field of photovoltaic components, and in particular to an anti-oxidation long-life photovoltaic frame and a preparation method thereof. Background Art

[0002] With the rapid development of modern industry, the global energy crisis and environmental pollution problems need to be solved urgently. With the gradual reduction of fossil fuels, solar energy has been widely used as a renewable emerging energy source, and photovoltaic power generation technology is a technology that uses the photovoltaic effect to convert light energy into a wider range of electrical energy. At present, my country is vigorously promoting the construction of photovoltaic power generation. As an important component of photovoltaic power generation, the photovoltaic frame mainly plays the role of protecting the edge of photovoltaic glass, fixing the sealing components, and strengthening the sealing performance of the components, and affects the overall service life of the photovoltaic components. Compared with the current mainstream aluminum alloy photovoltaic frame, the emerging composite material photovoltaic frame has the advantages of good insulation, good corrosion resistance, and light weight, but its poor resistance to thermal oxygen aging and UV aging is also a problem that needs to be solved now. Summary of the invention

[0003] The purpose of the present invention is to provide an oxidation-resistant and long-life photovoltaic frame and a preparation method thereof, so as to solve the problem that the composite photovoltaic frame has poor resistance to thermal oxygen aging and ultraviolet aging.

[0004] In order to solve the above technical problems, the present invention provides the following technical solutions: A method for preparing an oxidation-resistant and long-life photovoltaic frame, the preparation method comprising: The hindered phenol grafted polyurethane prepolymer, 4,4'-diaminodiphenylmethane and other additives are mixed, the temperature is raised to 70-90°C, the mixture is stirred at 400-600 rpm for 1-5 minutes, the mixture is vacuumed for 3-7 minutes, and the mixture is poured into a mold containing KH-550 activated kaolin modified basalt fiber cloth at 90-110°C, and the mixture is cured at 90-110°C for 14-18 hours and at room temperature for 2-4 days to obtain a photovoltaic frame resin matrix. After the photovoltaic frame resin matrix is ​​shaped, the photovoltaic frame is taken out, and nano-titanium dioxide modified silica sol is evenly sprayed on the photovoltaic frame resin matrix, and the photovoltaic frame is dried to obtain an antioxidant and long-life photovoltaic frame.

[0005] As a limitation of the present invention, the preparation method of the hindered phenol grafted polyurethane prepolymer is: Mix diisocyanate and 3,5-di-tert-butyl-4-hydroxybenzoic acid, stir evenly, react at 70-90°C and 50-100rpm for 2-4h to obtain hindered phenol grafted diisocyanate, and vacuum dry the hindered phenol grafted diisocyanate and oligomer polyol at 95-105°C for 0.5-1.5h, respectively. After drying, cool, mix, stir evenly, and react at 70-80°C for 2-4h to obtain hindered phenol grafted polyurethane prepolymer.

[0006] As a limitation of the present invention, the diisocyanate is one of diphenylmethane diisocyanate, toluene diisocyanate, hexamethylene diisocyanate, and dicyclohexylmethane diisocyanate, and the oligomer polyol is one of polytetramethylene glycol, polypropylene glycol, and polytetramethylene glycol.

[0007] As a limitation of the present invention, the other additives include, by weight, 0.5 to 1 parts of stannous octoate, 1.5 to 2.5 parts of tris(2,4-di-tert-butylphenyl)phosphite, 2 to 4 parts of melamine, and 0.5 to 1.5 parts of sodium dodecyl sulfate.

[0008] As a limitation of the present invention, the preparation method of KH-550 activated kaolin modified basalt fiber cloth is: The basalt fiber cloth was rinsed with acetone and deionized water, and vacuum dried to obtain the pretreated basalt fiber cloth. KH-550 activated kaolin, ethanol and deionized water were mixed, stirred evenly, and ultrasonically dispersed for 0.4 to 0.6 hours to obtain a KH-550 activated kaolin solution. The pretreated basalt fiber cloth was immersed in the KH-550 activated kaolin solution for 0.9 to 1.1 hours, taken out after sufficient immersion, and dried at 45 to 55° C. for 2 to 4 hours to obtain a KH-550 activated kaolin modified basalt fiber cloth.

[0009] As a limitation of the present invention, the preparation method of the KH-550 activated kaolin is: Mix KH-550, succinic anhydride and dimethylformamide, stir evenly, react at 75-85°C for 2-4h to obtain KH-550 / succinic anhydride solution, mix ultrafine kaolin, dimethylformamide and deionized water, stir evenly, and ultrasonically disperse for 0.4-0.6h to obtain kaolin dispersion, mix the KH-550 / succinic anhydride solution and the kaolin dispersion, react at 35-45°C and 100-300rpm for 2-4h, centrifuge after the reaction is completed, wash with ethanol, and dry to obtain carboxylated kaolin; The carboxylated kaolin and dimethylformamide are mixed, and ultrasonically dispersed for 0.4 to 0.6 hours to obtain a carboxylated kaolin organic solution. The carboxylated kaolin organic solution, dicyclohexylcarbodiimide, KH-550, ethanol, and deionized water are mixed, stirred evenly, and reacted at 35 to 45°C for 2 to 4 hours. After the reaction is completed, centrifuge and dry to obtain KH-550 activated kaolin.

[0010] As a limitation of the present invention, the preparation of KH-550 activated kaolin includes 0.9 to 1.1 parts of ultrafine kaolin, 0.9 to 1.1 parts of succinic anhydride, and 0.9 to 1.1 parts of dicyclohexylcarbodiimide, by weight.

[0011] As a limitation of the present invention, the preparation method of the nano-titanium dioxide modified silica sol is: Mix ethyl orthosilicate, KH-550, ethanol and deionized water, stir evenly, adjust the pH with acetic acid, react at 65-75°C and 90-110rpm for 2-4h to obtain neutral silica sol, add dispersant and nano-titanium dioxide to the neutral silica sol, stir evenly, ultrasonically disperse for 20-40min, and stand for aging for 0.5-1.5h to obtain nano-titanium dioxide modified silica sol.

[0012] As a limitation of the present invention, the preparation of nano-titanium dioxide modified silica sol includes 8 to 12 parts of ethyl orthosilicate, 5.0 to 5.5 parts of KH-550, 1 to 2 parts of dispersant, and 7 to 8 parts of nano-titanium dioxide, by weight.

[0013] Compared with the prior art, the present invention has the following beneficial effects: The basalt fiber cloth was treated with KH-550 activated kaolin solution, which improved the surface inertness of the basalt fiber, covered the fiber surface with a layer of nanoparticles and introduced organic molecular chains, increased the specific surface area and surface roughness of the fiber, and improved the compatibility of the nanoparticles with the matrix resin, thereby improving the wettability of the fiber surface, increasing the bonding strength between the basalt fiber and the matrix resin, and thus improving the mechanical properties of the composite material.

[0014] By modifying silica nanotubes with silane coupling agents, more active sites are introduced on the silica nanotubes, which better interact with polymer molecular chains, improve the compatibility between silica nanotubes and polymers, reduce the occurrence of agglomeration of silica nanotubes in the polymer matrix, and make the silica nanotubes more evenly dispersed in the polymer.

[0015] 3,5-di-tert-butyl-4-hydroxybenzoic acid is grafted onto isocyanate to introduce it into the polymer chain, increasing the friction between the molecular chains in the system and enhancing the hydrogen bonding between the hindered phenol molecules and the polyurethane resin, thereby improving the strength of the composite material. In addition, when aging occurs, the phenolic hydroxyl groups of the hindered phenol molecules can provide protons to combine with the peroxyl free radicals generated by polyurethane aging, causing them to lose their activity and forming relatively stable phenol oxygen free radicals, which terminate the continued occurrence of the aging reaction.

[0016] Nano-titanium dioxide filler is added to the silica sol prepared by tetraethyl orthosilicate and KH-550. The titanium dioxide filler improves the UV blocking ability of the coating and reduces the influence of ultraviolet light on the matrix resin. The silicon dioxide generated by the hydrolysis and condensation of tetraethyl orthosilicate adheres to the surface of the nano-titanium dioxide, which can not only hinder the redox reaction between the electrons and holes generated by titanium dioxide under the action of ultraviolet light and the resin matrix, inhibiting the photocatalytic activity of titanium dioxide, but also improve the hardness and wear resistance of the coating, thereby improving the mechanical properties of the composite material. DETAILED DESCRIPTION

[0017] 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.

[0018] Basalt fiber cloth (300g / m 2 ) was provided by Sichuan Juyuan, ultrafine kaolin (11μm), tris(2,4-di-tert-butylphenyl) phosphite (T822863), polytetramethylene glycol (Mn=2000), tetraethyl orthosilicate (T819505), nano titanium dioxide (rutile, 60nm) was provided by Shanghai MacLean, dispersant BYK-111 (1.16g / cm 3 ) is provided by Shanghai BYD.

[0019] Embodiment 1: A method for preparing an oxidation-resistant and long-life photovoltaic frame, specifically: Step 1: Preparation of Carboxylated Kaolin By mass, 2.1 parts of KH-550, 1 part of succinic anhydride, and 73 parts of dimethylformamide were mixed, stirred evenly, and reacted at 80°C for 3 hours to obtain a KH-550 / succinic anhydride solution; 5.16 parts of ultrafine kaolin, 73 parts of dimethylformamide, and 18 parts of deionized water were mixed, stirred evenly, and ultrasonically dispersed for 0.5 hours to obtain a kaolin dispersion; 73.1 parts of KH-550 / succinic anhydride solution and 96.16 parts of kaolin dispersion were mixed, reacted at 40°C and 200rpm for 3 hours, centrifuged after the reaction was completed, washed with ethanol, and dried to obtain carboxylated kaolin.

[0020] Step 2: Preparation of KH-550 activated kaolin By mass, 1.5 parts of carboxylated kaolin and 23.5 parts of dimethylformamide were mixed, and ultrasonically dispersed for 0.5h to obtain a carboxylated kaolin organic solution; 25 parts of carboxylated kaolin organic solution, 0.52 parts of dicyclohexylcarbodiimide, 1.5 parts of KH-550, 80 parts of ethanol, and 20 parts of deionized water were mixed, stirred evenly, and reacted at 35-45°C for 2-4h. After the reaction was completed, the mixture was centrifuged and dried to obtain KH-550 activated kaolin.

[0021] Step 3: Preparation of KH-550 activated kaolin modified basalt fiber cloth By mass, the basalt fiber cloth was rinsed with acetone and deionized water, and vacuum dried to obtain the pretreated basalt fiber cloth, 1.5 parts of KH-550 activated kaolin, 80 parts of ethanol, and 18.5 parts of deionized water were mixed, stirred evenly, and ultrasonically dispersed for 0.5 h to obtain a KH-550 activated kaolin solution, and the treated basalt fiber cloth was immersed in the KH-550 activated kaolin solution for 1 h, taken out after sufficient immersion, and dried at 50 ° C for 3 h to obtain a KH-550 activated kaolin modified basalt fiber cloth.

[0022] Step 4: Preparation of hindered phenol grafted polyurethane prepolymer By mass, 17 parts of diphenylmethane diisocyanate and 0.3 parts of 3,5-di-tert-butyl-4-hydroxybenzoic acid were mixed, stirred evenly, and reacted at 80°C, 80rpm for 3 hours to obtain hindered phenol grafted diisocyanate, and 17.3 parts of hindered phenol grafted diisocyanate and 40 parts of polytetrahydrofuran ether diol were vacuum dried at 100°C for 1 hour, cooled after drying, mixed, stirred evenly, and reacted at 75°C for 3 hours to obtain hindered phenol grafted polyurethane prepolymer.

[0023] Step 5: Preparation of nano-titanium dioxide modified silica sol By mass, 10 parts of ethyl orthosilicate, 5.3 parts of KH-550, 120 parts of ethanol and 30 parts of deionized water were mixed and stirred evenly, the pH was adjusted to neutral with acetic acid, and the reaction was carried out at 70°C and 100 rpm for 3 hours to obtain a neutral silica sol. 1.5 parts of dispersant BYK-111 and 7.5 parts of nano-titanium dioxide were added to 165.3 parts of the neutral silica sol, and the mixture was stirred evenly, ultrasonically dispersed for 30 minutes, and allowed to stand for 1 hour to obtain a nano-titanium dioxide modified silica sol.

[0024] Step 6: Prepare oxidation-resistant and long-life photovoltaic frames By mass, 57.3 parts of hindered phenol grafted polyurethane prepolymer, 0.1 part of 4,4'-diaminodiphenylmethane, 0.75 part of stannous octoate, 2 parts of tri(2,4-di-tert-butylphenyl)phosphite, 3 parts of melamine and 1 part of sodium dodecyl sulfate were mixed, the temperature was raised to 80°C, stirred at 500rpm for 3 minutes, vacuumed for 5 minutes, poured into a mold containing a layer of KH-550 activated kaolin modified basalt fiber cloth at 100°C, cured at 100°C for 16 hours and at room temperature for 3 days to obtain a photovoltaic frame resin matrix, the photovoltaic frame resin matrix was taken out after being shaped, nano-titanium dioxide modified silica sol was evenly sprayed on the photovoltaic frame resin matrix, the coating thickness was 40μm, and dried to obtain an antioxidant and long-life photovoltaic frame.

[0025] Embodiment 2: A method for preparing an oxidation-resistant and long-life photovoltaic frame, specifically: Step 1: Preparation of Carboxylated Kaolin By mass, 2.1 parts of KH-550, 1 part of succinic anhydride, and 73 parts of dimethylformamide were mixed, stirred evenly, and reacted at 80°C for 3 hours to obtain a KH-550 / succinic anhydride solution; 5.16 parts of ultrafine kaolin, 73 parts of dimethylformamide, and 18 parts of deionized water were mixed, stirred evenly, and ultrasonically dispersed for 0.5 hours to obtain a kaolin dispersion; 73.1 parts of KH-550 / succinic anhydride solution and 96.16 parts of kaolin dispersion were mixed, reacted at 40°C and 200rpm for 3 hours, centrifuged after the reaction was completed, washed with ethanol, and dried to obtain carboxylated kaolin.

[0026] Step 2: Preparation of KH-550 activated kaolin By mass, 1.5 parts of carboxylated kaolin and 23.5 parts of dimethylformamide were mixed, and ultrasonically dispersed for 0.5h to obtain a carboxylated kaolin organic solution; 25 parts of carboxylated kaolin organic solution, 0.52 parts of dicyclohexylcarbodiimide, 1.5 parts of KH-550, 80 parts of ethanol, and 20 parts of deionized water were mixed, stirred evenly, and reacted at 35-45°C for 2-4h. After the reaction was completed, the mixture was centrifuged and dried to obtain KH-550 activated kaolin.

[0027] Step 3: Preparation of KH-550 activated kaolin modified basalt fiber cloth By mass, the basalt fiber cloth was rinsed with acetone and deionized water, and vacuum dried to obtain the pretreated basalt fiber cloth; 1 part of KH-550 activated kaolin, 80 parts of ethanol, and 19 parts of deionized water were mixed, stirred evenly, and ultrasonically dispersed for 0.5 h to obtain a KH-550 activated kaolin solution; the treated basalt fiber cloth was immersed in the KH-550 activated kaolin solution for 1 h, taken out after sufficient immersion, and dried at 50 ° C for 3 h to obtain a KH-550 activated kaolin modified basalt fiber cloth.

[0028] Step 4: Preparation of hindered phenol grafted polyurethane prepolymer By mass, 17 parts of diphenylmethane diisocyanate and 0.3 parts of 3,5-di-tert-butyl-4-hydroxybenzoic acid were mixed, stirred evenly, and reacted at 80°C, 80rpm for 3 hours to obtain hindered phenol grafted diisocyanate, and 17.3 parts of hindered phenol grafted diisocyanate and 40 parts of polytetrahydrofuran ether diol were vacuum dried at 100°C for 1 hour, cooled after drying, mixed, stirred evenly, and reacted at 75°C for 3 hours to obtain hindered phenol grafted polyurethane prepolymer.

[0029] Step 5: Preparation of nano-titanium dioxide modified silica sol By mass, 10 parts of ethyl orthosilicate, 5.3 parts of KH-550, 120 parts of ethanol and 30 parts of deionized water were mixed and stirred evenly, the pH was adjusted to neutral with acetic acid, and the reaction was carried out at 70°C and 100 rpm for 3 hours to obtain neutral silica sol. 1 part of dispersant BYK-111 and 7 parts of nano-titanium dioxide were added to 165.3 parts of neutral silica sol, and the mixture was stirred evenly, ultrasonically dispersed for 30 minutes, and allowed to stand for 1 hour to obtain nano-titanium dioxide modified silica sol.

[0030] Step 6: Prepare oxidation-resistant and long-life photovoltaic frames By mass, 57.3 parts of hindered phenol grafted polyurethane prepolymer, 0.1 part of 4,4'-diaminodiphenylmethane, 0.5 part of stannous octoate, 1.5 parts of tri(2,4-di-tert-butylphenyl)phosphite, 2 parts of melamine and 0.5 part of sodium dodecyl sulfate were mixed, the temperature was raised to 80°C, stirred at 500rpm for 3min, vacuumed for 5min, poured into a mold containing a layer of KH-550 activated kaolin modified basalt fiber cloth at 100°C, cured at 100°C for 16h and at room temperature for 3 days to obtain a photovoltaic frame resin matrix, the photovoltaic frame resin matrix was taken out after shaping, nano-titanium dioxide modified silica sol was evenly sprayed on the photovoltaic frame resin matrix, the coating thickness was 40μm, and dried to obtain an antioxidant and long-life photovoltaic frame.

[0031] Embodiment 3: A method for preparing an oxidation-resistant and long-life photovoltaic frame, specifically: Step 1: Preparation of Carboxylated Kaolin By mass, 2.1 parts of KH-550, 1 part of succinic anhydride, and 73 parts of dimethylformamide were mixed, stirred evenly, and reacted at 80°C for 3 hours to obtain a KH-550 / succinic anhydride solution; 5.16 parts of ultrafine kaolin, 73 parts of dimethylformamide, and 18 parts of deionized water were mixed, stirred evenly, and ultrasonically dispersed for 0.5 hours to obtain a kaolin dispersion; 73.1 parts of KH-550 / succinic anhydride solution and 96.16 parts of kaolin dispersion were mixed, reacted at 40°C and 200rpm for 3 hours, centrifuged after the reaction was completed, washed with ethanol, and dried to obtain carboxylated kaolin.

[0032] Step 2: Preparation of KH-550 activated kaolin By mass, 1.5 parts of carboxylated kaolin and 23.5 parts of dimethylformamide were mixed, and ultrasonically dispersed for 0.5h to obtain a carboxylated kaolin organic solution; 25 parts of carboxylated kaolin organic solution, 0.52 parts of dicyclohexylcarbodiimide, 1.5 parts of KH-550, 80 parts of ethanol, and 20 parts of deionized water were mixed, stirred evenly, and reacted at 35-45°C for 2-4h. After the reaction was completed, the mixture was centrifuged and dried to obtain KH-550 activated kaolin.

[0033] Step 3: Preparation of KH-550 activated kaolin modified basalt fiber cloth The basalt fiber cloth was rinsed with acetone and deionized water, and vacuum dried to obtain the pretreated basalt fiber cloth. 2 parts of KH-550 activated kaolin, 80 parts of ethanol, and 18 parts of deionized water were mixed, stirred evenly, and ultrasonically dispersed for 0.5 h to obtain a KH-550 activated kaolin solution. The treated basalt fiber cloth was immersed in the KH-550 activated kaolin solution for 1 h, taken out after sufficient immersion, and dried at 50 ° C for 3 h to obtain a KH-550 activated kaolin modified basalt fiber cloth.

[0034] Step 4: Preparation of hindered phenol grafted polyurethane prepolymer By mass, 17 parts of diphenylmethane diisocyanate and 0.3 parts of 3,5-di-tert-butyl-4-hydroxybenzoic acid were mixed, stirred evenly, and reacted at 80°C, 80rpm for 3 hours to obtain hindered phenol grafted diisocyanate, and 17.3 parts of hindered phenol grafted diisocyanate and 40 parts of polytetrahydrofuran ether diol were vacuum dried at 100°C for 1 hour, cooled after drying, mixed, stirred evenly, and reacted at 75°C for 3 hours to obtain hindered phenol grafted polyurethane prepolymer.

[0035] Step 5: Preparation of nano-titanium dioxide modified silica sol By mass, 10 parts of ethyl orthosilicate, 5.3 parts of KH-550, 120 parts of ethanol and 30 parts of deionized water were mixed and stirred evenly, the pH was adjusted to neutral with acetic acid, and the reaction was carried out at 70°C and 100 rpm for 3 hours to obtain a neutral silica sol. To 165.3 parts of the neutral silica sol, 2 parts of dispersant BYK-111 and 8 parts of nano-titanium dioxide were added, stirred evenly, ultrasonically dispersed for 30 minutes, and allowed to stand for 1 hour to obtain a nano-titanium dioxide modified silica sol.

[0036] Step 6: Prepare oxidation-resistant and long-life photovoltaic frames By mass, 57.3 parts of hindered phenol grafted polyurethane prepolymer, 0.1 part of 4,4'-diaminodiphenylmethane, 1 part of stannous octoate, 2.5 parts of tri(2,4-di-tert-butylphenyl)phosphite, 4 parts of melamine and 1.5 parts of sodium dodecyl sulfate were mixed, the temperature was raised to 80°C, stirred at 500rpm for 3min, vacuumed for 5min, poured into a mold containing a layer of KH-550 activated kaolin modified basalt fiber cloth at 100°C, cured at 100°C for 16h and at room temperature for 3 days to obtain a photovoltaic frame resin matrix, the photovoltaic frame resin matrix was taken out after being shaped, nano-titanium dioxide modified silica sol was evenly sprayed on the photovoltaic frame resin matrix, the coating thickness was 40μm, and dried to obtain an antioxidant and long-life photovoltaic frame.

[0037] Based on Example 1, control experiments were carried out, specifically Comparative Example 1, Comparative Example 2 and Comparative Example 3, as described below: Comparative Example 1: No 3,5-di-tert-butyl-4-hydroxybenzoic acid was added, and the remaining conditions were the same as those in Example 1.

[0038] A method for preparing an oxidation-resistant and long-life photovoltaic frame, specifically comprising: Step 1: Preparation of Carboxylated Kaolin By mass, 2.1 parts of KH-550, 1 part of succinic anhydride, and 73 parts of dimethylformamide were mixed, stirred evenly, and reacted at 80°C for 3 hours to obtain a KH-550 / succinic anhydride solution; 5.16 parts of ultrafine kaolin, 73 parts of dimethylformamide, and 18 parts of deionized water were mixed, stirred evenly, and ultrasonically dispersed for 0.5 hours to obtain a kaolin dispersion; 73.1 parts of KH-550 / succinic anhydride solution and 96.16 parts of kaolin dispersion were mixed, reacted at 40°C and 200rpm for 3 hours, centrifuged after the reaction was completed, washed with ethanol, and dried to obtain carboxylated kaolin.

[0039] Step 2: Preparation of KH-550 activated kaolin By mass, 1.5 parts of carboxylated kaolin and 23.5 parts of dimethylformamide were mixed, and ultrasonically dispersed for 0.5h to obtain a carboxylated kaolin organic solution; 25 parts of carboxylated kaolin organic solution, 0.52 parts of dicyclohexylcarbodiimide, 1.5 parts of KH-550, 80 parts of ethanol, and 20 parts of deionized water were mixed, stirred evenly, and reacted at 35-45°C for 2-4h. After the reaction was completed, the mixture was centrifuged and dried to obtain KH-550 activated kaolin.

[0040] Step 3: Preparation of KH-550 activated kaolin modified basalt fiber cloth By mass, the basalt fiber cloth was rinsed with acetone and deionized water, and vacuum dried to obtain the pretreated basalt fiber cloth, 1.5 parts of KH-550 activated kaolin, 80 parts of ethanol, and 18.5 parts of deionized water were mixed, stirred evenly, and ultrasonically dispersed for 0.5 h to obtain a KH-550 activated kaolin solution, and the treated basalt fiber cloth was immersed in the KH-550 activated kaolin solution for 1 h, taken out after sufficient immersion, and dried at 50 ° C for 3 h to obtain a KH-550 activated kaolin modified basalt fiber cloth.

[0041] Step 4: Preparation of polyurethane prepolymer 17.3 parts of diphenylmethane diisocyanate and 40 parts of polytetramethylene ether diol were vacuum dried at 100° C. for 1 hour, cooled, mixed, stirred evenly, and reacted at 75° C. for 3 hours to obtain a polyurethane prepolymer.

[0042] Step 5: Preparation of nano-titanium dioxide modified silica sol By mass, 10 parts of ethyl orthosilicate, 5.3 parts of KH-550, 120 parts of ethanol and 30 parts of deionized water were mixed and stirred evenly, the pH was adjusted to neutral with acetic acid, and the reaction was carried out at 70°C and 100 rpm for 3 hours to obtain a neutral silica sol. 1.5 parts of dispersant BYK-111 and 7.5 parts of nano-titanium dioxide were added to 165.3 parts of the neutral silica sol, and the mixture was stirred evenly, ultrasonically dispersed for 30 minutes, and allowed to stand for 1 hour to obtain a nano-titanium dioxide modified silica sol.

[0043] Step 6: Prepare oxidation-resistant and long-life photovoltaic frames By mass, 57.3 parts of polyurethane prepolymer, 0.1 part of 4,4'-diaminodiphenylmethane, 0.75 part of stannous octoate, 2 parts of tri(2,4-di-tert-butylphenyl)phosphite, 3 parts of melamine and 1 part of sodium dodecyl sulfate were mixed, the temperature was raised to 80°C, stirred at 500rpm for 3 minutes, vacuumed for 5 minutes, poured into a mold containing a layer of KH-550 activated kaolin modified basalt fiber cloth at 100°C, cured at 100°C for 16 hours and at room temperature for 3 days to obtain a photovoltaic frame resin matrix, the photovoltaic frame resin matrix was taken out after being shaped, nano-titanium dioxide modified silica sol was evenly sprayed on the photovoltaic frame resin matrix, the coating thickness was 40μm, and dried to obtain an antioxidant and long-life photovoltaic frame.

[0044] Comparative Example 2: No nano titanium dioxide was added, and the other conditions were the same as those in Example 1.

[0045] A method for preparing an oxidation-resistant and long-life photovoltaic frame, specifically comprising: Step 1: Preparation of Carboxylated Kaolin By mass, 2.1 parts of KH-550, 1 part of succinic anhydride, and 73 parts of dimethylformamide were mixed, stirred evenly, and reacted at 80°C for 3 hours to obtain a KH-550 / succinic anhydride solution; 5.16 parts of ultrafine kaolin, 73 parts of dimethylformamide, and 18 parts of deionized water were mixed, stirred evenly, and ultrasonically dispersed for 0.5 hours to obtain a kaolin dispersion; 73.1 parts of KH-550 / succinic anhydride solution and 96.16 parts of kaolin dispersion were mixed, reacted at 40°C and 200rpm for 3 hours, centrifuged after the reaction was completed, washed with ethanol, and dried to obtain carboxylated kaolin.

[0046] Step 2: Preparation of KH-550 activated kaolin By mass, 1.5 parts of carboxylated kaolin and 23.5 parts of dimethylformamide were mixed, and ultrasonically dispersed for 0.5h to obtain a carboxylated kaolin organic solution; 25 parts of carboxylated kaolin organic solution, 0.52 parts of dicyclohexylcarbodiimide, 1.5 parts of KH-550, 80 parts of ethanol, and 20 parts of deionized water were mixed, stirred evenly, and reacted at 35-45°C for 2-4h. After the reaction was completed, the mixture was centrifuged and dried to obtain KH-550 activated kaolin.

[0047] Step 3: Preparation of KH-550 activated kaolin modified basalt fiber cloth By mass, the basalt fiber cloth was rinsed with acetone and deionized water, and vacuum dried to obtain the pretreated basalt fiber cloth, 1.5 parts of KH-550 activated kaolin, 80 parts of ethanol, and 18.5 parts of deionized water were mixed, stirred evenly, and ultrasonically dispersed for 0.5 h to obtain a KH-550 activated kaolin solution, and the treated basalt fiber cloth was immersed in the KH-550 activated kaolin solution for 1 h, taken out after sufficient immersion, and dried at 50 ° C for 3 h to obtain a KH-550 activated kaolin modified basalt fiber cloth.

[0048] Step 4: Preparation of hindered phenol grafted polyurethane prepolymer By mass, 17 parts of diphenylmethane diisocyanate and 0.3 parts of 3,5-di-tert-butyl-4-hydroxybenzoic acid were mixed, stirred evenly, and reacted at 80°C, 80rpm for 3 hours to obtain hindered phenol grafted diisocyanate, and 17.3 parts of hindered phenol grafted diisocyanate and 40 parts of polytetrahydrofuran ether diol were vacuum dried at 100°C for 1 hour, cooled after drying, mixed, stirred evenly, and reacted at 75°C for 3 hours to obtain hindered phenol grafted polyurethane prepolymer.

[0049] Step 5: Preparation of neutral silica sol By mass, 10 parts of ethyl orthosilicate, 5.3 parts of KH-550, 120 parts of ethanol, and 30 parts of deionized water were mixed and stirred evenly. The pH was adjusted to neutral with acetic acid, and the mixture was reacted at 70° C. and 100 rpm for 3 hours to obtain a neutral silica sol.

[0050] Step 6: Prepare oxidation-resistant and long-life photovoltaic frames By mass, 57.3 parts of hindered phenol grafted polyurethane prepolymer, 0.1 part of 4,4'-diaminodiphenylmethane, 0.75 part of stannous octoate, 2 parts of tri(2,4-di-tert-butylphenyl)phosphite, 3 parts of melamine and 1 part of sodium dodecyl sulfate were mixed, the temperature was raised to 80°C, stirred at 500rpm for 3min, vacuumed for 5min, poured into a mold containing a layer of KH-550 activated kaolin modified basalt fiber cloth at 100°C, cured at 100°C for 16h and at room temperature for 3 days to obtain a photovoltaic frame resin matrix, the photovoltaic frame resin matrix was taken out after shaping, neutral silica sol was evenly sprayed on the photovoltaic frame resin matrix, the coating thickness was 40μm, and dried to obtain an antioxidant and long-life photovoltaic frame.

[0051] Comparative Example 3: No KH-550 activated kaolin was added, and the other conditions were the same as those in Example 1.

[0052] A method for preparing an oxidation-resistant and long-life photovoltaic frame, specifically comprising: Step 1: Preparation of hindered phenol grafted polyurethane prepolymer By mass, 17 parts of diphenylmethane diisocyanate and 0.3 parts of 3,5-di-tert-butyl-4-hydroxybenzoic acid were mixed, stirred evenly, and reacted at 80°C, 80rpm for 3 hours to obtain hindered phenol grafted diisocyanate, and 17.3 parts of hindered phenol grafted diisocyanate and 40 parts of polytetrahydrofuran ether diol were vacuum dried at 100°C for 1 hour, cooled after drying, mixed, stirred evenly, and reacted at 75°C for 3 hours to obtain hindered phenol grafted polyurethane prepolymer.

[0053] Step 2: Preparation of nano-titanium dioxide modified silica sol By mass, 10 parts of ethyl orthosilicate, 5.3 parts of KH-550, 120 parts of ethanol and 30 parts of deionized water were mixed and stirred evenly, the pH was adjusted to neutral with acetic acid, and the reaction was carried out at 70°C and 100 rpm for 3 hours to obtain a neutral silica sol. 1.5 parts of dispersant BYK-111 and 7.5 parts of nano-titanium dioxide were added to 165.3 parts of the neutral silica sol, and the mixture was stirred evenly, ultrasonically dispersed for 30 minutes, and allowed to stand for 1 hour to obtain a nano-titanium dioxide modified silica sol.

[0054] Step 3: Preparation of oxidation-resistant and long-life photovoltaic frame The basalt fiber cloth was rinsed with acetone and deionized water by mass, and vacuum dried to obtain the pretreated basalt fiber cloth. 57.3 parts of hindered phenol grafted polyurethane prepolymer, 0.1 parts of 4,4'-diaminodiphenylmethane, 0.75 parts of stannous octoate, 2 parts of tris(2,4-di-tert-butylphenyl)phosphite, 3 parts of melamine, and 1 part of sodium dodecyl sulfate were mixed, heated to 80°C, stirred at 500rpm for 3min, vacuum treated for 5min, poured into a mold with the pretreated basalt fiber cloth at 100°C, cured at 100°C for 16h and at room temperature for 3 days to obtain a photovoltaic frame resin matrix. The photovoltaic frame resin matrix was taken out after being shaped, and nano-titanium dioxide modified silica sol was evenly sprayed on the photovoltaic frame resin matrix with a coating thickness of 40μm, and dried to obtain an antioxidant and long-life photovoltaic frame.

[0055] Detection experiment: The plate-shaped test products required for the test were prepared according to the preparation methods in Example 1, Example 2, Example 3, Comparative Example 1, Comparative Example 2, and Comparative Example 3, respectively.

[0056] Mechanical properties test: According to the "Test Method for Tensile Properties of Oriented Fiber Reinforced Plastics" (GB / T 3354-1999), a universal mechanical testing machine was used to test. Samples were cut from the 6 prepared plate-shaped test products. The sample size was 250mm×50mm×6mm. The samples were placed flat on the support, and the load was applied to the samples at a uniform speed. The tensile strength and bending strength of the samples were measured.

[0057] Thermal oxygen aging performance test: Cut specimens from the 6 prepared plate-shaped test products, with a size of 250mm×50mm×6mm, put the specimens into an electric blast drying oven, set the temperature to 120°C, and dry for 7 days. Take out the specimens after 7 days, measure the tensile strength of the specimens at this time, and calculate the tensile strength retention rate after aging.

[0058] UV aging performance test: Cut samples from the 6 prepared plate-shaped test products, with a size of 250mm×50mm×6mm. Place the samples in an environment with only ultraviolet light as the light source for 7 days. The power of the ultraviolet light is 500W, and the irradiation wavelength is 300nm. Take out the samples after 7 days, measure the tensile strength of the samples at this time, and calculate the tensile strength retention rate after aging.

[0059] Coating adhesion test: According to the "Determination of Adhesion of Paint Films" (GB / T 1270-1979), the circle method is used to measure adhesion. Cut samples from the prepared 6 plate-shaped test products, the sample size is 100mm×50mm×6mm, install the sample on the test machine workbench, and press it with a pressure plate, shake the hand wheel, start the test, and evaluate the integrity of the coating within the range of the circular rolling line scratch, which is divided into 7 levels, among which level 1 is the best and level 7 is the worst.

[0060]

[0061] Conclusion: It can be seen from the experiment that the tensile strength, bending strength, heat-oxidation aging resistance and ultraviolet aging resistance of the plate-shaped test product prepared by the preparation method of Example 1 are better than those of the plate-shaped test products prepared by the preparation methods of Comparative Examples 1, 2 and 3, and the prepared coating has strong adhesion and is not easy to fall off. The performance of the antioxidant and long-life photovoltaic frame prepared in Example 1 is better than that of the antioxidant and long-life photovoltaic frames prepared by the preparation methods of Comparative Examples 1, 2 and 3, which solves the problem of poor heat-oxidation aging resistance and ultraviolet aging resistance of composite material photovoltaic frames.

[0062] It will be apparent to those skilled in the art that the present invention is not limited to the details of the exemplary embodiments described above and that the present invention can be implemented in other specific forms without departing from the spirit or essential features of the present invention. Therefore, the embodiments should be considered exemplary and non-restrictive in all respects, and the scope of the present invention is defined by the appended claims rather than the above description, and it is intended that all changes falling within the meaning and scope of the equivalent elements of the claims be included in the present invention.

Claims

1. A method for preparing an oxidation-resistant and long-life photovoltaic frame, characterized in that: The preparation method is: The hindered phenol grafted polyurethane prepolymer, 4,4'-diaminodiphenylmethane and other additives are mixed, the temperature is raised to 70-90°C, the mixture is stirred at 400-600 rpm for 1-5 minutes, the mixture is vacuumed for 3-7 minutes, and the mixture is poured into a mold containing KH-550 activated kaolin modified basalt fiber cloth at 90-110°C, and the mixture is cured at 90-110°C for 14-18 hours and at room temperature for 2-4 days to obtain a photovoltaic frame resin matrix. After the photovoltaic frame resin matrix is ​​shaped, the photovoltaic frame is taken out, and nano-titanium dioxide modified silica sol is evenly sprayed on the photovoltaic frame resin matrix, and the photovoltaic frame is dried to obtain an antioxidant and long-life photovoltaic frame.

2. The method for preparing an oxidation-resistant and long-life photovoltaic frame according to claim 1, characterized in that: The preparation method of hindered phenol grafted polyurethane prepolymer is as follows: Mix diisocyanate and 3,5-di-tert-butyl-4-hydroxybenzoic acid, stir evenly, react at 70-90°C and 50-100rpm for 2-4h to obtain hindered phenol grafted diisocyanate, and vacuum dry the hindered phenol grafted diisocyanate and oligomer polyol at 95-105°C for 0.5-1.5h, respectively. After drying, cool, mix, stir evenly, and react at 70-80°C for 2-4h to obtain hindered phenol grafted polyurethane prepolymer.

3. The method for preparing an oxidation-resistant and long-life photovoltaic frame according to claim 2, characterized in that: The diisocyanate is one of diphenylmethane diisocyanate, toluene diisocyanate, hexamethylene diisocyanate, and dicyclohexylmethane diisocyanate; and the oligomer polyol is one of polytetramethylene glycol, polypropylene glycol, and polytetramethylene glycol.

4. The method for preparing an oxidation-resistant and long-life photovoltaic frame according to claim 1, characterized in that: In parts by mass, the other additives include 0.5 to 1 parts of stannous octoate, 1.5 to 2.5 parts of tris(2,4-di-tert-butylphenyl)phosphite, 2 to 4 parts of melamine, and 0.5 to 1.5 parts of sodium dodecyl sulfate.

5. The method for preparing an oxidation-resistant and long-life photovoltaic frame according to claim 1, characterized in that: The preparation method of KH-550 activated kaolin modified basalt fiber cloth is as follows: The basalt fiber cloth was rinsed with acetone and deionized water, and vacuum dried to obtain the pretreated basalt fiber cloth. KH-550 activated kaolin, ethanol and deionized water were mixed, stirred evenly, and ultrasonically dispersed for 0.4 to 0.6 hours to obtain a KH-550 activated kaolin solution. The pretreated basalt fiber cloth was immersed in the KH-550 activated kaolin solution for 0.9 to 1.1 hours, taken out after sufficient immersion, and dried at 45 to 55° C. for 2 to 4 hours to obtain a KH-550 activated kaolin modified basalt fiber cloth.

6. The method for preparing an oxidation-resistant and long-life photovoltaic frame according to claim 5, characterized in that: The preparation method of KH-550 activated kaolin is: Mix KH-550, succinic anhydride and dimethylformamide, stir evenly, react at 75-85°C for 2-4h to obtain KH-550 / succinic anhydride solution, mix ultrafine kaolin, dimethylformamide and deionized water, stir evenly, and ultrasonically disperse for 0.4-0.6h to obtain kaolin dispersion, mix the KH-550 / succinic anhydride solution and the kaolin dispersion, react at 35-45°C and 100-300rpm for 2-4h, centrifuge after the reaction is completed, wash with ethanol, and dry to obtain carboxylated kaolin; The carboxylated kaolin and dimethylformamide are mixed, and ultrasonically dispersed for 0.4 to 0.6 hours to obtain a carboxylated kaolin organic solution. The carboxylated kaolin organic solution, dicyclohexylcarbodiimide, KH-550, ethanol, and deionized water are mixed, stirred evenly, and reacted at 35 to 45°C for 2 to 4 hours. After the reaction is completed, centrifuge and dry to obtain KH-550 activated kaolin.

7. The method for preparing an oxidation-resistant and long-life photovoltaic frame according to claim 6, characterized in that: The preparation of KH-550 activated kaolin includes 0.9 to 1.1 parts of ultrafine kaolin, 0.9 to 1.1 parts of succinic anhydride, and 0.9 to 1.1 parts of dicyclohexylcarbodiimide, by weight.

8. The method for preparing an oxidation-resistant and long-life photovoltaic frame according to claim 1, characterized in that: The preparation method of nano titanium dioxide modified silica sol is: Mix ethyl orthosilicate, KH-550, ethanol and deionized water, stir evenly, adjust the pH with acetic acid, react at 65-75°C and 90-110rpm for 2-4h to obtain neutral silica sol, add dispersant and nano-titanium dioxide to the neutral silica sol, stir evenly, ultrasonically disperse for 20-40min, and stand for aging for 0.5-1.5h to obtain nano-titanium dioxide modified silica sol.

9. The method for preparing an oxidation-resistant and long-life photovoltaic frame according to claim 8, characterized in that: By weight, the nano-titanium dioxide modified silica sol includes 8 to 12 parts of ethyl orthosilicate, 5.0 to 5.5 parts of KH-550, 1 to 2 parts of dispersant, and 7 to 8 parts of nano-titanium dioxide.

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