Coupling-type macromolecular light conversion agent, preparation method thereof, encapsulating composition, encapsulating adhesive film and photovoltaic module

Abstract

This application provides a coupled macromolecular light-converting agent, its preparation method, encapsulation composition, encapsulation film, and photovoltaic module. The coupled macromolecular light-converting agent provided in this application includes a first light-converting agent and a second light-converting agent, which are coupled together. Each of the first and second light-converting agents is independently a benzotriazole compound having the structure shown in formula (I). The coupled macromolecular light-converting agent provided in this application is a coupling of the first and second light-converting agents of the benzotriazole compound. Its molecular weight is significantly increased, which not only significantly improves its compatibility with the matrix but also effectively inhibits its transfer in the encapsulation film, thus significantly improving light conversion performance.

Description

Technical Field

[0001] This application relates to the field of light conversion agent technology, and more specifically, to a coupling-type macromolecular light conversion agent and its preparation method, encapsulation composition, encapsulation film, and photovoltaic module. Background Technology

[0002] Encapsulating films containing light conversion agents can convert low-utilization ultraviolet light from solar cells into high-utilization visible light, broadening the spectral response range of solar cells, improving their photoelectric conversion efficiency, and protecting the passivation layer from ultraviolet light damage, thus extending the lifespan of the solar cells. Depending on the structure of the solar cell in practical applications, light conversion materials are typically mixed with ethylene-vinyl acetate copolymer (EVA) resin, ethylene-alpha olefin copolymer (POE) resin, polyvinyl butyral (PVB) resin, liquid silicone, etc., to construct encapsulating films or adhesives with light conversion functions, which are then applied to the light-receiving surface of the solar cell module. Currently, light conversion EVA encapsulating films are available on the market, but their performance is still unsatisfactory. The main problem is that organic small-molecule light conversion agents migrate slowly from the light-receiving encapsulating film to the back-light encapsulating film, causing a decrease in light conversion performance; while inorganic light conversion agents usually have poor compatibility with the matrix resin, resulting in a decrease in the light transmittance of the encapsulating film.

[0003] Existing technologies disclose the introduction of light-converting agents into the polymer matrix through grafting or copolymerization to prevent agent transfer. However, both grafting and copolymerization require changes to the chemical structure at the resin level, which places high demands on equipment and processes. Moreover, grafting cannot achieve a 100% grafting rate, resulting in residual byproducts in the system; copolymerization, on the other hand, presents the problem of polymerization competition, requiring significant adjustments to the catalyst, reaction medium, and polymerization process.

[0004] In view of the above, this application is hereby submitted. Summary of the Invention

[0005] The main objective of this application is to provide a coupling-type macromolecular light-converting agent and its preparation method, encapsulation composition, encapsulation film, and photovoltaic module, in order to solve the problems in the prior art where the light-converting agent is introduced into the polymer matrix by grafting to avoid the transfer of the light-converting agent, which results in the presence of byproducts in the system. On the other hand, the use of copolymerization to introduce the light-converting agent into the polymer matrix to avoid the transfer of the light-converting agent results in the problem of the polymerization competition rate, and the catalyst, reaction medium, and polymerization all need to be greatly adjusted.

[0006] To achieve the above objectives, according to one aspect of this application, a coupled macromolecular light-converting agent is provided, comprising a first light-converting agent and a second light-converting agent, wherein the first light-converting agent and the second light-converting agent are coupled together, wherein the first light-converting agent and the second light-converting agent are each independently a benzotriazole compound having the structure shown in formula (I):

[0007]

[0008] Wherein, n is 1 or 2, R1 is selected from H, substituted or unsubstituted C1-C20 alkyl groups or a first group; R2 and R3 are each independently selected from H, substituted or unsubstituted C1-C20 alkyl groups; the general formula of R and the first group is R5-R4*, where R5 represents a terminal group, R5 is selected from at least one of mercapto, carboxyl, hydroxyl, primary amino, secondary amino, epoxy, vinyl, ethynyl; R4 is selected from a direct bond, substituted or unsubstituted C1-C20 alkyl group, and the C and H in the alkyl group may be selectively substituted by O.

[0009] Furthermore, R is selected from *CH2-(CH2)5-CH=CH2, *CH2-CH2COO-CH=CH2, *CH2-(CH2)2-COOH, *CH2-(CH2)2-CH2OH, *CH2-(CH2)3-SH, and *CH2-(CH2)3-NH2.

[0010] Furthermore, R1 is selected from H, C1-C6 alkyl groups, *CH2-(CH2)5-CH=CH, CH2-(CH2)2-COOH, *CH2-(CH2)2-CH2OH, *CH2-(CH2)3-NH2, and *CH2-(CH2)3-SH.

[0011] Furthermore, R2 and R3 are each independently selected from H or C1-C6 alkyl groups.

[0012] Furthermore, the molecular weight of the coupling-type macromolecular light-converting agent is 1000-100000 g / mol.

[0013] Furthermore, the maximum absorption wavelength of the coupling-type macromolecular light-converting agent is between 300-400 nm, and the maximum emission wavelength is greater than 400 nm.

[0014] Furthermore, the first and second light-converting agents are each independently selected from at least one of the following compounds:

[0015]

[0016]

[0017]

[0018] According to a second aspect of this application, a method for preparing the coupling-type macromolecular light-converting agent provided in the first aspect is also provided. The preparation method includes: step S1, dissolving a first light-converting agent and a second light-converting agent in a solvent to obtain a first light-converting agent solution and a second light-converting agent solution; step S2, mixing the first light-converting agent solution, the second light-converting agent solution, a coupling agent, and an optional initiator to carry out a coupling reaction to obtain the coupling-type macromolecular light-converting agent.

[0019] Further, the coupling agent is selected from at least one of bis(2-mercaptoethyl) ether, 4,4'-bis(mercaptomethyl)biphenyl, C2-C10 diols, polyethylene glycol, polytetrahydrofuran, poloxamer, polyvinyl alcohol, hydroxyl-terminated (poly)-terminated polybutadiene, hydroxyl-terminated (poly)-terminated polyethylene, hydroxyl-terminated liquid nitrile rubber, C2-C10 dicarboxylic acid, carboxyl-terminated polybutadiene, carboxyl-terminated polyethylene, carboxyl-terminated nitrile rubber, polyacrylic acid, polymethacrylic acid, C2-C10 diamine, polyetheramine, amino-terminated liquid nitrile rubber, amino-terminated polybutadiene, amino-terminated polyethylene, 1,4-butanediol glycidyl ether, glycidyl ether, epoxy resin, C4-C18 diene, polybutadiene, ethylene propylene diene monomer (EPDM), and styrene-butadiene rubber.

[0020] According to a third aspect of this application, an encapsulation composition is also provided, comprising the following components in parts by mass: 100 parts of matrix resin, 0.01-1 parts of macromolecular light-converting agent, 0-1 parts of hindered amine light stabilizer, 0-2 parts of organic peroxide, 0-3 parts of co-crosslinking agent, and 0-3 parts of tackifier; wherein the macromolecular light-converting agent is the coupling-type macromolecular light-converting agent provided in the first aspect above.

[0021] Furthermore, the matrix resin includes at least one of EVA resin, POE resin, PVB resin, ethylene-acrylate resin, ethylene-methacrylate resin, and liquid silicone.

[0022] Furthermore, the hindered amine stabilizers include at least one of the following: hexadecyl 3,5-di-tert-butyl-4-hydroxybenzoate, tris(1,2,2,6,6-pentamethyl-4-piperidinyl)phosphite sebacate bis-2,2,6,6-tetramethylpiperidinol ester, bis-1-decanooxy-2,2,6,6-tetramethylpiperidin-4-ol sebacate, a polymer of succinic acid and 4-hydroxy-2,2,6,6-tetramethyl-1-piperidinol, N,N'-bis(2,2,6,6-tetramethyl-4-piperidinyl)1,6-hexanediamine, and a polymer of morpholine-2,4,6-trichloro-1,3,5-triazine.

[0023] Furthermore, the organic peroxide includes at least one of peroxydiacyl, dialkyl peroxide, peroxide ester, and peroxide ketal.

[0024] Furthermore, the crosslinking agent includes at least one of triallyl isocyanurate, triallyl cyanurate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, and pentaerythritol triacrylate.

[0025] Furthermore, the tackifier includes at least one of γ-aminopropyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-(2,3-epoxypropoxy)propyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, vinyltriethoxysilane, vinyltri(β-methoxyethoxysilane), and allyltrimethoxysilane.

[0026] According to a fourth aspect of this application, an encapsulating film is provided, the material of which includes the coupling-type macromolecular light-converting agent provided in the first aspect or the encapsulating composition provided in the third aspect.

[0027] According to a fifth aspect of this application, a photovoltaic module is provided, the photovoltaic module including an encapsulating film, the material of which includes the coupling-type macromolecular light-converting agent provided in the first aspect or the encapsulation composition provided in the third aspect.

[0028] Applying the technical solution of this application, the coupling macromolecular light-converting agent provided by this application is a coupling of the first and second light-converting agents of benzotriazole compounds. Its molecular weight is significantly increased, which not only significantly improves its compatibility with the matrix, but also significantly increases its molecular weight, effectively inhibiting its transfer in the film and significantly improving the light conversion performance. Detailed Implementation

[0029] It should be noted that, unless otherwise specified, the embodiments and features described in this application can be combined with each other. The present application will now be described in detail with reference to the embodiments.

[0030] As described in the background section of this application, the small organic molecule light-converting agent in commercially available light-converting EVA films migrates slowly from the light-receiving encapsulation film to the back-light-receiving encapsulation film, causing a decrease in light conversion performance. Existing technologies disclose methods to prevent the migration of the light-converting agent by introducing it into the polymer matrix through grafting or copolymerization. However, grafting cannot achieve a 100% grafting rate, resulting in residual byproducts in the system. Copolymerization presents challenges due to the competitive polymerization rate, requiring significant adjustments to the catalyst, reaction medium, and polymerization process, which is very difficult. To address these issues, this application provides a coupling-type macromolecular light-converting agent, its preparation method, an encapsulation film, an encapsulation composition, and a photovoltaic module.

[0031] In one typical embodiment of this application, a coupled macromolecular light-converting agent is provided, comprising a first light-converting agent and a second light-converting agent, which are coupled together; wherein the first light-converting agent and the second light-converting agent are each independently a benzotriazole compound having the structure shown in formula (I):

[0032]

[0033] Wherein, n is 1 or 2, R1 is selected from H, substituted or unsubstituted C1-C20 alkyl groups, or a first group; R2 and R3 are each independently selected from H, substituted or unsubstituted C1-C20 alkyl groups; R and the first group have the general formulas R5-R4*, where R5 represents a terminal group, and R5 is selected from at least one of mercapto, carboxyl, hydroxyl, primary amino, secondary amino, epoxy, vinyl, and ethynyl; R4 is selected from a direct bond, substituted or unsubstituted C1-C20 alkyl groups.

[0034] In this application, "*" represents a linking bond. Alkyl groups include both straight-chain and branched alkyl groups, which can be either straight-chain or branched. Examples of C1-C20 alkyl groups include: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, 2-methylbutyl, n-pentyl, sec-pentyl, neopentyl, n-hexyl-neohexyl, n-heptyl, n-octyl, 2-ethylhexyl, trifluoromethyl, pentafluoroethyl, 2,2,2-trifluoroethyl, etc.

[0035] In this application, the term "substituted or unsubstituted" refers to substitution by one or more substituents selected from the following: deuterium; halogen group; nitrile group; nitro group; hydroxyl group; carbonyl group; ester group; imide group; amino group; phosphine oxide group; alkoxy group; aryloxy group; alkyl thio group; aryl thio group; alkyl sulfonyl group; silyl group; boron group; alkyl group; cycloalkyl group; alkenyl group; aryl group; aralkyl group; arylenyl group; alkylaryl group; alkylamine group; aralkylamine group; heteroarylamine group; arylamine group; arylphosphine group; or heterocyclic group containing at least one of N, O, and S, or without substituents, or substituted by substituents linked together with two or more of the exemplified substituents, or without substituents. For example, the term "substituents linked together with two or more substituents" can be biphenyl. That is, biphenyl can be aryl, or can be interpreted as substituents linked together with two phenyl groups.

[0036] The coupling macromolecular light-converting agent provided in this application is a coupling of the first and second light-converting agents of benzotriazole compounds. Its molecular weight is significantly increased, which not only significantly improves its compatibility with the matrix, but also significantly increases its molecular weight, effectively inhibiting its transfer in the film and significantly improving the light-converting performance.

[0037] In some embodiments, R being *CH2-(CH2)5-CH=CH2, *CH2-CH2COO-CH=CH2, *CH2-(CH2)2-COOH, *CH2-(CH2)2-CH2OH, *CH2-(CH2)3-SH, or *CH2-(CH2)3-NH2 is more conducive to simplifying the preparation process of coupling-type macromolecular light-converting agents.

[0038] In some embodiments, R1 is H, a C1-C6 alkyl group, CH2-(CH2)5-CH=CH2, *CH2-CH2COO-CH=CH2, *CH2-(CH2)2-COOH, *CH2-(CH2)2-CH2OH, *CH2-(CH2)3-SH, or *CH2-(CH2)3-NH2, wherein the C1-C6 alkyl group is such as methyl, ethyl, n-propyl, or isopropyl.

[0039] In some embodiments, R2 and R3 are each independently C1-C6 alkyl groups, such as methyl, ethyl, n-propyl, isopropyl, etc.

[0040] To further improve the stability of the coupling-type macromolecular light-converting agent in the encapsulation film, the molecular weight of the coupling-type macromolecular light-converting agent is preferably 1000-100000 g / mol, such as 1000 g / mol, 2000 g / mol, 5000 g / mol, 8000 g / mol, 10000 g / mol, 20000 g / mol, 30000 g / mol, 50000 g / mol, 60000 g / mol, 80000 g / mol, 90000 g / mol, 100000 g / mol, or any range of two values.

[0041] To further improve the light conversion performance, the maximum absorption wavelength of the coupling-type macromolecular light conversion agent is preferably between 300-400 nm, and the maximum emission wavelength is greater than 400 nm.

[0042] In some specific embodiments, the first and second light-converting agents are each independently selected from at least one of the following compounds:

[0043]

[0044]

[0045]

[0046]

[0047] In a second typical embodiment of this application, a method for preparing the above-mentioned coupling macromolecular light-converting agent is also provided. The preparation method includes: step S1, dissolving the first light-converting agent and the second light-converting agent in a solvent to obtain a first light-converting agent solution and a second light-converting agent solution; step S2, mixing the first light-converting agent solution, the second light-converting agent solution, the coupling agent and an optional initiator to carry out a coupling reaction to obtain the coupling macromolecular light-converting agent.

[0048] The preparation method of the coupling-type macromolecular light-converting agent provided in this application is simple, easy to implement, and low in cost. It does not introduce byproducts or other impurities and can effectively ensure the quality of the encapsulation film.

[0049] In this application, the specific type of coupling agent is not limited, and any commonly used coupling agents in the art are acceptable, including but not limited to bis(2-mercaptoethyl) ether, 4,4′-bis(mercaptomethyl)biphenyl, C2-C10 diols, polyethylene glycol, polytetrahydrofuran, poloxamer, polyvinyl alcohol, hydroxyl-terminated (poly)-terminated polybutadiene, hydroxyl-terminated (poly)-terminated polyethylene, hydroxyl-terminated liquid nitrile rubber, C2-C10 dicarboxylic acid, carboxyl-terminated polybutadiene, carboxyl-terminated polyethylene, carboxyl-terminated nitrile rubber, polyacrylic acid, polymethacrylic acid, C2-C10 diamine, polyetheramine, amino-terminated liquid nitrile rubber, amino-terminated polybutadiene, amino-terminated polyethylene, 1,4-butanediol glycidyl ether, glycidyl ether, epoxy resin, C4-C18 diene, polybutadiene, ethylene propylene diene monomer (EPDM) rubber, and styrene-butadiene rubber, or any one or more mixtures thereof.

[0050] The "C2-C10 diols" mentioned above refer to diols containing two hydroxyl groups (-OH) with a carbon chain length between 2 and 10 carbon atoms. "C2" represents two carbon atoms, while "C10" represents ten carbon atoms.

[0051] The aforementioned "C2-C10 dicarboxylic acids" refer to organic acids containing two carboxyl groups (-COOH), with a carbon chain length between 2 and 10 carbon atoms. "C2" indicates two carbon atoms, while "C10" indicates ten carbon atoms.

[0052] The aforementioned "C2-C10 diamine" refers to a compound containing two primary amino groups (-NH2), which are attached to carbon atoms, and the chain length of these carbon atoms ranges from 2 to 10 carbon atoms.

[0053] The aforementioned "terminal (multi)hydroxyl polybutadiene" refers to polymers that contain hydroxyl (-OH) functional groups at the ends or multiple positions of the polybutadiene molecular chain.

[0054] The aforementioned "terminal (multi) hydroxyl polyethylene" refers to a polymer that contains hydroxyl (-OH) functional groups at the ends or multiple positions of the polyethylene molecular chain.

[0055] To further improve the efficiency of the coupling reaction, the preferred temperature for the coupling reaction is 0-95℃, and the preferred reaction time is 10-24h.

[0056] Typical, but not limiting, temperatures for coupling reactions include 0°C, 5°C, 10°C, 20°C, 30°C, 40°C, 50°C, 55°C, 60°C, 65°C, 70°C, 75°C, 80°C, 85°C, 90°C, 95°C, or any range of two values; and reaction times include 10h, 11h, 12h, 13h, 14h, 15h, 18h, 20h, 22h, 24h, or any range of two values.

[0057] In some specific embodiments, in step S2 above, the first light-converting agent solution, the second light-converting agent solution, the coupling agent and the optional initiator are mixed and reacted at 0-95°C for 10-24 hours to obtain a coupling-type light-converting macromolecule reaction solution. The coupling-type light-converting macromolecule reaction solution is then purified to obtain a coupling-type light-converting macromolecule light-converting agent.

[0058] For example, the purification of the coupling-type optically convertible macromolecule reaction solution includes the following steps: adding ethyl acetate to the coupling-type optically convertible macromolecule reaction solution for precipitation, then separating the solid and liquid to obtain a solid reactant, washing the solid reactant multiple times with ethyl acetate, and then vacuum drying it overnight at 30°C to obtain the coupling-type optically convertible macromolecule optically converting agent.

[0059] An exemplary preparation process for a coupling-type macromolecular light-converting agent is shown below:

[0060]

[0061] Note: "cyclohexane" refers to cyclohexane; "LP" refers to lauroyl peroxide.

[0062] In a third typical embodiment of this application, an encapsulation composition is provided, comprising the following components by mass parts: 100 parts of matrix resin, 0.01-1 parts of macromolecular light-converting agent, 0-1 parts of hindered amine light stabilizer, 0-2 parts of organic peroxide, 0-3 parts of co-crosslinking agent, and 0-3 parts of tackifier; wherein the macromolecular light-converting agent is the coupling-type macromolecular light-converting agent provided in the first typical embodiment above.

[0063] Typical, but not limiting, in the encapsulation compositions provided in this application, the amount of the coupling-type macromolecular light-converting agent, based on 100 parts by weight of the matrix resin, is such as 0.01 parts, 0.02 parts, 0.05 parts, 0.08 parts, 0.1 parts, 0.15 parts, 0.2 parts, 0.3 parts, 0.4 parts, 0.5 parts, 0.6 parts, 0.7 parts, 0.8 parts, 1 part, or any range of two such values; the amount of the hindered amine light stabilizer is such as 0 parts, 0.01 parts, 0.02 parts, 0.05 parts, 0.08 parts, 0.1 parts, 0.15 parts, 0.2 parts, 0.3 parts, 0.4 parts, 0.5 parts, 0.6 parts, 0.7 parts, 0.8 parts, 0.9 parts, 1 part, or any range of two values; the amount of organic peroxide used is 0 parts, 0.01 parts, 0.02 parts, 0.05 parts, 0.08 parts, 0.1 parts, 0.15 parts, 0.2 parts, 0.3 parts, 0.4 parts, 0 0.5 parts, 0.6 parts, 0.7 parts, 0.8 parts, 0.9 parts, 1 part, 1.1 parts, 1.2 parts, 1.3 parts, 1.4 parts, 1.5 parts, 1.6 parts, 1.7 parts, 1.8 parts, 1.9 parts, 2 parts, or any range of two values; the amount of crosslinking agent is 0 parts, 0.01 parts, 0.02 parts, 0.05 parts, 0.08 parts, 0.1 parts, 0.2 parts, 0.5 parts, 0.8 parts, 1.0 parts, 1.2 parts, 1. 5 parts, 1.8 parts, 2.0 parts, 2.2 parts, 2.5 parts, 2.8 parts, 3.0 parts, or any range of two values; for tackifiers, 0 parts, 0.01 parts, 0.02 parts, 0.05 parts, 0.08 parts, 0.1 parts, 0.2 parts, 0.5 parts, 0.8 parts, 1.0 parts, 1.2 parts, 1.5 parts, 1.8 parts, 2.0 parts, 2.2 parts, 2.5 parts, 2.8 parts, 3.0 parts, or any range of two values.

[0064] The encapsulation composition provided in this application forms an encapsulation film by combining a coupling-type macromolecular light-converting agent with a matrix resin and optional additives. The coupling-type macromolecular light-converting agent is stably dispersed in the encapsulation film and is not prone to migration, which can effectively broaden the spectral response range of solar cells and improve the photoelectric conversion efficiency of solar cells.

[0065] [Matrix resin]

[0066] In this application, the matrix resin is a commonly used resin in the art, including but not limited to one or more of EVA resin, POE resin, PVB resin, ethylene-acrylate resin, ethylene-methacrylate resin, and liquid silicone. The aforementioned EVA resin refers to ethylene-vinyl acetate copolymer; POE resin refers to polyolefin elastomer; and PVB resin refers to polyvinyl butyral resin.

[0067] [Hindered amine stabilizers]

[0068] In this application, hindered amine stabilizers are commonly used stabilizers in the art, including but not limited to any one or more of the following: hexadecyl 3,5-di-tert-butyl-4-hydroxybenzoate, tris(1,2,2,6,6-pentamethyl-4-piperidinyl)phosphite sebacate bis-2,2,6,6-tetramethylpiperidinol ester, bis-1-decyloxy-2,2,6,6-tetramethylpiperidin-4-ol sebacate, polymers of succinic acid and 4-hydroxy-2,2,6,6-tetramethyl-1-piperidinol, N,N'-bis(2,2,6,6-tetramethyl-4-piperidinyl)1,6-hexanediamine, and polymers of morpholine-2,4,6-trichloro-1,3,5-triazine.

[0069] [Organic peroxides]

[0070] In this application, the organic peroxide is a commonly used organic peroxide in the art, including but not limited to any one or more of diacyl peroxide, dialkyl peroxide, peroxide ester, and peroxide ketal.

[0071] The aforementioned peroxide esters include any one or more combinations of ethyl 3,3-bis(tert-butylperoxy)butyrate, ethyl 3,3-bis(tert-pentylperoxy)butyrate, tert-butyl peroxybenzoate, tert-butyl peroxyacetate, tert-butyl peroxyisopropyl carbonate, tert-butyl peroxide-3,5,5-trimethylhexanoate, tert-butyl peroxide-2-ethylhexyl carbonate, n-butyl 4,4-bis(tert-butylperoxy)valerate, tert-pentyl peroxybenzoate, tert-pentyl peroxyacetate, tert-pentyl peroxide-3,5,5-trimethylhexanoate, tert-pentyl peroxide-2-ethylhexyl carbonate, tert-pentyl peroxyisobutyrate, and 2,5-dimethyl-2,5-bis(benzoylperoxy)hexane.

[0072] The aforementioned diacyl peroxide includes any one or a combination of benzoyl peroxide, lauric acid peroxide, and decanoic acid peroxide.

[0073] The aforementioned peroxide ketal includes any one or more combinations of 2,2-bis(tert-butylperoxy)butane, 1,1-bis(tert-butylperoxy)cyclohexane, 1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane, 1,1-bis(tert-pentylperoxy)cyclohexane, and 1,1-bis(tert-pentylperoxy)-3,3,5-trimethylcyclohexane.

[0074] The aforementioned dialkyl peroxides include dicumyl peroxide and / or 2,5-dimethyl-2,5-bis-(tert-butylperoxy)hexane.

[0075] [Cross-linking agent]

[0076] In this application, the co-crosslinking agent is a commonly used co-crosslinking agent in the art, including but not limited to any one or more of allyl isocyanurate, triallyl cyanurate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, and pentaerythritol triacrylate.

[0077] [Tackifier]

[0078] In this application, the tackifier is a commonly used tackifier in the art, including but not limited to any one or more of γ-aminopropyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-(2,3-epoxypropoxy)propyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, vinyltriethoxysilane, vinyltri(β-methoxyethoxysilane), and allyltrimethoxysilane.

[0079] In the fourth typical embodiment of this application, an encapsulating film is also provided, the material of which includes the coupling-type macromolecular light-converting agent provided in the first typical embodiment or the encapsulating composition provided in the third typical embodiment.

[0080] The encapsulating film provided in this application contains a coupling-type macromolecular light-converting agent. This coupling-type macromolecular light-converting agent is stably dispersed in the encapsulating film and is not prone to migration, which can effectively broaden the spectral response range of photovoltaic modules and improve the photoelectric conversion efficiency of photovoltaic modules.

[0081] In a fifth exemplary embodiment of this application, a photovoltaic module is also provided, the photovoltaic module including an encapsulating film, the material of which includes the coupling-type macromolecular light-converting agent provided in the first exemplary embodiment or the encapsulating composition provided in the second exemplary embodiment.

[0082] The photovoltaic module provided in this application uses an encapsulating film containing a coupling-type macromolecular light-converting agent. This coupling-type macromolecular light-converting agent is stably dispersed in the encapsulating film and is not prone to migration, which can effectively broaden the spectral response range of the photovoltaic module and improve the photoelectric conversion efficiency of the photovoltaic module.

[0083] The beneficial effects of this application will be further illustrated below with reference to embodiments and comparative examples.

[0084] Example 1

[0085] This embodiment provides a coupling-type macromolecular light-converting agent, the structural formula of which is shown in formula (1) below:

[0086]

[0087] Its preparation method includes the following steps:

[0088] 9.31 g (20 mmol) of 4,7-bis(4-tert-butylphenyl)-(6-hexenyl)-2H-benzotriazole was completely dissolved in 50 mL of cyclohexane. 1.24 g (9 mmol) of bis(2-mercaptoethyl) ether was added, followed by 0.30 g of lauroyl peroxide LP as the initiator. The mixture was then heated and stirred at 75 °C for 12 hours. After the reaction was complete, the reaction solution was cooled to room temperature, the solvent was removed by rotary evaporation, and the product was separated by column chromatography. The product was dried under vacuum at 30 °C overnight to give 8.4 g of compound 1, with a calculated yield of 87%.

[0089] Example 2

[0090] This embodiment provides a coupling-type macromolecular light-converting agent, the structural formula of which is shown in formula (2) below:

[0091]

[0092] Its preparation method includes the following steps:

[0093] 9.43 g (20 mmol) of 4,7-bis(4-tert-butylphenyl)-(4-butyritinyl)-2H-benzotriazole was completely dissolved in 50 mL of cyclohexane. 0.74 g (9 mmol) of 1,6-hexadiene and 0.30 g of lauroyl peroxide LP (initiator) were added, and the mixture was heated and stirred at 75 °C for 12 hours. After the reaction was complete, the reaction solution was cooled to room temperature, the solvent was removed by rotary evaporation, and the product was separated by column chromatography. The product was dried under vacuum at 30 °C overnight to give 7.8 g of the compound, with a calculated yield of 85%.

[0094] Example 3

[0095] This embodiment provides a coupling-type macromolecular light-converting agent, the structural formula of which is shown in formula (3) below:

[0096]

[0097] Its preparation method includes the following steps:

[0098] 9.39 g (20 mmol) of 4,7-bis(4-tert-butylphenyl)-(butyric acid)-2H-benzotriazole was completely dissolved in 50 mL of dichloromethane. Polyethylene glycol (18 g, Mn = 2000 g / mol), 0.9 g of 4-dimethylaminopyridine catalyst, and 3.8 g of dicyclohexylcarbodiimide dehydrating agent were added. The mixture was then heated and stirred at 25 °C for 24 hours. After the reaction was complete, the mixture was filtered, and the filtrate was washed several times with water. Anhydrous sodium sulfate was added to absorb the water, and the mixture was filtered again. The solvent was removed by rotary evaporation of the filtrate. The product was dried under vacuum at 30 °C overnight to obtain 25 g of the compound, with a calculated yield of 85%.

[0099] Example 4

[0100] This embodiment provides a coupling-type macromolecular light-converting agent, the structural formula of which is shown in formula (4) below:

[0101]

[0102] Its preparation method includes the following steps:

[0103] 9.11 g (20 mmol) of 4,7-bis(4-tert-butylphenyl)-(4-butanol)-2H-benzotriazole was completely dissolved in 50 mL of dichloromethane. 27 g of carboxyl-terminated polybutadiene (Mn = 3000 g / mol), 0.90 g of 4-dimethylaminopyridine catalyst, and 3.6 g of dicyclohexylcarbodiimide dehydrating agent were added. The mixture was then heated and stirred at 25 °C for 24 hours. After the reaction was complete, the mixture was filtered, and the filtrate was washed several times with water. 500 mL of ethyl acetate was added to precipitate the macromolecular light-converting agent. The mixture was then filtered again, and the filtrate was discarded. The residue was washed three times with 100 mL of ethyl acetate and dried under vacuum at 30 °C overnight to obtain 31 g of the compound, with a calculated yield of 80%.

[0104] Example 5

[0105] This embodiment provides a coupling-type macromolecular light-converting agent, the structural formula of which is shown in formula (5) below:

[0106]

[0107] Its preparation method includes the following steps:

[0108] 9.09 g (20 mmol) of 4,7-bis(4-tert-butylphenyl)-(4-butylamino)-2H-benzotriazole was completely dissolved in 50 mL of cyclohexane. 0.74 g (9 mmol) of 1,4-butanediol glycidyl ether was added, followed by 0.09 g of triethylamine catalyst. The mixture was then heated and stirred at 75 °C for 24 hours. After the reaction was complete, the reaction solution was cooled to room temperature, the solvent was removed by rotary evaporation, and the product was separated by column chromatography. The product was dried under vacuum at 30 °C overnight to give 7.2 g of the compound, with a calculated yield of 81%.

[0109] Example 6

[0110] This embodiment provides a coupling-type macromolecular light-converting agent, the structural formula of which is shown in formula (6) below:

[0111]

[0112] Its preparation method includes the following steps:

[0113] 9.07 g (20 mmol) of 4,7-bis(4-tert-butylphenyl)-(3,4-butepoxy)-2H-benzotriazole was completely dissolved in 50 mL of cyclohexane. 36 g of terminal amine polybutadiene (Mn = 4000 g / mol) and 0.09 g of triethylamine catalyst were added, followed by heating and stirring at 75 °C for 24 hours. After the reaction was complete, the mixture was filtered, and the filtrate was washed several times with water. 500 mL of ethyl acetate was added to precipitate the macromolecular light-converting agent, followed by filtration. The filtrate was discarded, and the residue was washed three times with 100 mL of ethyl acetate and dried under vacuum at 30 °C overnight to obtain 34 g of the compound, with a calculated yield of 78%.

[0114] Example 7

[0115] This embodiment provides a coupling-type macromolecular light-converting agent, the structural formula of which is shown in formula (7) below:

[0116]

[0117] Its preparation method includes the following steps:

[0118] 9.37 g (20 mmol) of 4,7-bis(4-tert-butylphenyl)-(4-butylamino)-2H-benzotriazole was completely dissolved in 50 mL of cyclohexane. 0.74 g (9 mmol) of 1,4-butanediol glycidyl ether was added, followed by 0.09 g of triethylamine catalyst. The mixture was then heated and stirred at 75 °C for 24 hours. After the reaction was complete, the reaction solution was cooled to room temperature, the solvent was removed by rotary evaporation, and the product was separated by column chromatography. The product was dried under vacuum at 30 °C overnight to give 6.9 g of the compound, with a calculated yield of 75%.

[0119] Example 8

[0120] This embodiment provides a coupling-type macromolecular light-converting agent, the structural formula of which is shown in formula (8) below:

[0121]

[0122] Its preparation method includes the following steps:

[0123] 9.27 g (20 mmol) of 4,7-bis(4-tert-butylphenyl)-(6-hexynyl)-2H-benzotriazole was completely dissolved in 50 mL of cyclohexane. 1.24 g (9 mmol) of bis(2-mercaptoethyl) ether and 0.30 g of azobisisobutyronitrile (azobisisobutyronitrile) initiator were added, and the mixture was heated and stirred at 75 °C for 12 hours. After the reaction was complete, the reaction solution was cooled to room temperature, the solvent was removed by rotary evaporation, and the product was separated by column chromatography. The product was dried under vacuum at 30 °C overnight to give 8.0 g of the compound, with a calculated yield of 83%.

[0124] Example 9

[0125] This embodiment provides a coupling-type macromolecular light-converting agent, the structural formula of which is shown in formula (9) below:

[0126]

[0127] Its preparation method includes the following steps:

[0128] 9.39 g (20 mmol) of 4,7-bis(4-tert-butylphenyl)-(butyric acid)-2H-benzotriazole was completely dissolved in 5000 mL of dichloromethane. Polyethylene glycol (810 g, Mn = 90000 g / mol), 0.9 g of 4-dimethylaminopyridine catalyst, and 10.0 g of dicyclohexylcarbodiimide dehydrating agent were added. The mixture was then heated and stirred at 25 °C for 24 hours. After the reaction was complete, the mixture was filtered, and the filtrate was washed several times with water. Anhydrous sodium sulfate was added to absorb the water, and the mixture was filtered again. The solvent was removed by rotary evaporation of the filtrate. The product was dried under vacuum at 30 °C overnight to obtain 795 g of the compound, with a calculated yield of 97%.

[0129] It should be noted that the difference between compound (9) and compound (3) is that the value of n is different. The value of n represents the degree of polymerization of polyethylene glycol. Since the molecular weight of polyethylene glycol used in Example 3 is completely different from that used in this example, compound (9) and compound (3) are also different.

[0130] Comparative Example 1

[0131] This comparative example provides an organic small molecule light-converting agent, which is 4,7-bis(4-tert-butylphenyl)-(6-hexenyl)-2H-benzotriazole (TAH).

[0132] Example 10

[0133] This embodiment provides an encapsulation composition comprising, by weight, 100 parts of EVA resin (Hanwha Total, model: E280PV), 0.5 parts of organic peroxide tert-amyl peroxide 2-ethylenehexyl carbonate (Arkema, model: Luperox TAEC), 0.6 parts of crosslinking agent triallyl isocyanurate TAIC, and 0.1 parts of macromolecular light-converting agent. The macromolecular light-converting agent is the coupling-type macromolecular light-converting agent provided in Example 1.

[0134] Example 11

[0135] The difference between this embodiment and Example 10 is that the amount of macromolecular light-converting agent used is 1 part.

[0136] Example 12

[0137] The difference between this embodiment and Example 10 is that the amount of macromolecular light-converting agent used is 0.01 parts.

[0138] Examples 13-19

[0139] The difference between Examples 13-19 and Example 10 is that the coupling-type macromolecular light-converting agent provided in Examples 2-8 is used instead of the coupling-type macromolecular light-converting agent provided in Example 1 as the macromolecular light-converting agent.

[0140] Example 20

[0141] The difference between this embodiment and Example 10 is that the macromolecular light-converting agent provided in Example 9 is used to replace the coupling-type macromolecular light-converting agent provided in Example 1 as the macromolecule, and the amount of the macromolecular light-converting agent provided in Example 9 is 1 part.

[0142] Comparative Example 2

[0143] The difference between this comparative example and Example 10 is that the small molecule light-converting agent provided in Comparative Example 1 is used instead of the coupling-type macromolecule light-converting agent provided in Example 1.

[0144] Test case

[0145] The encapsulation compositions provided in the examples and comparative examples were prepared into encapsulation films. The specific steps included: thoroughly mixing the components of the encapsulation composition using a mixer, and then melt-extruding the mixture using a screw extruder to obtain a film with a density of 450 g / m³. 2 The encapsulation film.

[0146] The above-mentioned encapsulation films are assembled into solar modules, specifically including the following steps: front glass, the above-mentioned encapsulation film, silicon heterojunction cell (Huasheng cell), ultraviolet-transmitting encapsulating film (Foster F406P), and back glass are arranged in the order from bottom to top to obtain a laminate. Then, the laminate is placed in a vacuum laminator and pressed at 145°C for 15 minutes to obtain a solar module. Except for the upper encapsulation film, the other conditions of each module are controlled to be the same.

[0147] Power retention rate test method: The above solar modules were left to stand at 25℃ for 6 hours, and then the power was measured using a solar power simulator (Gsola GIV-20A). The initial power was recorded as P1. The solar modules were then placed in a UV aging chamber for UV irradiation, with a total irradiation measurement of 300 kWh. The power after irradiation was recorded as P2, and the power retention rate was calculated as P2 / P1*100%.

[0148] Test method for light transfer agent migration distance: Take the newly prepared solar module and let it stand at 25℃ for 6 hours. Then bake it in an oven at 120℃ for 48 hours, 144 hours and 288 hours. Measure the distance (unit / cm) from the edge of the cell to the back of the cell. The greater the distance, the more severe the migration of the light transfer agent.

[0149] The results are shown in Table 1 below.

[0150] Table 1

[0151]

[0152]

[0153] As can be seen from the above description, the above embodiments of this application achieve the following technical effects: The encapsulation composition provided by this application forms an encapsulation film by combining a coupling macromolecular light-converting agent with a matrix resin and optional additives. The coupling macromolecular light-converting agent is stably dispersed in the encapsulation film and is not prone to migration, which can effectively broaden the spectral response range of the solar cell and improve the photoelectric conversion efficiency of the solar cell.

[0154] The above description is merely a preferred embodiment of this application and is not intended to limit this application. Various modifications and variations can be made to this application by those skilled in the art. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of this application should be included within the protection scope of this application.

Claims

1. A coupling-type macromolecule sunscreen agent, characterized by comprising a macromolecule having a plurality of hydroxyl groups and a coupling agent having a plurality of isocyanate groups. The coupled macromolecular light-converting agent includes a first light-converting agent and a second light-converting agent, and the first light-converting agent and the second light-converting agent are coupled together; wherein, the first light-converting agent and the second light-converting agent are each independently a benzotriazole compound, and the benzotriazole compound has the structure shown in formula (I): Wherein, n is 1 or 2, and R1 is selected from H, substituted or unsubstituted C1-C20 alkyl groups, or the first group; R2 and R3 are each independently selected from H, substituted or unsubstituted C1-C20 alkyl groups; R and the first group each have the general formula R5-R4*, wherein R5 represents a terminal group, and R5 is selected from at least one of mercapto, carboxyl, hydroxyl, primary amino, secondary amino, epoxy, vinyl, and ethynyl; R4 is selected from a direct bond, substituted or unsubstituted C1-C20 alkyl group, and the C and H in the alkyl group may be selectively substituted by O.

2. The coupling-type macromolecular light-converting agent according to claim 1, characterized in that, The R is selected from *CH2-(CH2)5-CH=CH2, *CH2-CH2COO-CH=CH2, *CH2-(CH2)2-COOH, *CH2-(CH2)2-CH2OH, *CH2-(CH2)3-SH, and *CH2-(CH2)3-NH2; And / or, R1 is selected from H, C1-C6 alkyl groups, *CH2-(CH2)5-CH=CH, CH2-(CH2)2-COOH, *CH2-(CH2)2-CH2OH, *CH2-(CH2)3-NH2, *CH2-(CH2)3-SH; And / or, R2 and R3 are each independently selected from H or C1-C6 alkyl groups.

3. The coupling-type macromolecular light-converting agent according to claim 1, characterized in that, The molecular weight of the coupling macromolecular light-converting agent is 1000-100000 g / mol; And / or, the maximum absorption wavelength of the coupled macromolecular light-converting agent is between 300-400 nm, and the maximum emission wavelength is greater than 400 nm.

4. The coupling-type macromolecular light-converting agent according to any one of claims 1 to 3, characterized in that, The first and second light-converting agents are each independently selected from at least one of the following compounds:

5. The method for preparing the coupling-type macromolecular light-converting agent according to any one of claims 1 to 4, characterized in that, The preparation method includes: Step S1: Dissolve the first light-converting agent and the second light-converting agent in a solvent to obtain a first light-converting agent solution and a second light-converting agent solution; Step S2: The first light-converting agent solution, the second light-converting agent solution, the coupling agent, and an optional initiator are mixed and subjected to a coupling reaction to obtain the coupled macromolecular light-converting agent.

6. The preparation method according to claim 5, characterized in that, In step S2, the coupling agent is selected from at least one of bis(2-mercaptoethyl) ether, 4,4′-bis(mercaptomethyl)biphenyl, C2-C10 diols, polyethylene glycol, polytetrahydrofuran, poloxamer, polyvinyl alcohol, hydroxyl-terminated (poly)-terminated polybutadiene, hydroxyl-terminated (poly)-terminated polyethylene, hydroxyl-terminated liquid nitrile rubber, C2-C10 dicarboxylic acid, carboxyl-terminated polybutadiene, carboxyl-terminated polyethylene, carboxyl-terminated nitrile rubber, polyacrylic acid, polymethacrylic acid, C2-C10 diamine, polyetheramine, amino-terminated liquid nitrile rubber, amino-terminated polybutadiene, amino-terminated polyethylene, 1,4-butanediol glycidyl ether, glycidyl ether, epoxy resin, C4-C18 diene, polybutadiene, ethylene propylene diene monomer (EPDM), and styrene-butadiene rubber.

7. An encapsulation composition, characterized in that, The encapsulation composition comprises the following components in parts by weight: 100 parts of matrix resin, 0.01-1 parts of macromolecular light-converting agent, 0-1 parts of hindered amine light stabilizer, 0-2 parts of organic peroxide, 0-3 parts of crosslinking agent, and 0-3 parts of tackifier; wherein the macromolecular light-converting agent is a coupling type macromolecular light-converting agent as described in any one of claims 1 to 4.

8. The encapsulation composition according to claim 7, characterized in that, The matrix resin includes at least one of EVA resin, POE resin, PVB resin, ethylene-acrylate resin, ethylene-methacrylate resin, and liquid silicone.

9. The encapsulation composition according to claim 7, characterized in that, The hindered amine stabilizers include at least one of the following: hexadecyl 3,5-di-tert-butyl-4-hydroxybenzoate, tris(1,2,2,6,6-pentamethyl-4-piperidinyl)phosphite sebacate bis-2,2,6,6-tetramethylpiperidinol ester, bis-1-decyloxy-2,2,6,6-tetramethylpiperidin-4-ol sebacate, a polymer of succinic acid and 4-hydroxy-2,2,6,6-tetramethyl-1-piperidinol, N,N'-bis(2,2,6,6-tetramethyl-4-piperidinyl)1,6-hexanediamine, and a polymer of morpholine-2,4,6-trichloro-1,3,5-triazine; And / or, the organic peroxide includes at least one of diacyl peroxide, dialkyl peroxide, peroxide ester, and peroxide ketal; And / or, the co-crosslinking agent includes at least one of triallyl isocyanurate, triallyl cyanurate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, and pentaerythritol triacrylate. And / or, the tackifier comprises at least one of γ-aminopropyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-(2,3-epoxypropoxy)propyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, vinyltriethoxysilane, vinyltri(β-methoxyethoxysilane), and allyltrimethoxysilane.

10. An encapsulating film, characterized in that, The material of the encapsulating film includes any one of the coupling macromolecular light-converting agents according to claims 1 to 4 or any one of the encapsulating compositions according to claims 7 to 9.

11. A photovoltaic module, characterized in that, The photovoltaic module includes an encapsulating film, the material of which includes the coupling macromolecular light-converting agent according to any one of claims 1 to 4 or the encapsulating composition according to any one of claims 7 to 9.

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