Modified filler, eva material and preparation method thereof, encapsulation adhesive film and application

Abstract

This invention discloses a modified filler, an EVA material, its preparation method, an encapsulating film, and its applications. The modified filler comprises a filler matrix and modifying groups, wherein the modifying groups are derived from a modifier, and the modifier is one or more selected from carbodiimide, cationic surfactant, and carbodiimide-modified cationic surfactant; the modifying groups account for less than 50% of the mass percentage of the modified filler. The EVA material comprises EVA resin and a filler; wherein the filler is the modified filler and / or the filler matrix. The EVA material provided by this invention has an ion adsorption effect, which can reduce the ion migration rate and inhibit EVA aging, and has good anti-PID performance.

Description

Technical Field

[0001] This invention specifically relates to a modified filler, EVA material and its preparation method, encapsulation film and its application. Background Technology

[0002] Against the backdrop of a growing global energy crisis and environmental problems, solar energy, as a clean and renewable energy source, has been widely developed and utilized. Solar panels are the core component of solar energy utilization, and their performance and lifespan directly affect the efficiency and economics of solar power generation systems.

[0003] Potential-induced degradation (PID) is one of the key issues affecting the long-term stable operation of solar panels. In high-temperature and high-humidity environments, the potential difference inside the solar panel causes ion migration in the encapsulation material, leading to a decrease in cell performance and power generation efficiency. Ethylene-vinyl acetate copolymer (EVA) is currently the main material for solar panel encapsulation films due to its good light transmittance, adhesion, and flexibility. However, ordinary EVA materials have significant shortcomings in anti-PID performance, exhibiting severe ion migration, making it difficult to meet the requirements of long-term use of solar panels in complex environments.

[0004] Currently, the preparation of EVA materials with excellent anti-PID function is an important research direction for improving the performance of encapsulating films for solar panels, and has significant practical significance and application value. Summary of the Invention

[0005] This invention primarily overcomes the shortcomings of existing EVA materials, such as high ion migration rates leading to poor PID resistance, by providing a modified filler, EVA material, its preparation method, encapsulating film, and its applications. The EVA material provided by this invention exhibits ion adsorption, reducing ion migration rates and inhibiting EVA aging, thus demonstrating excellent PID resistance.

[0006] In a first aspect, the present invention provides a modified filler comprising a filler matrix and modified groups, wherein the modified groups are derived from a modifier, and the modifier is one or more of carbodiimide, cationic surfactant, and carbodiimide-modified cationic surfactant; the modified groups account for less than 50% of the mass percentage of the modified filler.

[0007] In this invention, the filler matrix can be any filler matrix conventionally used in the art; preferably, it is one or more of silicates, clays, glass flakes, talc, and zirconium phosphate.

[0008] Preferably, the silicate is one or more of mica, montmorillonite, aluminum silicate, magnesium silicate, magnesium aluminum silicate, and sodium aluminum silicate.

[0009] The clay is preferably one or more of kaolin, hydrotalcite, and bentonite.

[0010] In this invention, the cationic surfactant and the carbodiimide-modified cationic surfactant are equivalent and parallel choices, each independently achieving the purpose of this invention, and there is no inclusion-subject relationship between them.

[0011] In this invention, the cationic surfactant may be one or more of quaternary ammonium salts, amine salts, polyamines, amides, imidazolines, and imidazoles.

[0012] Preferably, the quaternary ammonium salt is one or more of dodecyl dihydroxyethyl methyl quaternary ammonium salt, dodecyl trimethyl quaternary ammonium salt, tetradecyl trimethyl quaternary ammonium salt, hexadecyl trimethyl quaternary ammonium salt, octadecyl trimethyl quaternary ammonium salt, didodecyl dimethyl quaternary ammonium salt, ditetradecyl dimethyl quaternary ammonium salt, dihexadecyl dimethyl quaternary ammonium salt, dioctadecyl dimethyl quaternary ammonium salt, and benzalkonium chloride; the quaternary ammonium salt is, for example, dodecyl dihydroxyethyl methyl ammonium chloride, didodecyl dimethyl ammonium chloride, didodecyl trimethyl ammonium chloride, octadecyl trimethyl ammonium chloride, dioctadecyl dimethyl ammonium chloride, or dodecyl trimethyl ammonium bromide.

[0013] Preferably, the polyamine is one or more of spermine, spermidine, ethylenediamine, propylenediamine, hexamethylenediamine, p-phenylenediamine, and m-phenylenediamine.

[0014] Preferably, the amine salt is one or more of dodecylamine salt, tetradecylamine salt, hexadecylamine salt, and octadecylamine salt.

[0015] The amide is preferably an amide quaternary ammonium salt and / or an aliphatic amide, such as N,N-dimethyloctylamide.

[0016] The imidazoline is preferably an alkyl imidazoline and / or an alkyl imidazoline quaternary ammonium salt, such as oleyl hydroxyethyl imidazoline.

[0017] The imidazole is preferably one or more of N-dodecylimidazolium, N-tetradecylimidazolium, N-hexadecylimidazolium, N-octadecylimidazolium, 2-imidazolium carboxylic acid, and 1H-imidazolium-2-acetic acid.

[0018] In this invention, the carbodiimide is a monocarbodiimide and / or a polycarbodiimide, and the polycarbodiimide is preferably a polytoluene diisocyanate or a polyisophorone diisocyanate.

[0019] In this invention, the carbodiimide may be polymerized from one or more of toluene diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, dicyclohexylmethane diisocyanate, diphenylmethane diisocyanate (MDI), and lysine diisocyanate; preferably, it is further end-capped, and the end-capping agent is one or more of C1-C10 alcohols, C1-C10 amines, and monoisocyanates.

[0020] In this invention, the carbodiimide-modified cationic surfactant may be a carbodiimide-modified alkylbis(hydroxyethyl)methyl ammonium halide and / or a carbodiimide-modified alkylbis(hydroxyethyl)methyl ammonium halide polymer.

[0021] Preferably, the carbodiimide-modified alkylbis(hydroxyethyl)methyl ammonium halide is one or more of the following: carbodiimide-modified dodecylbis(hydroxyethyl)methyl ammonium halide, carbodiimide-modified tetradecylbis(hydroxyethyl)methyl ammonium halide, carbodiimide-modified hexadecylbis(hydroxyethyl)methyl ammonium halide, and carbodiimide-modified octadecylbis(hydroxyethyl)methyl ammonium halide, such as carbodiimide-modified dodecylbis(hydroxyethyl)methyl ammonium chloride or carbodiimide-modified bis(octadecyl)bis(hydroxyethyl)methyl ammonium chloride.

[0022] Preferably, the carbodiimide-modified alkylbis(hydroxyethyl)methyl ammonium halide is one or more of the following polymers: carbodiimide-modified dodecylbis(hydroxyethyl)methyl ammonium halide polymer, carbodiimide-modified tetradecylbis(hydroxyethyl)methyl ammonium halide polymer, carbodiimide-modified hexadecylbis(hydroxyethyl)methyl ammonium halide polymer, and carbodiimide-modified octadecylbis(hydroxyethyl)methyl ammonium halide polymer, such as carbodiimide-modified dodecylbis(hydroxyethyl)methyl ammonium chloride polymer or carbodiimide-modified bis(octadecyl)bis(hydroxyethyl)methyl ammonium chloride polymer.

[0023] In some specific embodiments, the structure of the carbodiimide-modified cationic surfactant may be as shown in Formula I:

[0024] Formula I; Where X is a halide ion, n=5~8, m=2~100; Wherein, A is one or more of the following: straight-chain or branched aliphatic divalent hydrocarbon group, alicyclic divalent hydrocarbon group, and aromatic divalent hydrocarbon group.

[0025] In some specific implementations, X represents chloride ions and n is 5.

[0026] In some specific embodiments, the straight-chain or branched aliphatic divalent hydrocarbon group may be -(CH2)6- and / or lysine-derived aliphatic group.

[0027] In some specific embodiments, the alicyclic divalent hydrocarbon group may be isophorone group and / or dicyclohexylmethane group.

[0028] In some specific embodiments, the aromatic divalent hydrocarbon group may be tolyl and / or diphenylmethane.

[0029] In this invention, the carbodiimide-modified cationic surfactant can be polymerized from the prepolymer shown in Formula I';

[0030] Formula I'; Where X is a halogen atom, n=5~8; A is one or more of the following: straight-chain or branched aliphatic divalent hydrocarbon group, alicyclic divalent hydrocarbon group, and aromatic divalent hydrocarbon group.

[0031] In some specific implementations, n=5, X is Cl, A is hexamethylene, and m=5.

[0032] Preferably, the prepolymer represented by formula I' is obtained by reacting monomer A and monomer B; The structure of monomer A is shown in formula I'-A; the structure of monomer B is shown in formula I'-B;

[0033] Formula I'-A;

[0034] Formula I'-B; In formula I'-A, X is a halogen atom, and n = 5~8; In formula I'-B, A is one or more of the following: straight-chain or branched aliphatic divalent hydrocarbon group, alicyclic divalent hydrocarbon group, and aromatic divalent hydrocarbon group; Preferably, the monomer B is one or more selected from toluene diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, dicyclohexylmethane diisocyanate, diphenylmethane diisocyanate, and lysine diisocyanate.

[0035] In some specific embodiments, the modified filler is one or more of the following: carbodiimide-modified dodecyl dihydroxyethyl methyl ammonium chloride-modified magnesium silicate, dodecyl dimethyl ammonium chloride-modified magnesium silicate, octadecyl trimethyl ammonium chloride-modified magnesium silicate, dodecyl dimethyl ammonium chloride-modified magnesium aluminum silicate, polytoluene diisocyanate-modified dodecyl dimethyl ammonium chloride-modified magnesium aluminum silicate, dodecyl dimethyl ammonium chloride-modified sodium aluminum silicate, spermine-modified sodium aluminum silicate, N,N-dimethyloctylamide-modified clay, dodecyl dimethyl ammonium chloride-modified montmorillonite, dodecyl trimethyl ammonium chloride-modified montmorillonite, dodecyl trimethyl ammonium bromide-modified hydrotalcite, oil-based hydroxyethyl imidazoline-modified zirconium phosphate, polyisophorone diisocyanate-modified mica, and spermine-modified mica.

[0036] In this invention, the modified groups account for 8%-45% of the mass percentage of the modified filler, preferably 8%-40%.

[0037] In some specific embodiments, the modified groups account for 9.2%, 20.1%, 24.0%, 19.9%, 25.0%, 29.8%, 30.5%, 36.2%, 38.1%, 38.6%, 38.9%, or 44.3% of the mass of the modified filler.

[0038] Secondly, the present invention provides a method for preparing the modified filler as described above, comprising the following steps: reacting the raw materials of the modified filler to obtain the modified filler; wherein the raw materials of the modified filler include the filler matrix and the modified component, and the modified component includes the modifier and / or the raw materials of the modifier.

[0039] In some embodiments, the reaction may be carried out in the presence of a solvent.

[0040] In the above embodiments, the reaction temperature is 50℃-80℃, for example, 60℃ or 80℃.

[0041] In the above implementation scheme, the reaction time is 2h-24h, for example 12h, 18h or 24h.

[0042] In the above embodiments, the solvent is an alcohol. Preferably, the alcohol is anhydrous ethanol and / or anhydrous methanol.

[0043] In other embodiments, the reaction is carried out by granulating the raw material of the modified filler.

[0044] In the above embodiments, the granulation processing temperature is 110℃-150℃, for example 130℃ or 140℃.

[0045] In the above embodiment, the granulation method is extrusion granulation. The equipment for extrusion granulation is an extruder, such as a twin-screw extruder. Preferably, the rotational speed for extrusion granulation is 100 r / min - 300 r / min, for example, 200 r / min or 250 r / min.

[0046] In other embodiments, the reaction is carried out by mixing the raw materials of the modified filler.

[0047] In this invention, the modifier accounts for 6%-69% of the mass percentage of the filler matrix, preferably 10%-68%, for example 11%, 25%, 33%, 43% or 67%.

[0048] In some embodiments, the raw materials for the modified filler include magnesium silicate and carbodiimide-modified dodecylbis(hydroxyethyl)methylammonium chloride.

[0049] In some embodiments, the raw materials for the modified filler include montmorillonite and dioctadecyl dimethyl ammonium chloride.

[0050] In some embodiments, the raw materials for the modified filler include hydrotalcite and dodecyltrimethylammonium bromide.

[0051] In some embodiments, the raw materials for the modified filler include zirconium phosphate and oil-based hydroxyethyl imidazoline.

[0052] In some embodiments, the raw materials for the modified filler include magnesium aluminum silicate, polytoluene diisocyanate, and dioctadecyl dimethyl ammonium chloride.

[0053] In some embodiments, the raw materials for the modified filler include mica and polyisophorone diisocyanate.

[0054] In some embodiments, the raw materials for the modified filler include sodium aluminum silicate and spermine.

[0055] In some embodiments, the raw materials for the modified filler include clay and N,N-dimethyloctylamide.

[0056] In some embodiments, the raw materials for the modified filler include magnesium silicate and dodecyl dimethyl ammonium chloride.

[0057] In some embodiments, the raw materials for the modified filler include hydrotalcite, aluminum silicate, and hexadecyltrimethylammonium bromide.

[0058] In some embodiments, the raw materials for the modified filler include montmorillonite, magnesium aluminum silicate, diphenylmethane diisocyanate, and dihexadecanyldimethylammonium bromide.

[0059] In some embodiments, the raw materials for the modified filler include magnesium aluminum silicate and dodecyl dimethyl ammonium chloride.

[0060] In some embodiments, the raw materials for the modified filler include sodium aluminum silicate and dodecyl dimethyl ammonium chloride.

[0061] In this invention, the modified filler, the filler matrix, and the modifier are defined and classified as described above.

[0062] Thirdly, the present invention provides an EVA material comprising EVA resin and filler; wherein the filler is a modified filler and / or filler matrix as described above.

[0063] In this invention, the filler accounts for 0.1%-40% of the mass percentage of the EVA material, preferably 5%-20%.

[0064] In some specific embodiments, the filler accounts for 3%, 7%, 10%, 13%, 14%, 16%, or 25% of the mass of the EVA material.

[0065] In this invention, the VA content of the EVA resin can be 25%-28%, for example, 25% or 28%.

[0066] In this invention, the melt index of the EVA resin can be 2-5 g / 10min, for example 3.5 g / 10min.

[0067] In some specific embodiments, the EVA material comprises, by weight, the following components: 93 parts EVA resin and 7 parts carbodiimide-modified dodecylbis(hydroxyethyl)methylammonium chloride-modified magnesium silicate.

[0068] In some specific embodiments, the EVA material comprises, by weight, 90 parts of EVA resin and 10 parts of bis(octadecyl)dimethylammonium chloride-modified montmorillonite.

[0069] In some specific embodiments, the EVA material comprises, by weight, 87 parts of EVA resin and 13 parts of dodecyltrimethylammonium bromide modified hydrotalcite.

[0070] In some specific embodiments, the EVA material comprises, by weight, 80 parts of EVA resin and 20 parts of oil-based hydroxyethyl imidazoline modified zirconium phosphate.

[0071] In some specific embodiments, the EVA material comprises, by weight, the following components: 97 parts EVA resin and 3 parts polytoluene diisocyanate modified dioctadecyl dimethyl ammonium chloride magnesium aluminum silicate.

[0072] In some specific embodiments, the EVA material comprises, by weight, the following components: 75 parts EVA resin and 25 parts polyisophorone diisocyanate modified mica.

[0073] In some specific embodiments, the EVA material comprises, by weight, 90 parts EVA resin and 10 parts bentonite.

[0074] In some specific embodiments, the EVA material comprises, by weight, 84 parts EVA resin and 16 parts arginine-modified sodium aluminum silicate.

[0075] In some specific embodiments, the EVA material comprises, by weight, 85 parts of EVA resin and 15 parts of N,N-dimethyloctylamide modified clay.

[0076] In some specific embodiments, the EVA material comprises, by weight, the following components: 87 parts EVA resin and 13 parts modified filler; wherein the modified filler comprises didodecyl dimethyl ammonium chloride modified magnesium silicate and / or polyhexamethylene diisocyanate modified didodecyl dimethyl ammonium chloride modified magnesium silicate.

[0077] In some specific embodiments, the EVA material comprises, by weight, 83 parts of EVA resin and 17 parts of filler; wherein the filler comprises one or more of hydrotalcite, hexadecyltrimethylammonium bromide-modified hydrotalcite, aluminum silicate, and hexadecyltrimethylammonium bromide-modified aluminum silicate.

[0078] In some specific embodiments, the EVA material comprises, by weight, the following components: 80 parts EVA resin and 20 parts filler; wherein the filler includes a filler matrix and / or modified filler, the filler matrix includes montmorillonite and / or magnesium aluminum silicate, the filler matrix of the modified filler includes montmorillonite and / or magnesium aluminum silicate, and the modifying groups of the modified filler are derived from polydiphenylmethane diisocyanate and / or dihexyldimethylammonium bromide.

[0079] In some specific embodiments, the EVA material comprises, by weight, the following components: 85 parts EVA resin and 15 parts modified filler, wherein the modified filler comprises one or more of the following: didodecyl dimethyl ammonium chloride modified magnesium aluminum silicate, didodecyl dimethyl ammonium chloride modified sodium aluminum silicate, polyhexamethylene diisocyanate modified didodecyl dimethyl ammonium chloride modified magnesium aluminum silicate, and polyhexamethylene diisocyanate modified didodecyl dimethyl ammonium chloride modified sodium aluminum silicate.

[0080] In this invention, the modified filler and the filler matrix are defined and classified as described above.

[0081] Fourthly, the present invention provides a method for preparing the EVA material as described above, which includes the following steps: granulating the raw material composition of the EVA material; The raw material composition of the EVA material includes the EVA resin and the filler; Alternatively, the raw material composition of the EVA material comprises the raw materials of the EVA resin and the modified filler, wherein the raw materials of the modified filler include the filler matrix and the modifying component, and the modifying component includes the modifier and / or the raw materials of the modifier.

[0082] In this invention, the granulation processing temperature can be 110℃-150℃, for example 130℃ or 140℃.

[0083] In this invention, the granulation method is extrusion granulation. The equipment for extrusion granulation is an extruder, such as a twin-screw extruder. Preferably, the rotational speed for extrusion granulation is 100 r / min - 300 r / min, for example, 200 r / min or 250 r / min.

[0084] In this invention, the modified filler, the filler matrix, and the modifier are defined and classified as described above.

[0085] Fifthly, the present invention provides an encapsulating film made of the EVA material as described above.

[0086] In a sixth aspect, the present invention provides the application of the modified filler, the EVA material, or the encapsulating film as described above in solar panels.

[0087] Based on common knowledge in the field, the above-mentioned preferred conditions can be combined arbitrarily to obtain various preferred embodiments of the present invention.

[0088] The reagents and raw materials used in this invention are all commercially available.

[0089] The positive and progressive effects of this invention are as follows: (1) The EVA material provided by this invention is effective against ions (e.g., Na+). + It has an adsorption effect, and the filler is uniformly distributed in the EVA matrix. Its layered structure can effectively block the ion migration path, significantly reduce the ion migration rate in the EVA material, greatly improve the anti-PID performance of the EVA material, inhibit EVA aging, and enable the encapsulation film prepared using this EVA material to effectively delay the PID phenomenon of solar panels.

[0090] (2) The EVA material provided by the present invention has good overall performance: the addition of modified filler not only improves the anti-PID performance of EVA, but also has little impact on the light transmittance of EVA material, ensuring that the basic performance of the encapsulation film meets the requirements for use.

[0091] (3) The preparation method of EVA material provided by the present invention is simple, the equipment used is conventional polymer material processing equipment, the raw material cost is relatively low, it is suitable for large-scale industrial production, and has broad market promotion prospects. Detailed Implementation

[0092] The present invention is further illustrated below by way of embodiments, but the invention is not limited to the scope of the embodiments described herein. Experimental methods in the following embodiments that do not specify specific conditions were performed according to conventional methods and conditions, or as selected according to the product instructions.

[0093] The reagents and raw materials used in this invention are all commercially available. The carbodiimide-modified dodecyl dihydroxyethyl methyl ammonium chloride is synthesized via the following technical route:

[0094] Where n=5, X is Cl, A is hexamethylene; m=5.

[0095] Example 1

[0096] (1) Take 60g of magnesium silicate, add it to 500mL of anhydrous ethanol, stir to form a suspension, sonicate for 30 minutes, add 40g of carbodiimide-modified dodecylbis(hydroxyethyl)methylammonium chloride to the suspension, stir and react at 60℃ for 24 hours; after the reaction is completed, filter the product, wash with anhydrous ethanol until no white precipitate is added to the filtrate with silver nitrate solution, dry and crush the product to obtain the modified filler (carbodiimide-modified dodecylbis(hydroxyethyl)methylammonium chloride-modified magnesium silicate); (2) According to the mass parts, 93 parts of EVA resin (VA content 28%, melt index 3.5 g / 10min) and 7 parts of the modified filler obtained in step (1) are mixed evenly. The mixture is added to a twin-screw extruder, the processing temperature is set to 130℃ and the screw speed is 200r / min, and the mixture is melt-blended, extruded and granulated to obtain EVA material.

[0097] Example 2

[0098] (1) Take 70g of montmorillonite and 30g of dioctadecyl dimethyl ammonium chloride, mix them evenly with a high-speed mixer to obtain the modified filler (dioctadecyl dimethyl ammonium chloride modified montmorillonite). (2) Mix 90 parts of EVA resin (VA content 25%, melt index 3.5 g / 10min) and 10 parts of the modified filler obtained in step (1) evenly according to the mass ratio. Add the mixture to a twin-screw extruder, set the processing temperature to 130℃ and the screw speed to 200r / min, and perform melt blending, extrusion granulation to obtain EVA material.

[0099] Example 3

[0100] (1) Take 60g of hydrotalcite and add it to 500mL of anhydrous methanol. Stir to form a suspension and sonicate for 30 minutes. Add 40g of dodecyltrimethylammonium bromide to the suspension and stir to react for 12 hours at 80℃. After the reaction is complete, filter the product and wash it with deionized water until no light yellow precipitate is added to the filtrate with silver nitrate solution. Dry and crush the product to obtain the modified filler (dodecyltrimethylammonium bromide modified hydrotalcite). (2) Mix 87 parts of EVA resin (VA content 25%, melt index 3.5 g / 10min) and 13 parts of the modified filler obtained in step (1) evenly according to the mass ratio. Add the mixture to a twin-screw extruder, set the processing temperature to 140℃ and the screw speed to 250r / min, and perform melt blending, extrusion granulation to obtain EVA material.

[0101] Example 4

[0102] (1) Take 75g of zirconium phosphate and 25g of oil-based hydroxyethyl imidazoline, mix them evenly with a high-speed mixer to obtain the modified filler (oil-based hydroxyethyl imidazoline modified zirconium phosphate). (2) Mix 80 parts of EVA resin (VA content 28%, melt index 3.5 g / 10min) and 20 parts of the modified filler obtained in step (1) evenly according to the mass ratio. Add the mixture to a twin-screw extruder, set the processing temperature to 130℃ and the screw speed to 200r / min, and perform melt blending, extrusion granulation to obtain EVA material.

[0103] Example 5

[0104] By weight, 97 parts of EVA resin (VA content 25%, melt index 3.5 g / 10min), 2.7 parts of magnesium aluminum silicate, 0.15 parts of polytoluene diisocyanate, and 0.15 parts of dioctadecyl dimethyl ammonium chloride were mixed evenly. The mixture was then fed into a twin-screw extruder, and the processing temperature was set to 130℃ and the screw speed to 200 r / min for melt blending, extrusion granulation, and finally, EVA material was obtained. The modified filler in the EVA material was polytoluene diisocyanate-modified dioctadecyl dimethyl ammonium chloride-modified magnesium aluminum silicate.

[0105] Example 6

[0106] By weight, 75 parts of EVA resin (VA content 25%, melt index 3.5 g / 10min), 20 parts of mica, and 5 parts of polyisophorone diisocyanate were mixed evenly. The mixture was then fed into a twin-screw extruder, and the processing temperature was set to 140℃ and the screw speed to 250 r / min for melt blending, extrusion granulation, and finally, EVA material was obtained. The modified filler in the EVA material was polyisophorone diisocyanate-modified mica.

[0107] Example 7

[0108] By weight, 90 parts of EVA resin (VA content 25%, melt index 3.5 g / 10min) and 10 parts of bentonite were mixed evenly. The mixture was added to a twin-screw extruder, and the processing temperature was set to 130℃ and the screw speed to 200 r / min. The mixture was then melt-blended, extruded and granulated to obtain the EVA material.

[0109] Example 8

[0110] (1) Take 80g of sodium aluminum silicate, add it to 500mL of anhydrous ethanol, stir to form a suspension, sonicate for 30 minutes, add 20g of spermine to the suspension, stir and react at 60℃ for 24 hours; after the reaction is completed, filter the product, wash with anhydrous ethanol until no white precipitate is added to the filtrate with silver nitrate solution, dry and crush the product to obtain the modified filler (spermine-modified sodium aluminum silicate). (2) Mix 84 parts of EVA resin (VA content 28%, melt index 3.5 g / 10min) and 16 parts of the modified filler obtained in step (1) evenly according to the mass ratio. Add the mixture to a twin-screw extruder, set the processing temperature to 130℃ and the screw speed to 200r / min, and perform melt blending, extrusion granulation to obtain EVA material.

[0111] Example 9

[0112] By weight, 85 parts of EVA resin (VA content 28%, melt index 3.5 g / 10min), 10 parts of clay, and 5 parts of N,N-dimethyloctylamide were mixed evenly. The mixture was then fed into a twin-screw extruder, and the processing temperature was set to 130℃ and the screw speed to 200 r / min for melt blending, extrusion granulation, and finally, the EVA material was obtained. The modified filler in the EVA material was N,N-dimethyloctylamide-modified clay.

[0113] Example 10

[0114] (1) Take 75g of magnesium silicate, add it to 500mL of anhydrous ethanol, stir to form a suspension, sonicate for 30 minutes, add 25g of dodecyl dimethyl ammonium chloride to the suspension, stir and react at 60℃ for 24 hours; after the reaction is completed, filter the product, wash with anhydrous ethanol until no white precipitate is added to the filtrate with silver nitrate solution, dry and crush the product to obtain the modified filler (dodecyl dimethyl ammonium chloride modified magnesium silicate); (2) By mass, 87 parts of EVA resin (VA content 28%, melt index 3.5 g / 10min), 12 parts of the modified filler obtained in step (1) and 1 part of hexamethylene diisocyanate are mixed evenly. The mixture is added to a twin-screw extruder, the processing temperature is set to 130℃ and the screw speed is 200r / min, and the mixture is melt-blended, extruded and granulated to obtain EVA material.

[0115] Example 11

[0116] By mass, 83 parts of EVA resin (VA content 25%, melt index 3.5 g / 10min), 9 parts of hydrotalcite, 4 parts of aluminum silicate, and 4 parts of hexadecyltrimethylammonium bromide were mixed evenly. The mixture was added to a twin-screw extruder, and the processing temperature was set to 130℃ and the screw speed to 200 r / min. The mixture was then melt-blended, extruded, and granulated to obtain the EVA material.

[0117] Example 12

[0118] By weight, 80 parts of EVA resin (VA content 25%, melt index 3.5 g / 10min), 7 parts of montmorillonite, 4 parts of magnesium aluminum silicate, 5 parts of diphenylmethane diisocyanate, and 4 parts of dihexadecanyl dimethyl ammonium bromide were mixed evenly. The mixture was added to a twin-screw extruder, and the processing temperature was set to 130℃ and the screw speed was set to 200 r / min. The mixture was then melt-blended, extruded, and granulated to obtain the EVA material.

[0119] Example 13

[0120] (1) Take 75g of magnesium aluminum silicate, add it to 500mL of anhydrous ethanol, stir to form a suspension, sonicate for 30 minutes, add 25g of dodecyl dimethyl ammonium chloride to the suspension, stir and react at 60℃ for 24 hours; after the reaction is completed, filter the product, wash with anhydrous ethanol until no white precipitate is added to the filtrate with silver nitrate solution, dry and crush the product to obtain the modified filler (dodecyl dimethyl ammonium chloride modified magnesium aluminum silicate). (2) Take 80g of sodium aluminum silicate, add it to 500mL of anhydrous ethanol, stir to form a suspension, sonicate for 30 minutes, add 20g of dodecyl dimethyl ammonium chloride to the suspension, stir and react at 60℃ for 24 hours; after the reaction is completed, filter the product, wash with anhydrous ethanol until no white precipitate is added to the filtrate with silver nitrate solution, dry and crush the product to obtain the modified filler (dodecyl dimethyl ammonium chloride modified sodium aluminum silicate). (3) By mass, 85 parts of EVA resin (VA content 28%, melt index 3.5 g / 10min), 7 parts of modified filler obtained in step (1), 7 parts of modified filler obtained in step (2), and 1 part of hexamethylene diisocyanate are mixed evenly. The mixture is added to a twin-screw extruder, the processing temperature is set to 130℃, the screw speed is 200r / min, and the mixture is melt-blended, extruded and granulated to obtain EVA material.

[0121] Example 14

[0122] (1) Take 100g of magnesium silicate, add it to 500mL of anhydrous ethanol, stir to form a suspension, sonicate for 30 minutes, add 3g of octadecyltrimethylammonium chloride to the suspension, stir and react at 60℃ for 24 hours; after the reaction is completed, filter the product, wash with anhydrous ethanol until no white precipitate is added to the filtrate with silver nitrate solution, dry and crush the product to obtain the modified filler (octadecyltrimethylammonium chloride modified magnesium silicate). (2) Mix 93 parts of EVA (VA content 28%, melt index 3.5 g / 10min) and 7 parts of the modified filler obtained in step (1) evenly according to mass. Add the mixture to a twin-screw extruder, set the processing temperature to 130℃ and the screw speed to 200r / min, and perform melt blending, extrusion granulation to obtain EVA material.

[0123] Example 15

[0124] (1) Take 100g of montmorillonite and 5g of dodecyltrimethylammonium chloride, mix them evenly with a high-speed mixer to obtain the modified filler (dodecyltrimethylammonium chloride modified montmorillonite). (2) Mix 90 parts of EVA (VA content 25%, melt index 3.5 g / 10min) and 10 parts of the modified filler obtained in step (1) evenly according to the mass ratio. Add the mixture to a twin-screw extruder, set the processing temperature to 130℃ and the screw speed to 200r / min, and carry out melt blending, extrusion granulation to obtain EVA material.

[0125] Comparative Example 1

[0126] 100 parts by weight of EVA resin (VA content 28%, melt index 3.5 g / 10min) were added to a twin-screw extruder. The processing temperature was set to 130℃ and the screw speed to 200 r / min. The mixture was melt-blended, extruded and granulated to obtain ordinary EVA material.

[0127] Comparative Example 2

[0128] By weight, 87 parts of EVA (VA content 25%, melt index 3.5 g / 10min), 6 parts of hydrotalcite, and 7 parts of polyhexamethylene diisocyanate were mixed evenly. The mixture was then fed into a twin-screw extruder, and the processing temperature was set to 140℃ and the screw speed to 250 r / min for melt blending, extrusion granulation, and the EVA material was obtained. The modified filler in the EVA material was polyhexamethylene diisocyanate-modified hydrotalcite.

[0129] Effect Example

[0130] 1. Volume resistivity

[0131] The volume resistivity of the EVA materials prepared in Examples 1-15 and Comparative Examples 1-2 was tested according to the method of GB / T1410-2006, and the test results are recorded in Table 1.

[0132] 2. Light transmittance

[0133] The light transmittance of the EVA materials prepared in Examples 1-15 and Comparative Examples 1-2 was tested according to the method of GB / T29848-2018, and the test results are recorded in Table 1.

[0134] 3. Percentage of modified groups in the modified filler by mass

[0135] For EVA materials modified by cationic surfactants and carbodiimide-modified cationic surfactants: The modified fillers prepared in the examples and comparative examples were titrated using a two-phase titration method with excess sodium dodecyl sulfate (SDS, an anionic surfactant). The remaining SDS was back-titrated with a cationic standard solution (benzyl dimethyl tetradecyl ammonium chloride). The mass of the modified groups in the modified filler was calculated by the volume of standard solution consumed, and then the mass percentage of the modified groups was determined. The results are recorded in Table 1.

[0136] For EVA materials modified with carbodiimide: The nitrogen content in the modified filler was tested using an elemental analyzer, and the mass of the carbodiimide groups was calculated. The mass percentage of the carbodiimide groups was then calculated, and the results are recorded in Table 1.

[0137] Table 1

[0138] The EVA material provided by this invention has a high volume resistivity, reaching up to 1.6 × 10⁻⁶. 15 The above indicates that EVA material has excellent anti-PID properties while maintaining good light transmittance, reaching over 82%, ensuring that the basic properties of the encapsulation film meet the usage requirements.

[0139] In Comparative Example 1, no filler was added, and its volume resistivity was significantly lower than that of the Example. This indicates that the modified filler has a significant impact on improving volume resistivity and enhancing anti-PID performance.

[0140] In Comparative Example 2, the percentage of modified groups in the modified filler mass was too high, indicating that the content of modified groups has a significant impact on volume resistivity, and an excessively high content cannot achieve the technical effect of this application.

[0141] In Examples 1-6 and Examples 8-15, different types of modified fillers were mixed with EVA resin, all of which improved the volume resistivity of the EVA material to varying degrees. Among them, the EVA material prepared by combining dodecyltrimethylammonium bromide modified hydrotalcite with EVA resin in Example 3 showed better volume resistivity and superior anti-PID performance.

[0142] The EVA material prepared by mixing EVA resin and filler matrix in Example 7 also showed a certain improvement in volume resistivity compared to Comparative Example 1 without filler matrix.

[0143] The specific embodiments described above further illustrate the purpose, technical solution, and beneficial effects of the present invention. It should be understood that the above descriptions are merely specific embodiments of the present invention and are not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the protection scope of the present invention.

Claims

1. A modified filler, characterized in that, The modified filler includes a filler matrix and modifying groups, wherein the modifying groups are derived from a modifier, and the modifier is one or more of carbodiimide, cationic surfactant, and carbodiimide-modified cationic surfactant; the modifying groups account for less than 50% of the mass percentage of the modified filler.

2. The modified filler as described in claim 1, characterized in that, The modified filler satisfies one or more of the following conditions: a. The filler matrix is ​​one or more of silicates, clay, glass flakes, talc, and zirconium phosphate; b. The cationic surfactant is one or more selected from quaternary ammonium salts, amine salts, polyamines, amides, imidazolines, and imidazoles; c. The carbodiimide is a monocarbodiimide and / or a polycarbodiimide; d. The carbodiimide is polymerized from one or more of toluene diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, dicyclohexylmethane diisocyanate, diphenylmethane diisocyanate and lysine diisocyanate; e. The carbodiimide-modified cationic surfactant is a carbodiimide-modified alkylbis(hydroxyethyl)methyl ammonium halide and / or a carbodiimide-modified alkylbis(hydroxyethyl)methyl ammonium halide polymer; f. The modified groups account for 8%-45% of the mass percentage of the modified filler.

3. The modified filler as described in claim 2, characterized in that, The modified filler satisfies one or more of the following conditions: a. The silicate is one or more selected from mica, montmorillonite, aluminum silicate, magnesium silicate, magnesium aluminum silicate, and sodium aluminum silicate; b. The clay is one or more of kaolin, hydrotalcite, and bentonite; c. The quaternary ammonium salt is one or more of the following: dodecyltrimethyl quaternary ammonium salt, tetradecyltrimethyl quaternary ammonium salt, hexadecyltrimethyl quaternary ammonium salt, octadecyltrimethyl quaternary ammonium salt, didodecyldimethyl quaternary ammonium salt, ditetradecyldimethyl quaternary ammonium salt, dihexadecyldimethyl quaternary ammonium salt, dioctadecyldimethyl quaternary ammonium salt, and benzalkonium chloride; d. The polyamine is one or more selected from spermine, spermidine, ethylenediamine, propylenediamine, hexamethylenediamine, p-phenylenediamine, and m-phenylenediamine; e. The amine salt is one or more selected from dodecylamine salt, tetradecylamine salt, hexadecylamine salt, and octadecylamine salt; f. The amide is an amide quaternary ammonium salt and / or an aliphatic amide; g. The imidazoline is an alkyl imidazoline and / or an alkyl imidazoline quaternary ammonium salt; h. The imidazole is one or more selected from N-dodecylimidazolium, N-tetradecylimidazolium, N-hexadecylimidazolium, N-octadecylimidazolium, 2-imidazolium carboxylic acid, and 1H-imidazolium-2-acetic acid; i. The carbodiimide-modified alkyl dihydroxyethyl methyl ammonium halide is one or more of the following: carbodiimide-modified dodecyl dihydroxyethyl methyl ammonium halide, carbodiimide-modified tetradecyl dihydroxyethyl methyl ammonium halide, carbodiimide-modified hexadecyl dihydroxyethyl methyl ammonium halide, and carbodiimide-modified octadecyl dihydroxyethyl methyl ammonium halide; j. The carbodiimide-modified alkyl dihydroxyethyl methyl ammonium halide is one or more of the following polymers: carbodiimide-modified dodecyl dihydroxyethyl methyl ammonium halide polymer, carbodiimide-modified tetradecyl dihydroxyethyl methyl ammonium halide polymer, carbodiimide-modified hexadecyl dihydroxyethyl methyl ammonium halide polymer, and carbodiimide-modified octadecyl dihydroxyethyl methyl ammonium halide polymer; k. The modified filler is one or more of the following: carbodiimide-modified dodecyl dihydroxyethyl methyl ammonium chloride-modified magnesium silicate, dodecyl dimethyl ammonium chloride-modified magnesium silicate, octadecyl trimethyl ammonium chloride-modified magnesium silicate, dodecyl dimethyl ammonium chloride-modified magnesium aluminum silicate, polytoluene diisocyanate-modified dodecyl dimethyl ammonium chloride-modified magnesium aluminum silicate, dodecyl dimethyl ammonium chloride-modified sodium aluminum silicate, spermine-modified sodium aluminum silicate, N,N-dimethyloctylamide-modified clay, dodecyl dimethyl ammonium chloride-modified montmorillonite, dodecyl trimethyl ammonium chloride-modified montmorillonite, dodecyl trimethyl ammonium bromide-modified hydrotalcite, oil-based hydroxyethyl imidazoline-modified zirconium phosphate, polyisophorone diisocyanate-modified mica, and spermine-modified mica.

4. A method for preparing a modified filler according to any one of claims 1-3, characterized in that, It includes the following steps: The modified filler is prepared by reacting the raw materials of the modified filler; wherein the raw materials of the modified filler include the filler matrix and the modifying component, and the modifying component includes the modifier and / or the raw materials of the modifier.

5. The method for preparing the modified filler as described in claim 4, characterized in that, It meets one or more of the following conditions: a. The reaction is carried out in the presence of a solvent, and the temperature of the reaction is 50°C-80°C; b. The reaction is carried out in the presence of a solvent for a period of 2-24 hours; c. The reaction is carried out in the presence of a solvent, wherein the solvent is an alcohol. d. The reaction is carried out by granulating the raw material of the modified filler, and the granulation processing temperature is 110℃-150℃; the granulation method is extrusion granulation; e. The reaction is carried out by mixing the raw materials of the modified filler; f. The modifier accounts for 6%-69% of the mass percentage of the filler matrix; g. The raw materials for the modified filler include magnesium silicate and carbodiimide-modified dodecylbis(hydroxyethyl)methylammonium chloride; Alternatively, the raw materials for the modified filler include montmorillonite and dioctadecyldimethylammonium chloride; Alternatively, the raw materials for the modified filler include hydrotalcite and dodecyltrimethylammonium bromide; Alternatively, the raw materials for the modified filler include zirconium phosphate and oil-based hydroxyethyl imidazoline; Alternatively, the raw materials for the modified filler include magnesium aluminum silicate, polytoluene diisocyanate, and dioctadecyl dimethyl ammonium chloride; Alternatively, the raw materials for the modified filler include mica and polyisophorone diisocyanate; Alternatively, the raw materials for the modified filler include sodium aluminum silicate and spermine; Alternatively, the raw materials for the modified filler include clay and N,N-dimethyloctylamide; Alternatively, the raw materials for the modified filler include magnesium silicate and dodecyl dimethyl ammonium chloride; Alternatively, the raw materials for the modified filler include hydrotalcite, aluminum silicate, and hexadecyltrimethylammonium bromide; Alternatively, the raw materials for the modified filler include montmorillonite, magnesium aluminum silicate, diphenylmethane diisocyanate, and dihexadecanyl dimethylammonium bromide; Alternatively, the raw materials for the modified filler include magnesium aluminum silicate and dodecyl dimethyl ammonium chloride; Alternatively, the raw materials for the modified filler may include sodium aluminum silicate and dodecyl dimethyl ammonium chloride.

6. An EVA material, characterized in that, It includes EVA resin and fillers; Wherein, the filler is a modified filler and / or filler matrix as described in any one of claims 1-3.

7. The EVA material as described in claim 6, characterized in that, The EVA material satisfies one or more of the following conditions: a. The VA content of the EVA resin is 25%-28%; b. The melt flow index of the EVA resin is 2-5 g / 10min; c. The filler accounts for 0.1%-40% of the mass percentage of the EVA material.

8. The EVA material as described in claim 6, characterized in that, The EVA material comprises, by weight, the following components: 93 parts EVA resin and 7 parts carbodiimide-modified dodecylbis(hydroxyethyl)methylammonium chloride-modified magnesium silicate; Alternatively, by weight, the EVA material comprises the following components: 90 parts EVA resin and 10 parts dioctadecyldimethylammonium chloride modified montmorillonite; Alternatively, by weight, the EVA material comprises the following components: 87 parts EVA resin and 13 parts dodecyltrimethylammonium bromide modified hydrotalcite; Alternatively, by weight, the EVA material comprises the following components: 80 parts EVA resin and 20 parts oil-based hydroxyethyl imidazoline modified zirconium phosphate; Alternatively, by weight, the EVA material comprises the following components: 97 parts EVA resin and 3 parts polytoluene diisocyanate modified dioctadecyl dimethyl ammonium chloride modified magnesium aluminum silicate; Alternatively, by weight, the EVA material comprises the following components: 75 parts EVA resin and 25 parts polyisophorone diisocyanate modified mica. Alternatively, by weight, the EVA material comprises the following components: 90 parts EVA resin and 10 parts bentonite; Alternatively, by weight, the EVA material comprises the following components: 84 parts EVA resin and 16 parts succinamine-modified sodium aluminum silicate. Alternatively, by weight, the EVA material comprises the following components: 85 parts EVA resin and 15 parts N,N-dimethyloctylamide modified clay; Alternatively, by weight, the EVA material comprises the following components: 87 parts EVA resin and 13 parts modified filler; wherein the modified filler comprises didodecyl dimethyl ammonium chloride modified magnesium silicate and / or polyhexamethylene diisocyanate modified didodecyl dimethyl ammonium chloride modified magnesium silicate; Alternatively, by weight, the EVA material comprises the following components: 83 parts EVA resin and 17 parts filler; wherein the filler comprises one or more of hydrotalcite, hexadecyltrimethylammonium bromide-modified hydrotalcite, aluminum silicate, and hexadecyltrimethylammonium bromide-modified aluminum silicate. Alternatively, by weight, the EVA material comprises the following components: 80 parts EVA resin and 20 parts filler; wherein the filler includes a filler matrix and / or a modified filler, the filler matrix includes montmorillonite and / or magnesium aluminum silicate, the filler matrix of the modified filler includes montmorillonite and / or magnesium aluminum silicate, and the modifying groups of the modified filler are derived from polydiphenylmethane diisocyanate and / or dihexyldimethylammonium bromide; Alternatively, by weight, the EVA material comprises the following components: 85 parts EVA resin and 15 parts modified filler, wherein the modified filler comprises one or more of the following: didodecyl dimethyl ammonium chloride modified magnesium aluminum silicate, didodecyl dimethyl ammonium chloride modified sodium aluminum silicate, polyhexamethylene diisocyanate modified didodecyl dimethyl ammonium chloride modified magnesium aluminum silicate, and polyhexamethylene diisocyanate modified didodecyl dimethyl ammonium chloride modified sodium aluminum silicate.

9. A method for preparing the EVA material according to any one of claims 6-8, characterized in that, It includes the following steps: The raw material composition of the EVA material is granulated; The raw material composition of the EVA material includes the EVA resin and the filler; Alternatively, the raw material composition of the EVA material comprises the raw materials of the EVA resin and the modified filler, wherein the raw materials of the modified filler include the filler matrix and the modifying component, and the modifying component includes the modifier and / or the raw materials of the modifier.

10. The method for preparing EVA material as described in claim 9, characterized in that, The method for preparing the EVA material satisfies one or more of the following conditions: a. The granulation processing temperature is 110℃-150℃; b. The granulation method is extrusion granulation.

11. An encapsulating film, characterized in that, It is made from EVA material as described in any one of claims 6-8.

12. The application of a modified filler as described in any one of claims 1-3, an EVA material as described in any one of claims 6-8, or an encapsulating film as described in claim 11 in a solar panel.

Images