Interpenetrating polymer network structure composition with super-weather-resistant function, preparation method and application

Abstract

The invention relates to the field of photovoltaic coatings, in particular to an interpenetrating polymer network structure composition with a super-weather-resistant function, a preparation method and application. The invention discloses an interpenetrating polymer network structure composition with a super-weather-resistant function, which comprises a matting system component and a UV shielding system component, the matting system component and the UV shielding system component are both core-shell structures, each core-shell structure comprises an inorganic particle core modified by a silane coupling agent, and the inorganic particle core is an inorganic particle core modified by a silane coupling agent. The surface of the inorganic particle inner core is coated with the organic shell layer, and the organic shell layer is formed by polymerizing acrylate modified monomers under the initiation of an initiator; functional groups on the extinction system component and the UV shielding system component are condensed to form an interpenetrating polymer network structure, the interpenetrating polymer network structure with stable chemical performance is formed, and the structural compactness is improved. The problem that inorganic particles are separated from a stable organic-inorganic stable system due to chemical bond breakage is effectively avoided, and the problem that an organic-inorganic interface cannot be fused is prevented.

Description

Technical Field

[0001] The invention relates to the field of photovoltaic coatings, and in particular to an interpenetrating polymer network structure composition with super weather resistance function, a preparation method and application thereof. Background Art

[0002] The information disclosed in this background technology section is only intended to increase the understanding of the overall background of the invention, and should not necessarily be regarded as an admission or any form of suggestion that the information already constitutes the prior art known to a person skilled in the art.

[0003] In recent years, solar cells have experienced great development, and battery technology has also contributed its technical strength at a rapid pace. Countries around the world have vigorously advocated and encouraged the industrial application of solar cells, and the application scenarios of solar cells have become increasingly extensive, with the emergence of bifacial cells and lightweight modules. Regardless of the various technical routes or application scenarios of solar cells, the reliability of packaging materials is the primary technical issue to consider. Whether it can be durable for more than 25 years is also an important assessment indicator for whether the solar module can guarantee a high return on investment.

[0004] The comprehensive outdoor conditions around the world include ultraviolet radiation in sunlight, high and low temperatures, humidity, hail impact, wind and sand impact, acid and alkali corrosion, and other complex and changeable conditions. The protective layer of the packaging material needs to have an ultra-dense structure, high radiation resistance, strong and tough balance, and resistance to acid and alkali corrosion penetration in order to withstand the long-term erosion of the above conditions for more than 25 years.

[0005] In terms of resisting ultraviolet radiation, the protective layer usually adopts the addition of UV absorbers or UV shielding agents to achieve the blocking of ultraviolet rays. UV absorbers are generally organic substances, and their disadvantage is that they are easily consumed during long-term use, so that the effect will gradually decrease. Especially when used as a protective layer material, its limited protective layer thickness is more likely to make the effect poor. Inorganic ultraviolet shielding agents avoid the defect of being relatively easy to be consumed. Inorganic UV shielding agents have good stability, and low addition amounts can produce UV resistance; little interference with the transparency of the coating; little effect on the mechanical properties and chemical properties of the coating; good suspension in liquid coatings, can be stored for a long time, and will not produce hard precipitation; little effect on the rheology of the coating; high chemical inertness. Therefore, inorganic shielding agents are often used as high-efficiency UV shielding agents in protective coatings.

[0006] On the other hand, when used as an outdoor weather-resistant protective coating, many application scenarios require that light pollution caused by diffuse reflection should not be allowed to exist. The specific means to solve this problem is usually achieved by adding matting agents. Organic matting agents also have similar problems as the above-mentioned UV absorbers. They are easily damaged by ultraviolet rays when used outdoors for a long time and the effect is poor; inorganic matting agents are the most commonly used type of additives, such as SiO2, CaCO3, ZrO2, etc.

[0007] When used as a protective coating, organic macromolecular resins, organic small molecule additives, inorganic fillers or inorganic functional additives are usually used as a combination. As a durable product, if the formula or product structure design is improper, it will easily cause many problems such as powdering, cracking, yellowing, and reduced light transmittance. The essential reasons for the above problems are: improper material selection, destruction of the interface between organic and inorganic materials, and insufficient density of the protective coating structure.

[0008] In order to solve the above technical problems, CN113234249A discloses a packaging material and preparation method for introducing nano zinc oxide protection, the packaging material comprises a resin layer of nano zinc oxide, a titanium dioxide resin layer and a substrate, and fluorocarbon, acrylic resin, isocyanate, PMA solvent, a first color paste containing titanium dioxide / a second color paste containing zinc oxide, epoxy resin, dispersant, leveling agent, etc. are successively coated and dried as the first protective layer and the second protective layer, thereby improving the utilization rate of visible light and the ultraviolet shielding effect. The implementation method in this method is actually a simple physical blending, which fails to solve the interface compatibility problem between the ultraviolet shielding agent nano titanium oxide and nano zinc oxide and the organic macromolecular polymers such as fluorocarbon, acrylic resin and epoxy resin. Once subjected to long-term irradiation of ultraviolet rays, interface phase separation and powdering are prone to occur. CN110452417B discloses a modified nano-SiO2 and a light-cured composite elastomer material, wherein a photoinitiator containing a hydroxyl group is selected to react with a coupling agent containing an isocyanate group to obtain a modified photoinitiator, and then the modified photoinitiator reacts with nano-SiO2 to obtain a modified nano-SiO2, which has a higher photoinitiator grafting rate, effectively reduces the surface energy of nano-SiO2, and further improves its dispersibility and interface compatibility in the resin system. However, the modified nanoparticles have poor stability and poor structural density, and still cannot be well integrated with the organic system interface. Based on the above situation, the present invention proposes an interpenetrating polymer network structure composition with super weather resistance.

[0009] The purpose of the present invention is to first solve the interface compatibility problem between the inorganic system and the organic system by a two-step method using a surface treatment + in-situ polymerization method, thereby significantly improving the interface separation phenomenon that is easy to occur in the organic-inorganic composite system under conditions such as ultraviolet radiation and humidity and heat; and further form a membrane layer structure with good density and the characteristics of an interpenetrating polymer network structure through a catalytic condensation reaction, thereby further enhancing the protective coating against various aging corrosion such as ultraviolet radiation, humidity and heat, acid and alkali, salt spray, wind and sand, high and low temperatures, etc. Summary of the invention

[0010] In order to solve the problem that inorganic matting agents, inorganic anti-UV blocking agents and organic systems have poor fusion effects in the prior art, which easily cause interface stratification, and cause photovoltaic modules to appear, turn white, age, and powder, the present invention proposes an interpenetrating polymer network structure composition with super weather-resistant function, wherein the polymer makes the matting particles and anti-UV particles become a whole with the organic system, improves its structural compactness, and solves the technical problem of organic-inorganic interface stratification. In addition, the present invention also provides a preparation method of the interpenetrating polymer network structure composition with super weather-resistant function, which is simple and easy to operate, and the raw materials are easy to obtain, and it will have good prospects for application in production. Finally, the present invention also provides an application of an interpenetrating polymer network structure composition with super weather-resistant function as a weather-resistant component in outdoor facility coatings, wherein the coating has a dense film-forming structure, super strong UV radiation resistance and wear resistance.

[0011] In a first aspect, the present invention provides an interpenetrating polymer network structure composition with super weather resistance, wherein the interpenetrating polymer network structure composition comprises an extinction system component and a UV shielding system component, wherein both the extinction system component and the UV shielding system component are core-shell structures, and the extinction system component and the UV shielding system component comprise at least one functional group selected from the group consisting of amino, hydroxyl and epoxy groups, and the functional groups on the extinction system component and the UV shielding system component are condensed to form an interpenetrating polymer network structure; and the molar ratio of the extinction system component to the UV shielding system component is (6-9):1.

[0012] The second aspect of the present invention provides a method for preparing an interpenetrating polymer network structure composition having super weather resistance, comprising: 1) Dispersion: Dispersing the matte particles and anti-UV particles into organic solvents to form a dispersed solution of inorganic particles; The inorganic particles are all pre-treated hydrophilic inorganic particles, and the surfaces of the inorganic particles contain hydroxyl groups; 2) Surface treatment: after dissolving the silane coupling agent, the inorganic particles are treated with the silane coupling agent solution; after the silane coupling agent is hydrolyzed, the surface of the inorganic particles is modified with hydroxyl groups; 3) In-situ polymerization: The acrylic modified monomer and the silane coupling agent are polymerized in-situ to achieve the coating of the silane-modified inorganic particles, and obtain the extinction system component and the UV shielding system component of the core-shell structure respectively; 4) Catalytic condensation: Catalyzing the extinction system components and the UV shielding system components to cause a condensation reaction between the two to obtain a composite material having an interpenetrating polymer network structure.

[0013] The third aspect of the present invention provides an interpenetrating polymer network structure composition with super weather resistance function, which is used as a weather resistance functional component of coatings in the fields of photovoltaic module supporting material protective layer, buildings, automobile paints, etc.

[0014] One or more technical solutions of the present invention have the following beneficial effects; 1) The interpenetrating polymer network structure composition with super weather resistance in the present invention comprises a matting system component and a UV shielding system component, wherein both the matting system component and the UV shielding system component are core-shell structures, wherein both the core-shell structures comprise an inorganic particle core modified with a silane coupling agent, and an organic shell layer coated on the surface of the inorganic particle core, wherein the organic shell layer is polymerized by an acrylate modified monomer under the initiation of an initiator; The extinction system component and the UV shielding system component include at least one functional group selected from amino, hydroxyl and epoxy groups, and the functional groups on the extinction system component and the UV shielding system component are condensed to form an interpenetrating network structure, forming an interpenetrating polymer network structure with stable chemical properties, thereby improving the structural compactness, effectively avoiding the inorganic particles from being separated from the stable organic-inorganic stabilization system due to the breaking of chemical bonds, and preventing the problem of the organic-inorganic interface being unable to fuse.

[0015] 2) The present invention improves the stability of the core-shell structure composition by precisely controlling the reaction conditions during the preparation process. DETAILED DESCRIPTION

[0016] The present invention is further described below in conjunction with specific examples. It should be understood that these examples are only used to illustrate the present invention and are not used to limit the scope of the present invention. The experimental methods without specific conditions in the following examples are usually carried out under conventional conditions or under conditions recommended by the manufacturer.

[0017] It should be noted that the terms used herein are only for describing specific embodiments and are not intended to limit the exemplary embodiments according to the present disclosure. As used herein, unless the context clearly indicates otherwise, the singular is intended to include the plural form, and it should also be understood that when the terms "comprise" and / or "include" are used in the present invention, it indicates the presence of features, steps, operations, devices, components and / or combinations thereof.

[0018] In order to solve the problem that inorganic matting particles and inorganic anti-UV particles in the prior art have poor fusion effects with organic systems, which easily cause interface stratification, and cause photovoltaic modules to appear, turn white, age, and powder, the present invention proposes an interpenetrating polymer network structure composition with super weather resistance, which makes the matting component, anti-UV component and organic system become a whole, and solves the technical problem of organic-inorganic interface stratification. In addition, the present invention also provides a preparation method of the interpenetrating polymer network structure composition with super weather resistance, which is simple and easy to operate, and the raw materials are easily available, and it will have good prospects for application in production.

[0019] The first aspect of the present invention provides an interpenetrating polymer network structure composition with super weather resistance function, characterized in that the interpenetrating network structure polymer includes an extinction system component and a UV shielding system component, the extinction system component and the UV shielding system component are both core-shell structures, the extinction system component and the UV shielding system component include at least one functional group selected from amino, hydroxyl and epoxy groups, and the functional groups on the extinction system component and the UV shielding system component are condensed to form an interpenetrating polymer network structure; the molar ratio of the extinction system component to the UV shielding system component is (6-9):1.

[0020] In order to obtain a stable interpenetrating polymer network structure composition having both extinction function and UV blocking function, in one or more embodiments of the present invention, the extinction system component includes an extinction particle core modified with a silane coupling agent, and an organic shell layer coated on the surface of the extinction particle core, and the organic shell layer is formed by polymerization of an acrylate-modified monomer under the initiation of an initiator; the UV shielding system component includes an anti-UV particle core modified with a silane coupling agent, and an organic shell layer coated on the surface of the anti-UV particle core, and the organic shell layer is formed by polymerization of an acrylate-modified monomer under the initiation of an initiator.

[0021] The matte particles are a mixture of one or more of SiO2, CaCO3, ZrO2, and CaF2; the anti-UV inorganic particles are a mixture of one or more of TiO2, ZnO, CeO, and BaSO4; in one or more embodiments of the present invention, the average particle size of the matte particles is ≤10μm, preferably 2-6μm. If the size of the inorganic particles is too large, the transparency of the product will be affected; if the size of the inorganic particles is too small, the matte performance cannot be effectively exerted; the particle size of the anti-UV particles needs to effectively block ultraviolet light in the 380-1100nm band, so the average particle size of the anti-UV inorganic particles is 20-100nm; preferably 50-80nm.

[0022] If the mass ratio of the silane coupling agent to the inorganic particles is too high, during the polymerization process, the functional groups on the polymer formed by part of the acrylate modified monomers are grafted with the excess remaining silane coupling agent, consuming the acrylate modified monomers and affecting the coating of the inorganic particles; if the mass ratio of the silane coupling agent to the inorganic particles is too low, the inorganic particles cannot be fully treated and modified, and a stable structure of the organic matter coating the inorganic particle core cannot be obtained. Therefore, in the present invention, the mass ratio of the silane coupling agent to the matte particles is preferably (0.05-0.20):1, preferably (0.08-0.12):1; the mass ratio of the silane coupling agent to the anti-UV particles is (0.10-0.20):1, preferably (0.12-0.15):1.

[0023] In the present invention, the inorganic particles modified by the silane coupling agent are linked with the functional groups on the polymer formed by the acrylate modified monomer to form a coating structure with stable chemical properties. In addition, the inorganic particles can also undergo an in-situ polymerization reaction with the acrylate modified monomer to obtain a core-shell structured composition, which effectively avoids the inorganic particles from being separated from the stable organic-inorganic stabilizing system due to the breaking of chemical bonds, thereby preventing the occurrence of interface fusion problems.

[0024] In one or more embodiments of the present invention, the silane coupling agent can treat the surface of the inorganic particles to obtain modified inorganic particles, and can also undergo polymerization reaction with the functional groups on the acrylate modified monomers. In one or more embodiments of the present invention, the silane coupling agent is a mixture of one or more of 3-methacryloxytriisopropoxysilane, trialkenyltriisopropoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltri(2-methoxyethoxy)silane, 3-methacrylpropyltrimethoxysilane, and 3-methacryloxypropyltriethoxysilane.

[0025] The acrylate modified monomer in the present invention is to undergo in-situ polymerization with the inorganic particles modified by the silane coupling agent to obtain a core-shell structure composition, and is to undergo a condensation reaction with another component to form an interpenetrating network structure polymer with stable chemical properties. In one or more embodiments of the present invention, the acrylate modified monomer includes a hydroxyl-containing acrylate modified monomer, an amino-containing acrylate modified monomer, and an epoxy-containing acrylate modified monomer; The hydroxyl-containing acrylate modified monomer is one or more of 2-hydroxyethyl acrylate, 3-(glycidyl-2-oxyethoxy)-2-hydroxypropyl methacrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl acrylate, hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, hydroxybutyl (meth)acrylate, 2-hydroxy-1,3-propanediol-2-acrylate, trimethylolpropane trimethacrylate, 3-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 2-hydroxy-3-chloropropyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, and trimethylolpropane trimethacrylate; Amino-containing acrylate-modified monomers are: carbamate (meth) acrylate, 2-(dimethylamino)ethyl methacrylate, dialkylaminoethyl acrylate, dimethylaminoethyl methacrylate, diethylaminoethyl acrylate and diethylaminoethyl methacrylate; Epoxy-containing acrylate-modified monomers include epoxy (meth) acrylate, bisphenol A epoxy acrylate, novolac epoxy acrylate, and novolac acid epoxy acrylate; Preferred are 3,4-epoxycyclohexyl methacrylate and 3,4-epoxycyclohexyl methyl methacrylate.

[0026] The second aspect of the present invention provides a method for preparing an interpenetrating polymer network structure composition having super weather resistance, comprising: 1) Dispersion: Dispersing the matte particles and anti-UV particles into organic solvents to form a dispersed solution of inorganic particles; The inorganic particles are all pre-treated hydrophilic inorganic particles, and the surfaces of the inorganic particles contain hydroxyl groups; 2) Surface treatment: after dissolving the silane coupling agent, the inorganic particles are treated with the silane coupling agent solution; after the silane coupling agent is hydrolyzed, the surface of the inorganic particles is modified with hydroxyl groups; 3) In-situ polymerization: The acrylic modified monomer and the silane coupling agent are polymerized in-situ to achieve the coating of the silane-modified inorganic particles, and obtain the extinction system component and the UV shielding system component of the core-shell structure respectively; 4) Catalytic condensation: The extinction system components and the UV shielding system components are catalyzed to cause a condensation reaction between the two to obtain a composite component having an interpenetrating polymer network structure.

[0027] In order to ensure the degree of reaction of the silane coupling agent to the surface treatment of the inorganic particles and avoid incomplete surface modification of the inorganic particles, the inorganic particles need to be dispersed in an organic solution system. In one or more embodiments of the present invention, the dispersion process is specifically as follows: the inorganic particles are added to an organic solvent, and ultrasonically dispersed at a power of 500-1000 W for 30-50 minutes to obtain a dispersed solution of inorganic particles with a concentration of 0.05-0.1 mol / L; In order to promote uniform dispersion of inorganic particles and provide a suitable reaction system for subsequent modification and polymerization reactions, in one or more embodiments of the present invention, the organic solvent includes one of ethyl acetate, butyl acetate, propylene glycol methyl ether acetate, toluene, xylene, and anhydrous ethanol.

[0028] Surface treatment of inorganic particles with silane coupling agents allows the inorganic particles modified with silane coupling agents to polymerize with acrylate-based modified monomers to obtain an extremely stable structure of an organic-coated inorganic particle core. If inorganic particles are modified with silane coupling agents, a stable structure of an organic-coated inorganic particle core cannot be obtained.

[0029] In order to fully modify the surface of the inorganic particles, in one or more embodiments of the present invention, the preparation steps of the silane coupling agent modified inorganic particles are specifically as follows: mixing water with the silane coupling agent at a mass ratio of 1: (0.2-0.3) and adjusting the pH to 3-5 with acetic acid, stirring at room temperature for 120-240 minutes to fully hydrolyze to form a silane coupling agent solution; The silane coupling agent solution is mixed with the inorganic particle dispersion solution obtained in step 1), and ultrasonically dispersed at 800-1000W power at 35-50°C for 1-3 hours, and allowed to stand for 20-60 minutes to obtain a solution of inorganic particles modified by the silane coupling agent, and then stirred, centrifuged, and the precipitate is collected and dried.

[0030] If the reaction temperature of the silane coupling agent surface treatment is too high, the silane coupling agent will be inactivated or decomposed. If the temperature reaction temperature is too low, the reaction rate will be low. Therefore, when the silane coupling agent is used to modify the inorganic particles in the present invention, the reaction temperature is 35-50°C. If the ultrasonic power is too high, the hydroxyl, amino, and epoxy groups on the silane coupling agent cannot be grafted with the functional groups on the surface of the inorganic particles, which will affect the modification effect of the silane coupling agent on the inorganic particles. If the ultrasonic power is too low, the uniform dispersion of the silane coupling agent and the inorganic particles will be affected, and the modification treatment efficiency of the silane coupling agent on the inorganic particles will be reduced. In the present invention, the ultrasonic power is 800-1000W and the ultrasonic time is 1-3h.

[0031] In order to promote the hydrolysis of the silane coupling agent and prevent self-polymerization, in one or more embodiments of the present invention, acetic acid is used to adjust the pH to 3-5.

[0032] In order to obtain a core-shell structure in which an inorganic particle core is coated with organic matter, after step 2), inorganic particles modified with a silane coupling agent have been obtained, and the formation of the organic shell requires the polymerization of an acrylate-modified monomer. In addition, in order to obtain a stable core-shell structure, the acrylate-modified monomer is also required to undergo a polymerization reaction with the silane coupling agent to stabilize the structure of the organic shell and the inorganic particle core modified with the silane coupling agent.

[0033] In order to achieve sufficient polymerization of the acrylate modified monomer and the silane coupling agent, in one or more embodiments of the present invention, the in-situ polymerization step 3) is specifically as follows: The initiator is dissolved in an organic solvent to obtain an initiator solution; the amount of the initiator is 0.5-1.5w% of the mass of the acrylate modified monomer polymerization system; the acrylate modified monomer is dissolved in an organic solvent, and the molar ratio of the acrylate modified monomer to the silane coupling agent is (1:1-1.3); the temperature in the reaction kettle is raised to 70-80°C of the acrylate modified monomer under stirring at 150-300 rpm, 1 / 5 of the acrylate modified monomer is added under stirring at 300-400 rpm, after stirring for 20-40 minutes, 1 / 3 of the initiator solution is added and the temperature is raised to 80-90°C, the remaining acrylate modified monomer and the initiator solution are slowly added to the reaction system at the same time, the addition is completed within 3-6 hours, and the reaction is continued for 2-4 hours to obtain the product.

[0034] If the ratio of the amount of the inorganic particle core modified by the silane coupling agent to the organic shell material is too high, it is easy to cause incomplete coating. If the ratio of the amount of the inorganic particle core modified by the silane coupling agent to the organic shell material is too low, it is easy to produce more impurities, and the excess monomers can undergo polymerization reactions and are difficult to remove. Therefore, the molar ratio of the acrylate modified monomer to the silane coupling agent in the present invention is (1:1-1.3).

[0035] In order to ensure the effective progress of the polymerization reaction, in one or more embodiments of the present invention, an azo initiator or a peroxide oil-soluble initiator; preferably, the azo initiator includes: 2,2'-azobisisobutyronitrile, 2,2'-azobis(methyl isobutyrate), 2,2'-azobis-2,4-dimethylvaleronitrile and 1,1'-azobis(1-acetoxy-1-phenylethane); Peroxide oil-soluble initiators include: dibenzoyl peroxide, tert-butyl benzoyl peroxide, methyl ethyl ketone peroxide, and diisopropyl peroxydicarbonate.

[0036] The extinction system components and the UV shielding system components are both core-shell structures, and the organic macromolecules formed still have the risk of precipitation during the specific application process, which affects the user experience. The extinction system components and the UV shielding system components are further condensed to obtain a composition having an interpenetrating polymer network structure, so that the extinction system components and the UV shielding system components are further integrated with the organic system. The interpenetrating polymer network structure composition can also be cross-linked with the organic system to reduce the risk of precipitation. In one or more embodiments of the present invention, step 4) catalytic condensation is specifically: the obtained extinction system components and UV shielding system components are mixed and a catalyst is added, ultrasonically dispersed at a power of 500-600 for 3-4 hours, and allowed to stand for 20-60 minutes to condense the functional groups on the extinction system components and the UV shielding system components to obtain an interpenetrating network structure polymer with weather resistance function; Preferably, the catalyst may be an acid catalyst, a base catalyst or an enzyme catalyst.

[0037] The third aspect of the present invention provides a coating, comprising the interpenetrating polymer network structure composition with super weather resistance function in any of the above schemes or the interpenetrating polymer network structure composition with super weather resistance function obtained by the preparation method in any of the above schemes.

[0038] The present invention will be further described in detail below in conjunction with specific embodiments. It should be noted that the specific embodiments are intended to explain the present invention rather than to limit it.

[0039] Example 1

[0040] 1) 100g SiO2 (XFF31-7440-21-3) was added to toluene (Nanjing Runsheng Petrochemical Co., Ltd.) solvent and ultrasonically dispersed at 800W power for 10 minutes to obtain a dispersed solution with a concentration of 0.06mol / L; 50 g of CeO2 was added to the toluene solvent and ultrasonically dispersed at 800 W for 10 minutes to obtain a dispersion solution with a concentration of 0.06 mol / L; 2) 10 g and 7.5 g of vinyl trimethoxysilane (Merrill-M73370) were mixed with 3 g and 2.5 g of deionized water respectively, and the pH was adjusted to 3.5 with acetic acid (Merrill-M22629), and stirred at 500 rpm for 150 minutes. The vinyl trimethoxysilane solution was mixed with the inorganic particle dispersion solution obtained in step 1), and ultrasonically dispersed at 900 W for 2 hours at 40° C., and allowed to stand for 45 minutes to obtain a solution of inorganic particles modified by a silane coupling agent, and stirred, centrifuged, and the precipitate was collected and dried; 3) Dissolve 0.3g and 0.25g of diisopropyl peroxydicarbonate (Annaiji A026059) in ethyl acetate (Merrill-M00615) solvent respectively and set aside; dissolve 13.5g and 12.5g of 2-hydroxypropyl acrylate (aladdin-H156905) in ethyl acetate respectively and set aside; dissolve 0.3g of dibenzoyl peroxide solution with 13.5g of 2-hydroxypropyl acrylate and 0.25g of diisopropyl peroxydicarbonate solution with 12.5g of propylene The 2-hydroxypropyl acrylate and the 2-hydroxypropyl acrylate are mixed into a reaction kettle and heated to 70° C. under stirring at 150-300 rpm, 1 / 5 of the 2-hydroxypropyl acrylate solution is added under stirring at 300-400 rpm, and after stirring for 20-40 minutes, 1 / 3 of the diisopropyl peroxydicarbonate solution is added and the temperature is raised to 80° C. The remaining 2-hydroxypropyl acrylate solution and the diisopropyl peroxydicarbonate solution are slowly added into the reaction system at the same time, and the addition is completed within 5 hours, and the reaction is continued for 2 hours to obtain the product.

[0041] 4) Mix the extinction system components obtained in step 3) with the UV shielding system components, add 10% (mass fraction) of dilute sulfuric acid solution, ultrasonically disperse at a power of 500-600 for 3-4 hours, and let stand for 20-60 minutes to obtain a polymer with an interpenetrating network structure.

[0042] Example 2

[0043] 1) 100g SiO2 was added to toluene solvent and ultrasonically dispersed at 700W power for 10 minutes to obtain a dispersion solution with a concentration of 0.05mol / L; 50g TiO2 (MERCK-718467) was added to toluene solvent and ultrasonically dispersed at 800W power for 10 minutes to obtain a dispersion solution with a concentration of 0.06mol / L; 2) 12g and 7.8g of 3-methacryloxytrimethoxysilane (Maitu A-174) were mixed with 4g and 2.8g of deionized water respectively, and the pH was adjusted to 3.5 with acetic acid, and stirred at 500 rpm for 150 minutes. The silane coupling agent solution was mixed with the inorganic particle dispersion solution obtained in step 1), and ultrasonically dispersed at 900W power for 2 hours at 40°C, and allowed to stand for 45 minutes to obtain a solution of inorganic particles modified by a silane coupling agent, which was stirred, centrifuged, and the precipitate was collected and dried; 3) 0.35g and 0.3g 2,2'-azobis(isobutyronitrile) (Annaiji B040239) were added respectively. Dissolve in ethyl acetate solvent for later use. Dissolve 15g and 13g of 4-hydroxybutyl acrylate (MERCK-275573) in ethyl acetate respectively for later use. Mix 0.35g of 2,2'-azobis(isobutyronitrile) and 15g of 4-hydroxybutyl acrylate in a reaction kettle and heat to 70°C under stirring at 150-300 rpm. Add 1 / 5 4-hydroxybutyl acrylate under stirring at 300-400 rpm. After stirring for 20-40 minutes, add 1 / 3 2,2'-azobis(isobutyronitrile) and raise the temperature to 80°C. Slowly add the remaining 4-hydroxybutyl acrylate solution and 2,2'-azobis(isobutyronitrile) solution to the reaction system at the same time. Add all the additions within 5 hours and continue the reaction for 2 hours to obtain the product.

[0044] 4) Mix the extinction system component obtained in step 3) with the UV shielding system component, add 10% (mass fraction) of dilute sulfuric acid solution, ultrasonically disperse at 600 power for 3-4 hours, and let stand for 20-60 minutes to obtain a composition with an interpenetrating polymer network structure.

[0045] Example 3

[0046] 1) 100g CaF2 (Langfang Qianyao Technology Co., Ltd.) was added to toluene solvent and ultrasonically dispersed at 800W power for 10 minutes to obtain a dispersed solution with a concentration of 0.06mol / L; 50 g of CeO2 was added to the toluene solvent and ultrasonically dispersed at 800 W for 10 minutes to obtain a dispersion solution with a concentration of 0.06 mol / L; 2) 10 g and 7.5 g of vinyltrimethoxysilane were mixed with 3 g and 2.5 g of deionized water respectively, and the pH was adjusted to 3.5 with acetic acid, and stirred at 500 rpm for 150 minutes, and the silane coupling agent solution was mixed with the inorganic particle dispersion solution obtained in step 1), and ultrasonically dispersed at 900 W for 2 hours at 40° C., and allowed to stand for 45 minutes to obtain a solution of inorganic particles modified with a silane coupling agent, and stirred, centrifuged, and the precipitate was collected and dried; 3) Dissolve 0.3g and 0.25g of 2,2'-2,2'-azobis(isobutyronitrile) in ethyl acetate solvent for later use, and dissolve 13.5g and 12.5g of 2-hydroxypropyl acrylate in ethyl acetate for later use; mix 0.3g of 2,2'-azobis(isobutyronitrile) solution and 13.5g of 2-hydroxypropyl acrylate in a reaction kettle and heat to 70°C under stirring at 150-300 rpm, add 1 / 5 of 2-hydroxypropyl acrylate solution under stirring at 300-400 rpm, stir for 20-40 minutes, then add 1 / 3 of 2,2'-azobis(isobutyronitrile) solution and heat to 80°C, slowly add the remaining 2-hydroxypropyl acrylate solution and 2,2'-azobis(isobutyronitrile) solution to the reaction system at the same time, complete the addition within 5 hours, and continue the reaction for 2 hours to obtain the product.

[0047] 4) Mix the extinction system component obtained in step 3) with the UV shielding system component, add 10% (mass fraction) of dilute sulfuric acid solution, ultrasonically disperse at a power of 500-600 for 3-4 hours, and let stand for 20-60 minutes to obtain a composition having an interpenetrating polymer network structure.

[0048] Comparative Example 1 A mixture is obtained by mixing SiO2, CeO2, a silane coupling agent, and an acrylate-based modified monomer in the same amount as that in Example 1.

[0049] Comparative Example 2 The same amount of SiO2 and CeO2 as in Example 1 were surface-modified with an equal amount of silane coupling agent, and then mixed with butyl acrylate modified monomer to obtain a mixture.

[0050] The products obtained in Examples 1, 2, 3, Comparative Examples 1 and 2, acrylic resin, curing agent, organic solvent, and functional additives were mixed and coated on a 100 μm PET sheet, and gloss, light transmittance, and aging tests were performed, wherein: Specifically, the gloss test is uniformly measured using Linshang Technology's universal 60-degree angle LS192: The light transmittance is uniformly measured using a YH600 haze meter; UV aging test: 55℃, UV irradiation -4KWh / day, total radiation amount is 1500KWh; Damp heat aging test: 85℃, 85% humidity, 3000h; The test results are shown in Table 1: Table 1- Performance comparison after aging test According to the above performance comparison, it can be seen that the stability performance of the interpenetrating polymer network structure composition with super weather resistance obtained in the present application is significantly improved, and the service life is greatly extended.

[0051] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Although the present invention has been described in detail with reference to the aforementioned embodiments, it is still possible for a person skilled in the art to modify the technical solutions described in the aforementioned examples, or to replace some of the technical features therein by equivalents. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention shall be included in the protection scope of the present invention.

Claims

1. An interpenetrating polymer network structure composition with super weather resistance, characterized in that: The interpenetrating polymer network structure composition comprises a matting system component and a UV shielding system component, both of which are core-shell structures, and both of which comprise at least one functional group selected from the group consisting of amino, hydroxyl and epoxy groups, and the functional groups of the matting system component and the UV shielding system component are condensed to form an interpenetrating polymer network structure; the molar ratio of the matting system component to the UV shielding system component is (6-9):1; Preferably, the matting system components include a matting particle core modified with a silane coupling agent, and an organic shell layer coated on the surface of the matting particle core, wherein the organic shell layer is polymerized by an acrylate modified monomer under the initiation of an initiator; The matte particles are a mixture of one or more of SiO2, CaCO3, ZrO2, and CaF2; The average particle size of the matte particles is ≤10 μm, preferably 2-6 μm; Preferably, the UV shielding system components include an anti-UV particle core modified with a silane coupling agent, and an organic shell layer coated on the surface of the anti-UV particle core, wherein the organic shell layer is polymerized by an acrylate modified monomer under the initiation of an initiator; The anti-UV inorganic particles are a mixture of one or more of TiO2, ZnO, CeO, and BaSO4; The average particle size of the UV-resistant inorganic particles is 20-100 nm, preferably 50-80 nm.

2. The interpenetrating polymer network structure composition with super weather resistance according to claim 1, characterized in that: The mass ratio of the silane coupling agent to the matte particles is (0.05-0.20):1, preferably (0.08-0.12):1; the mass ratio of the silane coupling agent to the anti-UV particles is (0.10-0.20):1, preferably (0.12-0.15):

1.

3. The interpenetrating polymer network structure composition with super weather resistance according to claim 1, characterized in that: The silane coupling agent is a mixture of one or more of 3-methacryloxytriisopropoxysilane, trialnyltriisopropoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltri(2-methoxyethoxy)silane, 3-methacrylpropyltrimethoxysilane, and 3-methacryloxypropyltriethoxysilane.

4. The interpenetrating polymer network structure composition with super weather resistance according to claim 1, characterized in that: The acrylate modified monomers include hydroxyl-containing acrylate modified monomers, amino-containing acrylate modified monomers, and epoxy-containing acrylate modified monomers; The hydroxyl-containing acrylate modified monomer is one or more of 2-hydroxyethyl acrylate, 3-(glycidyl-2-oxyethoxy)-2-hydroxypropyl methacrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl acrylate, hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, hydroxybutyl (meth)acrylate, 2-hydroxy-1,3-propanediol-2-acrylate, trimethylolpropane trimethacrylate, 3-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 2-hydroxy-3-chloropropyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, and trimethylolpropane trimethacrylate; Amino-containing acrylate-modified monomers are: carbamate (meth) acrylate, 2-(dimethylamino)ethyl methacrylate, dialkylaminoethyl acrylate, dimethylaminoethyl methacrylate, diethylaminoethyl acrylate and diethylaminoethyl methacrylate; Epoxy-containing acrylate-modified monomers include epoxy (meth) acrylate, bisphenol A epoxy acrylate, novolac epoxy acrylate, and novolac acid epoxy acrylate; Preferred are 3,4-epoxycyclohexyl methacrylate and 3,4-epoxycyclohexyl methyl methacrylate.

5. The method for preparing the interpenetrating polymer network structure composition with super weather resistance according to any one of claims 1 to 4, characterized in that: include: 1) Dispersion: Dispersing the matte particles and anti-UV particles into organic solvents to form a dispersed solution of inorganic particles; The inorganic particles are all pre-treated hydrophilic inorganic particles, and the surfaces of the inorganic particles contain hydroxyl groups; 2) Surface treatment: after dissolving the silane coupling agent, the inorganic particles are treated with the silane coupling agent solution; after the silane coupling agent is hydrolyzed, the surface of the inorganic particles is modified with hydroxyl groups; 3) In-situ polymerization: The acrylic modified monomer and the silane coupling agent are polymerized in-situ to achieve the coating of the silane-modified inorganic particles, and obtain the extinction system component and the UV shielding system component of the core-shell structure respectively; 4) Catalytic condensation: The extinction system components and the UV shielding system components are catalyzed to cause a condensation reaction between the two to obtain a composition having a dense interpenetrating polymer network structure.

6. The method for preparing the interpenetrating polymer network structure composition with super weather resistance according to claim 5, characterized in that: The dispersion process, i.e., step 1), is specifically as follows: adding the inorganic particles into an organic solvent, and ultrasonically dispersing the organic particles at a power of 500-1000 W for 30-50 minutes to obtain a dispersion solution of the inorganic particles having a concentration of 0.05-0.1 mol / L; Preferably, the organic solvent includes one of ethyl acetate, butyl acetate, propylene glycol methyl ether acetate, toluene, xylene, and anhydrous ethanol.

7. The method for preparing the interpenetrating polymer network structure composition with super weather resistance according to claim 5, characterized in that: The preparation step 2) of the silane coupling agent modified inorganic particles is specifically as follows: mixing water and the silane coupling agent at a mass ratio of 1:(0.2-0.3) and adjusting the pH to 3-5 with acetic acid, stirring at room temperature for 120-240 minutes to fully hydrolyze and form a silane coupling agent solution; The silane coupling agent solution is mixed with the inorganic particle dispersion solution obtained in step 1), and ultrasonically dispersed at 800-1000W power at 35-50°C for 1-3 hours, and allowed to stand for 20-60 minutes to obtain a solution of inorganic particles modified by the silane coupling agent, and then stirred, centrifuged, and the precipitate is collected and dried.

8. The method for preparing the interpenetrating polymer network structure composition with super weather resistance according to claim 5, characterized in that: The in-situ polymerization step 3) is specifically as follows: The initiator is dissolved in an organic solvent to obtain an initiator solution; the amount of the initiator is 0.5-1.5w% of the mass of the acrylate modified monomer polymerization system; the acrylate modified monomer is dissolved in an organic solvent, and the molar ratio of the acrylate modified monomer to the silane coupling agent is (1:1-1.3); the temperature in the reaction kettle is raised to 70-80°C under stirring at 150-300 rpm, 1 / 5 of the acrylate modified monomer is added under stirring at 300-400 rpm, and after stirring for 20-40 minutes, 1 / 3 of the initiator solution is added and the temperature is raised to 80-90°C, and the remaining acrylate modified monomer and the initiator solution are slowly added to the reaction system at the same time, and the addition is completed within 3-6 hours, and the reaction is continued for 2-4 hours to obtain the product; Preferably, the initiator is an azo initiator or a peroxide oil-soluble initiator; preferably, the azo initiator includes: 2,2'-azobisisobutyronitrile, 2,2'-azobis(methyl isobutyrate), 2,2'-azobis-2,4-dimethylvaleronitrile and 1,1'-azobis(1-acetoxy-1-phenylethane); Peroxide oil-soluble initiators include: benzoyl peroxide, tert-butyl benzoyl peroxide, methyl ethyl ketone peroxide, and diisopropyl peroxydicarbonate.

9. The method for preparing the interpenetrating polymer network structure composition with super weather resistance according to claim 5, characterized in that: The specific process of the catalytic polymerization 4) is: mixing the obtained extinction system component and UV shielding system component and adding a catalyst, ultrasonically dispersing at a power of 500-600W for 3-4 hours, and standing for 20-60 minutes to condense the functional groups of the extinction system component and the UV shielding system component to obtain an interpenetrating polymer network structure composition with weather resistance function; Preferably, the catalyst may be an acid catalyst, a base catalyst or an enzyme catalyst.

10. Application of the interpenetrating polymer network structure composition with super weather resistance as claimed in any one of claims 1 to 4 or the interpenetrating polymer network structure composition with super weather resistance prepared by the preparation method of the interpenetrating polymer network structure composition with super weather resistance as claimed in any one of claims 5 to 9 as a weather resistance component of coatings in the fields of protective layers of supporting materials for photovoltaic modules, buildings, automotive paints, etc.

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