High transparency acrylic resin composition, its preparation process and application on photovoltaic

Abstract

The application relates to the technical field of acrylic resins, in particular to a high-transparency acrylic resin composition, a preparation process thereof and application of the high-transparency acrylic resin composition to photovoltaics. The high-transparency acrylic resin composition comprises a glycidyl acrylic resin, a curing agent, a plasticizer and a leveling agent, wherein the curing agent is prepared by the following method: firstly, porous nanoparticles are prepared by adopting a sol-gel method with a template agent; secondly, the porous nanoparticles are modified by carboxylation; and finally, the carboxyl-modified porous nanoparticles are grafted with a polyphenol type hindered phenolic antioxidant. In addition, a polysiloxane with a fatty ring structure and an epoxy group is introduced into the glycidyl acrylic resin. The above acrylic resin composition is not only light in quality, has high transparency, but also has good aging resistance, and is an excellent choice as a photovoltaic module packaging material.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of acrylic resin, in particular to a high-transparency acrylic resin composition, a preparation process thereof and application thereof in photovoltaics. BACKGROUND

[0002] With the increasing demand for clean energy worldwide, the photovoltaic industry has entered a period of rapid development. Photovoltaic modules, as the core components of photovoltaic systems, directly affect the power generation efficiency and economic benefits of the entire photovoltaic system. In the production process of photovoltaic modules, encapsulating materials, as the key part to protect photovoltaic cells and improve photoelectric conversion efficiency, directly affect the quality and service life of photovoltaic modules.

[0003] Currently, traditional photovoltaic encapsulating materials mainly include glass, EVA adhesive film, POE adhesive film, etc. However, these traditional encapsulating materials have some shortcomings. For example, although glass has high light transmittance and mechanical strength, it is heavy and easy to break, increasing transportation and installation costs, and has poor adaptability in complex environments. Although EVA adhesive film and POE adhesive film have good flexibility and adhesion, they are prone to yellowing and aging during long-term use, resulting in a decrease in light transmittance and affecting the power generation efficiency of photovoltaic modules.

[0004] High-transparency acrylic resin, as a new type of photovoltaic encapsulating material, has the advantages of light weight, easy bending, not easy to break, high light transmittance, good chemical resistance, etc., and is expected to replace traditional encapsulating materials and be widely used in the photovoltaic field. However, since photovoltaic modules are usually used outdoors for a long time, they are affected by various environmental factors such as ultraviolet light, high temperature, high humidity, and oxygen, which can cause the molecular chain of the acrylic resin to break and degrade, resulting in a decrease in material performance, such as a decrease in light transmittance, yellowing, and embrittlement, which seriously affects the power generation efficiency and service life of photovoltaic modules.

[0005] In the prior art, the commonly used method to improve the aging resistance of acrylic resin is to add antioxidants, ultraviolet absorbers, and other additives. However, the amount of antioxidants and ultraviolet absorbers needs to be accurately controlled, and excessive addition may affect other properties of the resin. Moreover, these additives may gradually lose their effectiveness during long-term use and cannot provide effective protection continuously.

[0006] Therefore, it is of great practical significance to develop a high-transparency acrylic resin with excellent aging resistance and apply it in the photovoltaic field. SUMMARY

[0007] In order to improve the aging resistance of high-transparency acrylic resin composition, the present application provides a high-transparency acrylic resin composition, a preparation process thereof and application thereof in photovoltaics.

[0008] A high transparency acrylic resin composition, comprising the following components by weight: glycidyl acrylic resin 100-180 parts, curing agent 10-40 parts, plasticizer 5-10 parts, leveling agent 0.5-2.5 parts; the glycidyl acrylic resin is prepared by polymerization of glycidyl methacrylate and mixed monomers; the mixed monomers include methyl methacrylate and butyl acrylate; the preparation method of the curing agent comprises the following steps:

[0009] S1: using metal alkoxide as raw material, adopting sol-gel method, and adding template agent to prepare porous nanoparticles;

[0010] S2: ultrasonic dispersion of the porous nanoparticles in water, and then reaction with bromoacetic acid to obtain carboxyl-modified porous nanoparticles;

[0011] S3: reaction of the carboxyl-modified porous nanoparticles with polyphenol type hindered phenolic antioxidant.

[0012] In the above technical solution, the glycidyl type acrylic resin contains epoxy groups, which can react with carboxyl groups to crosslink and achieve curing, and no by-products are generated during the curing process, and the prepared material has excellent gloss retention and aging resistance, and is particularly suitable for outdoor high-decorative packaging materials. In the present application, the curing agent is carboxylated porous nanoparticles grafted with polyphenol type hindered phenolic antioxidant, so that, on the one hand, the presence of carboxyl groups can accelerate the curing rate of the acrylic resin; on the other hand, the porous nanoparticles have a high specific surface area, which is beneficial to reducing the light energy reflected to the outside, improving the light utilization rate, and also reducing the influence of ultraviolet rays on the acrylic resin; thirdly, grafting the polyphenol type hindered phenolic antioxidant on the carboxylated porous nanoparticles can further reduce the influence of oxygen on the acrylic resin, and also improve the dispersibility of the antioxidant in the acrylic resin.

[0013] Preferably, in the step S1, the template agent is one or more of polyvinyl alcohol, polyethylene glycol and polyvinylpyrrolidone;

[0014] And / or, the metal alkoxide is one or more of silicon alkoxide, titanium alkoxide and zirconium alkoxide.

[0015] In the above technical solution, the nanoparticles have good ultraviolet absorption or shielding function, which can reduce the damage of ultraviolet rays to the acrylic resin, thereby improving the aging resistance of the acrylic resin. In addition, the template agent is added during the preparation of the porous nanoparticles, and after the removal of the template agent, a porous structure is formed, which can improve the aging resistance and light utilization rate of the acrylic resin.

[0016] Preferably, in the step S1, the zinc salt and the metal alkoxide are added simultaneously, and the mass ratio of the zinc salt to the metal alkoxide is 1: (20-32).

[0017] By the above technical scheme, the zinc oxide has strong ultraviolet absorption and almost no visible light absorption, so that the influence of ultraviolet on the acrylic resin can be effectively reduced, but the dispersion of the zinc oxide nanoparticles is poor and easy to agglomerate, and the dispersion of the zinc oxide on the porous nanoparticles can be effectively improved by the above method, so that the aging resistance of the acrylic resin is further improved.

[0018] In some embodiments, in the step S1, the mass ratio of the zinc salt to the metal alkoxide can be 1:20, 1:22, 1:25, 1:27, 1:30 or 1:32, and in general, in the step S1, the mass ratio of the zinc salt to the metal alkoxide is 1:25, and better experimental results can be obtained.

[0019] Preferably, in the step S2, the mass ratio of the porous nanoparticles to bromoacetic acid is 1: (15-30).

[0020] In some embodiments, in the step S2, the mass ratio of the porous nanoparticles to bromoacetic acid can be 1:15, 1:18, 1:20, 1:22, 1:25, 1:27 or 1:30, and in general, in the step S2, the mass ratio of the porous nanoparticles to bromoacetic acid is 1:25, and better experimental results can be obtained.

[0021] Preferably, in the step S3, the mass ratio of the carboxylated porous nanoparticles to the polyphenol hindered phenolic antioxidant is 1: (0.2-0.8).

[0022] In some embodiments, in the step S3, the mass ratio of the carboxylated porous nanoparticles to the polyphenol hindered phenolic antioxidant can be 1:0.2, 1:0.3, 1:0.4, 1:0.5, 1:0.6, 1:0.7 or 1:0.8, and in general, in the step S3, the mass ratio of the carboxylated porous nanoparticles to the polyphenol hindered phenolic antioxidant is 1:0.5, and better experimental results can be obtained.

[0023] Preferably, the preparation method of the glycidyl acrylic resin is as follows:

[0024] 1) The vinyl siloxane and 2-(3,4-epoxycyclohexyl) ethyl triethoxysilane are reacted under the action of a catalyst to obtain polysiloxane.

[0025] 2) The polysiloxane, styrene, butyl acrylate, methyl methacrylate and glycidyl methacrylate are uniformly mixed, an initiator is added, and then reacted, and then a chain transfer agent is added and continuously reacted.

[0026] In the above technical solution, the polysiloxane containing a fatty ring structure, an epoxy group and a carbon-carbon double bond is introduced into the acrylic resin. On the one hand, the flexible chain segment of the polysiloxane is beneficial to improve the toughness and hydrophobicity of the acrylic resin and reduce the attack of moisture and heat on the acrylic resin. On the other hand, the fatty ring structure can produce a large steric hindrance, which can prevent water molecules and the like from penetrating into the interior of the acrylic resin, reduce the risk of hydrolysis of the acrylic resin, hinder the free radical chain reaction caused by ultraviolet light, and reduce the photooxidation rate. Moreover, the fatty ring structure can form a more compact cross-linking structure with the acrylic resin matrix, thereby effectively resisting the swelling or deformation caused by moisture and heat, and improving the aging resistance of the acrylic resin. In addition, the number of epoxy groups in the acrylic resin is increased, the cross-linking degree of the acrylic resin is improved, the attack of water, oxygen and the like on the acrylic resin is further reduced, and the aging resistance is improved. Furthermore, the double bond can participate in the polymerization of other monomers in the acrylic resin, thereby improving the compatibility of the polysiloxane with the acrylic resin.

[0027] Further preferably, in the step 1), the vinyl siloxane is one or more of vinyltrimethoxysilane, vinyltriethoxysilane and vinyltris(β-methoxyethoxy)silane.

[0028] And / or, the mass ratio of the vinyl siloxane to 2-(3,4-epoxycyclohexyl)ethyl triethoxysilane is 1:(0.8-2).

[0029] In some embodiments, in the step 1), the mass ratio of the vinyl siloxane to 2-(3,4-epoxycyclohexyl)ethyl triethoxysilane can be 1:0.8, 1:0.9, 1:1, 1:1.1, 1:1.2, 1:1.3, 1:1.4, 1:1.5, 1:1.6, 1:1.7, 1:1.8, 1:1.9, 1:2.0. In general, in the step 1), when the mass ratio of the vinyl siloxane to 2-(3,4-epoxycyclohexyl)ethyl triethoxysilane is 1:1.2, better experimental results can be obtained.

[0030] Further preferably, in the step 2), the mass ratio of the polysiloxane, styrene, butyl acrylate, methyl methacrylate and glycidyl methacrylate is 1:(1-2):(2-4):(2-4):(2-4).

[0031] The different monomer combinations give the acrylic resin diversified performance advantages. The polysiloxane can improve the toughness and hydrophobicity of the acrylic resin; the styrene improves the hardness and processing performance of the resin; the butyl acrylate enhances the flexibility and impact resistance of the resin; the methyl methacrylate ensures the high transparency and gloss of the resin; the introduction of the glycidyl methacrylate can significantly improve the crosslinking density and hardness of the resin, and enhance the mechanical strength and stability. The synergistic effect of the multiple monomers makes the acrylic resin composition have good mechanical properties, weather resistance, chemical stability and processing performance, and can stably protect the photovoltaic cell in a complex outdoor environment for a long time, and prolong the service life of the photovoltaic module.

[0032] A preparation process of a high-transparency acrylic resin composition, comprising the following steps:

[0033] According to the formula, the glycidyl acrylic resin, the curing agent, the plasticizer and the leveling agent are uniformly mixed, extruded and granulated through a double-screw extruder, and then ground and sieved.

[0034] In the above technical scheme, the length-diameter ratio of the double-screw extruder is (20-40):1, the screw rotation speed is 100-150 r / min, and the temperature of each section of the screw extruder is set to 80-100℃, 100-120℃ and 80-100℃. When the length-diameter ratio of the double-screw extruder is 35:1, the screw rotation speed is 110 r / min, and the temperature of each section of the screw extruder is set to 90℃, 110℃ and 80℃, better experimental results can be obtained.

[0035] The application of the high-transparency acrylic resin composition is applied to the packaging material of the photovoltaic module.

[0036] In the above technical scheme, the high-transparency acrylic resin composition has good optical performance, aging resistance and mechanical properties, and therefore, when used as the packaging material of the photovoltaic module, has the advantages of light weight, high light transmittance and good aging resistance compared with glass, EVA and POE.

[0037] Compared with the prior art, the present application has the following beneficial effects:

[0038] 1. The carboxylated porous nanoparticles grafted polyphenol hindered phenolic antioxidant is used as the curing agent in the present application, which has good curing effect on the glycidyl acrylic resin, and the prepared material has good light transmittance and aging resistance.

[0039] 2. The polysiloxane containing a fatty ring and an epoxy group is introduced into the glycidyl acrylic resin in the present application, which further improves the aging resistance of the acrylic resin and improves the flexibility of the acrylic resin.

[0040] 3、The application uses zinc oxide nanoparticles with good anti-ultraviolet performance in the preparation of the curing agent, which can further improve the ultraviolet resistance of the acrylic resin without having a great impact on the light conversion efficiency. BRIEF DESCRIPTION OF DRAWINGS

[0041] Figure 1 The light transmittance of the acrylic resin composition coating film before and after aging.

[0042] Figure 2 The yellowing index of the acrylic resin composition coating film before and after aging.

[0043] Figure 3 The moisture absorption-time curve of the acrylic resin composition coating film.

[0044] Figure 4 The TEM image of the porous silica nanoparticles of Example 1 and Example 2. DETAILED DESCRIPTION

[0045] The technical solutions in the embodiments of the application will be described clearly and completely below with reference to the drawings in the embodiments of the application. Obviously, the described embodiments are only part of the embodiments of the application, rather than all the embodiments. Based on the embodiments in the application, all other embodiments obtained by those skilled in the art without creative labor fall within the scope of protection of the application.

[0046] Example 1

[0047] The high-transparency acrylic resin composition of the present embodiment comprises the following components by weight: glycidyl acrylate 100 parts, curing agent 10 parts, resin plasticizer 5 parts, LP88 leveling agent 0.5 parts.

[0048] The preparation method of the glycidyl acrylate of the present embodiment is as follows:

[0049] Styrene 20 g, butyl acrylate 30 g, glycidyl methacrylate 30 g and methyl methacrylate 20 g were weighed and placed in a reaction kettle with stirring device. The stirring was turned on to mix the monomers uniformly, then 2 g of azobisisobutyronitrile was added, and the stirring was continued until complete dissolution to form a uniform solution. The temperature was raised to 60°C, and after 2 h of reaction, 0.5 g of dodecyl mercaptan was added, and the reaction was continued for 2 h. After cooling to room temperature, the insoluble substances generated during the reaction were removed by filtration, and the unreacted monomers and small molecular impurities were removed by washing. Finally, drying treatment was performed.

[0050] The preparation method of the curing agent of the present embodiment comprises the following steps:

[0051] S1: 25 g of polyethylene glycol 600 dissolved in ammonia water was weighed, after stirring vigorously for 2 min, the mixed solution was added dropwise into a beaker containing 250 mL of ethanol, then 240 g of tetraethyl orthosilicate was added dropwise into the beaker in five portions within 1 h, stirring was continued at room temperature for 12 h, after centrifugation, washing and drying, porous silica nanoparticles were obtained;

[0052] S2: 0.3 g of porous silica nanoparticles was weighed, 50 mL of deionized water was added, after stirring and mixing, ultrasonic dispersion was carried out for 1 h, 3 g of sodium hydroxide was added, ultrasonic dispersion was continued for 30 min, then 4.5 g of bromoacetic acid was added, ultrasonic dispersion and reaction at room temperature were carried out for 5 h, the product was separated by suction filtration using a PTFE filter membrane, then washed with distilled water, the product was dried at 45℃ under vacuum for 12 h, carboxylated porous silica nanoparticles were obtained;

[0053] S3: In a three-necked flask equipped with a reflux condenser, a stirrer and a thermometer, 50 mL of anhydrous ether, 6 g of carboxylated porous silica nanoparticles, 1.2 g of 2246 antioxidant, 5.2 g of DCC dehydrating agent and 0.1 g of DMAP catalyst were added, stirring was slowly carried out at room temperature for 3 h, after the ether was volatilized, the solid was soaked with petroleum ether, filtration was carried out, the precipitate was removed, the petroleum ether layer was washed with saturated brine, anhydrous magnesium sulfate was used for drying, and the petroleum ether was removed by distillation;

[0054] The preparation process of the high-transparency acrylic resin composition of the present embodiment is as follows:

[0055] According to the formula, 1 kg of glycidyl acrylate, 100 g of curing agent, 50 g of resin plasticizer and 5 g of LP88 leveling agent were weighed, mixed uniformly in a premixing tank, then added into the hopper of a twin-screw extruder by vacuum suction, granulated and discharged, the screw rotation speed was 110 r / min, the temperature of each section of the screw extruder was 90℃, 110℃ and 80℃, and after the granules were ground, they were sieved through a 200-mesh screen.

[0056] Example 2

[0057] The high-transparency acrylic resin composition of the present embodiment comprises the following components by weight: 100 parts of glycidyl acrylate, 10 parts of curing agent, 5 parts of resin plasticizer and 0.5 parts of LP88 leveling agent;

[0058] The preparation method of the glycidyl acrylate of the present embodiment is the same as that of Example 1.

[0059] The preparation method of the curing agent of the present embodiment comprises the following steps:

[0060] S1: 25 g of polyethylene glycol 600 dissolved in ammonia water, after stirring vigorously for 2 min, add 12 g of zinc acetate dihydrate, stir and mix uniformly, add the mixed solution dropwise into a beaker containing 250 mL of ethanol, then add tetraethyl orthosilicate 240 g dropwise into the beaker in five times within 1 h, continue stirring at room temperature for 12 h, centrifuge, wash, dry, and obtain porous silica nanoparticles;

[0061] S2: Take 0.3 g of porous silica nanoparticles, add 50 mL of deionized water, stir and mix, then ultrasonic dispersion for 1 h, add 3 g of sodium hydroxide, continue ultrasonic dispersion for 30 min, then add 9 g of bromoacetic acid, ultrasonic dispersion and reaction at room temperature for 5 h, the product is separated by PTFE filter membrane, washed with distilled water, and the product is dried at 45℃ under vacuum for 12 h, to obtain carboxylated porous silica nanoparticles;

[0062] S3: In a three-necked flask equipped with reflux condenser, stirrer and thermometer, add 50 mL of anhydrous ether, 6 g of carboxylated porous silica nanoparticles, 4.8 g of 2246 antioxidant, 5.2 g of DCC dehydrating agent, and 0.1 g of DMAP catalyst, slowly stir at room temperature for 3 h, after the ether volatilizes, soak the solid with petroleum ether, filter, remove the precipitate, wash the petroleum ether layer with saturated brine, dry with anhydrous magnesium sulfate, and distill off the petroleum ether;

[0063] The preparation process of the high transparency acrylic resin composition of this example is the same as that of Example 1.

[0064] Example 3

[0065] The high transparency acrylic resin composition of this example comprises the following components by weight: glycidyl acrylic resin 180 parts, curing agent 40 parts, resin plasticizer 10 parts, LP88 leveling agent 2.5 parts;

[0066] The preparation method of the glycidyl acrylic resin of this example is as follows:

[0067] 1) Take 20 g of vinyltriethoxysilane and 15 g of 2-(3,4-epoxycyclohexyl) ethyl triethoxysilane, place them in a three-necked flask with a stirrer, dropping funnel and reflux condenser, stir for 10 min, add 15 g of deionized water and 0.45 g of dibutyltin dilaurate, pre-react at room temperature for 15 min, then place the three-necked flask in a 80℃ water bath, react for 5 h, after reaction, place the product in a rotary evaporator to remove solvents, water and by-products, and obtain polysiloxane;

[0068] 2) Take 20 g of polysiloxane, 20 g of styrene, 40 g of butyl acrylate, 60 g of glycidyl methacrylate and 40 g of methyl methacrylate, and place them in a reaction kettle with stirring device. Turn on the stirring to mix the monomers uniformly, then add 2.2 g of dicumyl peroxide, continue stirring until completely dissolved to form a uniform solution. Heat to 70℃, react for 1 h, then add 0.8 g of octadecyl mercaptan, continue to react for 3 h, cool to room temperature, filter to remove insoluble substances that may be produced during the reaction, wash to remove unreacted monomers and small molecular impurities, and finally dry to obtain;

[0069] The preparation method of the curing agent of the present embodiment comprises the following steps:

[0070] S1: Take 25 g of polyethylene glycol 600 dissolved in ammonia water, stir vigorously for 2 min, then add 9.6 g of zinc acetate dihydrate, stir and mix uniformly, then add the mixed solution dropwise into a beaker containing 250 mL of ethanol, then add 240 g of titanium isopropyl titanate into the beaker in five portions within 1 h, continue to stir at room temperature for 12 h, and obtain porous titanium dioxide nanoparticles by centrifugation, washing and drying;

[0071] S2: Take 0.3 g of porous titanium dioxide nanoparticles, add 50 mL of deionized water, stir and mix, then ultrasonic dispersion for 1 h, add 3 g of sodium hydroxide, continue to ultrasonic dispersion for 30 min, then add 7.5 g of bromoacetic acid, ultrasonic dispersion and react at room temperature for 5 h, separate the product by PTFE filter membrane, wash with distilled water, and dry the product at 45℃ under vacuum for 12 h to obtain carboxylated porous titanium dioxide nanoparticles;

[0072] S3: In a three-necked flask equipped with reflux condenser, stirrer and thermometer, add 50 mL of anhydrous ether, 6 g of carboxylated porous titanium dioxide nanoparticles, 3 g of 2246 antioxidant, 5.2 g of DCC dehydrating agent and 0.1 g of DMAP catalyst, slowly stir at room temperature for 3 h, then soak the solid in petroleum ether after the ether volatilizes, filter to remove the precipitate, wash the petroleum ether layer with saturated brine, dry with anhydrous magnesium sulfate, and distill off the petroleum ether to obtain the product.

[0073] The preparation process of the high-transparency acrylic resin composition of the present embodiment is as follows:

[0074] According to the formula, take 1.8 kg of glycidyl acrylate resin, 400 g of curing agent, 100 g of resin plasticizer and 25 g of LP88 leveling agent, mix them uniformly in a premixing tank, then add them into the hopper of a twin-screw extruder by vacuum suction, granulate the output, the screw rotation speed is 110 r / min, the temperature of each section of the screw extruder is 90℃, 110℃ and 80℃, and the granules are ground and passed through a 200 mesh sieve.

[0075] Comparative Example 1

[0076] The acrylic resin composition of the present comparative example comprises the following components by weight: glycidyl acrylic resin 100 parts, adipic acid 10 parts, resin plasticizer 5 parts, LP88 leveling agent 0.5 parts;

[0077] The preparation method of the glycidyl acrylic resin of the present comparative example is as follows:

[0078] Take 20 g of styrene, 30 g of butyl acrylate, 30 g of glycidyl methacrylate and 20 g of methyl methacrylate, and place them in a reaction kettle with stirring device. Turn on the stirring to mix the monomers uniformly, then add 2 g of azobisisobutyronitrile, continue to stir until completely dissolved to form a uniform solution. Heat to 60℃, react for 2h, then add 0.5g of dodecyl mercaptan, continue to react for 2h, cool to room temperature, filter to remove insoluble substances that may be produced during the reaction, wash to remove unreacted monomers and small molecular impurities, and finally dry to obtain the product.

[0079] The preparation process of the high transparency acrylic resin composition of the present comparative example is as follows:

[0080] According to the formula, take 1 kg of glycidyl acrylic resin, 100 g of adipic acid, 50 g of resin plasticizer and 5 g of LP88 leveling agent, mix them uniformly in a premixing tank, then add them into the hopper of a twin-screw extruder through vacuum suction, granulate the outcoming material, the screw rotation speed is 110 r / min, the temperature of each section of the screw extruder is 90℃, 110℃ and 80℃, and the granules are ground and sieved through a 200 mesh sieve.

[0081] Performance testing

[0082] Coating film preparation

[0083] The acrylic resin compositions of Examples 1-3 and Comparative Example 1 are sprayed on clean polytetrafluoroethylene plates using a small electrostatic spraying device, placed in an oven at 160℃ for 20 min, and left to stand at room temperature for 24 h before use. The coating film thickness is 2 mm.

[0084] 1. Light transmittance test

[0085] The optical properties of the coating film are tested using a UV-visible spectrophotometer according to standard GB / T2410-2008, with a scanning range of 250-850 nm and a resolution of 1 nm.

[0086] 2. Yellowing index test

[0087] The yellowing index test is performed using a color difference meter according to standard HG / T3689-2014A.

[0088] 3. Aging resistance test

[0089] The coated films were cut into 30mm x 30mm x 2mm samples and placed in an aging oven for 1000h for transmittance and yellowing index determination, three samples were tested in each group and the average value was taken, the transmittance test results are shown in Figure 1 , and the yellowing index test results are shown in Figure 2 ; the test conditions of each aging test are as follows:

[0090] ① Thermal-oxidative aging: the air replacement rate in the aging oven is 4 times / h, the temperature of the aging oven is 100℃, and the distance between each sample is not less than 5mm;

[0091] ② Humid heat aging: the temperature of the aging oven is 85℃, the relative humidity is 100%, and the distance between each sample is not less than 5mm;

[0092] ③ UV aging: the temperature of the aging oven is 65℃, the relative humidity is 10%, the wavelength of the ultraviolet light is 340nm, and the ultraviolet irradiation intensity is 0.83W / m 2 .

[0093] 4. Hygroscopicity test

[0094] Test method: the coated film was cut into 30mm x 30mm x 2mm size, the mass was weighed, then placed in a condition of temperature 85℃ and relative humidity 85% for a certain time, then the mass was weighed again, and the hygroscopicity-time curve is shown in Figure 3 .

[0095] 5. Transmission electron microscopy

[0096] The porous silica nanoparticles of Example 1 and Example 2 were observed by transmission electron microscopy, and the TEM images are shown in Figure 4 .

[0097] Result analysis

[0098] From Figure 1 , it can be seen that the initial transmittance of the acrylic resin composition of the examples is greater than 90%, indicating that the transparency is high, and after thermal-oxidative aging, humid heat aging and ultraviolet aging, the transmittance decreases, but the decrease is small, indicating that the acrylic resin composition of the examples has more excellent aging resistance. Comparing the data of Examples 1 and 2, it can be seen that after introducing zinc oxide, the acrylic resin composition has better ultraviolet aging resistance; comparing the data of Examples 2 and 3, it can be seen that introducing polysiloxane segments into the glycidyl acrylate resin improves the humid heat aging resistance and ultraviolet aging resistance.

[0099] From Figure 2As can be seen from the data of the examples 1-3 and the comparative example 1, the acrylic resin compositions of the examples have better aging resistance.

[0100] As can be seen from the data of the examples 1-3 and the comparative example 1, the acrylic resin compositions of the examples have better aging resistance. Figure 3 As can be seen from the data of the examples 1-3 and the comparative example 1, the acrylic resin compositions of the examples have better aging resistance.

[0101] As can be seen from the data of the examples 1-3 and the comparative example 1, the acrylic resin compositions of the examples have better aging resistance. Figure 4 As can be seen from the data of the examples 1-3 and the comparative example 1, the acrylic resin compositions of the examples have better aging resistance.

[0102] Although the present application has been described in detail with reference to the foregoing embodiments, those skilled in the art can make modifications to the technical solutions recorded in the foregoing embodiments, or make equivalent replacements to some of the technical features, and any modifications, equivalent replacements, improvements, etc. made within the spirit and principles of the present application shall be included in the protection scope of the present application.

Claims

1. A high transparency acrylic resin composition, characterized by, The composition comprises the following components by weight: 100-180 parts of glycidyl acrylate resin, 10-40 parts of curing agent, 5-10 parts of plasticizer, and 0.5-2.5 parts of leveling agent; the preparation method of the glycidyl acrylate resin is as follows: 1) reacting vinyl siloxane with 2-(3,4-epoxycyclohexyl) ethyl triethoxysilane in the presence of a catalyst to obtain polysiloxane; 2) mixing polysiloxane, styrene, butyl acrylate, methyl methacrylate and glycidyl methacrylate, adding an initiator to react, and then adding a chain transfer agent to continue the reaction; the mass ratio of the polysiloxane, styrene, butyl acrylate, methyl methacrylate and glycidyl methacrylate is 1:(1-2):(2-4):(2-4):(2-4); The preparation method of the curing agent comprises the following steps: S1: using silanol or titanium alkoxide as raw material, preparing porous nanoparticles by adding a template agent through sol-gel method; S2: ultrasonic dispersion of the porous nanoparticles in water, and then reaction with bromoacetic acid to obtain carboxylated porous nanoparticles; the mass ratio of the porous nanoparticles to bromoacetic acid is 1:(15-30); S3: reacting the carboxylated porous nanoparticles with a polyphenol type hindered phenolic antioxidant; the mass ratio of the carboxylated porous nanoparticles to the polyphenol type hindered phenolic antioxidant is 1:(0.2-0.8).

2. The high transparency acrylic resin composition according to claim 1, characterized by, In the step S1, the template agent is one or more of polyvinyl alcohol, polyethylene glycol and polyvinylpyrrolidone.

3. The high transparency acrylic resin composition according to claim 1, characterized by, In the step S1, zinc salt is also added at the same time as the template agent, and the mass ratio of the zinc salt to the silanol or titanium alkoxide is 1:(20-32).

4. The high transparency acrylic resin composition according to claim 1, characterized by, In the step 1), the vinyl siloxane is one or more of vinyltrimethoxysilane, vinyltriethoxysilane and vinyltris(β-methoxyethoxy)silane; And / or, the mass ratio of the vinyl siloxane to 2-(3,4-epoxycyclohexyl) ethyl triethoxysilane is 1:(0.8-2).

5. A process for the production of the high transparency acrylic resin composition according to any one of claims 1 to 4, characterized by, The method comprises the following steps: According to the formula, the glycidyl acrylate resin, the curing agent, the plasticizer and the leveling agent are mixed uniformly, extruded and granulated through a double screw extruder, and then ground and sieved.

6. Use of the high transparency acrylic resin composition according to any one of claims 1 to 4, characterized in that, The high-transparency acrylic resin composition is applied to the packaging material of photovoltaic modules.

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