Anti-delamination EPE co-extrusion packaging adhesive film based on dynamic cross-linking and preparation method of anti-delamination EPE co-extrusion packaging adhesive film

Abstract

The invention belongs to the field of photovoltaic materials. The invention relates to an anti-delamination EPE (Expandable Polyethylene) co-extrusion packaging adhesive film based on dynamic crosslinking, which comprises three layers arranged in sequence, namely an EVA (Ethylene Vinyl Acetate) layer I, a POE (Polyolefin Elastomer) layer and an EVA layer II, the thickness of the EVA layer I is 50 to 150 [mu] m; the thickness of the POE layer is 150 to 350 [mu] m; the thickness of the EVA layer II is 50 to 150 [mu] m; the first EVA layer, the POE layer and the second EVA layer all contain disulfide bond structures with dynamic reaction. The raw materials in the EVA layer and the POE layer are compounded by using a self-made functional auxiliary agent I and a self-made functional auxiliary agent II, the materials are blended according to the formula, the blended materials are injected into a double-screw extruder for three-layer co-extrusion, and film casting is performed to obtain the anti-delamination EPE co-extrusion packaging adhesive film based on dynamic crosslinking. The novel EPE adhesive film effectively solves the problem that in the prior art, an assistant is migrated to an interface, so that layering between an EVA adhesive film layer and a POE adhesive film layer in the later period is caused, and the service life of a material is influenced.

Description

Technical Field

[0001] The invention relates to an anti-stripping EPE co-extruded packaging film based on dynamic cross-linking and a preparation method thereof. The invention belongs to the field of photovoltaic materials. Background Art

[0002] Photovoltaic encapsulation film is one of the key materials that affects the service life and power generation of photovoltaic modules. The technical research and development and upgrading of photovoltaic encapsulation film have a driving significance for the development of the photovoltaic industry. In addition to the two main encapsulation films of EVA and POE, a new type of composite film (EPE) has gradually developed in the industry. It is obtained by co-extruding EVA and POE, with POE as the middle layer and EVA as the outer layer on both sides, and the film product is obtained by compounding. This kind of film solves the adhesion problem of POE film and the PID effect problem of EVA film, and can reduce costs and increase efficiency to a certain extent. However, EPE film has problems such as delamination of EVA and POE, migration of POE layer additives (mainly migration of cross-linking agents and silane coupling agents), etc., which affect the service life of EPE film and seriously hinder the widespread application of EPE film.

[0003] There are currently two conventional methods to solve the problem of interlayer bonding of EPE film. One is to make the additives macromolecular, but this also affects the dispersion of the additives in the matrix, thereby affecting the material performance; the other is to solve the interface delamination problem of EVA and POE layers through compatibilizers, but there is currently no effective means to make the compatibilizer exist at the interface as much as possible and play a role. Moreover, photovoltaics are used in harsh outdoor environments, and simple compatibility is difficult to maintain long-term interlayer bonding. In addition, there is a risk of damage such as cracks or breaks in the film during transportation, installation, and use. When the above situation occurs, on the one hand, it will cause a rapid decrease in the bonding and peeling force, and on the other hand, it will expose the encapsulated object to the external environment, increasing its possibility of damage, which will greatly reduce the utilization rate and efficiency of the final encapsulated components, directly affecting the service life. Summary of the invention

[0004] The purpose of the present invention is to provide a delamination-resistant EPE co-extruded packaging film based on dynamic cross-linking and a preparation method thereof, in order to solve the defects of the prior art that the EPE film has a large difference in polarity between POE and EVA, which causes the additives in POE to migrate to the interface, thereby causing the film to age too quickly in the later stage, and the stratification problem between the EVA film layer and the POE film layer, thereby affecting the service life of the material. The present invention prepares self-made functional additives I and II through molecular design, and after compounding and using them through formula design, they are prepared by three-layer co-extrusion technology, which can effectively solve the above problems and has a broad application space. The technical solution adopted by the present invention to solve its technical problems is: The invention provides an anti-peeling layer EPE co-extruded packaging film based on dynamic cross-linking. The EPE packaging film comprises three layers arranged in sequence, namely a first EVA layer, a POE layer, and a second EVA layer; the thickness of the first EVA layer is 50-150 μm; the thickness of the POE layer is 150-350 μm; the thickness of the second EVA layer is 50-150 μm; the first EVA layer, the POE layer, and the second EVA layer all contain a disulfide bond structure with dynamic reaction.

[0005] The POE layer comprises the following raw materials in parts by weight: POE resin 100 parts; Cross-linking agent 0.5-1.5 parts; Functional additive I 6.0-12.0 parts; Functional additive II 3.0-6.0 parts; Antioxidant 0.05-0.30 parts; Light stabilizer 0.05-0.30 parts; The first EVA layer and the second EVA layer include the following raw materials in parts by weight: EVA resin 100 parts; Cross-linking agent 0.5-1.5 parts; Functional additive I 5.0-10.0 parts; Functional additive II 2.5-5.0 parts; Antioxidant 0.1-0.5 parts; Light stabilizer 0.1-0.5 parts; Silane coupling agent 0.2-0.5 parts; The preparation method of the functional additive I comprises the following steps: S11, performing silylation coupling reaction on nano-silicon and aminosilane coupling agent to obtain intermediate product 1I; The dosage ratio of the nano-silicon to the aminosilane coupling agent is 1g:3.0-5.0g; S12, subjecting the intermediate product 1I to urea reaction with an asymmetric diisocyanate to obtain an intermediate product 1II; The intermediate product 1I and the asymmetric diisocyanate are added at a molar ratio of amino group to isocyanate group of 1:2; S13, reacting the intermediate 1II with 2,2'-dithiodiethanol to obtain the intermediate 1III; The intermediate product III and 2,2'-dithiodiethanol are added at a molar ratio of isocyanate group to hydroxyl group of 1:2; S14, subjecting the intermediate product 1III to a nucleophilic addition reaction with an electrophilic reagent containing a carbon-carbon double bond to obtain a target product, i.e., a functional additive I; The preparation method of the functional additive II comprises the following steps: S21, 2,2'-dithiodiethanol undergoes a nucleophilic addition reaction with an electrophilic reagent containing a carbon-carbon double bond to obtain an intermediate product 2I; S22, subjecting the intermediate product 2I, acrylate, and acrylamide to a free radical polymerization reaction to obtain a target product, i.e., a functional additive II; The molar ratio of the intermediate product 2I, acrylate and acrylamide is 0.6-0.8: 0.05-0.15: 0.15-0.25.

[0006] Furthermore, the asymmetric diisocyanate is toluene diisocyanate or isophorone diisocyanate.

[0007] Further, The structure containing a carbon-carbon double bond is a vinyl structure or an acryloxy structure; and The electrophilic reagent structure is an acyl structure or an isocyanate structure.

[0008] Furthermore, the acrylate includes hydroxy acrylate.

[0009] Furthermore, the octene content in the POE resin is 20-35wt%.

[0010] Furthermore, the functional additive I and the functional additive II are added in a mass ratio of 1.5-2.5:1.

[0011] Furthermore, the antioxidant is a mixture of a hindered phenol antioxidant and a phosphite antioxidant in a mass ratio of 1:1-3.

[0012] Furthermore, the light stabilizer is a mixture of a hindered amine light stabilizer and an ultraviolet absorber in a mass ratio of 1:1-3.

[0013] Another object of the present invention is to provide a method for preparing a delamination-resistant EPE co-extruded packaging film based on dynamic cross-linking, comprising the following steps: S31, mixing, i.e. The raw materials of each layer are mixed and configured according to the formula in a mixer to obtain mixed raw materials for standby use; S32, co-extrusion, i.e. The POE layer raw materials are placed in a twin-screw extruder for melt blending; the EVA layer raw materials are placed in a twin-screw extruder for melt blending, and the materials are discharged through a co-extrusion cast film die, pulled, and stretched; S33, film formation, i.e. The anti-stripping layer EPE co-extruded packaging film is obtained through thickness measurement, edge pressing, shaping, edge cutting and winding.

[0014] Further, The POE layer extrusion process is as follows: barrel temperature 85-110°C, rotation speed 45-50rpm; and The EVA layer extrusion process is as follows: barrel temperature is 75-105° C. and rotation speed is 45-50 rpm.

[0015] Beneficial effects of the present invention: (1) The present invention provides an anti-delamination EPE co-extruded packaging film based on dynamic cross-linking, wherein each layer of the EPE formulation system contains a self-made functional additive I, which is a hyperbranched structure with nano-silicon as the core and an organic chain embedded; wherein the organic chain is a siloxane, containing a urea group, a carbamate (or ester group), a disulfide bond, and a structure with a carbon-carbon double bond as the end cap. First, the nano-silicon structure has excellent optical properties, such as uniform light and increased transmittance, which can improve the light absorption efficiency; second, the urea and carbamate (or ester) structures are polar groups, which can adsorb polar additives in the formula system and reduce the overall mobility of the additives, thereby improving the interlayer bonding force of the film; third, the carbon-carbon double bond of the terminal group can be used as a co-crosslinking agent to increase the crosslinking density of the system and improve the mechanical properties; at the same time, it can improve the low mobility of the polar additives in the POE layer; fourth, when the film is processed and used in subsequent extreme environments, the disulfide bond structure in the organic chain has a dynamic reaction effect, which can generate new chemical bonds at the broken bonds, and has the function of self-repair to increase the service life of the film; at the same time, the functional additive I is a hyperbranched stereostructure, which further increases the contact probability between the disulfide bonds and improves the performance.

[0016] (2) The present invention provides an anti-peeling EPE co-extruded packaging film based on dynamic cross-linking. The EPE formulation system of each layer contains a self-made functional additive II, which is a macromolecule containing carbamate (or ester group) and disulfide bond structure in the main chain; the side chain contains hydroxyl group and part of the disulfide bond structure. First, the macromolecular chain structure has a large chain entanglement with the matrix resin and has low mobility; second, the polar groups in the macromolecular chain can also adsorb the polar additive in the formulation system, reduce the overall mobility of the additive, and improve the interlayer bonding force; third, the disulfide bonds in the main chain and side chain structure also have a dynamic reaction effect, while increasing the structural unit density of the disulfide bond and improving the reaction efficiency.

[0017] (3) The present invention provides an anti-delamination EPE co-extruded packaging film based on dynamic cross-linking, in which the self-made functional additive I and functional additive II are compounded and used in the EPE formulation system of each layer. First, the hyperbranched structure of functional additive I and the linear macromolecular structure of functional additive II form a "point-line combination", so that the dynamic reaction is effectively filled and dispersed in the entire system; second, functional additive I is a hyperbranched structure and contains a siloxane structure, which has better fluidity and a higher distribution density at the interface during processing, effectively exerting the dynamic cross-linking reaction of disulfide bonds at the interface, improving the interface bonding force, and avoiding delamination and performance failure.

[0018] (4) The present invention provides a method for preparing an anti-delamination EPE co-extruded packaging film based on dynamic cross-linking. By using the co-extrusion technology, the EPE layer can be bonded in a softened state, thereby further improving the interlayer bonding strength and extending the service life. DETAILED DESCRIPTION

[0019] The present invention is described in detail below with reference to the examples. However, it should be understood that the following examples are only illustrative of the embodiments of the present invention, and are not intended to limit the scope of the present invention.

[0020] The purpose of the present invention is to develop an anti-delamination EPE co-extruded packaging film based on dynamic cross-linking to meet the application requirements of existing photovoltaic packaging materials. The idea of ​​implementation is: the currently commonly used small molecule additives are macromolecularized and the use of compatibilizers has certain problems. The present invention takes a different approach and adopts dynamic reaction cross-linking technology. The EVA layer and the POE layer are designed to contain chemical structures that can react dynamically, which can ensure the presence of chemical reactions at the interface and improve the interlayer bonding force through chemical bonds, which has better effects; at the same time, the chemical structure that can react dynamically also has the function of self-repair, which improves the ultimate service life of the EPE film. Specifically, functional additives I and II are designed, wherein functional additives I are hyperbranched structures, which can provide a large number of chemical structures with dynamic reactions; functional additives II are linear macromolecular structures, and both the main chain and the side chain can react dynamically; compounding functional additives I and functional additives II can effectively fill the matrix material and have efficient reaction sites. More specifically: Functional additive I has nanosilicon as the branching center and disulfide bond structure as the branching chain; Functional additive II has disulfide bond structure in both the main chain and the side chain; it can effectively improve the interface reaction and make the EPE film tend to be integrated. The theoretical basis for realization is: for functional additive I, firstly, nanosilicon and aminosilane coupling agent are subjected to silane coupling reaction, then nucleophilic addition reaction is carried out with asymmetric diisocyanate to obtain isocyanate-terminated nanosilicon, then nucleophilic addition reaction is carried out with 2,2'-dithiodiethanol to obtain hydroxyl-terminated nanosilicon containing disulfide bond structure, and finally reacted with electrophilic reagent containing carbon-carbon double bond to obtain nanosilicon containing carbon-carbon double bond, which is functional additive I; for functional additive II, firstly, 2,2'-dithiodiethanol is reacted with electrophilic reagent containing carbon-carbon double bond to obtain disulfide bond structure containing carbon-carbon double bond, and then free radical copolymerization is carried out with unsaturated structure to obtain macromolecule containing disulfide bond structure, which is functional additive II. The functional additives I and II are compounded and added to the formula system, and three-layer co-extrusion is performed to prepare an EPE film. The EPE film has high inter-layer bonding strength due to chemical bonding between layers, and the surface also has excellent self-healing effect. The embodiments of the present invention are as follows: The embodiment of the present invention provides an anti-stripping layer EPE co-extruded packaging film based on dynamic cross-linking, wherein the EPE packaging film comprises three layers arranged in sequence, namely a first EVA layer, a POE layer, and a second EVA layer; the thickness of the first EVA layer is 50-150 μm; the thickness of the POE layer is 150-350 μm; the thickness of the second EVA layer is 50-150 μm; The POE layer comprises the following raw materials in parts by weight: POE resin 100 parts; Cross-linking agent 0.5-1.5 parts; Functional additive I 6.0-12.0 parts; Functional additive II 3.0-6.0 parts; Antioxidant 0.05-0.30 parts; Light stabilizer 0.05-0.30 parts; The first EVA layer and the second EVA layer include the following raw materials in parts by weight: EVA resin 100 parts; Cross-linking agent 0.5-1.5 parts; Functional additive I 5.0-10.0 parts; Functional additive II 2.5-5.0 parts; Antioxidant 0.1-0.5 parts; Light stabilizer 0.1-0.5 parts; Silane coupling agent 0.2-0.5 parts; The preparation method of the functional additive I comprises the following steps: S11, place nano-silicon in a four-necked flask filled with ethyl acetate A, ultrasonically disperse for 1 hour, add aminosilane coupling agent and deionized water, slowly heat to 70°C, heat and stir for 10 hours; after the reaction is completed, cool to room temperature, filter, wash with ethyl acetate B, and vacuum dry at 80°C to constant weight to obtain intermediate product 1I.

[0021] The dosage ratio of the nano-silicon, ethyl acetate A, aminosilane coupling agent, deionized water and ethyl acetate B is: 1g:50mL:3.0-5.0g:0.60g:150mL.

[0022] The nano-silicon has an average particle size of 100 nm and is purchased from Cabot Corporation.

[0023] The aminosilane coupling agent may be silane coupling agent KH901, silane coupling agent KH902, silane coupling agent KH540, silane coupling agent KH550, silane coupling agent KH602, or silane coupling agent KH792; and preferably, silane coupling agent KH550.

[0024] S12, add the intermediate product 1I to anhydrous N,N-dimethylformamide A, ultrasonicate for 0.5h, and add it dropwise to anhydrous N,N-dimethylformamide B containing asymmetric diisocyanate through a peristaltic pump. After the addition is completed, continue stirring at room temperature for 2-4h. After the reaction is completed, distill under reduced pressure and dry under vacuum at 60°C for 12h to obtain the intermediate product 1II.

[0025] The intermediate product 1I and the asymmetric diisocyanate are added at a molar ratio of amino group to isocyanate group of 1:2; The usage ratio of the anhydrous N,N-dimethylformamide A, the asymmetric diisocyanate, and the anhydrous N,N-dimethylformamide B is 100 mL: 0.1 mol: 300 mL; The asymmetric diisocyanate is toluene diisocyanate or isophorone diisocyanate; The toluene diisocyanate may be toluene-2,3-diisocyanate, toluene-2,4-diisocyanate, toluene-2,5-diisocyanate or toluene-3,4-diisocyanate; and preferably toluene-2,4-diisocyanate; Meanwhile, when the asymmetric diisocyanate is isophorone diisocyanate, S12 can be simplified to S121, that is, S121, add the intermediate product 1I and isophorone diisocyanate to anhydrous N,N-dimethylformamide, ultrasonicate for 0.5 h, stir at room temperature for 2-4 h, and after the reaction is completed, distill under reduced pressure and vacuum dry at 60°C for 12 h to obtain the intermediate product 1II.

[0026] The intermediate product 1I and isophorone diisocyanate are added at a molar ratio of amino group to isocyanate group of 1:2; The dosage ratio of isophorone diisocyanate and anhydrous N,N-dimethylformamide is: 0.1 mol: 400 mL.

[0027] S13, N2 protection, add the intermediate product 1II and dibutyltin dilaurate to anhydrous N,N-dimethylformamide C, stir, add to anhydrous N,N-dimethylformamide D containing 2,2'-dithiodiethanol through a peristaltic pump, stir, react at 30-60°C, and the reaction end point is determined by the result of infrared detection of isocyanate; after the reaction, concentrate the solution, distill under reduced pressure, and dry in vacuum at 80°C for 4h to obtain the intermediate product 1III.

[0028] The intermediate product III and 2,2'-dithiodiethanol are added at a molar ratio of isocyanate group to hydroxyl group of 1:2; The dosage ratio of the anhydrous N,N-dimethylformamide C, 2,2'-dithiodiethanol, and anhydrous N,N-dimethylformamide D is: 100mL: 0.1mol: 300mL; The amount of dibutyltin dilaurate used is 1.0wt% of the mass of 2,2'-dithiodiethanol.

[0029] S14, subjecting the intermediate product 1III to a nucleophilic addition reaction with an electrophilic reagent containing a carbon-carbon double bond to obtain a target product, i.e., a functional additive I; The structure containing a carbon-carbon double bond is a vinyl structure or an acryloxy structure; and The electrophilic reagent structure is an acyl structure or an isocyanate structure.

[0030] When the electrophilic reagent structure is an acyl structure, more specifically an acyl chloride structure, S14 can be specifically S141, that is, S141, protect from light, dissolve the acyl chloride containing carbon-carbon double bond in dichloromethane A and place it in a constant pressure dropping funnel, slowly add it dropwise to dichloromethane B containing intermediate product 1III and triethylamine, ice bath, stir, after the addition is completed, control the temperature to continue stirring at 0-5°C for 8-14h, after the reaction is completed; filter, take the filtrate, add saturated sodium bicarbonate solution to wash 3 times, then wash with deionized water 3 times, separate the liquids, take the organic phase, dry it with anhydrous sodium sulfate, filter, distill the filtrate under reduced pressure, and dry it in a vacuum at 40°C for 12h to obtain the target product, i.e. functional additive I.

[0031] The acyl chloride containing a carbon-carbon double bond and the intermediate product 1III are added at a molar ratio of acyl chloride to hydroxyl of 1:1; The usage ratio of the acyl chloride containing a carbon-carbon double bond, dichloromethane A, triethylamine, dichloromethane B, saturated sodium bicarbonate solution, deionized water, and anhydrous sodium sulfate is 0.1 mol: 100 mL: 0.1 mol: 200 mL: 400 mL: 400 mL: 5 g.

[0032] The acyl chloride containing a carbon-carbon double bond may be acryloyl chloride, 4-pentenoyl chloride, 5-hexenoyl chloride, 10-undecenoyl chloride, etc.; and acryloyl chloride is preferred.

[0033] When the electrophilic reagent structure is an isocyanate structure, S14 can be specifically S142, that is, S142, add the intermediate product 1III, dibutyltin dilaurate, p-hydroxyanisole, and isocyanate containing a carbon-carbon double bond to anhydrous N,N-dimethylformamide E, raise the temperature to 60-80°C, stir for 5-10 hours, let stand, distill under reduced pressure, and vacuum dry at 40°C for 12 hours to obtain the target product, i.e., functional additive I.

[0034] The intermediate product 1III and the isocyanate containing a carbon-carbon double bond are added at a molar ratio of hydroxyl group to isocyanate group of 1:1; The usage ratio of the isocyanate containing a carbon-carbon double bond and anhydrous N,N-dimethylformamide E is: 0.1 mol: 300 mL; The amount of dibutyltin dilaurate is 1wt% of the mass of the isocyanate with carbon-carbon double bonds; The dosage of the p-hydroxyanisole is 1wt% of the mass of the isocyanate with carbon-carbon double bonds.

[0035] The isocyanate containing a carbon-carbon double bond may be isocyanoethyl methacrylate or the like.

[0036] The preparation method of the functional additive II comprises the following steps: S21, 2,2'-dithiodiethanol undergoes a nucleophilic addition reaction with an electrophilic reagent containing a carbon-carbon double bond to obtain an intermediate product 2I; The structure containing a carbon-carbon double bond is a vinyl structure or an acryloxy structure; and The electrophilic reagent structure is an acyl structure or an isocyanate structure.

[0037] Similarly, when the electrophilic reagent structure is an acyl structure, more specifically an acyl chloride structure, S21 can be specifically S211, that is, S211, protect from light, dissolve the acyl chloride containing carbon-carbon double bond in dichloromethane A and place it in a constant pressure dropping funnel, slowly add it dropwise to dichloromethane B containing 2,2'-dithiodiethanol and triethylamine, ice bath, stir, after the addition is completed, control the temperature at 0-5℃ and continue stirring for 8-14h, after the reaction is completed; filter, take the filtrate, add saturated sodium bicarbonate solution to wash 3 times, then wash with deionized water 3 times, separate the liquids, take the organic phase, dry it with anhydrous sodium sulfate, filter, distill the filtrate under reduced pressure, and dry it in a vacuum at 40℃ for 12h to obtain the target product, i.e. functional additive II.

[0038] The acyl chloride containing a carbon-carbon double bond and 2,2'-dithiodiethanol are added at a molar ratio of acyl chloride to hydroxyl of 0.65-0.90:1; The usage ratio of the acyl chloride containing a carbon-carbon double bond, dichloromethane A, triethylamine, dichloromethane B, saturated sodium bicarbonate solution, deionized water, and anhydrous sodium sulfate is 0.1 mol: 100 mL: 0.1 mol: 200 mL: 400 mL: 400 mL: 5 g.

[0039] The acyl chloride containing a carbon-carbon double bond may be acryloyl chloride, 4-pentenoyl chloride, 5-hexenoyl chloride, 10-undecenoyl chloride, etc.; and acryloyl chloride is preferred.

[0040] When the electrophilic reagent structure is an isocyanate structure, S21 can be specifically S212, that is, S212, add p-hydroxyanisole and isocyanate containing carbon-carbon double bonds to anhydrous N,N-dimethylformamide A and place it in a constant pressure dropping funnel, slowly add it dropwise to N,N-dimethylformamide B containing 2,2'-dithiodiethanol and dibutyltin dilaurate, raise the temperature to 60-80°C and stir, continue stirring for 4-6 hours after the addition is completed, let it stand, distill under reduced pressure, and vacuum dry at 40°C for 12 hours to obtain the target product, i.e., functional additive II.

[0041] The isocyanate containing a carbon-carbon double bond and 2,2'-dithiodiethanol are added at a molar ratio of isocyanate group to hydroxyl group of 0.65-0.90:1; The usage ratio of the carbon-carbon double bond-containing isocyanate, anhydrous N,N-dimethylformamide A, and anhydrous N,N-dimethylformamide B is: 0.1 mol: 100 mL: 300 mL; The amount of dibutyltin dilaurate is 1wt% of the mass of the isocyanate with carbon-carbon double bonds; The dosage of the p-hydroxyanisole is 1wt% of the mass of the isocyanate with carbon-carbon double bonds.

[0042] The isocyanate containing a carbon-carbon double bond may be isocyanoethyl methacrylate or the like.

[0043] S22, pass N2, add intermediate product 2I, acrylate, acrylamide, initiator AIBN to anhydrous N,N-dimethylformamide C, heat to 75-85°C, and stir for 6-10h; after the reaction is completed, cool to room temperature, filter, take the filtrate, distill under reduced pressure, inject anhydrous methanol into the concentrate, stir, filter, take the insoluble matter, and place it at 60°C under vacuum and dry for 6h to obtain the target product, i.e. functional additive II.

[0044] The dosage of the intermediate product 2I, acrylate, acrylamide, anhydrous N,N-dimethylformamide C, and anhydrous methanol is 0.6-0.8 mol: 0.05-0.15 mol: 0.15-0.25 mol: 300 mL: 400 mL.

[0045] The acrylate includes hydroxy acrylate; it can also be other acrylates; The hydroxy acrylate may be hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, etc. The other acrylates may be methyl (meth)acrylate, butyl (meth)acrylate, isooctyl (meth)acrylate, dicyclopentyl methacrylate, lauryl acrylate, glycidyl methacrylate, and the like.

[0046] The amount of the initiator AIBN used is 2.0wt% of the total mass of the reactants.

[0047] The functional additive I described in the present invention is a structure with nano-silicon as the branching center and disulfide bonds in the branched chain, which can maximize the dynamic reaction of disulfide bonds; the functional additive II is a macromolecular structure with disulfide bonds in both the main chain and the side chain; among them, the functional additive I (POE level), functional additive II (POE level), functional additive I (EVA level) and functional additive I (EVA level) distributed at the interface can react dynamically with each other; at the same time, the functional additive I is a hyperbranched structure with a wide extension of the branched chain, and the functional additive II is a linear macromolecular structure with a long length; any two-way reaction is conducive to forming chemical bonds at the interface and improving the interface bonding strength.

[0048] Second, the dynamic reaction of the disulfide bond has a self-repairing function, which can repair scratches on the surface of the film, improve light transmittance, mechanical properties, light conversion efficiency, etc., thereby increasing the service life.

[0049] Third, the molecular design of functional additive II has side hydroxyl groups and amide groups, which can assist in capturing free carboxyl groups and Na+ in EVA, and help improve the anti-PID function.

[0050] The octene content in the POE resin of the present invention is 20-35wt%; it can be 20wt%, 25wt%, 30wt%, 35wt% or a range consisting of any two values.

[0051] The crosslinking agent in the present invention is an organic peroxide; specifically, it can be tert-butyl peroxide 2-ethylhexyl carbonate, dibenzoyl peroxide, 2,5-dimethyl-2,5-bis(benzoylperoxide)hexane or 1,1-(tert-butyl peroxide)-3,3,5-trimethylcyclohexane, etc.; and the crosslinking agent in the following embodiments of the present invention is dibenzoyl peroxide.

[0052] The mass ratio of the functional additive I to the functional additive II in the present invention is 1.5-2.5:1.

[0053] The antioxidant in the present invention is a mixture of a hindered phenol antioxidant and a phosphite antioxidant in a mass ratio of 1:1-3; The hindered phenol antioxidant can be antioxidant 1010, antioxidant 1076, antioxidant 264, antioxidant 2246, etc., and antioxidant 1010 is preferred; the phosphite antioxidant can be antioxidant 168, antioxidant 242, antioxidant TPP, etc., and antioxidant 168 is preferred; the antioxidant described in the following embodiments of the present invention is antioxidant 1010 and antioxidant 168 added in a mass ratio of 1:1-3.

[0054] The light stabilizer in the present invention is a mixture of a hindered amine light stabilizer and an ultraviolet absorber in a mass ratio of 1:1-3; The hindered amine light stabilizer can be UV-292, UV-770 or GW540, etc., and UV-292 is preferred; the ultraviolet absorber can be UV-326, UV-327 or UV-531, etc., and UV-531 is preferred; the light stabilizer described in the following embodiments of the present invention is UV-292 and UV-531 added in a mass ratio of 1:1-3.

[0055] The EVA resin described in the present invention has a VA content of 33% and a melt index (MI) of 31, and is purchased from DuPont Company of the United States.

[0056] The silane coupling agent described in the present invention can be a vinyl silane coupling agent, specifically silane coupling agent KH151, silane coupling agent KH171 or silane coupling agent KH172, etc.; and, the silane coupling agent described in the following embodiments of the present invention is silane coupling agent KH172.

[0057] Another object of the embodiment of the present invention is to provide a method for preparing a debonding-resistant EPE co-extruded packaging film based on dynamic cross-linking, comprising the following steps: S31, mixing, i.e. The raw materials of each layer were mixed and configured according to the formula in a mixer, and mixed and stirred at a temperature of 40° C. and a speed of 80 rpm for 2 h to obtain a mixed raw material for standby use; S32, co-extrusion, i.e. The POE layer raw materials are placed in a twin-screw extruder for melt blending; the EVA layer raw materials are placed in a twin-screw extruder for melt blending, and the materials are discharged through a co-extrusion cast film die, pulled, and stretched; The POE layer extrusion process is as follows: barrel temperature 85-110°C, rotation speed 45-50rpm; and The EVA layer extrusion process is as follows: barrel temperature is 75-105° C. and rotation speed is 45-50 rpm.

[0058] S33, film formation, i.e. The anti-stripping layer EPE co-extruded packaging film is obtained through thickness measurement, edge pressing, shaping, edge cutting and winding.

[0059] In order to further understand the present invention, the anti-debonding layer EPE co-extruded packaging film based on dynamic cross-linking provided by the present invention is described in detail below in conjunction with specific embodiments, and the protection scope of the present invention is not limited by the following embodiments.

[0060] Example 1 This embodiment provides an anti-stripping layer EPE co-extruded packaging film based on dynamic cross-linking, wherein the EPE packaging film comprises three layers arranged in sequence, namely a first EVA layer, a POE layer, and a second EVA layer; the thickness of the first EVA layer is 100 μm; the thickness of the POE layer is 250 μm; the thickness of the second EVA layer is 100 μm; The POE layer comprises the following raw materials in parts by weight: POE resin (octene content: 25wt%) 100 parts; 1.0 part of cross-linking agent; Functional additive I 9.0 parts; Functional additive II 4.5 parts; 0.15 parts of antioxidant; Light stabilizer 0.10 parts; The first EVA layer and the second EVA layer include the following raw materials in parts by weight: EVA resin 100 parts; 1.2 parts of cross-linking agent; Functional additive I 7.0 parts; Functional additive II 3.5 parts; 0.3 parts of antioxidant; Light stabilizer 0.25 parts; Silane coupling agent 0.4 parts; The preparation method of the functional additive I comprises the following steps: S11, place nano-silicon in a four-necked flask filled with ethyl acetate A, ultrasonically disperse for 1 hour, add silane coupling agent KH550 and deionized water, slowly heat to 70°C, heat and stir for 10 hours; after the reaction is completed, cool to room temperature, filter, wash with ethyl acetate B, and vacuum dry at 80°C to constant weight to obtain intermediate product 1I.

[0061] The dosage ratio of the nano-silicon, ethyl acetate A, silane coupling agent KH550, deionized water, and ethyl acetate B is: 1g:50mL:4.0g:0.60g:150mL.

[0062] Its infrared data is as follows: 3438cm -1 :-OH weakens; 3320 cm -1 : -NH- sharp peak exists; 1109 cm -1 、797cm -1 :-Si-O- exists.

[0063] S12, add the intermediate product 1I and isophorone diisocyanate to anhydrous N,N-dimethylformamide, ultrasonicate for 0.5 h, stir at room temperature for 3 h, and after the reaction is completed, distill under reduced pressure and vacuum dry at 60°C for 12 h to obtain the intermediate product 1II.

[0064] The intermediate product 1I and isophorone diisocyanate are added at a molar ratio of amino group to isocyanate group of 1:2; The dosage ratio of isophorone diisocyanate and anhydrous N,N-dimethylformamide is: 0.1 mol: 400 mL.

[0065] Its infrared data is as follows: 3438cm -1 :-OH exists; 3320 cm -1 : -NH- peak exists and weakens; 1551 cm -1 : -NH- exists; 1676 cm -1 :-C=O exists; 1109 cm -1 、797cm -1 :-Si-O- exists; 2270 cm -1 :-NCO exists and weakens.

[0066] S13, N2 protection, add the intermediate product 1II and dibutyltin dilaurate to anhydrous N,N-dimethylformamide C, stir, add to anhydrous N,N-dimethylformamide D containing 2,2'-dithiodiethanol through a peristaltic pump, stir, react at 50°C, and the reaction end point is determined by the result of infrared detection of isocyanate; after the reaction, concentrate the solution, distill under reduced pressure, and dry in vacuum at 80°C for 4h to obtain the intermediate product 1III.

[0067] The intermediate product III and 2,2'-dithiodiethanol are added at a molar ratio of isocyanate group to hydroxyl group of 1:2; The dosage ratio of the anhydrous N,N-dimethylformamide C, 2,2'-dithiodiethanol, and anhydrous N,N-dimethylformamide D is: 100mL: 0.1mol: 300mL; The amount of dibutyltin dilaurate used is 1.0wt% of the mass of 2,2'-dithiodiethanol.

[0068] Its infrared data is as follows: 3442cm -1 :-OH exists and enhances; 3320 cm -1 : -NH- sharp peak exists; 1551 cm -1 : -NH- exists; 1702 cm -1 、1676 cm -1 :-C=O exists; 1109 cm -1 、797cm -1 :-Si-O- exists; 2270 cm -1 :-NCO does not exist; 535 cm -1 :-SS- exists.

[0069] S14, add the intermediate product 1III, dibutyltin dilaurate, p-hydroxyanisole, and isocyanoethyl methacrylate to anhydrous N,N-dimethylformamide E, heat to 70°C, stir for 8 hours, let stand, distill under reduced pressure, and vacuum dry at 40°C for 12 hours to obtain the target product, i.e., functional additive I.

[0070] The intermediate product 1III and isocyanoethyl methacrylate are added at a molar ratio of hydroxyl group to isocyanate group of 1:1; The dosage ratio of isocyanoethyl methacrylate and anhydrous N,N-dimethylformamide E is: 0.1 mol: 300 mL; The amount of dibutyltin dilaurate is 1wt% of the mass of isocyanoethyl methacrylate; The dosage of the p-hydroxyanisole is 1wt% of the mass of isocyanoethyl methacrylate.

[0071] Its infrared data is as follows: 3438cm -1 :-OH exists; 3320 cm -1 : -NH- sharp peak exists and is enhanced; 1551 cm -1 :-NH- exists and is enhanced; 1735 cm -1 、1702 cm -1 、1676 cm -1 :-C=O exists; 1605 cm -1 、811 cm -1 :-C=C- exists; 1109 cm -1 、797cm -1 :-Si-O- exists; 2270 cm -1 :-NCO does not exist; 535 cm -1 :-SS- exists.

[0072] The preparation method of the functional additive II comprises the following steps: S21, add p-hydroxyanisole and isocyanoethyl methacrylate to anhydrous N,N-dimethylformamide A and place it in a constant pressure dropping funnel, slowly add it dropwise to N,N-dimethylformamide B containing 2,2'-dithiodiethanol and dibutyltin dilaurate, heat to 70°C and stir, continue stirring for 5.5h after the addition is completed, let it stand, distill under reduced pressure, and vacuum dry at 40°C for 12h to obtain the target product, i.e., functional additive II.

[0073] The isocyanoethyl methacrylate and 2,2'-dithiodiethanol are added at a molar ratio of isocyanate group to hydroxyl group of 0.80:1; The dosage ratio of isocyanoethyl methacrylate, anhydrous N,N-dimethylformamide A, and anhydrous N,N-dimethylformamide B is: 0.1 mol: 100 mL: 300 mL; The amount of dibutyltin dilaurate is 1wt% of the mass of isocyanoethyl methacrylate; The dosage of the p-hydroxyanisole is 1wt% of the mass of isocyanoethyl methacrylate.

[0074] Its infrared data is as follows: 3443cm -1 :-OH exists and weakens; 3320 cm -1 : -NH- sharp peak exists; 1551 cm -1 :-NH- exists; 1735 cm -1 、1702 cm -1 :-C=O exists; 1605 cm -1 、811 cm -1 :-C=C- exists; 2270 cm-1 :-NCO does not exist; 535 cm -1 :-SS- exists.

[0075] S22, pass N2, add the intermediate product 2I, hydroxyethyl acrylate, acrylamide, initiator AIBN to anhydrous N,N-dimethylformamide C, heat to 80°C, and stir for 7.5h; after the reaction, cool to room temperature, filter, take the filtrate, distill under reduced pressure, inject anhydrous methanol into the concentrate, stir, filter, take the insoluble matter, and place it at 60°C for 6h in vacuum drying to obtain the target product, i.e. functional additive II ( ).

[0076] The usage ratio of the intermediate product 2I, hydroxyethyl acrylate, acrylamide, anhydrous N,N-dimethylformamide C, and anhydrous methanol is 0.7 mol: 0.1 mol: 0.2 mol: 300 mL: 400 mL.

[0077] The amount of the initiator AIBN used is 2.0wt% of the total mass of the reactants.

[0078] Its infrared data is as follows: 3443cm -1 :-OH exists and enhances; 3320 cm -1 : -NH- sharp peak exists and is enhanced; 1551 cm -1 :-NH- exists and is enhanced; 1735 cm -1 、1702 cm -1 、1672 cm -1 :-C=O exists and is enhanced; 1605 cm -1 、811 cm -1 :-C=C- does not exist; 535 cm -1 :-SS- exists.

[0079] The antioxidants are antioxidant 1010 and antioxidant 168 added in a mass ratio of 1:2.

[0080] The light stabilizer is UV-292 and UV-531 added in a mass ratio of 1:2.

[0081] Another object of this embodiment is to provide a method for preparing a delamination-resistant EPE co-extruded packaging film based on dynamic cross-linking, comprising the following steps: S31, mixing, i.e. The raw materials of each layer were mixed and configured according to the formula in a mixer, and mixed and stirred for 2 hours at a temperature of 40° C. and a rotation speed of 80 rpm to obtain a mixed raw material for standby use.

[0082] S32, co-extrusion, i.e. The POE layer raw materials are placed in a twin-screw extruder for melt blending; the EVA layer raw materials are placed in a twin-screw extruder for melt blending, and the materials are discharged through a co-extrusion cast film die, pulled, and stretched; The POE layer extrusion process is as follows: the temperature of the barrel zone 1 is 90°C, the temperature of the zone 2 is 100°C, the temperature of the zone 3 is 105°C, the die head temperature is 108°C, and the rotation speed is 50 rpm; and The EVA layer extrusion process is as follows: the temperature of the barrel zone 1 is 80° C., the temperature of the barrel zone 2 is 90° C., the temperature of the barrel zone 3 is 98° C., the die head temperature is 103° C., and the rotation speed is 50 rpm.

[0083] S33, film formation, i.e. The anti-stripping layer EPE co-extruded packaging film is obtained through thickness measurement, edge pressing, shaping, edge cutting and winding.

[0084] Example 2 This embodiment provides an anti-stripping layer EPE co-extruded packaging film based on dynamic cross-linking, wherein the EPE packaging film comprises three layers arranged in sequence, namely a first EVA layer, a POE layer, and a second EVA layer; the thickness of the first EVA layer is 150 μm; the thickness of the POE layer is 150 μm; the thickness of the second EVA layer is 150 μm; The POE layer comprises the following raw materials in parts by weight: POE resin (octene content: 20wt%) 100 parts; 0.5 part of cross-linking agent; Functional additive I 12.0 parts; Functional additive II 6.0 parts; Antioxidant 0.05 parts; Light stabilizer 0.30 parts; The first EVA layer and the second EVA layer include the following raw materials in parts by weight: EVA resin 100 parts; 1.5 parts of cross-linking agent; Functional additive I 5.0 parts; Functional additive II 2.5 parts; Antioxidant 0.1 part; 0.5 parts of light stabilizer; 0.5 parts of silane coupling agent; The preparation method of the functional additive I comprises the following steps: S11, place nano-silicon in a four-necked flask filled with ethyl acetate A, ultrasonically disperse for 1 hour, add silane coupling agent KH550 and deionized water, slowly heat to 70°C, heat and stir for 10 hours; after the reaction is completed, cool to room temperature, filter, wash with ethyl acetate B, and vacuum dry at 80°C to constant weight to obtain intermediate product 1I.

[0085] The dosage ratio of the nano-silicon, ethyl acetate A, silane coupling agent KH550, deionized water, and ethyl acetate B is: 1g:50mL:3.0g:0.60g:150mL.

[0086] S12, add the intermediate product 1I and isophorone diisocyanate to anhydrous N,N-dimethylformamide, ultrasonicate for 0.5 h, stir at room temperature for 4 h, and after the reaction is completed, distill under reduced pressure and vacuum dry at 60°C for 12 h to obtain the intermediate product 1II.

[0087] The intermediate product 1I and isophorone diisocyanate are added at a molar ratio of amino group to isocyanate group of 1:2; The dosage ratio of isophorone diisocyanate and anhydrous N,N-dimethylformamide is: 0.1 mol: 400 mL.

[0088] S13, N2 protection, add the intermediate product 1II and dibutyltin dilaurate to anhydrous N,N-dimethylformamide C, stir, add to anhydrous N,N-dimethylformamide D containing 2,2'-dithiodiethanol through a peristaltic pump, stir, react at 30°C, and the reaction end point is determined by the result of infrared detection of isocyanate; after the reaction, concentrate the solution, distill under reduced pressure, and dry in vacuum at 80°C for 4h to obtain the intermediate product 1III.

[0089] The intermediate product III and 2,2'-dithiodiethanol are added at a molar ratio of isocyanate group to hydroxyl group of 1:2; The dosage ratio of the anhydrous N,N-dimethylformamide C, 2,2'-dithiodiethanol, and anhydrous N,N-dimethylformamide D is: 100mL: 0.1mol: 300mL; The amount of dibutyltin dilaurate used is 1.0wt% of the mass of 2,2'-dithiodiethanol.

[0090] S14, add the intermediate product 1III, dibutyltin dilaurate, p-hydroxyanisole, and isocyanoethyl methacrylate to anhydrous N,N-dimethylformamide E, heat to 80°C, stir for 5 hours, let stand, distill under reduced pressure, and vacuum dry at 40°C for 12 hours to obtain the target product, i.e., functional additive I.

[0091] The intermediate product 1III and isocyanoethyl methacrylate are added at a molar ratio of hydroxyl group to isocyanate group of 1:1; The dosage ratio of isocyanoethyl methacrylate and anhydrous N,N-dimethylformamide E is: 0.1 mol: 300 mL; The amount of dibutyltin dilaurate is 1wt% of the mass of isocyanoethyl methacrylate; The dosage of the p-hydroxyanisole is 1wt% of the mass of isocyanoethyl methacrylate.

[0092] The preparation method of the functional additive II comprises the following steps: S21, add p-hydroxyanisole and isocyanoethyl methacrylate to anhydrous N,N-dimethylformamide A and place it in a constant pressure dropping funnel, slowly add it dropwise to N,N-dimethylformamide B containing 2,2'-dithiodiethanol and dibutyltin dilaurate, heat to 80°C and stir, continue stirring for 4 hours after the addition is completed, let it stand, distill under reduced pressure, and vacuum dry at 40°C for 12 hours to obtain the target product, i.e., functional additive II.

[0093] The isocyanoethyl methacrylate and 2,2'-dithiodiethanol are added at a molar ratio of isocyanate group to hydroxyl group of 0.80:1; The dosage ratio of isocyanoethyl methacrylate, anhydrous N,N-dimethylformamide A, and anhydrous N,N-dimethylformamide B is: 0.1 mol: 100 mL: 300 mL; The amount of dibutyltin dilaurate is 1wt% of the mass of isocyanoethyl methacrylate; The dosage of the p-hydroxyanisole is 1wt% of the mass of isocyanoethyl methacrylate.

[0094] S22, pass N2, add the intermediate product 2I, hydroxyethyl acrylate, acrylamide, initiator AIBN to anhydrous N,N-dimethylformamide C, heat to 75°C, and stir for 10 hours. After the reaction, cool to room temperature, filter, take the filtrate, distill under reduced pressure, inject anhydrous methanol into the concentrate, stir, filter, take the insoluble matter, and place it at 60°C for 6 hours in vacuum to obtain the target product, i.e. functional additive II ( ).

[0095] The usage ratio of the intermediate product 2I, hydroxyethyl acrylate, acrylamide, anhydrous N,N-dimethylformamide C, and anhydrous methanol is 0.7 mol: 0.1 mol: 0.2 mol: 300 mL: 400 mL.

[0096] The amount of the initiator AIBN used is 2.0wt% of the total mass of the reactants.

[0097] The antioxidants are antioxidant 1010 and antioxidant 168 added in a mass ratio of 1:2.

[0098] The light stabilizer is UV-292 and UV-531 added in a mass ratio of 1:2.

[0099] Another object of this embodiment is to provide a method for preparing a delamination-resistant EPE co-extruded packaging film based on dynamic cross-linking, comprising the following steps: S31, mixing, i.e. The raw materials of each layer were mixed and configured according to the formula in a mixer, and mixed and stirred for 2 hours at a temperature of 40° C. and a rotation speed of 80 rpm to obtain a mixed raw material for standby use.

[0100] S32, co-extrusion, i.e. The POE layer raw materials are placed in a twin-screw extruder for melt blending; the EVA layer raw materials are placed in a twin-screw extruder for melt blending, and the materials are discharged through a co-extrusion cast film die, pulled, and stretched; The POE layer extrusion process is as follows: the temperature of the barrel zone 1 is 95°C, the temperature of the zone 2 is 105°C, the temperature of the zone 3 is 110°C, the die head temperature is 110°C, and the rotation speed is 45 rpm; and The EVA layer extrusion process is as follows: the temperature of the barrel zone 1 is 75° C., the temperature of the barrel zone 2 is 85° C., the temperature of the barrel zone 3 is 95° C., the die head temperature is 102° C., and the rotation speed is 50 rpm.

[0101] S33, film formation, i.e. The anti-stripping layer EPE co-extruded packaging film is obtained through thickness measurement, edge pressing, shaping, edge cutting and winding.

[0102] Example 3 This embodiment provides an anti-stripping layer EPE co-extruded packaging film based on dynamic cross-linking, wherein the EPE packaging film comprises three layers arranged in sequence, namely a first EVA layer, a POE layer, and a second EVA layer; the thickness of the first EVA layer is 50 μm; the thickness of the POE layer is 350 μm; the thickness of the second EVA layer is 50 μm; The POE layer comprises the following raw materials in parts by weight: POE resin (octene content: 35wt%) 100 parts; 1.5 parts of cross-linking agent; Functional additive I 6.0 parts; Functional additive II 3.0 parts; Antioxidant 0.30 parts; Light stabilizer 0.05 parts; The first EVA layer and the second EVA layer include the following raw materials in parts by weight: EVA resin 100 parts; 0.5 part of cross-linking agent; Functional additive I 10.0 parts; Functional additive II 5.0 parts; 0.5 parts of antioxidant; Light stabilizer 0.1 part; Silane coupling agent 0.2 parts; The preparation method of the functional additive I comprises the following steps: S11, place nano-silicon in a four-necked flask filled with ethyl acetate A, ultrasonically disperse for 1 hour, add silane coupling agent KH550 and deionized water, slowly heat to 70°C, heat and stir for 10 hours; after the reaction is completed, cool to room temperature, filter, wash with ethyl acetate B, and vacuum dry at 80°C to constant weight to obtain intermediate product 1I.

[0103] The dosage ratio of the nano-silicon, ethyl acetate A, silane coupling agent KH550, deionized water, and ethyl acetate B is: 1g:50mL:5.0g:0.60g:150mL.

[0104] S12, add the intermediate product 1I and isophorone diisocyanate to anhydrous N,N-dimethylformamide, ultrasonicate for 0.5 h, stir at room temperature for 2 h, and after the reaction is completed, distill under reduced pressure and vacuum dry at 60°C for 12 h to obtain the intermediate product 1II.

[0105] The intermediate product 1I and isophorone diisocyanate are added at a molar ratio of amino group to isocyanate group of 1:2; The dosage ratio of isophorone diisocyanate and anhydrous N,N-dimethylformamide is: 0.1 mol: 400 mL.

[0106] S13, N2 protection, add the intermediate product 1II and dibutyltin dilaurate to anhydrous N,N-dimethylformamide C, stir, add to anhydrous N,N-dimethylformamide D containing 2,2'-dithiodiethanol through a peristaltic pump, stir, react at 60°C, and the reaction end point is determined by the result of infrared detection of isocyanate; after the reaction, concentrate the solution, distill under reduced pressure, and dry in vacuum at 80°C for 4h to obtain the intermediate product 1III.

[0107] The intermediate product III and 2,2'-dithiodiethanol are added at a molar ratio of isocyanate group to hydroxyl group of 1:2; The dosage ratio of the anhydrous N,N-dimethylformamide C, 2,2'-dithiodiethanol, and anhydrous N,N-dimethylformamide D is: 100mL: 0.1mol: 300mL; The amount of dibutyltin dilaurate used is 1.0wt% of the mass of 2,2'-dithiodiethanol.

[0108] S14, add the intermediate product 1III, dibutyltin dilaurate, p-hydroxyanisole, and isocyanoethyl methacrylate to anhydrous N,N-dimethylformamide E, heat to 60°C, stir for 10 hours, let stand, distill under reduced pressure, and vacuum dry at 40°C for 12 hours to obtain the target product, i.e., functional additive I.

[0109] The intermediate product 1III and isocyanoethyl methacrylate are added at a molar ratio of hydroxyl group to isocyanate group of 1:1; The dosage ratio of isocyanoethyl methacrylate and anhydrous N,N-dimethylformamide E is: 0.1 mol: 300 mL; The amount of dibutyltin dilaurate is 1wt% of the mass of isocyanoethyl methacrylate; The dosage of the p-hydroxyanisole is 1wt% of the mass of isocyanoethyl methacrylate.

[0110] The preparation method of the functional additive II comprises the following steps: S21, add p-hydroxyanisole and isocyanoethyl methacrylate to anhydrous N,N-dimethylformamide A and place it in a constant pressure dropping funnel, slowly add it dropwise to N,N-dimethylformamide B containing 2,2'-dithiodiethanol and dibutyltin dilaurate, raise the temperature to 60°C and stir, continue stirring for 6 hours after the addition is completed, let it stand, distill under reduced pressure, and vacuum dry at 40°C for 12 hours to obtain the target product, i.e., functional additive II.

[0111] The isocyanoethyl methacrylate and 2,2'-dithiodiethanol are added at a molar ratio of isocyanate group to hydroxyl group of 0.80:1; The dosage ratio of isocyanoethyl methacrylate, anhydrous N,N-dimethylformamide A, and anhydrous N,N-dimethylformamide B is: 0.1 mol: 100 mL: 300 mL; The amount of dibutyltin dilaurate is 1wt% of the mass of isocyanoethyl methacrylate; The dosage of the p-hydroxyanisole is 1wt% of the mass of isocyanoethyl methacrylate.

[0112] S22, pass N2, add the intermediate product 2I, hydroxyethyl acrylate, acrylamide, initiator AIBN to anhydrous N,N-dimethylformamide C, heat to 85°C, and stir for 6 hours; after the reaction, cool to room temperature, filter, take the filtrate, distill under reduced pressure, inject anhydrous methanol into the concentrate, stir, filter, take the insoluble matter, and place it at 60°C for 6 hours in vacuum to obtain the target product, i.e. functional additive II ( ).

[0113] The usage ratio of the intermediate product 2I, hydroxyethyl acrylate, acrylamide, anhydrous N,N-dimethylformamide C, and anhydrous methanol is 0.7 mol: 0.1 mol: 0.2 mol: 300 mL: 400 mL.

[0114] The amount of the initiator AIBN used is 2.0wt% of the total mass of the reactants.

[0115] The antioxidants are antioxidant 1010 and antioxidant 168 added in a mass ratio of 1:2.

[0116] The light stabilizer is UV-292 and UV-531 added in a mass ratio of 1:2.

[0117] Another object of this embodiment is to provide a method for preparing a delamination-resistant EPE co-extruded packaging film based on dynamic cross-linking, comprising the following steps: S31, mixing, i.e. The raw materials of each layer were mixed and configured according to the formula in a mixer, and mixed and stirred for 2 hours at a temperature of 40° C. and a rotation speed of 80 rpm to obtain a mixed raw material for standby use.

[0118] S32, co-extrusion, i.e. The POE layer raw materials are placed in a twin-screw extruder for melt blending; the EVA layer raw materials are placed in a twin-screw extruder for melt blending, and the materials are discharged through a co-extrusion cast film die, pulled, and stretched; The POE layer extrusion process is as follows: the temperature of the barrel zone 1 is 85°C, the temperature of the zone 2 is 95°C, the temperature of the zone 3 is 100°C, the die head temperature is 105°C, and the rotation speed is 50 rpm; and The EVA layer extrusion process is as follows: the temperature of the barrel zone 1 is 85° C., the temperature of the barrel zone 2 is 95° C., the temperature of the barrel zone 3 is 100° C., the die head temperature is 105° C., and the rotation speed is 40 rpm.

[0119] S33, film formation, i.e. The anti-stripping layer EPE co-extruded packaging film is obtained through thickness measurement, edge pressing, shaping, edge cutting and winding.

[0120] Example 4 The rest is the same as in Example 1, except that: Anti-delamination EPE co-extruded packaging film based on dynamic cross-linking, The POE layer comprises the following raw materials in parts by weight: POE resin (octene content: 25wt%) 100 parts; 1.0 part of cross-linking agent; Functional additive I 9.0 parts; Functional additive II 3.6 parts; 0.15 parts of antioxidant; Light stabilizer 0.10 parts; The first EVA layer and the second EVA layer include the following raw materials in parts by weight: EVA resin 100 parts; 1.2 parts of cross-linking agent; Functional additive I 7.0 parts; Functional additive II 2.8 parts; 0.3 parts of antioxidant; Light stabilizer 0.25 parts; Silane coupling agent 0.4 parts

[0121] Example 5 The rest is the same as in Example 1, except that: Anti-delamination EPE co-extruded packaging film based on dynamic cross-linking, The POE layer comprises the following raw materials in parts by weight: POE resin (octene content: 25wt%) 100 parts; 1.0 part of cross-linking agent; Functional additive I 9.0 parts; Functional additive II 6.0 parts; 0.15 parts of antioxidant; Light stabilizer 0.10 parts; The first EVA layer and the second EVA layer include the following raw materials in parts by weight: EVA resin 100 parts; 1.2 parts of cross-linking agent; Functional additive I 7.0 parts; Functional additive II 4.7 parts; 0.3 parts of antioxidant; Light stabilizer 0.25 parts; Silane coupling agent 0.4 parts

[0122] Example 6 The rest is the same as in Example 1, except that: Anti-delamination EPE co-extruded packaging film based on dynamic cross-linking, In the POE layer and EVA layer formula, The antioxidants are antioxidant 1010 and antioxidant 168 added in a mass ratio of 1:1.

[0123] Example 7 The rest is the same as in Example 1, except that: Anti-delamination EPE co-extruded packaging film based on dynamic cross-linking, In the POE layer and EVA layer formula, The antioxidants are antioxidant 1010 and antioxidant 168 added in a mass ratio of 1:3.

[0124] Example 8 The rest is the same as in Example 1, except that: Anti-delamination EPE co-extruded packaging film based on dynamic cross-linking, In the POE layer and EVA layer formula, The light stabilizer is UV-292 and UV-531 added in a mass ratio of 1:1.

[0125] Example 9 The rest is the same as in Example 1, except that: Anti-delamination EPE co-extruded packaging film based on dynamic cross-linking, In the POE layer and EVA layer formula, The light stabilizer is UV-292 and UV-531 added in a mass ratio of 1:3.

[0126] Example 10 The rest is the same as in Example 1, except that: Anti-delamination EPE co-extruded packaging film based on dynamic cross-linking, In the POE layer and EVA layer formula, The preparation method of the functional additive I, step S12 is: S12, add the intermediate product 1I to anhydrous N,N-dimethylformamide A, ultrasonicate for 0.5h, and add it dropwise to anhydrous N,N-dimethylformamide B containing toluene-2,4-diisocyanate through a peristaltic pump. After the addition is completed, continue stirring at room temperature for 4h. After the reaction is completed, distill under reduced pressure and dry in vacuum at 60°C for 12h to obtain the intermediate product 1II.

[0127] The intermediate product 1I and toluene-2,4-diisocyanate are added at a molar ratio of amino group to isocyanate group of 1:2; The usage ratio of the anhydrous N,N-dimethylformamide A, toluene-2,4-diisocyanate, and anhydrous N,N-dimethylformamide B is 100 mL: 0.1 mol: 300 mL.

[0128] Its infrared data is as follows: 3438cm -1 :-OH exists; 3320 cm -1 : -NH- peak exists and weakens; 3013cm -1 : benzene ring -CH exists; 1495cm -1 、1597cm -1 : benzene ring exists; 1551 cm -1 : -NH- exists; 1676 cm-1 :-C=O exists; 1109 cm -1 、797cm -1 :-Si-O- exists; 2270 cm -1 :-NCO exists and weakens.

[0129] Embodiment 11 The rest is the same as in Example 1, except that: Anti-delamination EPE co-extruded packaging film based on dynamic cross-linking, In the POE layer and EVA layer formula, The preparation method of the functional additive I, step S14 is: S14, protect from light, dissolve acryloyl chloride in dichloromethane A and place in a constant pressure dropping funnel, slowly add dropwise to dichloromethane B containing intermediate product 1III and triethylamine, ice bath, stir, after the addition is completed, control the stirring at 0°C for 14 hours, after the reaction is completed; filter, take the filtrate, add saturated sodium bicarbonate solution to wash 3 times, then wash with deionized water 3 times, separate the liquids, take the organic phase, dry it with anhydrous sodium sulfate, filter, distill the filtrate under reduced pressure, and dry it in vacuum at 40°C for 12 hours to obtain the target product, i.e. functional additive I.

[0130] The acryloyl chloride and the intermediate product 1III are added in a molar ratio of acyl chloride to hydroxyl of 1:1; The usage ratio of acryloyl chloride, dichloromethane A, triethylamine, dichloromethane B, saturated sodium bicarbonate solution, deionized water, and anhydrous sodium sulfate is 0.1 mol: 100 mL: 0.1 mol: 200 mL: 400 mL: 400 mL: 5 g.

[0131] Its infrared data is as follows: 3438cm -1 :-OH exists; 3320 cm -1 : -NH- sharp peak exists and is enhanced; 1551 cm -1 :-NH- exists and is enhanced; 1735 cm -1 、1702 cm -1 、1676 cm -1 :-C=O exists; 1605 cm -1 、811 cm -1 :-C=C- exists; 1109 cm -1 、797cm -1 :-Si-O- exists; 736 cm -1 :-C-Cl does not exist; 535 cm -1 :-SS- exists.

[0132] The preparation method of the functional additive II, step S21 is: S21, protect from light, dissolve acryloyl chloride in dichloromethane A and place in a constant pressure dropping funnel, slowly add dropwise to dichloromethane B containing 2,2'-dithiodiethanol and triethylamine, ice bath, stir, after the addition is completed, control the stirring at 5℃ for 8h, after the reaction is completed; filter, take the filtrate, add saturated sodium bicarbonate solution to wash 3 times, then wash with deionized water 3 times, separate the liquids, take the organic phase, dry with anhydrous sodium sulfate, filter, distill the filtrate under reduced pressure, and dry in vacuum at 40℃ for 12h to obtain the target product, i.e. functional additive II.

[0133] The acryloyl chloride and 2,2'-dithiodiethanol are added at a molar ratio of acyl chloride to hydroxyl group of 0.80:1; The usage ratio of acryloyl chloride, dichloromethane A, triethylamine, dichloromethane B, saturated sodium bicarbonate solution, deionized water, and anhydrous sodium sulfate is 0.1 mol: 100 mL: 0.1 mol: 200 mL: 400 mL: 400 mL: 5 g.

[0134] Its infrared data is as follows: 3443cm -1 :-OH exists and weakens; 3320 cm -1 : -NH- sharp peak exists; 1551 cm -1 :-NH- exists; 1735 cm -1 :-C=O exists; 1605 cm -1 、811 cm -1 :-C=C- exists; 736 cm -1 :-C-Cl does not exist; 535 cm -1 :-SS- exists.

[0135] Example 12 The rest is the same as in Example 1, except that: Anti-delamination EPE co-extruded packaging film based on dynamic cross-linking, In the POE layer and EVA layer formula, The preparation method of the functional auxiliary agent II, in S21, The isocyanoethyl methacrylate and 2,2'-dithiodiethanol are added in a molar ratio of isocyanate group to hydroxyl group of 0.65:1.

[0136] Example 13 The rest is the same as in Example 1, except that: Anti-delamination EPE co-extruded packaging film based on dynamic cross-linking, In the POE layer and EVA layer formula, The preparation method of the functional auxiliary agent II, in S21, The isocyanoethyl methacrylate and 2,2'-dithiodiethanol are added in a molar ratio of isocyanate group to hydroxyl group of 0.90:1.

[0137] Embodiment 14 The rest is the same as in Example 1, except that: Anti-delamination EPE co-extruded packaging film based on dynamic cross-linking, In the POE layer and EVA layer formula, The preparation method of the functional additive II, in S22, The usage ratio of the intermediate product 2I, hydroxyethyl acrylate, acrylamide, anhydrous N,N-dimethylformamide C, and anhydrous methanol is 0.6 mol: 0.15 mol: 0.25 mol: 300 mL: 400 mL.

[0138] Embodiment 15 The rest is the same as in Example 1, except that: Anti-delamination EPE co-extruded packaging film based on dynamic cross-linking, In the POE layer and EVA layer formula, The preparation method of the functional additive II, in S22, The usage ratio of the intermediate product 2I, hydroxyethyl acrylate, acrylamide, anhydrous N,N-dimethylformamide C, and anhydrous methanol is 0.8 mol: 0.05 mol: 0.15 mol: 300 mL: 400 mL.

[0139] Example 16 The rest is the same as in Example 1, except that: Anti-delamination EPE co-extruded packaging film based on dynamic cross-linking, In the POE layer and EVA layer formula, The preparation method of the functional additive II, in S22, The hydroxyethyl acrylate is replaced by a mixture of hydroxyethyl acrylate and lauryl acrylate in a molar ratio of 2:1.

[0140] The EPE packaging films in the following comparative examples are compared with Example 1: Comparative Example 1 The rest is the same as in Example 1, except that: Anti-delamination EPE co-extruded packaging film based on dynamic cross-linking, In the POE layer and EVA layer formula, no functional additive I is added.

[0141] Comparative Example 2 The rest is the same as in Example 1, except that: Anti-delamination EPE co-extruded packaging film based on dynamic cross-linking, No functional additive II is added to the POE layer and EVA layer formulas.

[0142] Comparative Example 3 The rest is the same as in Example 1, except that: Anti-delamination EPE co-extruded packaging film based on dynamic cross-linking, In the POE layer formula, no functional additive I and functional additive II are added.

[0143] Comparative Example 4 The rest is the same as in Example 1, except that: Anti-delamination EPE co-extruded packaging film based on dynamic cross-linking, In the EVA layer formula, no functional additive I and functional additive II are added.

[0144] Comparative Example 5 The rest is the same as in Example 1, except that: Anti-delamination EPE co-extruded packaging film based on dynamic cross-linking, The POE layer comprises the following raw materials in parts by weight: POE resin (octene content: 25wt%) 100 parts; 1.0 part of cross-linking agent; Functional additive I 9.0 parts; Functional additive II 9.0 parts; 0.15 parts of antioxidant; Light stabilizer 0.10 parts; The first EVA layer and the second EVA layer include the following raw materials in parts by weight: EVA resin 100 parts; 1.2 parts of cross-linking agent; Functional additive I 7.0 parts; Functional additive II 7.0 parts; 0.3 parts of antioxidant; Light stabilizer 0.25 parts; Silane coupling agent 0.4 parts

[0145] Comparative Example 6 The rest is the same as in Example 1, except that: Anti-delamination EPE co-extruded packaging film based on dynamic cross-linking, The POE layer comprises the following raw materials in parts by weight: POE resin (octene content: 25wt%) 100 parts; 1.0 part of cross-linking agent; Functional additive I 9.0 parts; Functional additive II 3.0 parts; 0.15 parts of antioxidant; Light stabilizer 0.10 parts; The first EVA layer and the second EVA layer include the following raw materials in parts by weight: EVA resin 100 parts; 1.2 parts of cross-linking agent; Functional additive I 7.0 parts; Functional additive II 2.3 parts; 0.3 parts of antioxidant; Light stabilizer 0.25 parts; Silane coupling agent 0.4 parts

[0146] Comparative Example 7 The rest is the same as in Example 1, except that: Anti-delamination EPE co-extruded packaging film based on dynamic cross-linking, In the POE layer and EVA layer formula, The preparation method of the functional additive I, in S11, The nano-silicon is replaced by nano-calcium carbonate.

[0147] Comparative Example 8 The rest is the same as in Example 1, except that: Anti-delamination EPE co-extruded packaging film based on dynamic cross-linking, In the POE layer and EVA layer formula, The preparation method of the functional additive I, in S12, The intermediate 1I is replaced by pentaerythritol.

[0148] Comparative Example 9 The rest is the same as in Example 1, except that: Anti-delamination EPE co-extruded packaging film based on dynamic cross-linking, In the POE layer and EVA layer formula, The functional auxiliary agent I is replaced by the intermediate product 1III.

[0149] Comparative Example 10 The rest is the same as in Example 1, except that: Anti-delamination EPE co-extruded packaging film based on dynamic cross-linking, In the POE layer and EVA layer formula, In the preparation method of the functional additive I and the functional additive II, The 2,2'-dithiodiethanol was replaced with ethylene glycol.

[0150] Comparative Example 11 The rest is the same as in Example 1, except that: Anti-delamination EPE co-extruded packaging film based on dynamic cross-linking, In the POE layer and EVA layer formula, The preparation method of the functional auxiliary agent II, in S21, The isocyanoethyl methacrylate and 2,2'-dithiodiethanol are added in a molar ratio of isocyanate group to hydroxyl group of 0.50:1.

[0151] Comparative Example 12 The rest is the same as in Example 1, except that: Anti-delamination EPE co-extruded packaging film based on dynamic cross-linking, In the POE layer and EVA layer formula, The preparation method of the functional auxiliary agent II, in S21, The isocyanoethyl methacrylate and 2,2'-dithiodiethanol are added in a molar ratio of isocyanate group to hydroxyl group of 1:1.

[0152] Comparative Example 13 The rest is the same as in Example 1, except that: Anti-delamination EPE co-extruded packaging film based on dynamic cross-linking, In the POE layer and EVA layer formula, The preparation method of the functional additive II, in S22, The usage ratio of the intermediate product 2I, hydroxyethyl acrylate, acrylamide, anhydrous N,N-dimethylformamide C, and anhydrous methanol is 0 mol: 0.1 mol: 0.2 mol: 300 mL: 400 mL; that is, the intermediate product 2I is not added.

[0153] Comparative Example 14 The rest is the same as in Example 1, except that: Anti-delamination EPE co-extruded packaging film based on dynamic cross-linking, In the POE layer and EVA layer formula, The preparation method of the functional additive II, in S22, The usage ratio of the intermediate product 2I, hydroxyethyl acrylate, acrylamide, anhydrous N,N-dimethylformamide C, and anhydrous methanol is 0.7 mol: 0 mol: 0.2 mol: 300 mL: 400 mL; that is, hydroxyethyl acrylate is not added.

[0154] Comparative Example 15 The rest is the same as in Example 1, except that: Anti-delamination EPE co-extruded packaging film based on dynamic cross-linking, In the POE layer and EVA layer formula, The preparation method of the functional additive II, in S22, The usage ratio of the intermediate product 2I, hydroxyethyl acrylate, acrylamide, anhydrous N,N-dimethylformamide C, and anhydrous methanol is 0.7 mol: 0.1 mol: 0 mol: 300 mL: 400 mL; that is, no acrylamide is added.

[0155] The physical properties of the EPE films prepared in the embodiments of the present invention and the comparative examples were measured respectively, and the results are shown in Table 1.

[0156] Table 1 Physical test performance of each embodiment Example Transmittance / % Peel force / N ▪cm-1 Delamination after humid heat aging Hygrothermal aging / tensile properties test UV aging yellowing index / ΔYI Membrane surface self-repair Example 1 92.3 173 No delamination Unstratified 1.6 5 Example 2 91.4 170 No delamination Unstratified 1.7 5 Example 3 92.6 158 No delamination Unstratified 2.2 4 Example 4 92.4 166 No delamination Unstratified 2.1 4 Example 5 92.1 162 No delamination Unstratified 2.0 5 Example 6 91.9 170 No delamination Unstratified 1.9 5 Example 7 91.4 168 No delamination Unstratified 2.1 5 Example 8 92.2 171 No delamination Unstratified 2.7 5 Example 9 92.0 170 No delamination Unstratified 2.9 5 Example 10 92.1 169 No delamination Unstratified 2.0 5 Embodiment 11 92.2 167 No delamination Unstratified 1.8 5 Example 12 92.4 156 No delamination Unstratified 2.0 4 Example 13 92.0 151 No delamination Unstratified 1.5 4 Embodiment 14 91.9 161 No delamination Unstratified 2.2 4 Embodiment 15 92.4 168 No delamination Unstratified 1.5 5 Example 16 92.1 167 No delamination Unstratified 1.9 5 Comparative Example 1 92.0 126 No delamination Layering 3.8 2 Comparative Example 2 92.1 131 No delamination Layering 3.6 3 Comparative Example 3 92.3 112 Delamination / 4.0 5 Comparative Example 4 92.0 104 Delamination / 4.7 1 Comparative Example 5 92.4 137 No delamination Unstratified 2.5 4 Comparative Example 6 92.2 134 No delamination Micro-layering 2.3 3 Comparative Example 7 89.3 166 No delamination Unstratified 1.8 5 Comparative Example 8 90.5 138 No delamination Layering 2.9 3 Comparative Example 9 92.2 132 No delamination Layering 3.1 3 Comparative Example 10 91.7 121 Delamination / 4.9 1 Comparative Example 11 92.2 140 No delamination Micro-layering 2.4 3 Comparative Example 12 91.8 134 No delamination Micro-layering 1.5 3 Comparative Example 13 91.9 132 No delamination Layering 3.8 3 Comparative Example 14 92.1 158 No delamination Micro-layering 2.4 4 Comparative Example 15 92.1 161 No delamination Micro-layering 1.9 4 Firstly, it can be concluded from Examples 1-16 in Table 1 that the anti-peeling layer EPE co-extruded packaging film of the present invention has excellent light transmittance, peel strength and interlayer bonding strength; at the same time, it also has certain anti-scratch self-repairing properties.

[0157] It can be observed from Example 1 and Comparative Examples 1-6 that the EPE film of the present invention uses self-made functional additives I and II, which have dynamic reaction cross-linking characteristics and can effectively improve the interlayer bonding strength of the film; at the same time, the surface EVA layer also has anti-scratch self-repairing properties, which can improve the use efficiency; in addition, it can be observed that the compounding of functional additives I and II has a synergistic effect and improves the interlayer bonding strength; It can be observed from Example 1 and Comparative Examples 7-9 that the use of the homemade functional additive I in the EPE film of the present invention has the advantages of improved light transmittance, self-repairing, and interlayer bonding strength; It can be observed from Example 1 and Comparative Example 10 that the EPE film of the present invention uses self-made functional additives I and II, wherein the disulfide bond structure is a dynamic cross-linking structure, which is crucial for self-repair and interlayer bonding performance; It can be observed from Example 1 and Comparative Examples 11-15 that the macromolecular structure of the homemade functional additive II used in the EPE film of the present invention has an important influence on the interlayer bonding performance; In summary, the anti-delamination EPE co-extruded packaging film of the present invention is formulated and prepared by co-extrusion using homemade functional additives I and II to enhance interlayer bonding strength; at the same time, it also has certain scratch resistance and self-repairing properties, which can effectively extend the service life of the product.

[0158] The test method is as follows: (1) Light transmittance: Tested in accordance with the method described in GB / T 29848-2013 “Ethylene-vinyl acetate copolymer (EVA) adhesive film for photovoltaic module encapsulation”.

[0159] (2) Peel force test: Sample preparation: 1) Prepare two pieces of adhesive film raw materials, one piece of glass and one piece of flexible backplane, all with a size of 300mm×150mm; 2) Stack the glass / film (two pieces) / flexible back sheet in sequence, put them into the vacuum laminator, and laminate them according to the temperature and time required by the product. There should be no bubbles in the film after lamination. Prepare 3 samples; 3) Cut the flexible backsheet / film layer into specimens with a width of 10 mm ± 0.5 mm at intervals of 5 mm in the width direction for testing the peeling force between the film and the glass.

[0160] Test process: According to the test method of GB / T 2790 1995, the peeling force F between the glass and the film is measured on a tensile testing machine at a tensile speed of 100mm / min ± 10mm / min.

[0161] Test results: The peel strength is calculated according to the following formula, and the arithmetic mean of 3 samples is taken, accurate to 0.1N / cm.

[0162] σ=F / B Where: σ—180° peel strength, N / cm; F—peel force, N; B—sample width, cm.

[0163] (3) Hygrothermal aging: The EPE film is subjected to a hygrothermal aging test. Conditions: Test conditions: +85°C, relative humidity 85%, test time 1000 hours. After the hygrothermal aging test, visual delamination and tensile destructive test are performed. After the tensile test is broken, observe whether there is any delamination between the layers on the cross section of the sample.

[0164] (4) UV aging: The obtained EPE film was subjected to UV irradiation aging test according to the requirements of the International Electrotechnical Commission standard IEC61345. Test conditions: the surface temperature of the test piece is 60±5℃, the UV wavelength range is 280-400nm, and the irradiation intensity is 15kW·h / m 2 , the UV irradiation test time is 2000hr.

[0165] The yellowing index (△YI) before and after the test was measured according to GB 2409.

[0166] (5) Self-repair of membrane surface: At 23.5°C, rub the membrane surface back and forth with a copper brush at a force of 1 kg. Stop after 10 back and forth movements and observe the membrane surface repair condition. If the membrane surface self-repairs within 10 seconds, it will be recorded as "5"; if the membrane surface self-repairs within 60 seconds, it will be recorded as "4"; if the membrane surface self-repairs within 120 seconds, it will be recorded as "3"; if the membrane surface self-repairs within 10 minutes, it will be recorded as "2"; if the membrane surface self-repairs for more than 10 minutes or there is a scratch, it will be recorded as "1".

[0167] Based on the above ideal embodiments of the present invention, the relevant staff can make various changes and modifications without departing from the technical concept of the present invention through the above description. The technical scope of the present invention is not limited to the contents of the specification, and its technical scope must be determined according to the scope of the claims.

Claims

1. An anti-stripping layer EPE co-extruded packaging film based on dynamic cross-linking, characterized in that the EPE packaging film includes three layers arranged in sequence, namely a first EVA layer, a POE layer, and a second EVA layer; the thickness of the first EVA layer is 50-150 μm; the thickness of the POE layer is 150-350 μm; the thickness of the second EVA layer is 50-150 μm; the first EVA layer, the POE layer, and the second EVA layer all contain a disulfide bond structure with dynamic reaction.

2. The anti-delamination EPE co-extruded packaging film based on dynamic cross-linking according to claim 1, characterized in that: The POE layer comprises the following raw materials in parts by weight: 100 parts of POE resin; Cross-linking agent 0.5-1.5 parts; Functional additive I 6.0-12.0 parts; Functional additive II 3.0-6.0 parts; Antioxidant 0.05-0.30 parts; Light stabilizer 0.05-0.30 parts.

3. The anti-stripping EPE co-extruded packaging film based on dynamic cross-linking according to claim 1 or 2, characterized in that: The first EVA layer and the second EVA layer include the following raw materials in parts by weight: EVA resin 100 parts; Cross-linking agent 0.5-1.5 parts; Functional additive I 5.0-10.0 parts; Functional additive II 2.5-5.0 parts; Antioxidant 0.1-0.5 parts; Light stabilizer 0.1-0.5 parts; Silane coupling agent 0.2-0.5 parts.

4. The anti-stripping EPE co-extruded packaging film based on dynamic cross-linking according to claim 2 or 3, characterized in that: The preparation method of the functional additive I comprises the following steps: S11, performing silylation coupling reaction on nano-silicon and aminosilane coupling agent to obtain intermediate product 1I; The dosage ratio of the nano-silicon to the aminosilane coupling agent is 1g:3.0-5.0g; S12, subjecting the intermediate product 1I to urea reaction with an asymmetric diisocyanate to obtain an intermediate product 1II; The intermediate product 1I and the asymmetric diisocyanate are added at a molar ratio of amino group to isocyanate group of 1:2; S13, reacting the intermediate 1II with 2,2'-dithiodiethanol to obtain the intermediate 1III; The intermediate product III and 2,2'-dithiodiethanol are added at a molar ratio of isocyanate group to hydroxyl group of 1:2; S14, the intermediate product 1III is subjected to a nucleophilic addition reaction with an electrophilic reagent containing a carbon-carbon double bond to obtain a target product, namely, a functional additive I.

5. The anti-delamination EPE co-extruded packaging film based on dynamic cross-linking according to claim 2 or 3, characterized in that: The preparation method of the functional additive II comprises the following steps: S21, 2,2'-dithiodiethanol undergoes a nucleophilic addition reaction with an electrophilic reagent containing a carbon-carbon double bond to obtain an intermediate 2I; S22, subjecting the intermediate product 2I, acrylate, and acrylamide to a free radical polymerization reaction to obtain a target product, i.e., a functional additive II; The molar ratio of the intermediate product 2I, acrylate and acrylamide is 0.6-0.8: 0.05-0.15: 0.15-0.

25.

6. The anti-delamination EPE co-extruded packaging film based on dynamic cross-linking according to claim 4, characterized in that: The asymmetric diisocyanate is toluene diisocyanate or isophorone diisocyanate.

7. The anti-delamination EPE co-extruded packaging film based on dynamic cross-linking according to claim 5, characterized in that: The structure containing a carbon-carbon double bond is a vinyl structure or an acryloxy structure; The electrophilic reagent structure is an acyl structure or an isocyanate structure; and The acrylate includes hydroxy acrylate.

8. The anti-delamination EPE co-extruded packaging film based on dynamic cross-linking according to claim 2, characterized in that: The octene content in the POE resin is 20-35wt%.

9. The anti-delamination EPE co-extruded packaging film based on dynamic cross-linking according to claim 1, characterized in that: The mass ratio of the functional additive I to the functional additive II is 1.5-2.5:

1.

10. The anti-delamination EPE co-extruded packaging film based on dynamic cross-linking according to claim 3, characterized in that: The antioxidant is a mixture of a hindered phenol antioxidant and a phosphite antioxidant in a mass ratio of 1:1-3.

11. The anti-delamination EPE co-extruded packaging film based on dynamic cross-linking according to claim 3, characterized in that: The light stabilizer is a mixture of a hindered amine light stabilizer and an ultraviolet absorber in a mass ratio of 1:1-3.

12. A method for preparing a delamination-resistant EPE co-extruded packaging film based on dynamic cross-linking, characterized in that: The following steps are involved: S31, mixing, i.e. The raw materials of each layer are mixed and configured according to the formula in a mixer to obtain mixed raw materials for standby use; S32, co-extrusion, i.e. The POE layer raw materials are placed in a twin-screw extruder for melt blending; the EVA layer raw materials are placed in a twin-screw extruder for melt blending, and the materials are discharged through a co-extrusion cast film die, pulled, and stretched; S33, film formation, i.e. The anti-stripping layer EPE co-extruded packaging film is obtained through thickness measurement, edge pressing, shaping, edge cutting and winding.

13. The method for preparing the anti-stripping EPE co-extruded packaging film based on dynamic cross-linking according to claim 12, characterized in that: The POE layer extrusion process is as follows: barrel temperature 85-110°C, rotation speed 45-50rpm; and The EVA layer extrusion process is as follows: barrel temperature is 75-105° C. and rotation speed is 45-50 rpm.