A polymer reversibly interlocking network adhesive film, its method of preparation and use

Abstract

The application belongs to the field of high polymer materials, and discloses a polymer reversible interlocking network adhesive film, a preparation method and application thereof.The polymer reversible interlocking network adhesive film comprises the following components by weight percentage: crosslinking polymer A containing dynamic disulfide bond 50%-75%, crosslinking polymer B containing dynamic borate ester bond 25%-50%.The polymer reversible interlocking network adhesive film prepared by the application has good dissipation performance, fully guarantees the bonding cohesive strength inside the adhesive film;under heating ultrasonic and vacuum hot pressing, the polymer reversible interlocking network adhesive film has substrate-induced self-layering effect, fully guarantees the adhesion strength of the bonding interface;from the interface to the inside, the bonding effect is fully guaranteed, and the strong bonding of two different substrates, i.e., glass and TPT fluorine-containing back plate, is realized on the basis of not damaging the substrate.The reversible covalent bond balance reaction in the polymer reversible interlocking network adhesive film can promote the recycling and repeated bonding of the adhesive film.

Description

Technical Field

[0001] This invention belongs to the field of polymer materials, specifically relating to a polymer reversible interlocking network film, its preparation method and application. Background Technology

[0002] With the increasing scarcity of conventional energy sources, the importance and necessity of developing new energy sources are becoming increasingly prominent, leading to the rapid development of the solar cell industry. Most solar cell encapsulation achieves bonding through the curing and cross-linking of EVA film during hot pressing. The EVA film needs to simultaneously bond two substrates with completely different properties: glass and a TPT (fluorinated polytetrafluoroethylene) backsheet. For glass substrates, this is generally achieved by adding silane coupling agents; for the low surface energy TPT backsheet, plasma treatment of the TPT backsheet's surface is necessary to improve adhesion. Furthermore, due to the limited lifespan of solar cells, their recycling is also a pressing issue. Currently, solar cell recycling methods mainly rely on inorganic acid solvents and high-temperature incineration, which are energy-intensive, polluting, and costly. Moreover, the inability to detach the EVA film after bonding makes it difficult to completely recover the silicon wafers and glass, further increasing costs. Therefore, achieving environmentally friendly and efficient debonding and recycling while simultaneously bonding glass and TPT backsheets has become a key challenge.

[0003] Because the surface energy of the TPT fluorinated backsheet is very low, it needs to be wetted to achieve adhesion. Therefore, materials with low surface energy must be selected to achieve adhesion with the TPT fluorinated backsheet. Glass bonding does not require low surface energy. Mixing two or more polymers together can achieve integrated optimization of different functions. To achieve this, existing technologies often use synchronous methods, stepwise methods, latex methods, and thermoplastic methods to prepare interpenetrating polymer networks (IPNs). IPNs achieve forced compatibilization through mechanical entanglement between different networks. However, since the two networks are inherently incompatible, synchronous IPNs will have differences in crosslinking rates, leading to micron or nanometer-level microphase separation within the IPN. This phase separation hinders the improvement of the material's mechanical properties and affects the final performance of the material. The emergence of interlocking networks overcomes the problem of microphase separation in IPNs, achieving true miscibility at the molecular level. Chinese invention patent CN 201810866569.4 discloses a dynamic topological interlocking dual network. It is achieved by cross-linking polyurethane dynamic reversible cross-linking network and polyacrylate dynamic reversible cross-linking network through dynamic covalent bonds. During the network composite process, the cross-linked network dynamic exchange tends to dissociate, while the networks are fully mixed. Then, the dynamic covalent bonds of the networks are recombined to obtain a dynamic topological interlocking dual network. However, it only has stronger mechanical properties than the initial single network and does not have the substrate-induced self-delamination effect or the function of simultaneously bonding two different substrates, glass and TPT fluorinated backsheet, to solar cell backsheets. Summary of the Invention

[0004] The purpose of this invention is to overcome the shortcomings of the prior art and provide a polymer reversible interlocking network film, its preparation method and application.

[0005] To achieve the above objectives, the technical solution adopted by the present invention is as follows:

[0006] In a first aspect, the present invention provides a polymer reversible interlocking network film, comprising, by weight percentage: 50%-75% of a crosslinked polymer A containing dynamic disulfide bonds and 25%-50% of a crosslinked polymer B containing dynamic borate ester bonds;

[0007] The crosslinked polymer A comprises the following raw materials in parts by weight: 24-30 parts of diisocyanate monomer, 45-55 parts of diol monomer, 8-11 parts of disulfide monomer, 2-4 parts of trihydroxy crosslinking agent, and 0.6-0.9 parts of metal chloride.

[0008] Interlocking networks involve the mixing, entanglement, and re-interlocking of two adaptive networks under certain conditions. The inter-network forces suppress microscopic phase separation, achieving uniform blending of different materials at the molecular level. The polymer reversible interlocking network film of this invention induces self-delamination with the substrate. The interlocking network imparts excellent dissipative mechanical properties to the film's interior, ensuring its adhesive cohesive strength. Furthermore, the substrate induces delamination on both sides, ensuring that the interface is dominated by corresponding matched components, further guaranteeing the film's adhesive strength. The polymer reversible interlocking network film contains numerous dynamic bonds, allowing for multiple bonding and reuse. When the solar cell reaches the end of its lifespan, the dynamic bonds within the polymer reversible interlocking network film can be opened under suitable conditions, enabling convenient recycling of the film. The ratio of the two crosslinked polymers in the reversible interlocking network film not only affects the formation and performance of the interlocking network, but also the self-delamination effect. By rationally optimizing the ratio, the present invention obtains a reversible interlocking network film with better dissipation performance than the two crosslinked polymers. Moreover, the most suitable adhesive components are enriched at the interface (crosslinked polymer component B at the glass interface and crosslinked polymer component A at the TPT fluorinated backing plate interface), while ensuring cohesive strength and adhesion strength.

[0009] As a preferred embodiment of the polymer reversible interlocking network film of the present invention, the crosslinked polymer B comprises the following raw materials in parts by weight: 70-90 parts of acrylate monomer, 20-25 parts of acrylic monomer, 180-220 parts of hydroxyl-containing acrylate monomer, 2-4 parts of boric acid-containing crosslinking agent, and 0.08-0.2 parts of free radical polymerization initiator.

[0010] As a preferred embodiment of the polymer reversible interlocking network film of the present invention, the diisocyanate monomer is at least one selected from isophorone diisocyanate, toluene diisocyanate, diphenylmethane diisocyanate, terephthalamide diisocyanate, and hexamethylene diisocyanate.

[0011] In a preferred embodiment of the polymer reversible interlocking network film of the present invention, the diol monomer is at least one of polytetrahydrofuran diol, polycaprolactone diol, polycarbonate diol, polylactic acid diol, polyethylene glycol, polypropylene glycol, and polybutylene glycol.

[0012] In a preferred embodiment of the polymer reversible interlocking network film of the present invention, the disulfide monomer is at least one of 2-hydroxyethyl disulfide, 2,2-diaminodiphenyl disulfide, and 4,4-diaminodiphenyl disulfide; the trihydroxy crosslinking agent is triethanolamine or glycerol; and the metal ion is at least one of zinc ion, zirconium ion, calcium ion, and iron ion.

[0013] In a preferred embodiment of the polymer reversible interlocking network film of the present invention, the acrylate monomer is at least one selected from methyl acrylate, ethyl acrylate, butyl acrylate, and isobutyl acrylate.

[0014] In a preferred embodiment of the polymer reversible interlocking network film of the present invention, the acrylic monomer is acrylic acid or methacrylic acid; the boric acid-containing crosslinking agent is 1,4-phenylenediboric acid or borax; and the free radical polymerization initiator is at least one of azobisisobutyronitrile, potassium persulfate, and benzoyl peroxide.

[0015] Secondly, the present invention also provides a method for preparing the above-mentioned polymer reversible interlocking network film, comprising the following steps:

[0016] (1) Take the cross-linked polymer A containing dynamic disulfide bonds and the cross-linked polymer B containing dynamic borate ester bonds respectively, crush, swell and stir to obtain solution A and solution B;

[0017] (2) Under the conditions of 60℃-80℃ and argon atmosphere, the obtained solution A and solution B are mixed, stirred and dried to obtain the final product.

[0018] The preparation process of the polymer reversible interlocking network film in this invention effectively avoids micro-phase separation and achieves optimal dissipation performance.

[0019] As a preferred embodiment of the preparation method of the present invention, in the preparation method of the polymer reversible interlocking network film, in step (1), the swelling time is 1h-2h; and the stirring time is 10min-20min.

[0020] As a preferred embodiment of the preparation method of the present invention, in step (2) of the preparation method of the polymer reversible interlocking network film, the mixing conditions are as follows: mix and stir for 20 min at 80°C under argon protection, remove most of the solvent by rotary evaporation, and then dry in an oven at 80°C until constant weight.

[0021] Thirdly, the present invention applies the polymer reversible interlocking network film to the encapsulation, debonding, and recycling of solar cell systems.

[0022] The method of using the polymer reversible interlocking network adhesive film in this invention achieves a substrate-induced self-delamination effect, causing both sides of different substrates to aggregate into the optimal wetting component, thus fully ensuring the adhesion strength of the bonding interface. The polymer reversible interlocking network adhesive film contains a large number of dynamic bonds, which can be opened under suitable conditions, enabling convenient recycling of the film for multiple bonding applications.

[0023] The application of the polymer reversible interlocking network film in solar cell system encapsulation includes the following steps:

[0024] (1) Take the polymer reversible interlocking network film, cut it into pieces, and heat press it to make a flat film sheet;

[0025] (2) Coat the front and back sides of the flat film with solvent, place it between two substrates, heat and sonicate for 0.5h-3.5h, and vacuum hot press at 60℃-150℃ for 5min-60min to obtain the film.

[0026] As a preferred embodiment of the application of the polymer reversible interlocking network film of the present invention in the encapsulation of a solar cell system, in step (2), the solvent used for coating is at least one of N,N-dimethylformamide, dichloromethane, and tetrahydrofuran.

[0027] As a preferred embodiment of the application of the polymer reversible interlocking network film of the present invention in the encapsulation of solar cell systems, in step (2), the heating and ultrasonic time is 0.5h-2h, the temperature of the vacuum hot pressing is 100℃-130℃, and the time is 5min-30min.

[0028] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0029] This invention utilizes two different dynamic bonds to prepare a polymer reversible interlocking network film, optimizing the film's dissipative mechanical properties and ensuring strong internal cohesive adhesion. The solvent-, temperature-, and pressure-assisted operation achieves a substrate-induced self-delamination effect, causing both substrate sides to aggregate into optimal wetting components, thus guaranteeing strong adhesion at the bonding interface. Overall, from the interface to the interior, the adhesive effect is comprehensively guaranteed, achieving strong adhesion between two different substrates—glass and TPT fluorinated backsheet—without damaging the substrate. The reversible covalent bond equilibrium reaction in the polymer reversible interlocking network film promotes film recycling and re-bonding, reducing battery costs, minimizing electronic waste, and improving utilization. Detailed Implementation

[0030] To better illustrate the objectives, technical solutions, and advantages of this invention, the invention will be further described below with reference to specific embodiments. Those skilled in the art should understand that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.

[0031] Unless otherwise specified, the raw materials and pharmaceuticals used in the embodiments are all commercially available conventional products. Any non-substantial changes and substitutions made by those skilled in the art based on this invention are within the scope of protection claimed by this invention.

[0032] Example 1: A crosslinked polymer PU1 containing dynamic disulfide bonds

[0033] The preparation method of the crosslinked polymer PU1 containing dynamic disulfide bonds is as follows:

[0034] 5g of polytetrahydrofuran diol and 2.67g of isophorone diisocyanate were dissolved in 20ml of N,N-dimethylformamide and added to a three-necked flask equipped with a gas protection device. The mixture was reacted at 60℃ for 12h. Then, 0.993g of 4,4-diaminodiphenyl disulfide and 10ml of N,N-dimethylformamide were added, and the reaction was continued for another 12h. Finally, 0.298g of triethanolamine was added, and the reaction was carried out for 24h. After the reaction was completed, 0.08g of zirconium chloride was added, stirred evenly, and poured into a mold to form a film. The film was then dried in an oven at 80℃ to constant weight to obtain the crosslinked polymer PU1 containing dynamic disulfide bonds.

[0035] Example 2: A crosslinked polymer PU2 containing dynamic disulfide bonds

[0036] The preparation method of the crosslinked polymer PU2 containing dynamic disulfide bonds is as follows:

[0037] 5g of polytetrahydrofuran diol and 2.67g of isophorone diisocyanate were dissolved in 20ml of N,N-dimethylformamide and added to a three-necked flask equipped with a gas protection device. The mixture was reacted at 60℃ for 12h. Then, 0.993g of 2,2-diaminodiphenyl disulfide and 10ml of N,N-dimethylformamide were added, and the reaction was continued for another 12h. Finally, 0.298g of triethanolamine was added, and the reaction was carried out for 24h. After the reaction was completed, 0.08g of zinc chloride was added, stirred evenly, and poured into a mold to form a film. The film was then dried in an oven at 80℃ to constant weight to obtain the crosslinked polymer PU2 containing dynamic disulfide bonds.

[0038] Example 3: A crosslinked polymer PA containing dynamic borate ester bonds

[0039] The preparation method of the crosslinked polymer PA containing dynamic borate ester bonds is as follows:

[0040] (1) Mix 20g glycidyl methacrylate and 180g water evenly at room temperature, then heat to 80℃ and react for 20h to obtain a colorless and transparent solution.

[0041] (2) The colorless and transparent solution was extracted multiple times with ethyl acetate. The extract was dried with anhydrous magnesium sulfate and then filtered and evaporated by rotary evaporation to obtain a colorless and transparent viscous liquid, which is the hydroxyl-containing acrylate monomer.

[0042] (3) Dissolve 0.8g of acrylate monomer, 0.0164g of azobisisobutyronitrile, 8.11g of butyl acrylate and 2.27g of acrylic acid in 40ml of tetrahydrofuran, add to a three-necked flask equipped with a gas protection device, ventilate at room temperature for 1h, then raise the temperature to 70℃ and react for 12h. After the reaction is completed, pour the resulting colorless viscous liquid into n-hexane, cool and precipitate, take the precipitate and dry it in a 60℃ oven to obtain polyacrylate.

[0043] (4) Dissolve the polyacrylate again in 40 ml of N,N-dimethylformamide, add 0.332 g of 1,4-phenylenediboronic acid and stir evenly. Pour into a mold and dry in an oven at 70 °C until constant weight to obtain the cross-linked polymer PA containing dynamic borate bonds.

[0044] Example 4: A polymer reversible interlocking network film ILN11

[0045] The polymer reversible interlocking network film ILN11 comprises the following components in parts by weight: 50 parts of a crosslinked network PU1 containing dynamic disulfide bonds and 50 parts of a crosslinked network PA containing dynamic borate ester bonds.

[0046] The preparation method of the polymer reversible interlocking network film ILN11 is as follows:

[0047] (1) 5g of PU1 obtained in Example 1 was crushed and swollen in N,N-dimethylformamide at room temperature for 2h. Then, it was stirred vigorously at 80℃ and under argon protection for 20min to obtain a transparent and clear solution.

[0048] (2) 5g of PA obtained in Example 3 was crushed, swollen in N,N-dimethylformamide and a small amount of water at room temperature for 1h, and then stirred vigorously at 80℃ and under argon protection for 10min to obtain a colorless and transparent solution.

[0049] (3) Mix the transparent clear solution and the colorless transparent solution, stir for 20 min under argon protection at 80℃, remove most of the solvent by rotary evaporation, and then dry in an 80℃ oven to constant weight to obtain the polymer reversible interlocking network film ILN11.

[0050] Example 5: A polymer reversible interlocking network film ILN21

[0051] The polymer reversible interlocking network film ILN21 comprises the following components in parts by weight: 66 parts of a crosslinked network PU1 containing dynamic disulfide bonds and 33 parts of a crosslinked network PA containing dynamic borate ester bonds.

[0052] The preparation method of the polymer reversible interlocking network film ILN21 is as follows:

[0053] (1) 4g of PU1 obtained in Example 1 was crushed and swollen in N,N-dimethylformamide at room temperature for 2h. Then, it was stirred vigorously at 80℃ and under argon protection for 20min to obtain a transparent and clear solution.

[0054] (2) 2g of PA obtained in Example 3 was crushed, swollen in N,N-dimethylformamide and a small amount of water at room temperature for 1h, and then stirred vigorously at 80℃ and under argon protection for 10min to obtain a colorless and transparent solution.

[0055] (3) Mix the transparent clear solution and the colorless transparent solution, stir for 20 minutes at 80°C under argon protection, remove most of the solvent by rotary evaporation, and then dry in an 80°C oven to constant weight to obtain the polymer reversible interlocking network film ILN21.

[0056] Example 6: A polymer reversible interlocking network film ILN31

[0057] The polymer reversible interlocking network film ILN31 comprises the following components in parts by weight: 75 parts of a crosslinked network PU1 containing dynamic disulfide bonds and 25 parts of a crosslinked network PA containing dynamic borate ester bonds.

[0058] The preparation method of the polymer reversible interlocking network film ILN31 is as follows:

[0059] (1) 6g of PU1 obtained in Example 1 was crushed and swollen in N,N-dimethylformamide at room temperature for 2h. Then, it was stirred vigorously at 80℃ and under argon protection for 20min to obtain a transparent and clear solution.

[0060] (2) 2g of PA obtained in Example 3 was crushed, swollen in N,N-dimethylformamide and a small amount of water at room temperature for 1h, and then stirred vigorously at 80℃ and under argon protection for 10min to obtain a colorless and transparent solution.

[0061] (3) Mix the transparent clear solution and the colorless transparent solution, stir for 20 minutes at 80°C under argon protection, remove most of the solvent by rotary evaporation, and then dry in an 80°C oven to constant weight to obtain the polymer reversible interlocking network film ILN31.

[0062] Example 7: A Synchronous Interpenetrating Polymer Network Film IPN1

[0063] The preparation method of the synchronous interpenetrating polymer network film IPN1 is as follows:

[0064] 5g of polytetrahydrofuran diol, 2.67g of isophorone diisocyanate, 0.993g of 4,4-diaminodiphenyl disulfide, 0.298g of triethanolamine, 0.08g of zirconium chloride, 0.624g of hydroxyl-containing acrylate monomer, 0.013g of azobisisobutyronitrile, 6.33g of butyl acrylate, 1.77g of acrylic acid, and 0.259g of 1,4-phenylenediboronic acid were added to 50ml of N,N-dimethylformamide and reacted at 60℃ under nitrogen protection for 48h. The mixture was then poured into a mold and dried in an oven at 80℃ until constant weight, yielding the synchronous interpenetrating polymer network film IPN1.

[0065] Example 8: A stepwise interpenetrating polymer network film IPN2

[0066] The method for preparing the stepwise interpenetrating polymer network film IPN2 is as follows:

[0067] (1) Add 5g of polytetrahydrofuran diol, 2.67g of isophorone diisocyanate, 0.993g of 4,4-diaminodiphenyl disulfide, 0.298g of triethanolamine and 0.08g of zirconium chloride to 25ml of N,N-dimethylformamide and mix thoroughly to obtain a mixed solution;

[0068] (2) Immerse 9g of PA obtained in Example 3 in a mixed solution and allow it to swell for 48h. Take out the gel and dry it to constant weight to obtain stepwise interpenetrating polymer network film IPN2.

[0069] Example 9: A method of using a polymer reversible interlocking network film

[0070] The method of use includes the following steps:

[0071] (1) The polymer reversible interlocking network film ILN11 obtained in Example 4 was uniformly cut into small pieces, quickly hot-pressed into a flat film, and then cut into a size suitable for the glass substrate.

[0072] (2) Place the cut polymer reversible interlocking network film ILN11 between the glass and the TPT fluorine-containing backplate, and vacuum hot press at 130°C for 5 minutes to obtain the final product.

[0073] Example 10: A method of using a polymer reversible interlocking network film

[0074] The method of use includes the following steps:

[0075] (1) The polymer reversible interlocking network film ILN11 obtained in Example 4 was uniformly cut into small pieces, quickly hot-pressed into a flat film, and then cut into a size suitable for the glass substrate.

[0076] (2) Place the cut polymer reversible interlocking network film ILN11 between the glass and the TPT fluorine-containing backplate, and vacuum hot press at 130°C for 10 minutes to obtain the final product.

[0077] Example 11: A method of using a polymer reversible interlocking network film

[0078] The method of use includes the following steps:

[0079] (1) The polymer reversible interlocking network film ILN11 obtained in Example 4 was uniformly cut into small pieces, quickly hot-pressed into a flat film, and then cut into a size suitable for the glass substrate.

[0080] (2) Place the cut polymer reversible interlocking network film ILN11 between the glass and the TPT fluorine-containing backplate, and vacuum hot press at 120°C for 15 minutes to obtain the final product.

[0081] Example 12: A method of using a polymer reversible interlocking network film

[0082] The method of use includes the following steps:

[0083] (1) The polymer reversible interlocking network film ILN11 obtained in Example 4 was uniformly cut into small pieces, quickly hot-pressed into a flat film, and then cut into a size suitable for the glass substrate.

[0084] (2) Place the cut polymer reversible interlocking network film ILN11 between the glass and the TPT fluorine-containing backplate, and vacuum hot press at 120°C for 20 minutes to obtain the final product.

[0085] Example 13: A method of using a polymer reversible interlocking network film

[0086] The method of use includes the following steps:

[0087] (1) The polymer reversible interlocking network film ILN11 obtained in Example 4 was uniformly cut into small pieces, quickly hot-pressed into a flat film, and then cut into a size suitable for the glass substrate.

[0088] (2) Coat both sides of the cut polymer reversible interlocking network film ILN11 with solvent, place it between glass and TPT fluorine-containing backing plate, fix it with clamps and heat and sonicate for 0.5h, take it out and vacuum hot press it at 130℃ for 5min to complete the process.

[0089] Example 14: A method of using a polymer reversible interlocking network film

[0090] The method of use includes the following steps:

[0091] (1) The polymer reversible interlocking network film ILN11 obtained in Example 4 was uniformly cut into small pieces, quickly hot-pressed into a flat film, and then cut into a size suitable for the glass substrate.

[0092] (2) Coat both sides of the cut polymer reversible interlocking network film ILN11 with solvent, place it between glass and TPT fluorine-containing backing plate, fix it with clips and heat and sonicate for 1 hour. After taking it out, vacuum hot press it at 130℃ for 10 minutes to obtain the final product.

[0093] Example 15: A method of using a polymer reversible interlocking network film

[0094] The method of use includes the following steps:

[0095] (1) The polymer reversible interlocking network film ILN11 obtained in Example 4 was uniformly cut into small pieces, quickly hot-pressed into a flat film, and then cut into a size suitable for the glass substrate.

[0096] (2) Coat both sides of the cut polymer reversible interlocking network film ILN11 with solvent, place it between glass and TPT fluorine-containing backing plate, fix it with clamps and heat and sonicate for 1.5h, take it out and vacuum hot press it at 120℃ for 15min to complete the process.

[0097] Example 16: A method of using a polymer reversible interlocking network film

[0098] The method of use includes the following steps:

[0099] (1) The polymer reversible interlocking network film ILN11 obtained in Example 4 was uniformly cut into small pieces, quickly hot-pressed into a flat film, and then cut into a size suitable for the glass substrate.

[0100] (2) Coat both sides of the cut polymer reversible interlocking network film ILN11 with solvent, place it between glass and TPT fluorine-containing backing plate, fix it with clamps and heat and sonicate for 2 hours. After taking it out, vacuum hot press it at 120℃ for 20 minutes to obtain the final product.

[0101] Example 17: A method for recycling and reusing a polymer reversible interlocking network film.

[0102] The recycling and reuse method includes the following steps:

[0103] (1) The polymer reversible interlocking network film ILN11 obtained in Example 4 was applied according to the usage method in Example 16. After the peeling failure, the entire film was soaked in an ethanol solution and heated and sonicated for 1 hour to obtain a polymer reversible interlocking network film that was recovered once.

[0104] (2) The recycled polymer reversible interlocking network film is applied and bonded again according to the method of use in Example 16, and the product is obtained.

[0105] Example 18: A method for recycling and reusing a polymer reversible interlocking network film.

[0106] The recycling and reuse method includes the following steps:

[0107] (1) The polymer reversible interlocking network film obtained in Example 17 was used according to the method of Example 16. After the peeling failure, the entire film was soaked in ethanol solution and heated and sonicated for 1 hour to obtain the polymer reversible interlocking network film that was recycled twice.

[0108] (2) The polymer reversible interlocking network film that has been recycled twice is applied and bonded again according to the method of use in Example 16, and the product is obtained.

[0109] Example 19: A method for recycling and reusing a polymer reversible interlocking network film.

[0110] The recycling and reuse method includes the following steps:

[0111] (1) The polymer reversible interlocking network film obtained twice in Example 18 was applied according to the usage method of Example 16. After the peeling failure, the entire film was immersed in an ethanol solution and heated and sonicated for 1 hour to obtain a polymer reversible interlocking network film that was recycled three times.

[0112] (2) The polymer reversible interlocking network film that has been recycled three times is applied and bonded again according to the method of use in Example 16, and the product is obtained.

[0113] Comparative Example 1: A method of using a commercial EVA film

[0114] The method of use includes the following steps:

[0115] Commercial EVA film is cut to a size suitable for glass substrates and then vacuum hot-pressed at 120°C for 20 minutes to obtain the final product.

[0116] Comparative Example 2: A method of using commercial double-sided tape

[0117] The method of use includes the following steps:

[0118] Cut commercially available 3M S52-1 high-strength double-sided tape to a size suitable for the glass substrate, then bond and press it together. Let it sit at room temperature for 2 days to complete the process.

[0119] Comparative Example 3: A method of using commercial double-sided tape

[0120] The method of use includes the following steps:

[0121] Cut commercially available double-sided tape to the appropriate size for the glass substrate, then adhere and press to bond. Let it sit at room temperature for 2 days to complete.

[0122] Comparative Example 4: A method of using a commercial adhesive

[0123] The method of use includes the following steps:

[0124] Mix the commercially available Baoligu BA-808AB adhesive evenly, apply it between the glass and TPT, press it to moisten, and let it stand at room temperature for 2 days to complete the process.

[0125] Comparative Example 5: A method of using a commercial adhesive

[0126] The method of use includes the following steps:

[0127] Apply commercially available Deli 502 all-purpose adhesive between the glass and TPT, press to moisten, and let stand at room temperature for 2 days to complete the process.

[0128] Experimental example:

[0129] The polymers prepared in Examples 1-8 were used as adhesive films, and their adhesive properties were tested. The adhesive properties of different applications of the same reversible interlocking network adhesive film (Examples 9-16), recycled reversible interlocking network adhesive films (Examples 17-19), industrial EVA adhesive films (Example 20), and various commercially available strong adhesives (Examples 21-24) were also tested.

[0130] Test method: The peel strength test was conducted according to GB / T2790-1995, "Adhesives 180° Peel Strength Test Method". The calculation formula is as follows:

[0131] σ 180° =F / B

[0132] Where: σ 180° —180° peel strength, kN / m;

[0133] F—peeling force, N;

[0134] B—Sample width, mm.

[0135] Table 1. Adhesion performance of interlocking network adhesive film and control sample

[0136]

[0137]

[0138] Table 1 shows that the peel strength of PU1 and PU2 to the glass-TPT fluorinated backsheet is 0 N / cm; the peel strength of PA to the glass-TPT fluorinated backsheet is 28 N / cm; the peel strength of the interlocking networks (ILN11, ILN21, and ILN31) with different formulations ranges from 6 N / cm to 22 N / cm. This indicates that the cross-linked polymers PU (PU1 and PU2) cannot bond to the glass substrate, and the cross-linked polymer PA cannot bond to the TPT fluorinated backsheet side. Using cross-linked polymers alone makes it difficult to bond two substrates simultaneously, while the interlocking network film can bond two substrates simultaneously, with a significantly better bonding effect than a single network. In Examples 7-8, the interpenetrating network film showed the highest bonding effect of 14 N / cm, indicating a fundamental difference between the interlocking network film and the interpenetrating network film. The interpenetrating network film cannot achieve the interlocking mixing effect, resulting in a significant difference in bonding effect, highlighting the advantages of the interlocking network. Examples 9-12, prepared solely through vacuum hot pressing without heating or ultrasound, achieved a maximum peel strength of 30 N / cm, demonstrating the significant impact of heating and ultrasound on delamination and adhesion. Examples 13-16, combining heating / ultrasound and vacuum hot pressing, resulted in a significantly improved adhesion, with a maximum peel strength of 70 N / cm. This indicates that simultaneous use of heating / ultrasound and vacuum hot pressing achieves optimal delamination and adhesion, further highlighting the crucial role of the interlocking network adhesive film in achieving superior adhesion. Examples 17-19 involved three recycling cycles of the interlocking network adhesive film. Even after three recycling cycles, the adhesive film still exhibited a high adhesion strength of 57 N / cm, achieved under mild recycling conditions, demonstrating the convenient and efficient recycling capability of the interlocking network adhesive film. Comparative Example 1 used a commonly used industrial EVA film. Under the same conditions, EVA's adhesion strength was only 19 N / cm, less than one-third of that of the present invention, indicating that the adhesion effect of the interlocking network adhesive film far surpasses that of the industrial EVA film. Comparative Examples 2-5 used several commercially available adhesive films and adhesives. Under the same conditions, commercial adhesives were insufficient to bond the two substrates. The best result was only 11 N / cm, which was far lower than the effect of the interlocking network adhesive film. This once again proved the huge advantages and strong effect of the interlocking network adhesive film in bonding.

[0139] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention and are not intended to limit the scope of protection of the present invention. Although the present invention has been described in detail with reference to preferred embodiments, those skilled in the art should understand that modifications or equivalent substitutions can be made to the technical solutions of the present invention without departing from the essence and scope of the technical solutions of the present invention.

Claims

1. The application of polymer reversible interlocking network film in the encapsulation, debonding, and recycling of solar cell systems, characterized in that, The polymer reversible interlocking network film comprises, by weight percentage: 50%-75% of crosslinked polymer A containing dynamic disulfide bonds and 25%-50% of crosslinked polymer B containing dynamic borate ester bonds; The crosslinked polymer A comprises the following raw materials in parts by weight: 24-30 parts of diisocyanate monomer, 45-55 parts of diol monomer, 8-11 parts of disulfide monomer, 2-4 parts of trihydroxy crosslinking agent, and 0.6-0.9 parts of metal chloride; The application of the polymer reversible interlocking network film in the encapsulation of solar cell systems includes the following steps: (1) Take the polymer reversible interlocking network film, cut it into pieces, and hot press it to make a flat film; (2) Coat the front and back sides of the flat film with solvent, place it between two substrates, heat and sonicate for 0.5 h-3.5 h, and vacuum hot press it at 60℃-150℃ for 5 min-60 min to obtain the final product; The two substrates are glass and TPT fluorinated backsheet; The preparation method of the crosslinked polymer B containing dynamic borate ester bonds is as follows: (1) 20 g glycidyl methacrylate and 180 g water are mixed evenly at room temperature, and then heated to 80℃ and reacted for 20 h to obtain a colorless and transparent solution; (2) The colorless and transparent solution is extracted multiple times with ethyl acetate, and the extract is dried with anhydrous magnesium sulfate and then filtered and evaporated to obtain a colorless and transparent viscous liquid, which is the hydroxyl-containing acrylate monomer; (3) 0.8 g acrylate monomer, 0.0164 g azobisisobutyronitrile, 8.11 g butyl acrylate and 2.27 g acrylic acid are dissolved in 40 ml tetrahydrofuran, added to a three-necked flask equipped with a gas protection device, ventilated at room temperature for 1 h, and then heated to 70℃ and reacted for 12 h. After the reaction is completed, the obtained colorless and viscous liquid is poured into n-hexane and cooled to precipitate. The precipitate is placed in a 60℃ oven and dried to obtain polyacrylate; (4) The polyacrylate is dissolved again in 40 ml N,N-dimethylformamide, and 0.332 The mixture of g of 1,4-phenylenediboronic acid was stirred until homogeneous, poured into a mold, and dried in an oven at 70°C until constant weight was obtained, thus yielding a cross-linked polymer containing dynamic borate ester bonds.

2. The application according to claim 1, characterized in that, The diisocyanate monomer is at least one of isophorone diisocyanate, toluene diisocyanate, diphenylmethane diisocyanate, terephthalimide diisocyanate, and hexamethylene diisocyanate.

3. The application according to claim 1, characterized in that, The diol monomer is at least one of polytetrahydrofuran diol, polycaprolactone diol, polycarbonate diol, polylactic acid diol, polyethylene glycol, polypropylene glycol, and polybutanediol.

4. The application according to claim 1, characterized in that, The disulfide monomer is at least one of 2-hydroxyethyl disulfide, 2,2-diaminodiphenyl disulfide, and 4,4-diaminodiphenyl disulfide; the trihydroxy crosslinking agent is triethanolamine or glycerol; and the metal ion in the metal chloride is at least one of zinc ion, zirconium ion, calcium ion, and iron ion.

5. The application according to any one of claims 1-4, characterized in that, The method for preparing the polymer reversible interlocking network film includes the following steps: (1) Take the cross-linked polymer A containing dynamic disulfide bonds and the cross-linked polymer B containing dynamic borate ester bonds respectively, crush, swell and stir to obtain solution A and solution B; (2) Under the conditions of 60℃-80℃ and argon atmosphere, the obtained solution A and solution B are mixed, stirred and dried to obtain the final product.

6. The application according to claim 5, characterized in that, In the preparation method of the polymer reversible interlocking network film, in step (1), the swelling time is 1 h-2 h; the stirring time is 10 min-20 min.

Images