Composite material for a paint-free one-shot molded photovoltaic frame and use thereof

Abstract

The present application relates to the technical field of epoxy resin, in particular to a composite material for coating-free one-time forming photovoltaic frame and application thereof.The composite material is composed of 8-10 parts of bisphenol A type epoxy resin E-55, 10-12 parts of dianhydride pre-cured body, 0.8-1 part of anti-ultraviolet nano additive, 1-1.5 parts of triphenyl phosphate and 0.02-0.03 parts of BYK-022 defoaming agent.The dianhydride pre-cured body is prepared by carrying out temperature catalytic reaction of alpha-terpinene, maleic anhydride and catalyst benzene sulfonic acid in dichloromethane solvent, ultrasonic mixing uniformity of terpene maleic anhydride which is ground into powder and tetrafluorophthalic anhydride, and then adding bisphenol A type epoxy resin E-55 and stirring uniformly.The prepared composite material has high strength and low thermal expansion coefficient, and also has excellent anti-ultraviolet performance, so that the photovoltaic frame prepared from the composite material has the characteristics of low density, high strength, strong weather resistance and excellent thermal stability.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of epoxy resin, in particular to a composite material for a one-time molding and coating-free photovoltaic frame and application thereof. BACKGROUND

[0002] With the rapid development of the photovoltaic industry, the application demand of photovoltaic modules continues to increase, leading to a sharp increase in the demand for photovoltaic panel frame materials. The frame material of the photovoltaic module mainly uses aluminum alloy, because it has low density, high strength, good plasticity and excellent electrical conductivity, thermal conductivity and corrosion resistance. After surface treatment, aluminum alloy can form a dense oxide layer to provide effective corrosion protection, so it becomes the first choice for photovoltaic frame materials.

[0003] However, with the continuous progress of photovoltaic technology, the requirements for frame materials of photovoltaic modules are also getting higher and higher. Although aluminum alloy has many advantages, its cost is relatively high in the production process, and the production process is relatively complex, especially multiple precise machining and surface treatment are required during manufacturing, which makes the overall production cost high. In addition, the heavy weight of the aluminum alloy frame is also a restricting factor. In some occasions where the installation weight is strictly required, such as roof photovoltaic systems, lighter frame materials are needed to reduce the overall load.

[0004] The density of resin material is relatively low, and compared with traditional aluminum alloy, resin material has lighter weight, and the cost of common thermosetting resin (such as epoxy resin, polyester resin, etc.) is also relatively low, which can be used as the preferred material for making photovoltaic frame. In order to meet the requirement that the photovoltaic frame can remain stable under light, anti-ultraviolet agents, flame retardants and reinforcing fillers are often added to the resin material. Due to the compatibility problem between these substances and resin material, anti-ultraviolet agents, flame retardants and reinforcing fillers cannot be added too much in resin to avoid performance degradation. Therefore, the performance improvement of these substances on resin material is limited, which makes it difficult for resin material to simultaneously obtain excellent anti-ultraviolet performance, high strength and thermal stability. SUMMARY

[0005] In order to solve the above technical defects, the present application researches a composite material for a one-time molding and coating-free photovoltaic frame, which has high strength and low thermal expansion coefficient, and also has excellent anti-ultraviolet performance. The photovoltaic frame prepared from the material has the characteristics of low density, high strength, good weather resistance and excellent thermal stability.

[0006] To achieve the above object, the present application provides a composite material for a paint-free one-off molded photovoltaic frame, comprising the following components: 8-10 parts of bisphenol A type epoxy resin E-55, 10-12 parts of dianhydride pre-cured body, 0.8-1 part of anti-ultraviolet nano additive, 1-1.5 parts of triphenyl phosphate, and 0.02-0.03 parts of BYK-022 defoaming agent;

[0007] The dianhydride pre-cured body is prepared by performing a temperature rising catalytic reaction on terpene maleic anhydride obtained from alpha-terpinene, maleic anhydride and a catalyst benzene sulfonic acid in dichloromethane solvent, uniformly mixing the terpene maleic anhydride with powdered tetrafluorophthalic anhydride, and then adding and uniformly stirring bisphenol A type epoxy resin E-55;

[0008] The anti-ultraviolet nano additive is prepared by first preparing 2-sulfonic terephthalic acid solution, Al(NO3)3 solution and graphene dispersion liquid from 2-sulfonic terephthalic acid, Al(NO3)3·9H2O and flake graphite powder respectively with N,N-dimethylformamide, then mixing and performing high-temperature heating reaction, centrifugal filtration to obtain nano organic metal particles loaded with graphene, dissolving fulvic acid in sodium hydroxide solution, adding a surfactant to obtain a fulvic acid solution, and then mixing the nano organic metal particles loaded with graphene, glutaraldehyde and the fulvic acid solution to perform stirring reaction, and cleaning and drying.

[0009] In the second aspect, the present application provides a preparation method of the composite material for the paint-free one-off molded photovoltaic frame, comprising the following steps:

[0010] S1: preparing nano organic metal particles loaded with graphene;

[0011] S2: preparing the anti-ultraviolet nano additive;

[0012] S3: preparing the dianhydride pre-cured body and compounding the epoxy resin.

[0013] Further, the step S1 of preparing the nano organic metal particles loaded with graphene comprises the following steps:

[0014] S1.1: placing 4-6 parts of 2-sulfonic terephthalic acid and 0.6-0.8 parts of anhydrous sodium acetate in a container, then adding 20-25 parts of N,N-dimethylformamide, and performing magnetic stirring at a speed of 250-300 rpm for 30-35 minutes to obtain 2-sulfonic terephthalic acid solution, and then mixing 2-3 parts of Al(NO3)3·9H2O and 25-30 parts of N,N-dimethylformamide to perform magnetic stirring until the Al(NO3)3·9H2O is completely dissolved to obtain Al(NO3)3 solution;

[0015] S1.2: 0.3-0.5 parts of flake graphite powder is placed in a container, 4-5 parts of ethanol solution with a concentration of 35-40% is added, then stirring is carried out at a stirring speed of 400-500 rpm for 10-15 minutes, and after standing for 15-20 minutes, filtration and drying are carried out to obtain clean flake graphite; the clean flake graphite and 0.2-0.3 parts of polyvinylpyrrolidone are uniformly mixed in a container, 8-10 parts of N, N-dimethylformamide is added and then uniformly stirred, and then the mixture is placed in an ultrasonic dispersing machine, ultrasonic treatment is carried out at an ultrasonic power of 50-60 w for 3-5 hours to obtain a graphene dispersion liquid;

[0016] S1.3: the 2-sulfonic acid terephthalic acid solution and the Al(NO3)3 solution prepared in step S1.1 are mixed and placed in a container, ultrasonic treatment is carried out at an ultrasonic frequency of 25-30 kHz for 15-20 minutes, then the mixture is transferred to a reaction kettle, heating is carried out at 120-140 °C, and after 10-12 hours, the mixture is transferred to an ultrasonic dispersing machine, the graphene dispersion liquid prepared in step S1.2 is added, ultrasonic treatment is carried out at an ultrasonic frequency of 25-30 kHz for 8-10 minutes, then the mixture is transferred to a reaction kettle, heating is carried out at 120-140 °C for 60-65 hours to obtain a mixed reaction liquid, the mixed reaction liquid is placed in a centrifuge after the reaction kettle is naturally cooled to room temperature, centrifugation is carried out at a rotating speed of 8000-10000 rpm for 5-8 minutes, and then suction filtration is carried out, and the obtained product is washed with N, N-dimethylformamide and methanol for 2-3 times to obtain graphene-loaded nano organic metal particles.

[0017] Further, the preparation of the anti-ultraviolet nano additive in step S2 includes the following steps:

[0018] S2.1: furil is dissolved in a sodium hydroxide solution with a concentration of 0.1-0.2 g / L to prepare a furil lye with a concentration of 0.06-0.08 g / L, then 0.1-0.2 wt% of a surfactant is added, the mixture is uniformly stirred, HCl solution is added to adjust the pH to 7.2-7.5, and then filtration is carried out by using a filter membrane with a pore size of 0.5-0.6 μm to obtain a furil solution;

[0019] S2.2: the graphene-loaded nano organic metal particles prepared in step S1.3 are placed in 120-150 parts of the furil solution, 0.02-0.03 wt% of glutaraldehyde is added, then stirring is carried out at a speed of 200-250 rpm for 8-12 hours, and then centrifugation is carried out at a rotating speed of 6000-7000 rpm for 4-5 minutes to obtain furil-doped nano particles, the obtained product is washed with methanol and deionized water for 2-3 times, and then the obtained product is placed in a vacuum drying oven and dried at a temperature of 60-65 °C for 20-24 hours to obtain an anti-ultraviolet nano additive.

[0020] Further, the preparation of the dianhydride pre-cured body and the compounding of the epoxy resin in step S3 comprises the following steps:

[0021] S3.1: Put a-pinene and maleic anhydride in a container at a molar ratio of 1:(1-1.05), add 0.1-0.5wt% of benzene sulfonic acid, then add 40-60 times the mass of dichloromethane, stir uniformly, then heat to 60-80℃, and keep the temperature for 10-12 hours, stir the reaction solution for 10-15 minutes every 40-60 minutes during the reaction, stop heating and naturally cool to room temperature, then filter to remove solid impurities, then place in a rotary evaporator, rotate at 80-100 rpm at 40-50℃ until the mass does not change, to obtain terpene maleic anhydride;

[0022] S3.2: Grind 1-2 parts of tetrafluorobenzenedicarboxylic anhydride into powder, pass through a 180-200 mesh sieve, and mix with 4-6 parts of terpene maleic anhydride in an ultrasonic water bath pot to obtain a dianhydride suspension, keep the temperature at 40-50℃, and pour 1-2 parts of bisphenol A type epoxy resin E-55 along the glass rod into the dianhydride suspension, stir for 10-15 minutes to obtain a dianhydride pre-cured body;

[0023] S3.3: Put 8-10 parts of bisphenol A type epoxy resin E-55, 10-12 parts of dianhydride pre-cured body, 0.8-1 part of anti-ultraviolet nano additive, 1-1.5 parts of triphenyl phosphate, and 0.02-0.03 parts of BYK-022 defoaming agent in a container, stir at 500-600 rpm at 40-50℃ for 20-30 minutes to obtain a composite material for a coating-free one-time molding photovoltaic frame.

[0024] Further, the surfactant in step S2.1 is cetyltrimethylammonium bromide.

[0025] Further, the temperature of the ultrasonic water bath pot in step S3.2 is 60-65℃, and the ultrasonic frequency is 28-30 kHz.

[0026] In a third aspect, the application also provides the use of the composite material for a coating-free one-time molding photovoltaic frame in a photovoltaic frame, which can be extruded in a double helix extruder and then one-time pultrusion molded in a mold to obtain a photovoltaic frame, and the obtained photovoltaic frame has good ultraviolet resistance, thermal stability and strength.

[0027] The beneficial effects are as follows: 1. This invention prepares terpene maleic anhydride by reacting α-terpinene and maleic anhydride with benzenesulfonic acid under catalysis. Then, tetrafluorophthalic anhydride is ground into powder and ultrasonically mixed with the liquid terpene maleic anhydride to obtain a dihydride suspension. A small amount of bisphenol A type epoxy resin E-55 is then introduced and pre-cured and cross-linked with the dihydride suspension. In the subsequent mixing process with epoxy resin, the tetrafluorophthalic anhydride with four fluorine atoms can provide high thermal stability and a low coefficient of thermal expansion for the epoxy resin. The terpene maleic anhydride, which is solid at room temperature and has poor compatibility with epoxy resin, can provide a good curing environment, avoiding the problems of slow reaction and incomplete reaction with epoxy resin, thereby improving the degree of network cross-linking. The synergistic effect of tetrafluorophthalic anhydride and terpene maleic anhydride can effectively improve the thermal stability of epoxy resin, reduce its coefficient of thermal expansion, and enhance its strength.

[0028] 2. This invention involves preparing 2-sulfonic acid terephthalic acid solution, Al(NO3)3·9H2O, and flake graphite powder with N,N-dimethylformamide to obtain 2-sulfonic acid terephthalic acid solution, Al(NO3)3 solution, and graphene dispersion, respectively. These are then mixed and subjected to high-temperature heating reaction, followed by centrifugation and filtration to obtain graphene-loaded metal-organic nanoparticles. During the formation of the Al-based metal-organic framework, graphene helps the Al-based metal-organic framework form more uniform nanoparticles, reducing agglomeration and resulting in smaller nanoparticles. The porous structure of the metal-organic framework can fully load graphene, enhancing the strength of the subsequent epoxy resin. Furthermore, the Al-based metal-organic framework can provide sufficient shielding against ultraviolet rays in the wavelength range of 100 nm to 400 nm. Doping into epoxy resin materials not only improves UV resistance but also ensures good compatibility between the organic framework and epoxy resin, preventing the doping of nanomaterials from affecting the strength of the composite material.

[0029] 3. This invention prepares an anti-UV nano-additive by dissolving fulvic acid in sodium hydroxide solution, adding a surfactant, and then mixing graphene-loaded organometallic nanoparticles, glutaraldehyde, and the fulvic acid solution with the mixture and stirring. This allows fulvic acid to be incorporated into the graphene-loaded organometallic nanoparticles. The fulvic acid contains a large number of functional groups such as phenolic hydroxyl groups and carboxyl groups. These functional groups can undergo chemical or electrostatic adsorption reactions with metal ions in the metal-organic framework and functional groups on the surface of graphene to form stable complexes, preventing the degradation of material performance. Furthermore, the functional groups in fulvic acid can absorb ultraviolet light and reduce the transmittance of ultraviolet light through adsorption or chemical bonding, thereby improving the UV resistance of the resin material. Attached Figure Description

[0030] Figure 1Flow chart of the preparation method of the composite material for the paint-free disposable molded photovoltaic frame adopted by the embodiments of the present application. DETAILED DESCRIPTION

[0031] The technical solutions in the embodiments of the present application will be clearly and completely described below with reference to the drawings in the embodiments of the present application. Obviously, the described embodiments are only a part of the embodiments of the present application, rather than all the embodiments of the present application. Based on the embodiments in the present application, all the other embodiments obtained by a person of ordinary skill in the art without creative work fall within the protection scope of the present application.

[0032] Embodiment 1

[0033] The composite material for the paint-free disposable molded photovoltaic frame comprises the following components: 8 parts of bisphenol A type epoxy resin E-55, 10 parts of dianhydride pre-cured body, 0.8 parts of anti-ultraviolet nano additive, 1 part of triphenyl phosphate and 0.02 part of BYK-022 defoaming agent.

[0034] The preparation method of the composite material for the paint-free disposable molded photovoltaic frame comprises the following steps as shown in Figure 1

[0035] S1: Preparation of graphene-loaded nano-organic metal particles

[0036] S1.1: 4 parts of 2-sulfonic acid terephthalic acid and 0.6 parts of anhydrous sodium acetate are placed in a container, then 20 parts of N, N-dimethylformamide is added, magnetic stirring is carried out at a speed of 250 rpm for 30 minutes to obtain a 2-sulfonic acid terephthalic acid solution, then 2 parts of Al(NO3)3·9H2O and 25 parts of N, N-dimethylformamide are mixed and magnetically stirred until Al(NO3)3·9H2O is completely dissolved to obtain an Al(NO3)3 solution;

[0037] S1.2: 0.3 parts of flake graphite powder are placed in a container, 4 parts of 35% ethanol solution are added, then stirring is carried out at a speed of 400 rpm for 10 minutes, and after standing for 15 minutes, filtration and drying are carried out to obtain clean flake graphite. The clean flake graphite and 0.2 parts of polyvinylpyrrolidone are uniformly mixed in a container, 8 parts of N, N-dimethylformamide is added and stirred uniformly, then it is placed in an ultrasonic disperser, ultrasonic treatment is carried out at an ultrasonic power of 50 w for 3 hours to obtain a graphene dispersion liquid;

[0038] ​S1.3: The 2-sulfonic acid terephthalic acid solution and the Al(NO3)3 solution prepared in step S1.1 were mixed in a container, and ultrasonic treatment was performed at an ultrasonic frequency of 25 kHz for 15 minutes, and then transferred to a reaction kettle for heating at a temperature of 120°C for 10 hours, and then transferred to an ultrasonic disperser, and the graphene dispersion liquid prepared in step S1.2 was added, and ultrasonic treatment was performed at an ultrasonic frequency of 25 kHz for 8 minutes, and then transferred to a reaction kettle for heating at 120°C for 60 hours to obtain a mixed reaction liquid, and the mixed reaction liquid was placed in a centrifuge for centrifugation at a speed of 8000 rpm for 5 minutes, and then suction filtration was performed, and then washed twice with N, N-dimethylformamide and methanol to obtain graphene-loaded nanometer organic metal particles.

[0039] S2: Preparation of anti-ultraviolet nano-additive

[0040] S2.1: Fulvic acid was dissolved in a sodium hydroxide solution with a concentration of 0.1 g / L to prepare a fulvic acid lye with a concentration of 0.06 g / L, and then 0.1 wt% of cetyltrimethylammonium bromide was added, and after stirring, HCl solution was added to adjust the pH to 7.2, and then 0.5 μm filter membrane was used for filtration to obtain a fulvic acid solution;

[0041] S2.2: The graphene-loaded nanometer organic metal particles prepared in step S1.3 were placed in 120 parts of the fulvic acid solution, and then 0.02 wt% of glutaraldehyde was added, and then stirring was continuously performed at a speed of 200 rpm for 8 hours, and then centrifugation was performed at a speed of 6000 rpm for 4 minutes to obtain fulvic acid-doped nanoparticles, and then methanol and deionized water were used for washing twice, and then the nanoparticles were placed in a vacuum drying oven for drying at a temperature of 60°C for 20 hours to obtain an anti-ultraviolet nano-additive.

[0042] S3: Preparation of dihydric anhydride pre-cured body and compounding of epoxy resin

[0043] S3.1: α-Terpinene and maleic anhydride were placed in a container in a molar ratio of 1:1, and then 0.1 wt% of benzenesulfonic acid was added, and then 40 times the mass of dichloromethane was added, and then stirring was performed, and then the temperature was raised to 60°C, and then incubation was performed for 10 hours, and then during the reaction, the reaction solution was stirred for 10 minutes every 40 minutes, and then after the heating was stopped, natural cooling was performed to room temperature, and then filtration was performed to remove solid impurities, and then the terpinene maleic anhydride was placed in a rotary evaporator, and then rotary evaporation was performed at a speed of 80 rpm at 40°C until the mass did not change.

[0044] S3.2: 1 part of tetrafluorophthalic anhydride was ground into powder, after passing through a 180 mesh sieve, it was mixed with 4 parts of terpene maleic anhydride in an ultrasonic water bath at a temperature of 60°C and an ultrasonic frequency of 28 kHz to obtain a dianhydride suspension, and the temperature was kept at 40°C, 1 part of bisphenol A type epoxy resin E-55 was introduced into the dianhydride suspension along the glass rod, and stirred for 10 minutes to obtain a dianhydride pre-cured body;

[0045] S3.3: 8 parts of bisphenol A type epoxy resin E-55, 10 parts of dianhydride pre-cured body, 0.8 parts of anti-ultraviolet nano additive, 1 part of triphenyl phosphate and 0.02 parts of BYK-022 defoaming agent were placed in a container, stirred at 500 rpm for 20 minutes at 40°C to obtain a composite material for a coating-free disposable molded photovoltaic frame.

[0046] Example 2

[0047] The composite material for the coating-free disposable molded photovoltaic frame comprises the following components: 10 parts of bisphenol A type epoxy resin E-55, 12 parts of dianhydride pre-cured body, 1 part of anti-ultraviolet nano additive, 1.5 parts of triphenyl phosphate and 0.03 parts of BYK-022 defoaming agent;

[0048] The preparation method of the composite material for the coating-free disposable molded photovoltaic frame, as shown in Figure 1 comprises the following steps:

[0049] S1: Preparation of graphene-loaded nano-organic metal particles

[0050] S1.1: 6 parts of 2-sulfonic terephthalic acid and 0.8 parts of anhydrous sodium acetate were placed in a container, then 25 parts of N, N-dimethylformamide was added, and magnetic stirring was carried out at a speed of 250 rpm for 30 minutes to obtain a 2-sulfonic terephthalic acid solution, then 3 parts of Al(NO3)3·9H2O and 30 parts of N, N-dimethylformamide were mixed and magnetically stirred until Al(NO3)3·9H2O was completely dissolved to obtain an Al(NO3)3 solution;

[0051] S1.2: 0.5 parts of flake graphite powder was placed in a container, 5 parts of 35% ethanol solution was added, then stirred at a speed of 400 rpm for 10 minutes, and after standing for 15 minutes, it was filtered and dried to obtain clean flake graphite, the clean flake graphite and 0.3 parts of polyvinylpyrrolidone were mixed uniformly in a container, 10 parts of N, N-dimethylformamide was added and stirred uniformly, then placed in an ultrasonic disperser, and ultrasonic treatment was carried out at an ultrasonic power of 50w for 3 hours to obtain a graphene dispersion liquid;

[0052] S1.3: The 2-sulfonic acid terephthalic acid solution and the Al(NO3)3 solution prepared in step S1.1 were mixed in a container, and ultrasonic treatment was performed at an ultrasonic frequency of 25 kHz for 15 minutes, and then transferred to a reaction kettle for heating at a temperature of 120°C for 10 hours, and then transferred to an ultrasonic disperser, and the graphene dispersion liquid prepared in step S1.2 was added, and ultrasonic treatment was performed at an ultrasonic frequency of 25 kHz for 8 minutes, and then transferred to a reaction kettle for heating at 120°C for 60 hours to obtain a mixed reaction liquid, and the mixed reaction liquid was placed in a centrifuge for centrifugation at a speed of 8000 rpm for 5 minutes, and then suction filtration was performed, and then washed twice with N, N-dimethylformamide and methanol respectively to obtain graphene-loaded nano organic metal particles.

[0053] S2: Preparation of anti-ultraviolet nano additive

[0054] S2.1: Fulvic acid was dissolved in a 0.1 g / L sodium hydroxide solution to prepare a 0.08 g / L fulvic acid lye, and then 0.2 wt% of cetyltrimethylammonium bromide was added, and stirred uniformly, and then a HCl solution was added to adjust the pH to 7.2, and then filtered using a 0.5 μm filter to obtain a fulvic acid solution;

[0055] S2.2: The graphene-loaded nano organic metal particles prepared in step S1.3 were placed in 150 parts of the fulvic acid solution, and then 0.03 wt% of glutaraldehyde was added, and then stirred at a speed of 200 rpm for 8 hours, and then centrifuged at a speed of 6000 rpm for 4 minutes to obtain fulvic acid-doped nanoparticles, and then washed twice with methanol and deionized water respectively, and then placed in a vacuum drying oven for drying at a temperature of 60°C for 20 hours to obtain an anti-ultraviolet nano additive.

[0056] S3: Preparation of dihydric anhydride pre-cured body and compounding of epoxy resin

[0057] S3.1: α-Terpinene and maleic anhydride were placed in a container at a molar ratio of 1:1.05, and then 0.5 wt% of benzenesulfonic acid was added, and then 60 times the mass of dichloromethane was added, and then stirred uniformly, and then warmed to 60°C, and then incubated for 10 hours, and then the reaction solution was stirred for 10 minutes every 40 minutes during the reaction, and then the heating was stopped, and then naturally cooled to room temperature, and then filtered to remove solid impurities, and then placed in a rotary evaporator, and then rotary evaporation was performed at a speed of 80 rpm at 40°C until the mass did not change to obtain terpene maleic anhydride.

[0058] S3.2: 2 parts of tetrafluorophthalic anhydride were ground into powder, mixed with 6 parts of terpene maleic anhydride in an ultrasonic water bath at 60°C and an ultrasonic frequency of 28 kHz to obtain a dianhydride suspension, and then 2 parts of bisphenol A type epoxy resin E-55 was introduced into the dianhydride suspension along a glass rod, stirred for 10 minutes to obtain a dianhydride pre-cured body;

[0059] S3.3: 10 parts of bisphenol A type epoxy resin E-55, 12 parts of dianhydride pre-cured body, 1 part of anti-ultraviolet nano additive, 1.5 parts of triphenyl phosphate and 0.03 parts of BYK-022 defoaming agent were placed in a container, stirred at 40°C and 500 rpm for 20 minutes to obtain a composite material for a coating-free disposable molded photovoltaic frame.

[0060] Example 3

[0061] A composite material for a coating-free disposable molded photovoltaic frame, comprising the following components: 8 parts of bisphenol A type epoxy resin E-55, 10 parts of dianhydride pre-cured body, 0.8 parts of anti-ultraviolet nano additive, 1 part of triphenyl phosphate and 0.02 parts of BYK-022 defoaming agent;

[0062] A method for preparing a composite material for a coating-free disposable molded photovoltaic frame, as shown in Figure 1 , comprising the following steps:

[0063] S1: Preparation of graphene-loaded nano-organic metal particles

[0064] S1.1: 4 parts of 2-sulfonic terephthalic acid and 0.6 parts of anhydrous sodium acetate were placed in a container, then 20 parts of N, N-dimethylformamide was added, and magnetic stirring was carried out at 300 rpm for 35 minutes to obtain a 2-sulfonic terephthalic acid solution, then 2 parts of Al(NO3)3·9H2O and 25 parts of N, N-dimethylformamide were mixed and magnetically stirred until Al(NO3)3·9H2O was completely dissolved to obtain an Al(NO3)3 solution;

[0065] S1.2: 0.3 parts of flake graphite powder was placed in a container, 4 parts of 40% ethanol solution was added, and then stirred at 500 rpm for 15 minutes, and then filtered and dried after standing for 20 minutes to obtain clean flake graphite. The clean flake graphite and 0.2 parts of polyvinylpyrrolidone were mixed uniformly in a container, 8 parts of N, N-dimethylformamide was added and stirred uniformly, and then placed in an ultrasonic disperser, and ultrasonic treatment was carried out at an ultrasonic power of 60w for 5 hours to obtain a graphene dispersion liquid;

[0066] S1.3: The 2-sulfonic acid terephthalic acid solution and the Al(NO3)3 solution prepared in step S1.1 were mixed in a container, and ultrasonic treatment was performed at an ultrasonic frequency of 30 kHz for 20 minutes, and then transferred to a reaction kettle for heating at a temperature of 140°C for 12 hours, and then transferred to an ultrasonic disperser, and the graphene dispersion liquid prepared in step S1.2 was added, and ultrasonic treatment was performed at an ultrasonic frequency of 30 kHz for 10 minutes, and then transferred to a reaction kettle for heating at 140°C for 65 hours to obtain a mixed reaction liquid, and the mixed reaction liquid was placed in a centrifuge for centrifugation at a speed of 10,000 rpm for 8 minutes, and then suction filtration was performed, and then washed with N, N-dimethylformamide and methanol three times respectively to obtain graphene-loaded nanometer organic metal particles.

[0067] S2: Preparation of anti-ultraviolet nano additive

[0068] S2.1: Fulvic acid was dissolved in a sodium hydroxide solution with a concentration of 0.2 g / L to prepare a fulvic acid lye with a concentration of 0.06 g / L, then 0.1 wt% of cetyltrimethylammonium bromide was added, stirred uniformly, and then a HCl solution was added to adjust the pH to 7.5, and then filtered using a filter membrane with a pore size of 0.6 μm to obtain a fulvic acid solution;

[0069] S2.2: The graphene-loaded nanometer organic metal particles prepared in step S1.3 were placed in 120 parts of the fulvic acid solution, and then 0.02 wt% of glutaraldehyde was added, and then stirred at a speed of 250 rpm for 12 hours, and then centrifuged at a speed of 7,000 rpm for 5 minutes to obtain fulvic acid-doped nanoparticles, and then washed with methanol and deionized water three times respectively, and then placed in a vacuum drying oven for drying at a temperature of 65°C for 24 hours to obtain an anti-ultraviolet nano additive.

[0070] S3: Preparation of dihydrazide pre-cured body and compounding of epoxy resin

[0071] S3.1: α-Terpinene and maleic anhydride were placed in a container in a molar ratio of 1:1, and then 0.1 wt% of benzenesulfonic acid was added, and then 60 times the mass of dichloromethane was added, and then stirred uniformly, and then heated to 80°C, and then incubated for 12 hours, and then the reaction solution was stirred for 15 minutes every 60 minutes during the reaction, and then the heating was stopped, and then naturally cooled to room temperature, and then filtered to remove solid impurities, and then placed in a rotary evaporator, and then rotary evaporation was performed at a speed of 100 rpm at 50°C until the mass did not change to obtain terpene maleic anhydride.

[0072] S3.2: Grind 1 part of tetrafluorophthalic anhydride into powder, pass it through a 200-mesh sieve, and mix it with 4 parts of terpene maleic anhydride in an ultrasonic water bath. The temperature of the ultrasonic water bath is 65℃ and the ultrasonic frequency is 30kHz to obtain a dihydric anhydride suspension. Maintain the temperature at 50℃, and guide 1 part of bisphenol A type epoxy resin E-55 along a glass rod into the dihydric anhydride suspension. Stir for 15 minutes to obtain a dihydric anhydride pre-cured body.

[0073] S3.3: Place 8 parts of bisphenol A type epoxy resin E-55, 10 parts of dianhydride precured body, 0.8 parts of UV-resistant nano-additive, 1 part of triphenyl phosphate and 0.02 parts of BYK-022 defoamer in a container, and stir at 600 rpm for 30 minutes at 50°C to obtain a composite material for one-time molding of photovoltaic frames without coating.

[0074] Comparative Example 1

[0075] Compared with Example 1, Comparative Example 1 differs in that tetrafluorophthalic anhydride was not added in step S3.2. Instead, 1 part of bisphenol A type epoxy resin E-55 was directly guided along a glass rod to 5 parts of terpene maleic anhydride at 40°C to obtain a terpene maleic anhydride precured body. The remaining steps were the same as in Example 1. The composite material prepared for coating-free one-time molding of photovoltaic frames was designated as Comparative Example 1.

[0076] Comparative Example 2

[0077] Compared with Example 1, Comparative Example 2 differs in that step S3.1 is removed and the terpene maleic anhydride in step S3.2 is replaced with an equal mass of methyl nadic anhydride to obtain a dihydride precured body. The remaining steps are the same as in Example 1. The composite material for coating-free one-time molding of photovoltaic frames obtained is referred to as Comparative Example 2.

[0078] Comparative Example 3

[0079] Compared with Example 1, Comparative Example 3 differs in that step S1 is removed and the graphene-loaded nano-organic metal particles in step S2.2 are replaced with an equal mass of graphene to obtain an anti-ultraviolet nano-additive. The remaining steps are the same as in Example 1. The composite material obtained for coating-free one-time molding of photovoltaic frames is referred to as Comparative Example 3.

[0080] Comparative Example 4

[0081] Compared with Example 1, Comparative Example 4 differs in that step S2 is removed and the UV-resistant nano-additive in step S3.3 is replaced with an equal mass of graphene-loaded nano-organic metal particles. The remaining steps are the same as in Example 1. The composite material prepared for coating-free one-time molding of photovoltaic frames is referred to as Comparative Example 4.

[0082] Experiment 1: Take the composite material for coating-free one-time molding photovoltaic frame prepared in Example 1-3 and Comparative Example 1-4, add it into a double screw extruder, extrude at 200℃ with a speed of 250 rpm, then pass through a draw bar, cool and cut to obtain a resin sample strip with a thickness of 5mm, a length of 5cm and a width of 2cm, test the tensile strength according to the standard ISO527, record it as Rm0; test the notched Izod impact strength at 23℃ and 60℃ according to the standard ISO180, record the data as 23℃ impact strength and 60℃ impact strength; test the heat distortion temperature according to the standard ISO75, the test condition is 0.45MPa; perform ultraviolet irradiation according to the standard IEC62790, the light condition is 120kWH for 2000 hours, then test the tensile strength after irradiation according to the standard ISO527, record it as Rm1, calculate the tensile strength decrease rate after irradiation = (Rm0-Rm1) / Rm0x100%, the lower the tensile strength decrease rate after irradiation, the better the ultraviolet resistance, each test is performed three times to take the average value, record the test results and make a table as shown in Table 1.

[0083] Table 1: Performance of resin sample strip

[0084]

[0085] As can be seen from Table 1, the resin sample strip prepared from the composite material for coating-free one-time molding photovoltaic frame of Example 1-3 is better than Comparative Example 1-4 in terms of the comprehensive strength of the material reflected in the tensile strength test and the notched Izod impact strength test at 23℃ and 60℃, the thermal stability of the material reflected in the heat distortion temperature test, and the ultraviolet resistance of the material reflected in the tensile strength decrease rate after irradiation. As can be seen from Example 1, Comparative Example 1 and Comparative Example 2, tetrafluorophthalic anhydride can improve the strength and thermal stability of the resin, and replacing terpene maleic anhydride with the same type of curing agent methyl nadic anhydride will decrease the strength and thermal stability, which proves that tetrafluorophthalic anhydride and terpene maleic anhydride have a synergistic effect, which can effectively improve the thermal stability of the epoxy resin, reduce its thermal expansion coefficient and enhance its strength.

[0086] And as can be seen from Example 1 and Comparative Example 3, the resin material prepared without loading graphene with nano-organic metal particles not only has a decrease in ultraviolet resistance and strength, but also has a small decrease in thermal stability, which proves that the Al-based metal organic framework can also provide Al ultraviolet shielding and improve the compatibility with the epoxy resin, thereby improving the strength and thermal stability performance;

[0087] As can be seen from Example 1 and Comparative Example 4, treating the graphene-loaded nano-organometallic particles with a solution of fulvic acid does not result in a decrease in the UV resistance of the resin material, which proves that fulvic acid can absorb UV light, thereby improving the UV resistance of the resin material, and a small decrease in the strength and thermal stability, which is presumably due to the fact that fulvic acid contains a large number of functional groups such as phenolic hydroxyl groups and carboxyl groups, which can improve the compatibility with the components, thereby enhancing the strength and thermal stability.

[0088] The above examples are only illustrative of the principles of the present application and its effects, and are not intended to limit the present application. Any person skilled in the art can modify or change the above examples without departing from the spirit and scope of the present application. Therefore, all equivalent modifications or changes made by those skilled in the art without departing from the spirit and technical ideas disclosed by the present application should be covered by the claims of the present application.

Claims

1. A composite material for paint-free, one-piece molded photovoltaic frames, characterized in that, Includes the following components: 8-10 parts bisphenol A type epoxy resin E-55, 10-12 parts dianhydride precured body, 0.8-1 part UV-resistant nano-additive, 1-1.5 parts triphenyl phosphate and 0.02-0.03 parts BYK-022 defoamer; The dianhydride precured body is prepared by mixing α-terpinene and maleic anhydride in a molar ratio of 1:(1-1.05), adding 0.1-0.5 wt% of benzenesulfonic acid as a catalyst, and then placing it in 40-60 times its mass of dichloromethane solvent for a heated catalytic reaction to obtain terpene maleic anhydride. 4-6 parts of terpene maleic anhydride are ultrasonically mixed with 1-2 parts of powdered tetrafluorophthalic anhydride, and then 1-2 parts of bisphenol A type epoxy resin E-55 are added and stirred evenly to obtain the product. The UV-resistant nano-additive is first prepared by reacting 2-sulfonic acid terephthalic acid, Al(NO3)3·9H2O and flake graphite powder with N,N-dimethylformamide to obtain 2-sulfonic acid terephthalic acid solution, Al(NO3)3 solution and graphene dispersion, respectively. Then, the mixture is heated at high temperature and centrifuged and filtered to obtain graphene-loaded organometallic nanoparticles. Then, fulvic acid solution is prepared by dissolving fulvic acid in sodium hydroxide solution and adding surfactant. Finally, the graphene-loaded organometallic nanoparticles, glutaraldehyde and fulvic acid solution are mixed and stirred to react. After washing and drying, the final product is obtained. The composite material used for coating-free one-time molding photovoltaic frames is prepared by placing 8-10 parts of bisphenol A type epoxy resin E-55, 10-12 parts of dianhydride precured body, 0.8-1 parts of anti-UV nano-additive, 1-1.5 parts of triphenyl phosphate and 0.02-0.03 parts of BYK-022 defoamer in a container and stirring at 500-600 rpm for 20-30 minutes at 40-50°C.

2. A method for preparing a composite material for a paint-free, one-time molded photovoltaic frame, characterized in that, This preparation method is used to prepare the composite material for one-time molding of a paint-free photovoltaic frame as described in claim 1. Includes the following steps: S1: Preparation of graphene-supported organometallic nanoparticles; S2: Preparation of UV-resistant nano-additives; S3: Preparation of dianhydride precured body and its composite with epoxy resin; Step S1 specifically includes the following steps: S1.1: Place 4-6 parts of 2-sulfonic terephthalic acid and 0.6-0.8 parts of anhydrous sodium acetate in a container, then add 20-25 parts of N,N-dimethylformamide, and magnetically stir at 250-300 rpm for 30-35 minutes to obtain a 2-sulfonic terephthalic acid solution. Then mix 2-3 parts of Al(NO3)3·9H2O and 25-30 parts of N,N-dimethylformamide and magnetically stir until Al(NO3)3·9H2O is completely dissolved to obtain an Al(NO3)3 solution. S1.2: Place 0.3-0.5 parts of flake graphite powder in a container, add 4-5 parts of ethanol solution with a concentration of 35-40%, then stir at a stirring speed of 400-500 rpm for 10-15 minutes, let stand for 15-20 minutes, filter and dry to obtain clean flake graphite. Mix the clean flake graphite and 0.2-0.3 parts of polyvinylpyrrolidone evenly in a container, add 8-10 parts of N,N-dimethylformamide and stir evenly, then place in an ultrasonic disperser and ultrasonically treat with an ultrasonic power of 50-60W for 3-5 hours to obtain graphene dispersion. S1.3: The 2-sulfonic acid terephthalic acid solution and Al(NO3)3 solution obtained in step S1.1 are mixed and placed in a container. The mixture is ultrasonically treated at a frequency of 25-30 kHz for 15-20 minutes. Then, it is transferred to a reaction vessel and heated at 120-140℃ for 10-12 hours. After that, it is transferred to an ultrasonic disperser and the graphene dispersion obtained in step S1.2 is added. The mixture is ultrasonically treated at a frequency of 25-30 kHz for 8-10 minutes. Then, it is transferred to a reaction vessel and heated at 120-140℃ for 60-65 hours to obtain a mixed reaction solution. After the reaction vessel is naturally cooled to room temperature, the mixed reaction solution is centrifuged at 8000-10000 rpm for 5-8 minutes and then filtered. The mixture is washed 2-3 times with N,N-dimethylformamide and methanol to obtain graphene-loaded nano-organic metal particles. Step S2 specifically includes the following steps: S2.1: Dissolve fulvic acid in a sodium hydroxide solution with a concentration of 0.1-0.2 g / L to prepare a fulvic acid alkaline solution with a concentration of 0.06-0.08 g / L. Then add 0.1-0.2 wt% surfactant, stir evenly, add HCl solution to adjust the pH to 7.2-7.5, and then filter using a 0.5-0.6 μm filter membrane to obtain the fulvic acid solution. S2.2: Place the graphene-loaded organometallic nanoparticles obtained in step S1.3 into 120-150 parts of fulvic acid solution, add 0.02-0.03wt% of glutaraldehyde, and then stir continuously at 200-250 rpm for 8-12 hours. Then centrifuge at 6000-7000 rpm for 4-5 minutes to obtain fulvic acid-doped nanoparticles. Wash them 2-3 times with methanol and deionized water, and then place them in a vacuum drying oven at 60-65℃ for 20-24 hours to obtain UV-resistant nano-additives. Step S3 specifically includes the following steps: S3.1: Place α-terpinene and maleic anhydride in a container at a molar ratio of 1:(1-1.05), add 0.1-0.5wt% benzenesulfonic acid, and then add 40-60 times the mass of dichloromethane. After stirring evenly, heat to 60-80℃ and maintain the temperature for 10-12 hours. During the reaction, stir the reaction solution for 10-15 minutes every 40-60 minutes. After stopping heating, allow it to cool naturally to room temperature. Then filter to remove solid impurities, and place it in a rotary evaporator. Rotate and evaporate at 40-50℃ and 80-100 rpm until the mass does not change, to obtain terpene maleic anhydride. S3.2: Grind 1-2 parts of tetrafluorophthalic anhydride into powder, pass it through a 180-200 mesh sieve, and mix it with 4-6 parts of terpene maleic anhydride in an ultrasonic water bath to obtain a dihydric anhydride suspension. Keep the temperature at 40-50℃, and guide 1-2 parts of bisphenol A type epoxy resin E-55 along a glass rod into the dihydric anhydride suspension. Stir for 10-15 minutes to obtain a dihydric anhydride pre-cured body. S3.3: Place 8-10 parts of bisphenol A type epoxy resin E-55, 10-12 parts of dianhydride precured body, 0.8-1 parts of UV-resistant nano-additive, 1-1.5 parts of triphenyl phosphate and 0.02-0.03 parts of BYK-022 defoamer in a container, and stir at 500-600 rpm for 20-30 minutes at 40-50℃ to obtain a composite material for one-time molding of photovoltaic frames without coating.

3. The method for preparing the composite material for a paint-free, one-time molded photovoltaic frame according to claim 2, characterized in that, The surfactant in step S2.1 is hexadecyltrimethylammonium bromide.

4. The method for preparing the composite material for a paint-free, one-time molded photovoltaic frame according to claim 2, characterized in that, Step S3.2 Mix evenly in an ultrasonic water bath. The temperature of the ultrasonic water bath is 60-65℃ and the ultrasonic frequency is 28-30kHz.

5. Application of composite materials for paint-free, one-piece molded photovoltaic frames, characterized in that, The composite material for a paint-free, one-time molded photovoltaic frame as described in claim 1 is placed in a twin-screw extruder for extrusion, and then pultruded in a die to obtain the photovoltaic frame.

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