POE film with anti-sedimentation additive and preparation method thereof

Abstract

The application provides a POE adhesive film capable of preventing the precipitation of an auxiliary agent and a preparation method thereof. The preparation raw material of the POE adhesive film capable of preventing the precipitation of an auxiliary agent comprises the following components: a POE resin, a cyclodextrin hydrogel, an initiator, an auxiliary crosslinking agent, a tackifier, a surfactant, a light stabilizer and an ultraviolet absorber. After the cyclodextrin hydrogel provided by the application is swelled in water, the outside of the cyclodextrin absorbs water, and the internal cavity of the cyclodextrin absorbs oily liquid auxiliary agents (the initiator, the auxiliary crosslinking agent and the tackifier). After the cyclodextrin hydrogel is vacuum dried, the external water is removed, and the internal oily auxiliary agents are retained. After the cyclodextrin hydrogel is used as the preparation raw material of the POE resin to prepare the POE adhesive film, the precipitation of the liquid auxiliary agents can be prevented.

Description

Technical Field

[0001] This invention belongs to the field of solar cell technology and relates to a POE film for preventing additive precipitation and its preparation method, specifically to a POE film for preventing liquid additive precipitation and its preparation method. Background Technology

[0002] Photovoltaic encapsulating film, as a core auxiliary material, covers the upper and lower surfaces of the solar cells. It is laminated with photovoltaic glass, backsheet, and other auxiliary materials in a vacuum environment to form photovoltaic modules. Its main function is to protect the solar cells and effectively extend the module's lifespan. A typical photovoltaic module structure, from top to bottom, consists of glass, encapsulating film, solar cells, encapsulating film again, and backsheet. Since photovoltaic modules need to operate continuously outdoors for many years, the quality of the encapsulating film is directly related to the module's reliability. If the encapsulating film yellows or cracks during operation, it will directly affect the module's use. Therefore, the encapsulating film directly determines the product quality and lifespan of the photovoltaic module.

[0003] Traditional photovoltaic encapsulant films are made from EVA (ethylene-vinyl acetate) polymer as the basic material, and are called EVA photovoltaic encapsulant films. However, vinyl acetate has a polar chemical structure and has defects such as high water vapor permeability and easy hydrolysis and aging. In humid environments, it cannot effectively protect photovoltaic modules. In particular, with the increasing popularity of bifacial cells in the photovoltaic industry, EVA photovoltaic encapsulant films cannot provide anti-PID (polyvinyl chloride) protection.

[0004] POE (ethylene-octene polymer) encapsulant film is the mainstream encapsulation material for double-glass modules due to its unique anti-PID properties, high resistivity, and resistance to hydrolysis. Photovoltaic encapsulant films are generally composed of resin and additives, most of which are liquids. Because POE resin is non-polar, it has poor absorption capacity for liquid additives. After prolonged storage, the liquid additives tend to gradually precipitate onto the film surface, leading to a decline in film performance and reduced product stability and reliability.

[0005] Therefore, in this field, it is desirable to develop a POE film that prevents the precipitation of additives, specifically liquid additives. Summary of the Invention

[0006] To address the shortcomings of existing technologies, the present invention aims to provide a POE film that prevents the precipitation of additives and a method for preparing the same, particularly a POE film that prevents the precipitation of liquid additives and a method for preparing the same.

[0007] To achieve this objective, the present invention adopts the following technical solution:

[0008] In a first aspect, the present invention provides a POE film for preventing the precipitation of additives, wherein the raw materials for preparing the POE film for preventing the precipitation of additives include the following components: POE resin, cyclodextrin hydrogel, initiator, crosslinking agent, tackifier, surfactant, light stabilizer and ultraviolet absorber.

[0009] Cyclodextrins possess hydrophobic cavities, enabling them to form inclusion complexes with organic molecules. When cyclodextrin hydrogels swell in water, the outer surface of the cyclodextrin absorbs moisture, while the internal cavities absorb oily liquid additives (initiators, crosslinking agents, and thickeners). Vacuum drying of the cyclodextrin hydrogel removes the external moisture while retaining the internal oily additives. Using this hydrogel as a raw material for preparing POE resin and then fabricating POE films prevents the precipitation of these liquid additives.

[0010] Preferably, the raw materials for preparing the POE film to prevent the precipitation of additives include the following components by weight:

[0011]

[0012] Preferably, the amount of cyclodextrin hydrogel used in the preparation of the POE film for preventing the precipitation of additives can be 2 parts, 3 parts, 4 parts, 5 parts, 6 parts, 7 parts, 8 parts, 9 parts, 10 parts, 11 parts, or 12 parts by weight.

[0013] Preferably, the amount of initiator used in the preparation of the POE film for preventing the precipitation of additives can be 0.4 parts, 0.5 parts, 0.6 parts, 0.7 parts, 0.8 parts, 0.9 parts, 1 part, 1.1 parts, 1.2 parts, 1.3 parts, 1.4 parts, 1.5 parts, 1.6 parts, 1.7 parts, 1.8 parts, 1.9 parts, or 2 parts, etc., by weight.

[0014] Preferably, the amount of crosslinking agent used in the preparation of the POE film for preventing the precipitation of additives can be 0.4 parts, 0.5 parts, 0.6 parts, 0.7 parts, 0.8 parts, 0.9 parts, 1 part, 1.1 parts, 1.2 parts, 1.3 parts, 1.4 parts, 1.5 parts, 1.6 parts, 1.7 parts, 1.8 parts, 1.9 parts, or 2 parts, etc., by weight.

[0015] Preferably, the amount of tackifier used in the preparation of the POE film for preventing the exudation of additives can be 0.2 parts, 0.3 parts, 0.4 parts, 0.5 parts, 0.6 parts, 0.7 parts, 0.8 parts, 0.9 parts, 1 part, 1.1 parts, 1.2 parts, 1.3 parts, 1.4 parts, 1.5 parts, 1.6 parts, 1.7 parts, 1.8 parts, 1.9 parts, or 2 parts, etc., by weight.

[0016] Preferably, the amount of surfactant used in the preparation of the POE film for preventing the precipitation of additives can be 0.02 parts, 0.05 parts, 0.08 parts, 0.1 parts, 0.13 parts, or 0.15 parts, etc., by weight.

[0017] Preferably, the amount of light stabilizer used in the preparation of the POE film for preventing the exudation of additives can be 0.05 parts, 0.06 parts, 0.07 parts, 0.08 parts, 0.09 parts, 0.1 parts, 0.2 parts, 0.3 parts, 0.4 parts, 0.5 parts, 0.6 parts, 0.7 parts, 0.8 parts, 0.9 parts, 1 part, 1.1 parts, 1.2 parts, 1.3 parts, 1.4 parts, or 1.5 parts, etc., by weight.

[0018] Preferably, the amount of ultraviolet absorber used in the preparation of the POE film for preventing the exudation of additives can be 0.05 parts, 0.06 parts, 0.07 parts, 0.08 parts, 0.09 parts, 0.1 parts, 0.2 parts, 0.3 parts, 0.4 parts, 0.5 parts, 0.6 parts, 0.7 parts, 0.8 parts, 0.9 parts, 1 part, 1.1 parts, 1.2 parts, 1.3 parts, 1.4 parts, or 1.5 parts, etc., by weight.

[0019] Preferably, the cyclodextrin hydrogel is prepared by the following method:

[0020] (1) β-cyclodextrin and maleic anhydride were dissolved in dimethylformamide, reacted, and post-treated to obtain MAH-β-CD;

[0021] (2) Dissolve MAH-β-CD, acrylic acid and azobisisobutyronitrile in dimethylformamide, react, precipitate, soak the precipitated product in distilled water, change the distilled water every 10-12 hours (e.g., 10 hours, 11 hours or 12 hours), take it out and air dry after 2-4 days (e.g., 2 days, 3 days or 4 days), and vacuum dry to constant weight to obtain the cyclodextrin hydrogel.

[0022] Preferably, the mass ratio of β-cyclodextrin to maleic anhydride is 1:(0.8-1.2), for example, 1:0.8, 1:0.9, 1:1, 1:1.1 or 1:1.2.

[0023] Preferably, the mass ratio of the sum of the β-cyclodextrin and maleic anhydride to the mass of the dimethylformamide is 1:(3-5), for example, 1:3, 1:4 or 1:5.

[0024] Preferably, the reaction in step (1) is carried out under an inert gas.

[0025] Preferably, the inert gas includes nitrogen.

[0026] Preferably, the reaction temperature in step (1) is 70-90℃, such as 70℃, 75℃, 80℃, 85℃ or 90℃, and the reaction time is 8-12h, such as 8h, 9h, 10h, 11h or 12h.

[0027] Preferably, the post-processing in step (1) includes precipitation, washing, and drying.

[0028] Preferably, the mass ratio of MAH-β-CD, acrylic acid and azobisisobutyronitrile is 1:1:(0.04-0.06), for example 1:1:0.04, 1:1:0.05 or 1:1:0.06.

[0029] Preferably, the mass ratio of the sum of the masses of MAH-β-CD, acrylic acid, and azobisisobutyronitrile to the mass of dimethylformamide is 1:(2-4), for example, 1:2, 1:3, or 1:4.

[0030] Preferably, before the reaction in step (2), the system is subjected to nitrogen purging for 20-40 minutes to remove oxygen, for example, 20 minutes, 30 minutes or 40 minutes.

[0031] Preferably, the reaction temperature in step (2) is 60-80℃, such as 60℃, 70℃ or 80℃, and the reaction time is 20-30h, such as 20h, 22h, 24h, 26h, 28h or 30h.

[0032] As a preferred embodiment of the present invention, the cyclodextrin hydrogel is prepared by the following method:

[0033] (1) β-cyclodextrin and maleic anhydride (MAH) were dissolved in 3-5 times the total mass of dimethylformamide (DMF) at a mass ratio of 1:(0.8-1.2). Nitrogen gas was introduced and the mixture was stirred at a constant temperature of 70-90℃ for 8-12 hours. After the reaction was completed, the mixture was cooled to room temperature, and the product was precipitated with chloroform. After washing with acetone, the product was dried under vacuum to obtain MAH-β-CD.

[0034] (2) Dissolve MAH-β-CD, acrylic acid and azobisisobutyronitrile in a mass ratio of 1:1:(0.04-0.06) in 2-4 times the total mass of dimethylformamide. After purging with nitrogen to remove oxygen for 20-40 min, react at 60-80℃ for 20-30 h. Precipitate the product with diethyl ether, then soak the precipitated product in distilled water, changing the distilled water every 10-12 h. After 2-4 days, take it out and air dry it, then vacuum dry it to constant weight to obtain the cyclodextrin hydrogel.

[0035] Preferably, the POE resin has a melting point of 70-80℃, such as 70℃, 75℃ or 80℃, and a melt index of 5-14g / 10min, such as 5g / 10min, 8g / 10min, 10g / 10min or 14g / 10min.

[0036] Preferably, the initiator comprises any one or a combination of at least two of tert-butyl peroxycarbonate, 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexane or 1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane.

[0037] Preferably, the crosslinking agent comprises any one or a combination of at least two of trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, tripropylene glycol diacrylate, dipropylene glycol diacrylate, or triethylene glycol methyl diacrylate.

[0038] Preferably, the tackifier comprises any one or a combination of at least two of γ-aminopropyltriethoxysilane, γ-methacryloyloxypropyltrimethoxysilane, or γ-(2,3-epoxypropoxy)propyltrimethoxysilane.

[0039] Preferably, the light stabilizer comprises any one or a combination of at least two of bis(2,2,6,6-tetramethyl-4-piperidinyl) sebacate, bis(1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate, or polysuccinate (4-hydroxy-2,2,6,6-tetramethyl-1-piperidinol).

[0040] Preferably, the ultraviolet absorber comprises any one or a combination of at least two of 2-(2-hydroxy-3-tert-butyl-5-methylphenyl)-5-chlorobenzotriazole, 2-(2-hydroxy-5-tert-octyl)phenylbenzotriazole, 2-(2-hydroxy-3,5-dicumylphenyl)benzotriazole, or 2-hydroxy-4-n-octyloxybenzophenone.

[0041] In a second aspect, the present invention provides a method for preparing a POE film for preventing the precipitation of additives as described in the first aspect, the method comprising the following steps:

[0042] The initiator, crosslinking agent, thickener, surfactant and water in the formula are mixed to obtain a mixture. Then cyclodextrin hydrogel is added. After the cyclodextrin hydrogel has completely absorbed the mixture, it is taken out, dried and ground into powder. Then POE resin, light stabilizer and ultraviolet absorber are added and mixed again. The mixture is melt-extruded and cast to obtain the POE film that prevents the precipitation of the additives.

[0043] Preferably, the remixing temperature is 30-40℃, such as 30℃, 35℃ or 40℃, and the remixing time is 4-6h, such as 4h, 5h or 6h.

[0044] Preferably, the temperature of the melt extrusion is 90-110°C, such as 90°C, 95°C, 100°C, 105°C, or 110°C.

[0045] Compared with the prior art, the present invention has at least the following beneficial effects:

[0046] The cyclodextrin hydrogel provided by this invention swells in water, with the outer surface of the cyclodextrin absorbing moisture and the inner cavity of the cyclodextrin absorbing oily liquid additives (initiators, crosslinking agents, and thickeners). After vacuum drying, the external moisture is removed while the internal oily additives are retained. When used as a raw material for preparing POE resin to make POE films, the precipitation of liquid additives can be prevented. Detailed Implementation

[0047] The technical solution of the present invention will be further illustrated below through specific embodiments. Those skilled in the art should understand that the embodiments described are merely illustrative of the present invention and should not be construed as limiting the invention in any way.

[0048] Preparation Example 1

[0049] This preparation example provides a cyclodextrin hydrogel, which is prepared by the following method:

[0050] (1) β-cyclodextrin and maleic anhydride (MAH) were dissolved in 4 times the total mass of dimethylformamide (DMF) at a mass ratio of 1:1. Nitrogen gas was introduced and the mixture was stirred at a constant temperature of 80°C for 10 h. After the reaction was completed, the mixture was cooled to room temperature, and the product was precipitated with chloroform. After washing with acetone, the product was dried under vacuum to obtain MAH-β-CD.

[0051] (2) MAH-β-CD, acrylic acid and azobisisobutyronitrile were dissolved in 3 times the total mass of dimethylformamide at a mass ratio of 1:1:0.05. After nitrogen deoxygenation for 30 min, the mixture was reacted at 70 °C for 24 h. The product was precipitated with diethyl ether. The precipitated product was then soaked in distilled water, and the distilled water was changed every 12 h. After 3 days, the product was taken out and dried, and then vacuum dried to constant weight to obtain the cyclodextrin hydrogel.

[0052] Example 1

[0053] This embodiment provides a POE film to prevent the precipitation of additives. The raw materials for preparing the POE film to prevent the precipitation of additives include the following components by weight:

[0054]

[0055] Among them, the POE resin is designated as Dow's ENGAGE. TM PV 8660 and ENGAGE TM PV 8669, with a mass ratio of 1:1, was prepared as a cyclodextrin hydrogel from Preparation Example 1. The initiator was tert-butyl peroxycarbonate isopropyl, the co-crosslinking agent was trimethylolpropane triacrylate, the thickener was γ-aminopropyltriethoxysilane, the surfactant was BYK-333, the light stabilizer was bis(2,2,6,6-tetramethyl-4-piperidinyl) sebacate, and the ultraviolet absorber was 2-(2-hydroxy-3-tert-butyl-5-methylphenyl)-5-chlorobenzotriazole.

[0056] The preparation method includes the following steps:

[0057] The initiator, crosslinking agent, thickener, surfactant and water (13 parts) in the formula are mixed to obtain a mixture. Then, cyclodextrin hydrogel is added. After the cyclodextrin hydrogel has completely absorbed the mixture, it is taken out, dried and ground into powder. Then, POE resin, light stabilizer and ultraviolet absorber are added. The mixture is stirred and mixed at 30°C for 6 hours. It is then melt-extruded at 90°C and cast to obtain the POE film that prevents the precipitation of the additives.

[0058] Example 2

[0059] This embodiment provides a POE film to prevent the precipitation of additives. The raw materials for preparing the POE film to prevent the precipitation of additives include the following components by weight:

[0060]

[0061] Among them, the POE resin is designated as Dow's ENGAGE. TM PV 8660 and ENGAGE TM PV 8669, with a mass ratio of 1:1, was prepared as a cyclodextrin hydrogel by Preparation Example 1. The initiator was 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexane, the co-crosslinking agent was trimethylolpropane trimethacrylate, the thickener was γ-methacryloyloxypropyltrimethoxysilane, the surfactant was BYK-333, the light stabilizer was bis(1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate, and the ultraviolet absorber was 2-(2-hydroxy-5-tert-octyl)phenylbenzotriazole.

[0062] The preparation method includes the following steps:

[0063] The initiator, crosslinking agent, thickener, surfactant and water (19 parts) in the formula are mixed to obtain a mixture. Then, cyclodextrin hydrogel is added. After the cyclodextrin hydrogel has completely absorbed the mixture, it is taken out, dried and ground into powder. Then, POE resin, light stabilizer and ultraviolet absorber are added. The mixture is stirred and mixed at 30°C for 6 hours. It is then melt-extruded at 90°C and cast to obtain the POE film that prevents the precipitation of the additives.

[0064] Example 3

[0065] This embodiment provides a POE film to prevent the precipitation of additives. The raw materials for preparing the POE film to prevent the precipitation of additives include the following components by weight:

[0066]

[0067] Among them, the POE resin is designated as Dow's ENGAGE. TM PV 8660 and ENGAGE TM PV 8669, with a mass ratio of 1:1, was prepared as a cyclodextrin hydrogel according to Preparation Example 1. The initiator was 1-bis(tert-butylperoxide)-3,3,5-trimethylcyclohexane, the co-crosslinking agent was triethylene glycol methyl diacrylate, the thickener was γ-(2,3-epoxypropoxy)propyltrimethoxysilane, the surfactant was BYK-333, the light stabilizer was poly(4-hydroxy-2,2,6,6-tetramethyl-1-piperidineethanol) ester, and the ultraviolet absorber was 2-(2-hydroxy-3,5-dicumylphenyl)benzotriazole.

[0068] The preparation method includes the following steps:

[0069] The initiator, crosslinking agent, thickener, surfactant and water (60 parts) in the formula are mixed to obtain a mixture. Then, cyclodextrin hydrogel is added. After the cyclodextrin hydrogel has completely absorbed the mixture, it is taken out, dried and ground into powder. Then, POE resin, light stabilizer and ultraviolet absorber are added. The mixture is stirred and mixed at 30°C for 6 hours. It is then melt-extruded at 90°C and cast to obtain the POE film that prevents the precipitation of the additives.

[0070] Example 4

[0071] This embodiment provides a POE film to prevent the precipitation of additives. The raw materials for preparing the POE film to prevent the precipitation of additives include the following components by weight:

[0072]

[0073] Among them, the POE resin is designated as Dow's ENGAGE. TM PV 8660 and ENGAGETM PV 8669, with a mass ratio of 1:1, was prepared as a cyclodextrin hydrogel from Preparation Example 1. The initiator was tert-butyl peroxycarbonate isopropyl, the co-crosslinking agent was trimethylolpropane triacrylate, the thickener was γ-aminopropyltriethoxysilane, the surfactant was BYK-333, the light stabilizer was bis(2,2,6,6-tetramethyl-4-piperidinyl) sebacate, and the ultraviolet absorber was 2-(2-hydroxy-3-tert-butyl-5-methylphenyl)-5-chlorobenzotriazole.

[0074] The initiator, crosslinking agent, thickener, surfactant and water (30 parts) in the formula are mixed to obtain a mixture. Then, cyclodextrin hydrogel is added. After the cyclodextrin hydrogel has completely absorbed the mixture, it is taken out, dried and ground into powder. Then, POE resin, light stabilizer and ultraviolet absorber are added. The mixture is stirred and mixed at 30°C for 6 hours. It is then melt-extruded at 90°C and cast to obtain the POE film that prevents the precipitation of the additives.

[0075] Comparative Example 1

[0076] This comparative example provides a POE film, the raw materials for preparing the POE film comprising the following components by weight:

[0077]

[0078] Among them, the POE resin is designated as Dow's ENGAGE. TM PV 8660 and ENGAGE TM PV 8669, with a mass ratio of 1:1, uses tert-butyl peroxycarbonate as the initiator, trimethylolpropane triacrylate as the co-crosslinking agent, γ-aminopropyltriethoxysilane as the tackifier, BYK-333 as the surfactant, bis(2,2,6,6-tetramethyl-4-piperidinyl) sebacate as the light stabilizer, and 2-(2-hydroxy-3-tert-butyl-5-methylphenyl)-5-chlorobenzotriazole as the UV absorber.

[0079] The preparation method includes the following steps:

[0080] The POE resin, initiator, crosslinking agent, tackifier, surfactant, light stabilizer and UV absorber in the specified amounts were stirred and mixed at 30°C for 6 hours, then melt-extruded at 90°C and cast to obtain the POE film.

[0081] Comparative Example 2

[0082] This comparative example provides a POE film, the raw materials for preparing the POE film comprising the following components by weight:

[0083]

[0084] Among them, the POE resin is designated as Dow's ENGAGE. TM PV 8660 and ENGAGE TM PV 8669, with a mass ratio of 1:1, uses 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexane as the initiator, trimethylolpropane trimethacrylate as the co-crosslinking agent, γ-methacryloyloxypropyltrimethoxysilane as the tackifier, BYK-333 as the surfactant, bis(1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate as the light stabilizer, and 2-(2-hydroxy-5-tertoctyl)phenylbenzotriazole as the UV absorber.

[0085] The preparation method is the same as that of Comparative Example 1.

[0086] Comparative Example 3

[0087] This comparative example provides a POE film, the raw materials for preparing the POE film comprising the following components by weight:

[0088]

[0089]

[0090] Among them, the POE resin is designated as Dow's ENGAGE. TM PV 8660 and ENGAGE TM PV 8669, with a mass ratio of 1:1, uses 1-bis(tert-butylperoxide)-3,3,5-trimethylcyclohexane as the initiator, triethylene glycol methyl diacrylate as the co-crosslinking agent, γ-(2,3-epoxypropoxy)propyltrimethoxysilane as the tackifier, BYK-333 as the surfactant, poly(4-hydroxy-2,2,6,6-tetramethyl-1-piperidineethanol) ester as the light stabilizer, and 2-(2-hydroxy-3,5-dicumylphenyl)benzotriazole as the UV absorber.

[0091] The preparation method is the same as that of Comparative Example 1.

[0092] Comparative Example 4

[0093] This comparative example provides a POE film, the raw materials for preparing the POE film comprising the following components by weight:

[0094]

[0095] Among them, the POE resin is designated as Dow's ENGAGE. TM PV 8660 and ENGAGE TMPV 8669, with a mass ratio of 1:1, was prepared as a cyclodextrin hydrogel from Preparation Example 1. The initiator was tert-butyl peroxycarbonate isopropyl, the co-crosslinking agent was trimethylolpropane triacrylate, the thickener was γ-aminopropyltriethoxysilane, the surfactant was BYK-333, the light stabilizer was bis(2,2,6,6-tetramethyl-4-piperidinyl) sebacate, and the ultraviolet absorber was 2-(2-hydroxy-3-tert-butyl-5-methylphenyl)-5-chlorobenzotriazole.

[0096] The preparation method includes the following steps:

[0097] First, the cyclodextrin hydrogel is ground into powder. Then, the formulated amounts of POE resin, initiator, crosslinking agent, thickener, surfactant, light stabilizer and UV absorber are stirred and mixed at 30°C for 6 hours. The mixture is then melt-extruded at 90°C and cast to obtain the POE film.

[0098] The performance of the POE films provided in the examples and comparative examples was tested using the following methods:

[0099] (1) Peel strength from glass: Tested according to the method in GB / T 29848-2018 Ethylene-vinyl acetate copolymer (EVA) film for photovoltaic module encapsulation;

[0100] (2) Crosslinking degree: Tested according to the method in GB / T 29848-2018 Ethylene-vinyl acetate copolymer (EVA) film for photovoltaic module encapsulation.

[0101] The performance test results are shown in Table 1.

[0102] Table 1

[0103]

[0104]

[0105] As can be seen from Table 1, the POE films provided in Examples 1-4 of the present invention showed little decrease in peel strength and crosslinking degree after being placed at 25°C and 50°C for 90 days, respectively, indicating that the amount of liquid additives precipitated was low.

[0106] Compared with Examples 1-3, the POE films provided in Comparative Examples 1-3 showed greater attenuation in peel strength and crosslinking degree after being placed at 25°C and 50°C for 90 days, respectively, indicating a higher amount of liquid additives precipitated.

[0107] Compared with Example 1, the POE film provided in Comparative Example 4 showed a greater decrease in peel strength and crosslinking degree to glass after being placed at 25°C and 50°C for 90 days, respectively, indicating that the amount of liquid additives precipitated was higher.

[0108] The applicant declares that the present invention illustrates the POE film for preventing the precipitation of additives and its preparation method through the above embodiments, but the present invention is not limited to the above embodiments, that is, it does not mean that the present invention must rely on the above embodiments to be implemented. Those skilled in the art should understand that any improvements to the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific methods, etc., all fall within the protection scope and disclosure scope of the present invention.

Claims

1. A POE film for preventing the precipitation of additives, characterized in that, The raw materials for preparing the POE film that prevents the exudation of additives include the following components by weight: 100 parts of POE resin 2-12 parts of cyclodextrin hydrogel Initiator 0.4-2 parts 0.4-2 parts of crosslinking agent 0.2-2 parts of tackifier Surfactant 0.02-0.15 parts Light stabilizer 0.05-1.5 parts 0.05-1.5 parts of ultraviolet absorber; The cyclodextrin hydrogel was prepared by the following method: (1) Dissolve β-cyclodextrin and maleic anhydride in dimethylformamide, react, and then process to obtain MAH-β-CD; (2) Dissolve MAH-β-CD, acrylic acid and azobisisobutyronitrile in dimethylformamide, react, precipitate, soak the precipitated product in distilled water, change the distilled water every 10-12 h, take it out and air dry after 2-4 days, vacuum dry to constant weight, and obtain the cyclodextrin hydrogel. The method for preparing POE film to prevent the precipitation of additives includes the following steps: The initiator, crosslinking agent, thickener, surfactant and water in the formula are mixed to obtain a mixture. Then cyclodextrin hydrogel is added. After the cyclodextrin hydrogel has completely absorbed the mixture, it is taken out, dried and ground into powder. Then POE resin, light stabilizer and ultraviolet absorber are added and mixed again. The mixture is melt-extruded and cast to obtain the POE film that prevents the precipitation of the additives.

2. The POE film for preventing additive precipitation according to claim 1, characterized in that, The mass ratio of β-cyclodextrin to maleic anhydride is 1:(0.8-1.2).

3. The POE film for preventing additive exudation according to claim 1 or 2, characterized in that, The mass ratio of the sum of the β-cyclodextrin and maleic anhydride to the mass of the dimethylformamide is 1:(3-5).

4. The POE film for preventing additive exudation according to claim 1 or 2, characterized in that, The reaction described in step (1) is carried out under an inert gas.

5. The POE film for preventing additive precipitation according to claim 1 or 2, characterized in that, The reaction temperature in step (1) is 70-90℃, and the reaction time is 8-12 h.

6. The POE film for preventing additive exudation according to claim 1 or 2, characterized in that, The post-processing in step (1) includes precipitation, washing, and drying.

7. The POE film for preventing additive precipitation according to claim 1 or 2, characterized in that, The mass ratio of MAH-β-CD, acrylic acid, and azobisisobutyronitrile is 1:1:(0.04-0.06).

8. The POE film for preventing the precipitation of additives according to claim 1 or 2, characterized in that, The mass ratio of the sum of the masses of MAH-β-CD, acrylic acid, and azobisisobutyronitrile to the mass of the dimethylformamide is 1:(2-4).

9. The POE film for preventing additive precipitation according to claim 1, characterized in that, Before the reaction described in step (2), the system is purged with nitrogen to remove oxygen for 20-40 min.

10. The POE film for preventing additive precipitation according to claim 1 or 9, characterized in that, The reaction temperature in step (2) is 60-80℃, and the reaction time is 20-30 h.

11. The POE film for preventing additive precipitation according to claim 1, characterized in that, The POE resin has a melting point of 70-80℃ and a melt index of 5-14 g / 10min.

12. The POE film for preventing the precipitation of additives according to claim 1 or 11, characterized in that, The initiator includes any one or a combination of at least two of the following: tert-butyl peroxycarbonate, 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexane, or 1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane.

13. The POE film for preventing the precipitation of additives according to claim 1 or 11, characterized in that, The co-crosslinking agent includes any one or a combination of at least two of the following: trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, tripropylene glycol diacrylate, dipropylene glycol diacrylate, or triethylene glycol methyl diacrylate.

14. The POE film for preventing the precipitation of additives according to claim 1 or 11, characterized in that, The tackifier includes any one or a combination of at least two of γ-aminopropyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, or γ-(2,3-epoxypropoxy)propyltrimethoxysilane.

15. The POE film for preventing the precipitation of additives according to claim 1 or 11, characterized in that, The light stabilizer comprises any one or a combination of at least two of bis(2,2,6,6-tetramethyl-4-piperidinyl) sebacate, bis(1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate, or polysuccinate (4-hydroxy-2,2,6,6-tetramethyl-1-piperidinol).

16. The POE film for preventing the precipitation of additives according to claim 1 or 11, characterized in that, The ultraviolet absorber includes any one or a combination of at least two of 2-(2-hydroxy-3-tert-butyl-5-methylphenyl)-5-chlorobenzotriazole, 2-(2-hydroxy-5-tert-octyl)phenylbenzotriazole, 2-(2-hydroxy-3,5-dicumylphenyl)benzotriazole, or 2-hydroxy-4-n-octyloxybenzophenone.

17. A method for preparing a POE film for preventing the precipitation of additives as described in any one of claims 1-16, characterized in that, The preparation method includes the following steps: The initiator, crosslinking agent, thickener, surfactant and water in the formula are mixed to obtain a mixture. Then cyclodextrin hydrogel is added. After the cyclodextrin hydrogel has completely absorbed the mixture, it is taken out, dried and ground into powder. Then POE resin, light stabilizer and ultraviolet absorber are added and mixed again. The mixture is melt-extruded and cast to obtain the POE film that prevents the precipitation of the additives.

18. The preparation method according to claim 17, characterized in that, The remixing temperature is 30-40℃, and the remixing time is 4-6 h.

19. The preparation method according to claim 17, characterized in that, The temperature of the melt extrusion is 90-110℃.

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