A macromolecular light-converting agent and its preparation method and photovoltaic encapsulation light-converting adhesive film

Abstract

The present invention belongs to the field of photovoltaic materials. The present invention relates to a macromolecular light conversion agent and a preparation method thereof, a photovoltaic encapsulation light conversion adhesive film, and the preparation method of the macromolecular light conversion agent comprises the following steps: subjecting benzotriazole to a substitution reaction with liquid bromine to obtain an intermediate product I; subjecting the intermediate product I to a substitution reaction with a bromoester to obtain an intermediate product II; subjecting the intermediate product II to a coupling reaction with a vinyl phenyl boronic acid derivative to obtain an intermediate product III; subjecting bromofluorene to a substitution reaction with an alkyl bromide to obtain an intermediate product IV; subjecting the intermediate product IV to a coupling reaction with a vinyl phenyl boronic acid derivative to obtain an intermediate product V; subjecting the intermediate product III to an intermediate product V to a free radical polymerization reaction to obtain a macromolecular light conversion agent. The self-made macromolecular light conversion agent effectively solves the problems of narrow and single absorption peak, low light utilization, poor stability, and easy precipitation of the organic light conversion agent benzotriazole commonly used in the current photovoltaic plugging eye adhesive film.

Description

Technical Field

[0001] The invention relates to a photovoltaic macromolecular light conversion agent and a photovoltaic encapsulation light conversion adhesive film. The invention belongs to the field of photovoltaic materials. Background Art

[0002] EVA (ethylene-vinyl acetate copolymer) is a thermoplastic polymer material. As a solar cell packaging material, it has many advantages, including low cost, easy molding, outstanding optical properties, excellent mechanical properties and electrical properties. However, if used for a longer period of time in harsh outdoor climates, EVA will age and yellow, resulting in a decrease in the photoelectric conversion efficiency of the battery components or failure due to short circuit damage. Ultraviolet aging is precisely the main factor causing the aging and yellowing of EVA film. The current technology mainly adds ultraviolet absorbers to EVA to reduce the damage of ultraviolet rays to EVA film; however, the addition of ultraviolet absorbers will convert ultraviolet light into low-energy heat energy that cannot be used by solar cells, resulting in the loss of light energy and reducing the efficiency of solar cells.

[0003] Therefore, it is necessary to develop a packaging material that can completely absorb the ultraviolet light in the sun and convert it into visible light that can be used by battery components, namely, a packaging light-converting adhesive film. This can not only effectively prevent ultraviolet light from damaging battery components, but also have a gain effect on the photoelectric conversion efficiency of the battery.

[0004] The key to developing encapsulated light-converting adhesive films is to develop efficient and stable light-converting agents. According to literature, compared with inorganic, organic, and inorganic composite light-converting agents, organic light-converting agents have more advantages in terms of price, structure, and compatibility with adhesive films. The currently reported organic light-converting agents based on benzotriazole have only one absorption peak, which is about 350nm, and the effective absorption range is narrow, and the absorption of ultraviolet light below 400nm is not sufficient. This will cause the corresponding light-converting adhesive film to be unable to effectively absorb ultraviolet rays in sunlight, and thus cannot effectively protect the battery components.

[0005] In view of the above factors, it is necessary to design an organic light conversion agent with a broader absorption peak to solve the technical problems existing in the existing industry. Summary of the invention

[0006] The purpose of the present invention is to provide a method for preparing a macromolecular light conversion agent in view of the problem that the organic light conversion agent used in the prior art encapsulation light conversion adhesive film has a narrow and single absorption peak. The present invention prepares a macromolecular light conversion agent by molecular design and through formula design, effectively solving the above-mentioned problem and having broad application potential. The technical solution adopted by the present invention to solve its technical problem is:

[0007] A method for preparing a macromolecular light conversion agent comprises the following steps:

[0008] S11, subjecting benzotriazole to a substitution reaction with liquid bromine to obtain an intermediate product I;

[0009] S12, subjecting the intermediate product I to a substitution reaction with a bromoester to obtain an intermediate product II;

[0010] S13, coupling the intermediate product II with a vinylbenzene boronic acid derivative to obtain an intermediate product III;

[0011] S14, subjecting bromofluorene to a substitution reaction with an alkyl bromide to obtain an intermediate product IV;

[0012] S15, coupling the intermediate product IV with a vinylbenzene boronic acid derivative to obtain an intermediate product V;

[0013] S16, subjecting the intermediate product III to a free radical polymerization reaction with the intermediate product V to obtain a macromolecular light conversion agent.

[0014] Furthermore, the molar ratio of the benzotriazole to the liquid bromine is 1:(1.2-1.5).

[0015] Furthermore, the molar ratio of the intermediate product I to the bromoester is 1:(1.2-1.5).

[0016] Furthermore, the molar ratio of the intermediate product II to the vinylbenzene boronic acid derivative is 1:(1.2-1.6).

[0017] Furthermore, the molar ratio of the bromofluorene to the alkyl bromide is 1:(2.4-3.0).

[0018] Furthermore, the molar ratio of the intermediate product IV to the vinylbenzene boronic acid derivative is 1:(1.2-1.6).

[0019] Furthermore, the molar ratio of the intermediate product III to the intermediate product V is (0.5-0.8): (0.2-0.5).

[0020] Another object of the present invention is to provide a macromolecular light conversion agent prepared by the above-mentioned method for preparing a macromolecular light conversion agent.

[0021] Another object of the present invention is to provide a photovoltaic encapsulation light conversion adhesive film, comprising the macromolecular light conversion agent as described above.

[0022] Further, the following raw materials are included in parts by weight:

[0023] 100 parts of polyolefin resin;

[0024] Cross-linking agent 0.5-1.5 parts;

[0025] 1.0-1.5 parts of auxiliary cross-linking agent;

[0026] 0.5-8.0 parts of the macromolecular light conversion agent;

[0027] Antioxidant 0.05-0.25 parts;

[0028] Light stabilizer 0.05-0.3 parts;

[0029] Coupling agent 0.3-0.8 parts.

[0030] Furthermore, the polyolefin resin is selected from at least one of EVA resin and POE resin.

[0031] Beneficial effects of the present invention:

[0032] (1) The present invention provides a macromolecular light conversion agent for photovoltaic use, which is a copolymer of fluorene and benzotriazole and contains chemical structures such as long-chain ester groups, long-chain hydrocarbon groups, and benzene rings. First, through molecular structure design, substitution of the benzene ring can change the symmetry of benzotriazole, so that it has a wide ultraviolet absorption at 300-400nm; fluorene has a large absorption at 250-350nm in the ultraviolet region; therefore, its copolymer can have a wide absorption in the range of 250-400nm; second, the structures of benzotriazole and fluorene are both substituted by benzene rings, and the benzene ring, as an electron-rich structure, has excellent electron transmission ability, can effectively conduct electrons and improve the photoelectric effect; third, the macromolecular structure of the copolymer is mostly a conjugated structure, which is conducive to the ability to directly transfer electrons along the macromolecular chain. transfer, with higher light conversion efficiency; fourth, the core light conversion structure in the copolymer is in the side chain, which can reduce the interaction between molecules caused by conjugated extension and has higher luminescence efficiency; fifth, the macromolecular copolymer structure has a larger red shift in the emission wavelength, which is beneficial to the absorption of battery energy; sixth, the long-chain ester structure and long fatty chain structure in the macromolecular copolymer structure have similar chemical structures to photovoltaics, which is beneficial to the improvement of the dispersion compatibility of the macromolecular light conversion agent; seventh, due to the chain entanglement of the macromolecular chain, it has the advantages of lower migration and precipitation performance, higher heat resistance and so on.

[0033] (2) The present invention provides a photovoltaic encapsulation light-converting adhesive film. The macromolecular light-converting agent in the formula system converts the ultraviolet light that is originally absorbed by the ultraviolet light absorber and lost into visible light, thereby fully utilizing the light and improving the photoelectric conversion efficiency of the solar cell. At the same time, it avoids the damage of ultraviolet light to the substrate photovoltaic adhesive film, which has great practical significance.

[0034] (3) The present invention provides a method for preparing a macromolecular light conversion agent for photovoltaics and a light conversion adhesive film for photovoltaic encapsulation. The light conversion agent in the formula system is prepared using common raw materials, and the photovoltaic light conversion adhesive film has the effect of an auxiliary light stabilizer after formula design, which is conducive to the industrialization of the product of the present invention and has strong operability. BRIEF DESCRIPTION OF THE DRAWINGS

[0035] The present invention is further described below in conjunction with the accompanying drawings and embodiments.

[0036] FIG1 is a hydrogen NMR spectrum of the intermediate product I in Example 1 of the present invention;

[0037] FIG2 is a hydrogen NMR spectrum of intermediate product II in Example 1 of the present invention;

[0038] FIG3 is a hydrogen NMR spectrum of the intermediate product III in Example 1 of the present invention;

[0039] FIG4 is a hydrogen NMR spectrum of the intermediate product IV in Example 1 of the present invention;

[0040] FIG5 is a hydrogen NMR spectrum of the intermediate product V in Example 1 of the present invention;

[0041] FIG6 is a hydrogen NMR spectrum of the macromolecular light conversion agent in Example 1 of the present invention. DETAILED DESCRIPTION

[0042] 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.

[0043] The existing organic light conversion agents have narrow and single absorption peaks. At the same time, due to their small molecular structure, they have poor stability. Therefore, it is necessary to design a new type of organic light conversion agent, whose structure and molecular weight are similar to those of the polymer matrix, so as to enhance its dispersibility and compatibility. It also has good stability, is not prone to oxidation and decomposition, and has a wider absorption peak to solve the technical problems existing in the existing industry.

[0044] The purpose of the present invention is to develop a photovoltaic macromolecular light conversion agent and photovoltaic encapsulation light conversion adhesive film to meet the application requirements of existing photovoltaic encapsulation materials. The idea of ​​realization is: to make a benzotriazole-based macromolecular light conversion agent to ensure its compatibility and dispersibility in photovoltaic encapsulation materials while having high stability and light conversion efficiency. Specifically: using benzotriazole as the parent body for asymmetric modification and electron-rich structure benzene ring bonding modification; and free radical copolymerization with fluorene to form a macromolecular chain structure with a core light conversion structure as a side group while expanding the absorption peak width. The theoretical basis of realization is: benzotriazole undergoes liquid bromine substitution reaction, then substitution reaction with bromoester, followed by coupling reaction with phenylboronic acid; fluorene undergoes substitution reaction with bromoalkane, followed by coupling reaction with phenylboronic acid; finally, the two intermediates are subjected to free radical polymerization to obtain a macromolecular light conversion agent. The above-mentioned macromolecular light conversion agent is a copolymer of fluorene and benzotriazole, and contains chemical structures such as long-chain ester groups, long-chain hydrocarbon groups, benzene rings, etc., has a larger absorption peak, excellent compatibility and stability with the matrix, and higher light conversion efficiency, etc., and does not migrate or precipitate. The implementation method of the present invention is as follows:

[0045] The present invention provides a method for preparing a macromolecular light conversion agent, comprising the following steps:

[0046] S11, add benzotriazole to hydrobromic acid, stir, slowly drop liquid bromine into the reaction system, heat and reflux for 18-24 hours, add saturated sodium bisulfite aqueous solution to quench, extract with dichloromethane, separate the liquids, take the organic phase, add anhydrous sodium sulfate to dry, filter, take the solution, separate by column chromatography (eluent: petroleum ether / dichloromethane = 1 / 10, V / V), and dry under vacuum at 40°C for 8 hours to obtain intermediate I;

[0047] Preferably, the usage ratio of benzotriazole, hydrobromic acid, liquid bromine, saturated sodium bisulfite aqueous solution, dichloromethane, and anhydrous sodium sulfate in this step is 0.1 mol: 0.75 mol: (0.12-0.15) mol: 400 mL: 300 mL: 5 g.

[0048] S12, take the intermediate product I, potassium carbonate and bromoester, add them to N,N-dimethylformamide, stir and heat at 40-60°C for 40-48h, cool to room temperature after the reaction is completed, wash with saturated ammonium chloride solution three times, extract with ethyl acetate, separate the liquids, take the organic phase, add anhydrous sodium sulfate to dry, filter, take the solution, separate by column chromatography (eluent: petroleum ether / dichloromethane = 1 / 5, V / V), and dry in vacuo at 40°C for 8h to obtain the intermediate product II.

[0049] Preferably, in this step, the usage ratio of the intermediate product I, potassium carbonate, bromoester, N,N-dimethylformamide, saturated ammonium chloride solution, ethyl acetate, and anhydrous sodium sulfate is 0.1 mol: 0.25 mol: (0.12-0.15) mol: 200 mL: 300 mL: 400 mL: 5 g.

[0050] The preferred carbon number of the bromoester is C6-C 10 , so as to avoid the number of C atoms being greater than 10, the reaction activity being low, affecting the reaction efficiency, and having an adverse effect on the subsequent reaction efficiency; the number of C atoms being less than 6, the molecular chain being too small, and being unable to form a good compatibility with the matrix resin, affecting the product performance; therefore, the bromoester in the present invention can be ethyl 4-bromovalerate, ethyl 5-bromovalerate, ethyl 6-bromohexanoate, ethyl 7-bromoheptanoate, tert-butyl 5-bromovalerate, ethyl 8-bromooctanoate, etc.; and preferably tert-butyl 5-bromovalerate.

[0051] S13, take the intermediate product II, vinylbenzene boronic acid derivative, potassium carbonate, tetrakis(triphenylphosphine)palladium, mix them and add them to the reactor, and perform N2 replacement protection; after adding the mixed solvent, stir and heat under reflux for 12-24 hours, add deionized water for oscillation, extract with dichloromethane, separate the liquids, take the organic phase, add anhydrous sodium sulfate for drying, filter, take the solution, separate by column chromatography (eluent: petroleum ether / dichloromethane = 1 / 10, V / V), and vacuum dry at 40°C for 8 hours to obtain a benzotriazole-containing monomer, i.e., the intermediate product III.

[0052] The usage ratio of intermediate II, vinylbenzene boronic acid derivative, potassium carbonate, tetrakis(triphenylphosphine)palladium, mixed solvent, deionized water, dichloromethane, and anhydrous sodium sulfate is 0.1 mol: (0.12-0.16) mol: 0.5 mol: 0.005-0.01 mol: 150 mL: 200 mL: 300 mL: 5 g;

[0053] The mixed solvent is toluene, n-butanol, and deionized water in a volume ratio of 3:5:1.

[0054] The vinylbenzeneboronic acid derivative may be 4-vinylbenzeneboronic acid, 3-vinylbenzeneboronic acid, 2-vinylbenzeneboronic acid, benzocyclobutene-4-boronic acid, 3-vinyl-5-fluorobenzeneboronic acid, 3-vinyl-4-fluorobenzeneboronic acid, 3-vinyl-5-chlorobenzeneboronic acid, etc., and preferably 4-vinylbenzeneboronic acid.

[0055] S14, add bromofluorene, alkyl bromide, tetrabutylammonium bromide and dimethyl sulfoxide to a 50wt% sodium hydroxide solution, stir, and heat to 75-85°C for reaction for 6-10h; after the reaction, add deionized water for oscillation, add petroleum ether for extraction, separate the liquids, take the upper organic phase, separate by column chromatography (eluent: petroleum ether), and vacuum dry at 40°C for 8h to obtain an intermediate product IV.

[0056] The dosage ratio of bromofluorene, alkyl bromide, dimethyl sulfoxide, 50wt% sodium hydroxide solution, deionized water, and petroleum ether is 0.1mol: (0.24-0.30)mol: 10mL: 40mL: 100mL: 150mL;

[0057] The amount of tetrabutylammonium bromide used is 2.0% of the molar number of bromofluorene;

[0058] Bromofluorene is a monobromo-substituted fluorene, and may be 1-bromo-9H-fluorene, 2-bromo-9H-fluorene, 3-bromo-9H-fluorene, 4-bromo-9H-fluorene, etc., and preferably 2-bromo-9H-fluorene.

[0059] Alkyl bromide is an aliphatic hydrocarbon bromide with a certain chain length, and its carbon number is C6-C 10 , which can be 1-bromohexane, 1-bromoheptane, 1-bromooctane, 1-bromononane, 1-bromodecane, etc.; and preferably 1-bromooctane.

[0060] S15, take the intermediate product IV, vinylbenzene boronic acid derivative, potassium carbonate, tetrakis(triphenylphosphine)palladium, mix them and add them to the reactor, and replace them with N2 for protection; after adding the mixed solvent, stir and heat under reflux for 12-24 hours, add deionized water for oscillation, extract with dichloromethane, separate the liquids, take the organic phase, add anhydrous sodium sulfate to dry, filter, take the solution, separate it by column chromatography (eluent: petroleum ether / dichloromethane = 1 / 10, V / V), and vacuum dry it at 40°C for 8 hours to obtain a fluorene-containing monomer, i.e., the intermediate product V.

[0061] The usage ratio of intermediate product IV, vinylbenzene boronic acid derivative, potassium carbonate, tetrakis(triphenylphosphine)palladium, mixed solvent, deionized water, dichloromethane, and anhydrous sodium sulfate is 0.1 mol: (0.12-0.16) mol: 0.5 mol: 0.005-0.01 mol: 150 mL: 200 mL: 300 mL: 5 g;

[0062] The mixed solvent is toluene, n-butanol, and deionized water in a volume ratio of 3:5:1.

[0063] The vinylbenzeneboronic acid derivative may be 4-vinylbenzeneboronic acid, 3-vinylbenzeneboronic acid, 2-vinylbenzeneboronic acid, benzocyclobutene-4-boronic acid, 3-vinyl-5-fluorobenzeneboronic acid, 3-vinyl-4-fluorobenzeneboronic acid, 3-vinyl-5-chlorobenzeneboronic acid, etc., and preferably 4-vinylbenzeneboronic acid.

[0064] S16, add intermediate III, intermediate V, and benzoyl peroxide to anhydrous toluene, evacuate, fill with nitrogen for protection, heat to 75-85°C and react for 20-28 hours; after the reaction, add methanol to obtain insoluble matter; add to acetone and shake for 6 hours, filter, take out the insoluble matter, and vacuum dry at 40°C for 8 hours to obtain the target product, i.e., the macromolecular light conversion agent.

[0065] The usage ratio of intermediate product III, intermediate product V, anhydrous toluene, methanol and acetone is (0.2-0.5) mol: (0.5-0.8) mol: 1000 mL: 3000 mL: 3000 mL;

[0066] The amount of benzoyl peroxide used was 1.0wt% of the total mass of the reactants.

[0067] The preparation process of the macromolecular light conversion agent is as follows:

[0068] ;

[0069] Wherein, m and n are both natural numbers greater than 1.

[0070] Another object of the present invention is to provide a macromolecular light conversion agent, which is prepared by the preparation method described above.

[0071] The macromolecular light conversion agent in the present invention is a copolymer of fluorene and benzotriazole. The long-chain ester group and long-chain hydrocarbon group in the molecule can improve the dispersibility with the matrix, and the macromolecular structure can form a chain entanglement with the matrix, effectively improving the compatibility with the matrix resin; fluorene, benzene ring, benzotriazole, etc. form a conjugated structure to enhance the electron transmission capacity and improve the light conversion efficiency; at the same time, benzotriazole is asymmetrically modified and copolymerized with fluorene to effectively broaden the absorption peak width in the ultraviolet region; and the molecular structure is further designed so that the core light conversion structure is in the side chain, reducing the adverse effects of conjugated extension and improving the luminous efficiency. In the structure of the macromolecular light conversion agent in the present invention, each chemical structure has the effect of synergistically promoting the improvement of light conversion efficiency.

[0072] Another object of the present invention is to provide a photovoltaic encapsulation light conversion adhesive film, which includes the macromolecular light conversion agent as described above.

[0073] Specifically, the photovoltaic encapsulation light-converting adhesive film of the present invention preferably comprises the following raw materials in parts by weight:

[0074] 100 parts of polyolefin resin;

[0075] Cross-linking agent 0.5-1.5 parts;

[0076] 1.0-1.5 parts of auxiliary cross-linking agent;

[0077] 0.5-8.0 parts of macromolecular light conversion agent;

[0078] Antioxidant 0.05-0.25 parts;

[0079] Light stabilizer 0.05-0.3 parts;

[0080] Coupling agent 0.3-0.8 parts.

[0081] Furthermore, it is preferred that the polyolefin resin is at least one selected from EVA resin and POE resin.

[0082] Wherein, when the polyolefin resin is EVA resin, the photovoltaic encapsulation light-converting adhesive film preferably includes the following raw materials in parts by weight:

[0083] EVA resin 100 parts;

[0084] Cross-linking agent 0.5-1.5 parts;

[0085] 1.0-1.5 parts of auxiliary cross-linking agent;

[0086] 0.5-8.0 parts of macromolecular light conversion agent;

[0087] Antioxidant 0.1-0.25 parts;

[0088] Light stabilizer 0.1-0.3 parts;

[0089] Coupling agent 0.3-0.5 parts.

[0090] When the polyolefin resin is POE resin, the photovoltaic encapsulation light-converting adhesive film preferably includes the following raw materials in parts by weight:

[0091] POE resin 100 parts;

[0092] Cross-linking agent 0.5-1.5 parts;

[0093] 1.0-1.5 parts of auxiliary cross-linking agent;

[0094] 0.5-8.0 parts of macromolecular light conversion agent;

[0095] Antioxidant 0.05-0.20 parts;

[0096] Light stabilizer 0.05-0.20 parts;

[0097] Coupling agent 0.4-0.8 parts.

[0098] The EVA resin in the present invention has a VA mass content of 28-33%. Unless otherwise specified, the following embodiments and comparative examples of the present invention preferably purchase EVA resin with a VA mass content of 33% and a melt index (MI) of 31 from DuPont, USA.

[0099] Unless otherwise specified, the POE resin in the following embodiments and comparative examples of the present invention is of model XUS38660, purchased from The Dow Chemical Company of the United States.

[0100] In the present invention, the crosslinking agent is preferably an organic peroxide, specifically benzoyl peroxide, 2,5-dimethyl-2,5-bis(benzoylperoxide)hexane, dicyclohexyl peroxycarbonate or diisopropylbenzene peroxide, etc.; unless otherwise specified, the crosslinking agent in the following examples and comparative examples of the present invention is benzoyl peroxide.

[0101] The auxiliary cross-linking agent in the present invention is a multifunctional allyl group and / or acryloxy group.

[0102] The allyl cross-linking aid may be triallyl cyanurate or triallyl isocyanurate.

[0103] The acryloxy cross-linking auxiliary agent may be any one of trimethylolpropane trimethacrylate, ethoxylated trimethylolpropane triacrylate, propoxylated trimethylolpropane triacrylate, propoxylated neopentyl glycol diacrylate, and pentaerythritol triacrylate, or a combination thereof.

[0104] Unless otherwise specified, the auxiliary crosslinking agent in the following examples and comparative examples of the present invention is triallyl isocyanurate, trimethylolpropane trimethacrylate, propoxylated trimethylolpropane triacrylate and pentaerythritol triacrylate added in a mass ratio of 7:2:4:2.

[0105] The antioxidant in the present invention is a combination of hindered phenols and phosphites. The hindered phenol antioxidant can be antioxidant 1010, antioxidant 1076, antioxidant 264, antioxidant 2246, etc.; and preferably antioxidant 1010. The phosphite antioxidant can be antioxidant 168, antioxidant 242, antioxidant TPP, etc.; and preferably antioxidant 168. Unless otherwise specified, the antioxidant in the following examples and comparative examples of the present invention is antioxidant 1010 and antioxidant 168 added in a mass ratio of 1:2.

[0106] The light stabilizer in the present invention is a hindered amine light stabilizer to avoid competition with the light conversion agent for ultraviolet rays. The hindered amine light stabilizer can be UV-292, UV-770 or GW540, etc., and preferably UV-292. Unless otherwise specified, the light stabilizer in the following examples and comparative examples of the present invention is UV-292.

[0107] The coupling agent in the following examples and comparative examples of the present invention is a silane coupling agent, specifically a vinyl silane coupling agent, which may be KH151, KH171 or KH172, etc.; and, unless otherwise specified, the coupling agent in the following examples and comparative examples is KH172.

[0108] In order to better understand the above invention, the present invention also provides a method for preparing a photovoltaic encapsulation light-converting adhesive film, which is operated as follows, including the following steps:

[0109] S21, mixing, i.e.

[0110] Add the raw materials according to the formula ratio into a mixer, mix and stir at a temperature of 40° C. and a rotation speed of 80 rpm for 2 h to obtain a mixed raw material;

[0111] S22, extrusion;

[0112] Specifically, the EVA extrusion process is as follows:

[0113] The mixed raw materials in S21 are placed in a twin-screw extruder, melt-blended and extruded at a temperature of 80°C in the first zone, 90°C in the second zone, 98°C in the third zone, a die temperature of 102°C, and a rotation speed of 50 rpm, and the mixture is cast through a cast film die and cooled through a casting roller;

[0114] The POE extrusion process is as follows:

[0115] The mixed raw materials in S21 are placed in a twin-screw extruder, melt blended and extruded at a temperature of 90°C in the first zone, 100°C in the second zone, 105°C in the third zone, a die temperature of 110°C, and a rotation speed of 50 rpm, and the mixture is cast through a cast film die and cooled through a casting roller;

[0116] The EPE co-extrusion process is as follows:

[0117] The EVA layer raw material in S21 is placed in a twin-screw extruder, and melt blended at a temperature of 80°C in the first zone, 90°C in the second zone, 98°C in the third zone, a die temperature of 102°C, and a rotation speed of 50rpm; the POE layer raw material in S21 is placed in a twin-screw extruder, and melt blended at a temperature of 90°C in the first zone, 100°C in the second zone, 105°C in the third zone, a die temperature of 110°C, and a rotation speed of 50rpm; the material is cast through a co-extrusion cast film die head, and cooled through a casting roller;

[0118] S23, film formation, i.e.

[0119] After thickness measurement, edge pressing, shaping, edge trimming and rolling, a photovoltaic encapsulation light-converting adhesive film with a thickness of 500 μm is obtained;

[0120] Among them, the EPE packaging light-converting film involved has a total thickness of 500μm.

[0121] In order to further understand the present invention, a photovoltaic macromolecular light conversion agent and a photovoltaic encapsulation light conversion adhesive film provided by the present invention are described in detail below in conjunction with specific embodiments. The protection scope of the present invention is not limited by the following embodiments.

[0122] Example 1

[0123] A method for preparing a macromolecular light conversion agent comprises the following steps:

[0124] S11, add benzotriazole to hydrobromic acid, stir, slowly add liquid bromine to the reaction system, heat and reflux for 20 hours; add saturated sodium bisulfite aqueous solution to quench, extract with dichloromethane, separate the liquids, take the organic phase, add anhydrous sodium sulfate to dry, filter, take the solution, separate by column chromatography (eluent: petroleum ether / dichloromethane = 1 / 10, V / V), and vacuum dry at 40°C for 8 hours to obtain intermediate I;

[0125] The usage ratio of benzotriazole, hydrobromic acid, liquid bromine, saturated sodium bisulfite aqueous solution, dichloromethane, and anhydrous sodium sulfate is 0.1 mol: 0.75 mol: 0.14 mol: 400 mL: 300 mL: 5 g.

[0126] Its H NMR spectrum can be found at Figure 1 As shown, the H NMR spectrum data are as follows: 1 H NMR (400 MHz, CDCl3, δ ppm): 7.2-7.8 (3H, benzene ring); 10.22 (1H, -NH-).

[0127] S12, take the intermediate product I, potassium carbonate, tert-butyl 5-bromovalerate, add them to N,N-dimethylformamide, stir and heat at 50°C for 46 hours, cool to room temperature after the reaction is completed, wash with saturated ammonium chloride solution three times, extract with ethyl acetate, separate the liquids, take the organic phase, add anhydrous sodium sulfate to dry, filter, take the solution, separate by column chromatography (eluent: petroleum ether / dichloromethane = 1 / 5, V / V), and dry in vacuo at 40°C for 8 hours to obtain the intermediate product II.

[0128] The usage ratio of intermediate product I, potassium carbonate, tert-butyl 5-bromovalerate, N,N-dimethylformamide, saturated ammonium chloride solution, ethyl acetate, and anhydrous sodium sulfate is 0.1 mol: 0.25 mol: 0.15 mol: 200 mL: 300 mL: 400 mL: 5 g.

[0129] Its H NMR spectrum can be found at Figure 2 As shown, the H NMR spectrum data are as follows: 1 H NMR (400MHz, CDCl3, δ ppm): 7.2-7.8(3H, benzene ring); 3.32(2H, -N-CH2-); 1.29(4H, -CH2-); 2.31(2H, -CH2-COO-); 1.20(9H, -CH3).

[0130] S13, take the intermediate product II, 4-vinylbenzeneboronic acid, potassium carbonate, tetrakis(triphenylphosphine)palladium, mix them and add them to the reactor, and replace them with N2 for protection; after adding the mixed solvent, stir and heat to reflux for 18 hours; add deionized water to shake, extract with dichloromethane, separate the liquids, take the organic phase, add anhydrous sodium sulfate to dry, filter, take the solution, separate it by column chromatography (eluent: petroleum ether / dichloromethane = 1 / 10, V / V), and dry it in vacuo at 40°C for 8 hours to obtain the intermediate product III.

[0131] The usage ratio of intermediate II, 4-vinylbenzeneboronic acid, potassium carbonate, tetrakis(triphenylphosphine)palladium, mixed solvent, deionized water, dichloromethane, and anhydrous sodium sulfate is 0.1 mol: 0.15 mol: 0.5 mol: 0.008 mol: 150 mL: 200 mL: 300 mL: 5 g;

[0132] The mixed solvent is toluene, n-butanol, and deionized water in a volume ratio of 3:5:1.

[0133] Its H NMR spectrum can be found at Figure 3 As shown, the H NMR spectrum data are as follows: 1 H NMR (400MHz, CDCl3, δ ppm):7.2-7.8(7H, benzene ring); 6.78(1H, CH2=CH-Ph); 5.79(1H, CH2=CH-Ph); 5.21(1H, CH2=CH-Ph); 3.32(2H, -N-CH2-); 1.29(4H, -CH2-); 2.31(2H,-CH2-COO-); 1.20(9H,-CH3).

[0134] S14, add 2-bromo-9H-fluorene, 1-bromooctane, tetrabutylammonium bromide and dimethyl sulfoxide to a 50wt% sodium hydroxide solution, stir, heat to 80°C and react for 8.5h; after the reaction, add deionized water for oscillation, add petroleum ether for extraction, separate the liquids, take the upper organic phase, separate by column chromatography (eluent: petroleum ether), and vacuum dry at 40°C for 8h to obtain an intermediate product IV.

[0135] The dosage ratio of 2-bromo-9H-fluorene, 1-bromooctane, dimethyl sulfoxide, 50wt% sodium hydroxide solution, deionized water, and petroleum ether is 0.1mol: 0.28mol: 10mL: 40mL: 100mL: 150mL;

[0136] The amount of tetrabutylammonium bromide used is 2.0% of the moles of 2-bromo-9H-fluorene;

[0137] Its H NMR spectrum can be found at Figure 4 As shown, the H NMR spectrum data are as follows: 1 H NMR (400 MHz, CDCl3, δ ppm): 7.2-7.8 (7H, benzene ring); 1.27 (28H, -CH2-); 0.93 (6H, -CH3).

[0138] S15, take the intermediate product IV, 4-vinylbenzeneboronic acid, potassium carbonate, tetrakis(triphenylphosphine)palladium, mix them and add them to the reactor, and perform N2 replacement protection; after adding the mixed solvent, stir and heat to reflux for 18 hours; add deionized water to shake, extract with dichloromethane, separate the liquids, take the organic phase, add anhydrous sodium sulfate to dry, filter, take the solution, separate it by column chromatography (eluent: petroleum ether / dichloromethane = 1 / 10, V / V), and dry it in vacuo at 40°C for 8 hours to obtain the intermediate product V.

[0139] The usage ratio of intermediate product IV, 4-vinylbenzeneboronic acid, potassium carbonate, tetrakis(triphenylphosphine)palladium, mixed solvent, deionized water, dichloromethane, and anhydrous sodium sulfate is 0.1 mol: 0.14 mol: 0.5 mol: 0.008 mol: 150 mL: 200 mL: 300 mL: 5 g;

[0140] The mixed solvent is toluene, n-butanol, and deionized water in a volume ratio of 3:5:1.

[0141] Its H NMR spectrum can be found at Figure 5 As shown, the H NMR spectrum data are as follows: 1H NMR (400MHz, CDCl3, δ ppm): 7.2-7.8(11H, benzene ring); 6.75(1H, CH2=CH-Ph); 5.73(1H, CH2=CH-Ph); 5.19(1H, CH2=CH-Ph); 1.27(28H, -CH2-); 0.93(6H, -CH3).

[0142] S16, add intermediate III, intermediate V, and benzoyl peroxide to anhydrous toluene, evacuate, fill with nitrogen for protection, and heat to 80°C for reaction for 22 hours; after the reaction, add methanol to obtain insoluble matter, add it to acetone and shake for 6 hours, filter, take out the insoluble matter, and vacuum dry it at 40°C for 8 hours to obtain the target product , that is, macromolecular light conversion agent.

[0143] The usage ratio of intermediate product III, intermediate product V, anhydrous toluene, methanol, and acetone is 0.7 mol: 0.3 mol: 1000 mL: 3000 mL: 3000 mL;

[0144] The amount of benzoyl peroxide used was 1.0wt% of the total mass of the reactants.

[0145] Its H NMR spectrum can be found at Figure 6 shown.

[0146] An EVA encapsulated light-converting adhesive film comprises the following raw materials in parts by weight:

[0147] EVA resin 100 parts;

[0148] 1.0 part of cross-linking agent;

[0149] 1.2 parts of auxiliary cross-linking agent;

[0150] 5.0 parts of macromolecular light conversion agent;

[0151] 0.2 parts of antioxidant;

[0152] Light stabilizer 0.2 parts;

[0153] 0.4 parts of coupling agent.

[0154] Example 2

[0155] A method for preparing a macromolecular light conversion agent comprises the following steps:

[0156] S11, add benzotriazole to hydrobromic acid, stir, slowly drop liquid bromine into the reaction system, heat and reflux for 18 hours; add saturated sodium bisulfite aqueous solution to quench, extract with dichloromethane, separate the liquids, take the organic phase, add anhydrous sodium sulfate to dry, filter, take the solution, separate by column chromatography (eluent: petroleum ether / dichloromethane = 1 / 10, V / V), and vacuum dry at 40°C for 8 hours to obtain intermediate I;

[0157] The usage ratio of benzotriazole, hydrobromic acid, liquid bromine, saturated sodium bisulfite aqueous solution, dichloromethane, and anhydrous sodium sulfate is 0.1 mol: 0.75 mol: 0.15 mol: 400 mL: 300 mL: 5 g.

[0158] S12, take the intermediate product I, potassium carbonate, tert-butyl 5-bromovalerate, add them to N,N-dimethylformamide, stir and heat at 60°C for 40 hours, cool to room temperature after the reaction is completed, wash with saturated ammonium chloride solution three times, extract with ethyl acetate, separate the liquids, take the organic phase, add anhydrous sodium sulfate to dry, filter, take the solution, separate by column chromatography (eluent: petroleum ether / dichloromethane = 1 / 5, V / V), and dry in vacuo at 40°C for 8 hours to obtain the intermediate product II.

[0159] The usage ratio of intermediate product I, potassium carbonate, tert-butyl 5-bromovalerate, N,N-dimethylformamide, saturated ammonium chloride solution, ethyl acetate, and anhydrous sodium sulfate is 0.1 mol: 0.25 mol: 0.12 mol: 200 mL: 300 mL: 400 mL: 5 g.

[0160] S13, take the intermediate product II, 4-vinylbenzeneboronic acid, potassium carbonate, tetrakis(triphenylphosphine)palladium, mix them and add them to the reactor, and replace them with N2 for protection; after adding the mixed solvent, stir and heat under reflux for 12 hours; add deionized water for oscillation, extract with dichloromethane, separate the liquids, take the organic phase, add anhydrous sodium sulfate to dry, filter, take the solution, separate it by column chromatography (eluent: petroleum ether / dichloromethane = 1 / 10, V / V), and dry it in vacuo at 40°C for 8 hours to obtain the intermediate product III.

[0161] The usage ratio of intermediate II, 4-vinylbenzeneboronic acid, potassium carbonate, tetrakis(triphenylphosphine)palladium, mixed solvent, deionized water, dichloromethane, and anhydrous sodium sulfate is 0.1 mol: 0.16 mol: 0.5 mol: 0.01 mol: 150 mL: 200 mL: 300 mL: 5 g;

[0162] The mixed solvent is toluene, n-butanol, and deionized water in a volume ratio of 3:5:1.

[0163] S14, add 2-bromo-9H-fluorene, 1-bromooctane, tetrabutylammonium bromide and dimethyl sulfoxide to a 50wt% sodium hydroxide solution, stir, and heat to 75°C for reaction for 10h; after the reaction, add deionized water for oscillation, add petroleum ether for extraction, separate the liquids, take the upper organic phase, separate by column chromatography (eluent: petroleum ether), and vacuum dry at 40°C for 8h to obtain an intermediate product IV.

[0164] The dosage ratio of 2-bromo-9H-fluorene, 1-bromooctane, dimethyl sulfoxide, 50wt% sodium hydroxide solution, deionized water, and petroleum ether is 0.1mol: 0.24mol: 10mL: 40mL: 100mL: 150mL;

[0165] The amount of tetrabutylammonium bromide used is 2.0% of the moles of 2-bromo-9H-fluorene;

[0166] S15, take the intermediate product IV, 4-vinylbenzeneboronic acid, potassium carbonate, tetrakis(triphenylphosphine)palladium, mix them and add them to the reactor, and perform N2 replacement protection; after adding the mixed solvent, stir and heat under reflux for 24 hours; add deionized water and shake, extract with dichloromethane, separate the liquids, take the organic phase, add anhydrous sodium sulfate to dry, filter, take the solution, separate by column chromatography (eluent: petroleum ether / dichloromethane = 1 / 10, V / V), and dry in vacuo at 40°C for 8 hours to obtain the intermediate product V.

[0167] The usage ratio of intermediate product IV, 4-vinylbenzeneboronic acid, potassium carbonate, tetrakis(triphenylphosphine)palladium, mixed solvent, deionized water, dichloromethane, and anhydrous sodium sulfate is 0.1 mol: 0.12 mol: 0.5 mol: 0.005 mol: 150 mL: 200 mL: 300 mL: 5 g;

[0168] The mixed solvent is toluene, n-butanol, and deionized water in a volume ratio of 3:5:1.

[0169] S16, add intermediate III, intermediate V, and benzoyl peroxide to anhydrous toluene, evacuate, fill with nitrogen for protection, and heat to 75°C for reaction for 28 hours; after the reaction, add methanol to obtain insoluble matter, add it to acetone and shake for 6 hours, filter, take the insoluble matter, and vacuum dry it at 40°C for 8 hours to obtain the target product , that is, macromolecular light conversion agent.

[0170] The usage ratio of intermediate product III, intermediate product V, anhydrous toluene, methanol, and acetone is 0.7 mol: 0.3 mol: 1000 mL: 3000 mL: 3000 mL;

[0171] The amount of benzoyl peroxide used was 1.0wt% of the total mass of the reactants.

[0172] An EVA encapsulated light-converting adhesive film comprises the following raw materials in parts by weight:

[0173] EVA resin 100 parts;

[0174] 0.5 parts of cross-linking agent;

[0175] 1.5 parts of auxiliary cross-linking agent;

[0176] 5.0 parts of macromolecular light conversion agent;

[0177] 0.2 parts of antioxidant;

[0178] Light stabilizer 0.2 parts;

[0179] 0.3 parts of coupling agent.

[0180] Example 3

[0181] A method for preparing a macromolecular light conversion agent comprises the following steps:

[0182] S11, add benzotriazole to hydrobromic acid, stir, slowly add liquid bromine to the reaction system, heat and reflux for 24 hours; add saturated sodium bisulfite aqueous solution to quench, extract with dichloromethane, separate the liquids, take the organic phase, add anhydrous sodium sulfate to dry, filter, take the solution, separate by column chromatography (eluent: petroleum ether / dichloromethane = 1 / 10, V / V), and vacuum dry at 40°C for 8 hours to obtain intermediate I;

[0183] The usage ratio of benzotriazole, hydrobromic acid, liquid bromine, saturated sodium bisulfite aqueous solution, dichloromethane, and anhydrous sodium sulfate is 0.1 mol: 0.75 mol: 0.12 mol: 400 mL: 300 mL: 5 g.

[0184] S12, take the intermediate product I, potassium carbonate, tert-butyl 5-bromovalerate, add them to N,N-dimethylformamide, stir and heat at 40°C for 48 hours, cool to room temperature after the reaction is completed, wash with saturated ammonium chloride solution three times, extract with ethyl acetate, separate the liquids, take the organic phase, add anhydrous sodium sulfate to dry, filter, take the solution, separate by column chromatography (eluent: petroleum ether / dichloromethane = 1 / 5, V / V), and dry in vacuo at 40°C for 8 hours to obtain the intermediate product II.

[0185] The usage ratio of intermediate product I, potassium carbonate, tert-butyl 5-bromovalerate, N,N-dimethylformamide, saturated ammonium chloride solution, ethyl acetate, and anhydrous sodium sulfate is 0.1 mol: 0.25 mol: 0.15 mol: 200 mL: 300 mL: 400 mL: 5 g.

[0186] S13, take the intermediate product II, 4-vinylbenzeneboronic acid, potassium carbonate, tetrakis(triphenylphosphine)palladium, mix them and add them to the reactor, and replace them with N2 for protection; after adding the mixed solvent, stir and heat under reflux for 24 hours; add deionized water for oscillation, extract with dichloromethane, separate the liquids, take the organic phase, add anhydrous sodium sulfate for drying, filter, take the solution, separate it by column chromatography (eluent: petroleum ether / dichloromethane = 1 / 10, V / V), and dry it in vacuo at 40°C for 8 hours to obtain the intermediate product III.

[0187] The usage ratio of intermediate II, 4-vinylbenzeneboronic acid, potassium carbonate, tetrakis(triphenylphosphine)palladium, mixed solvent, deionized water, dichloromethane, and anhydrous sodium sulfate is 0.1 mol: 0.12 mol: 0.5 mol: 0.005 mol: 150 mL: 200 mL: 300 mL: 5 g;

[0188] The mixed solvent is toluene, n-butanol, and deionized water in a volume ratio of 3:5:1.

[0189] S14, add 2-bromo-9H-fluorene, 1-bromooctane, tetrabutylammonium bromide and dimethyl sulfoxide to a 50wt% sodium hydroxide solution, stir, and heat to 85°C for reaction for 6h; after the reaction, add deionized water for oscillation, add petroleum ether for extraction, separate the liquids, take the upper organic phase, separate by column chromatography (eluent: petroleum ether), and vacuum dry at 40°C for 8h to obtain an intermediate product IV.

[0190] The dosage ratio of 2-bromo-9H-fluorene, 1-bromooctane, dimethyl sulfoxide, 50wt% sodium hydroxide solution, deionized water, and petroleum ether is 0.1mol: 0.30mol: 10mL: 40mL: 100mL: 150mL;

[0191] The amount of tetrabutylammonium bromide used is 2.0% of the moles of 2-bromo-9H-fluorene;

[0192] S15, take the intermediate product IV, 4-vinylbenzeneboronic acid, potassium carbonate, tetrakis(triphenylphosphine)palladium, mix them and add them to the reactor, and perform N2 replacement protection; after adding the mixed solvent, stir and heat under reflux for 12 hours; add deionized water to shake, extract with dichloromethane, separate the liquids, take the organic phase, add anhydrous sodium sulfate to dry, filter, take the solution, separate it by column chromatography (eluent: petroleum ether / dichloromethane = 1 / 10, V / V), and dry it in vacuo at 40°C for 8 hours to obtain the intermediate product V.

[0193] The usage ratio of intermediate product IV, 4-vinylbenzeneboronic acid, potassium carbonate, tetrakis(triphenylphosphine)palladium, mixed solvent, deionized water, dichloromethane, and anhydrous sodium sulfate is 0.1 mol: 0.16 mol: 0.5 mol: 0.01 mol: 150 mL: 200 mL: 300 mL: 5 g;

[0194] The mixed solvent is toluene, n-butanol, and deionized water in a volume ratio of 3:5:1.

[0195] S16, add intermediate III, intermediate V, and benzoyl peroxide to anhydrous toluene, evacuate, fill with nitrogen for protection, and heat to 85°C for reaction for 20 hours; after the reaction, add methanol to obtain insoluble matter, add it to acetone and shake for 6 hours, filter, take the insoluble matter, and vacuum dry it at 40°C for 8 hours to obtain the target product , that is, macromolecular light conversion agent.

[0196] The usage ratio of intermediate product III, intermediate product V, anhydrous toluene, methanol, and acetone is 0.7 mol: 0.3 mol: 1000 mL: 3000 mL: 3000 mL;

[0197] The amount of benzoyl peroxide used was 1.0wt% of the total mass of the reactants.

[0198] An EVA encapsulated light-converting adhesive film comprises the following raw materials in parts by weight:

[0199] EVA resin 100 parts;

[0200] 1.5 parts of cross-linking agent;

[0201] 1.0 part of auxiliary cross-linking agent;

[0202] 5.0 parts of macromolecular light conversion agent;

[0203] 0.2 parts of antioxidant;

[0204] Light stabilizer 0.2 parts;

[0205] 0.5 parts of coupling agent.

[0206] Example 4

[0207] The rest is the same as in Example 1, except that:

[0208] A method for preparing a macromolecular light conversion agent, wherein in S16,

[0209] The usage ratio of intermediate product III, intermediate product V, anhydrous toluene, methanol and acetone is 0.8 mol: 0.2 mol: 1000 mL: 3000 mL: 3000 mL.

[0210] Example 5

[0211] The rest is the same as in Example 1, except that:

[0212] A method for preparing a macromolecular light conversion agent, wherein in S16,

[0213] The usage ratio of intermediate product III, intermediate product V, anhydrous toluene, methanol and acetone is 0.5 mol: 0.5 mol: 1000 mL: 3000 mL: 3000 mL.

[0214] Example 6

[0215] The rest is the same as in Example 1, except that:

[0216] An EVA encapsulated light-converting adhesive film comprises the following raw materials in parts by weight:

[0217] EVA resin 100 parts;

[0218] 1.0 part of cross-linking agent;

[0219] 1.2 parts of auxiliary cross-linking agent;

[0220] 5.0 parts of macromolecular light conversion agent;

[0221] Antioxidant 0.1 part;

[0222] Light stabilizer 0.3 parts;

[0223] 0.4 parts of coupling agent.

[0224] Example 7

[0225] The rest is the same as in Example 1, except that:

[0226] An EVA encapsulated light-converting adhesive film comprises the following raw materials in parts by weight:

[0227] EVA resin 100 parts;

[0228] 1.0 part of cross-linking agent;

[0229] 1.2 parts of auxiliary cross-linking agent;

[0230] 5.0 parts of macromolecular light conversion agent;

[0231] 0.25 parts of antioxidant;

[0232] Light stabilizer 0.1 part;

[0233] 0.4 parts of coupling agent.

[0234] Example 8

[0235] The rest is the same as in Example 1, except that:

[0236] An EVA encapsulated light-converting adhesive film comprises the following raw materials in parts by weight:

[0237] EVA resin 100 parts;

[0238] 1.0 part of cross-linking agent;

[0239] 1.2 parts of auxiliary cross-linking agent;

[0240] 0.5 parts of macromolecular light conversion agent;

[0241] 0.2 parts of antioxidant;

[0242] Light stabilizer 0.2 parts;

[0243] 0.4 parts of coupling agent.

[0244] Example 9

[0245] The rest is the same as in Example 1, except that:

[0246] An EVA encapsulated light-converting adhesive film comprises the following raw materials in parts by weight:

[0247] EVA resin 100 parts;

[0248] 1.0 part of cross-linking agent;

[0249] 1.2 parts of auxiliary cross-linking agent;

[0250] 1.0 part of macromolecular light conversion agent;

[0251] 0.2 parts of antioxidant;

[0252] Light stabilizer 0.2 parts;

[0253] 0.4 parts of coupling agent.

[0254] Example 10

[0255] The rest is the same as in Example 1, except that:

[0256] An EVA encapsulated light-converting adhesive film comprises the following raw materials in parts by weight:

[0257] EVA resin 100 parts;

[0258] 1.0 part of cross-linking agent;

[0259] 1.2 parts of auxiliary cross-linking agent;

[0260] 2.0 parts of macromolecular light conversion agent;

[0261] 0.2 parts of antioxidant;

[0262] Light stabilizer 0.2 parts;

[0263] 0.4 parts of coupling agent.

[0264] Embodiment 11

[0265] The rest is the same as in Example 1, except that:

[0266] An EVA encapsulated light-converting adhesive film comprises the following raw materials in parts by weight:

[0267] EVA resin 100 parts;

[0268] 1.0 part of cross-linking agent;

[0269] 1.2 parts of auxiliary cross-linking agent;

[0270] 8.0 parts of macromolecular light conversion agent;

[0271] 0.2 parts of antioxidant;

[0272] Light stabilizer 0.2 parts;

[0273] 0.4 parts of coupling agent.

[0274] Example 12

[0275] The rest is the same as in Example 1, except that:

[0276] A POE encapsulation light-converting adhesive film, comprising the following raw materials in parts by weight:

[0277] POE resin 100 parts;

[0278] 1.0 part of cross-linking agent;

[0279] 1.2 parts of auxiliary cross-linking agent;

[0280] 5.0 parts of macromolecular light conversion agent;

[0281] Antioxidant 0.05 parts;

[0282] Light stabilizer 0.05 parts;

[0283] 0.8 parts of coupling agent.

[0284] Embodiment 13

[0285] The rest is the same as in Example 1, except that:

[0286] An EPE encapsulation light-converting adhesive film comprises an EVA layer (100 μm thick) and a POE layer (300 μm thick).

[0287] The EVA layer includes the following raw materials in parts by weight:

[0288] EVA resin 100 parts;

[0289] 1.0 part of cross-linking agent;

[0290] 1.2 parts of auxiliary cross-linking agent;

[0291] 5.0 parts of macromolecular light conversion agent;

[0292] 0.2 parts of antioxidant;

[0293] Light stabilizer 0.2 parts;

[0294] 0.4 parts of coupling agent.

[0295] A POE layer includes the following raw materials in parts by weight:

[0296] POE resin 100 parts;

[0297] 1.0 part of cross-linking agent;

[0298] 1.2 parts of auxiliary cross-linking agent;

[0299] 5.0 parts of macromolecular light conversion agent;

[0300] Antioxidant 0.05 parts;

[0301] Light stabilizer 0.05 parts;

[0302] 0.8 parts of coupling agent.

[0303] The following comparative examples are compared with Example 1:

[0304] Comparative Example 1

[0305] The rest is the same as in Example 1, except that:

[0306] No macromolecular light conversion agent is added to the formula of photovoltaic encapsulation light conversion film.

[0307] Comparative Example 2

[0308] The rest is the same as in Example 1, except that:

[0309] In the formulation of photovoltaic encapsulation light-converting adhesive film, the macromolecular light-converting agent is replaced with benzotriazole.

[0310] Comparative Example 3

[0311] The rest is the same as in Comparative Example 1, except that:

[0312] In the formulation of photovoltaic encapsulation light-converting adhesive film, the macromolecular light-converting agent is replaced by a mixture of benzotriazole and intermediate product V in a molar ratio of 7:3.

[0313] Comparative Example 4

[0314] The rest is the same as in Example 1, except that:

[0315] In the formulation of photovoltaic encapsulation light-converting adhesive film, the macromolecular light-converting agent is replaced by a mixture of intermediate product III and intermediate product V in a molar ratio of 7:3.

[0316] Comparative Example 5

[0317] The rest is the same as in Example 1, except that:

[0318] In the preparation method of the macromolecular light conversion agent, in S11, the usage ratio of benzotriazole, hydrobromic acid, liquid bromine, saturated sodium bisulfite aqueous solution, dichloromethane, and anhydrous sodium sulfate is 0.1 mol: 0.75 mol: 0.28 mol: 400 mL: 300 mL: 5 g.

[0319] In S13, the intermediate product II, 4-vinylbenzeneboronic acid, potassium carbonate and tetrakis(triphenylphosphine)palladium are mixed and added to the reactor for N2 replacement protection; after adding the mixed solvent, stirring and heating to reflux for 18 hours; adding phenylboric acid, continuing to heat to reflux for 18 hours; adding deionized water to shake, extracting with dichloromethane, separating the liquids, taking the organic phase, adding anhydrous sodium sulfate to dry, filtering, taking the solution, separating by column chromatography (eluent: petroleum ether / dichloromethane = 1 / 10, V / V), and vacuum drying at 40°C for 8 hours to obtain the intermediate product III.

[0320] The usage ratio of intermediate product II, 4-vinylbenzeneboronic acid, potassium carbonate, tetrakis(triphenylphosphine)palladium, mixed solvent, phenylboric acid, deionized water, dichloromethane, and anhydrous sodium sulfate is 0.1 mol: 0.15 mol: 0.5 mol: 0.008 mol: 150 mL: 0.15 mol: 200 mL: 300 mL: 5 g.

[0321] Comparative Example 6

[0322] The rest is the same as in Example 1, except that:

[0323] The preparation method of the macromolecular light conversion agent, in S11, the usage ratio of benzotriazole, hydrobromic acid, liquid bromine, saturated sodium bisulfite aqueous solution, dichloromethane, and anhydrous sodium sulfate is 0.1 mol: 0.75 mol: 0.28 mol: 400 mL: 300 mL: 5 g.

[0324] In S13, the usage ratio of intermediate product II, 4-vinylbenzeneboric acid, potassium carbonate, tetrakis(triphenylphosphine)palladium, mixed solvent, deionized water, dichloromethane, and anhydrous sodium sulfate is 0.1 mol: 0.30 mol: 0.5 mol: 0.008 mol: 150 mL: 200 mL: 300 mL: 5 g.

[0325] Comparative Example 7

[0326] The rest is the same as in Example 1, except that:

[0327] The preparation method of the macromolecular light conversion agent, in S13 and S15, 4-vinylbenzeneboronic acid is replaced by 4-penteneboronic acid.

[0328] Comparative Example 8

[0329] The rest is the same as in Example 1, except that:

[0330] The method for preparing a macromolecular light conversion agent, in S12, 5-tert-butyl bromopentanoate is replaced with butyl bromide; and

[0331] In S14, 1-bromooctane is replaced by bromobutyl.

[0332] The physical properties of the photovoltaic encapsulation light conversion adhesive films prepared in the examples of the present invention and the comparative examples were measured respectively, and the results are shown in Table 1.

[0333]

[0334] First, it can be concluded from Examples 1-13 in Table 1 that the photovoltaic macromolecular light conversion agent and photovoltaic encapsulation light conversion adhesive film of the present invention have obvious advantages in improving the photoelectric conversion efficiency and other performances, and also have better aging resistance (stability).

[0335] Second, it can be observed from Example 1 and Comparative Example 1 that the photovoltaic encapsulation light-conversion adhesive film of the present invention uses a self-made macromolecular light-conversion agent with excellent light-conversion efficiency. It can be observed from Example 1 and Comparative Examples 2-4 that the photovoltaic adhesive film of the present invention uses a self-made macromolecular light-conversion agent; compared with the small molecule structure, it has a higher half-peak width and light-conversion efficiency; and has low migration performance; it can be observed from Example 1 and Comparative Examples 5-7 that the asymmetric substitution structure in the macromolecular light-conversion agent, the core light-conversion structure located in the side chain, and the electron-rich benzene ring as the linking structure have a significant positive effect on improving the light-conversion efficiency; it can be observed from Example 1 and Comparative Example 8 that the long fatty chain and long-chain ester structure in the macromolecular light-conversion agent structure help to effectively improve the compatibility, thereby improving the light-conversion efficiency.

[0336] Third, it can be observed from the examples that the photovoltaic encapsulation light-converting adhesive film of the present invention has a long-lasting high light-conversion efficiency, and thus should have excellent optical properties and stability.

[0337] In summary, the photovoltaic macromolecular light conversion agent and photovoltaic encapsulation light conversion adhesive film of the present invention use a self-made light conversion agent and have excellent light conversion performance, low migration, high stability and power gain function.

[0338] The test method is as follows:

[0339] (1) Absorption half-peak width: Test the fluorescence excitation spectrum of the light conversion film.

[0340] (2) Light conversion efficiency: Horiba spectrometer FL-3, absolute quantum efficiency test was performed using an integrating sphere at room temperature.

[0341] (3) Resistance to humidity and heat aging: The photovoltaic film is subjected to humidity and heat aging test. Conditions: Test conditions: +85°C, relative humidity 85%.

[0342] The test was carried out before and after, and the retention rate was calculated according to the following formula:

[0343] Retention rate = average value after the test / average value before the test × 100%.

[0344] (4) UV aging resistance: The obtained photovoltaic 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.

[0345] The test was carried out before and after, and the retention rate was calculated according to the following formula:

[0346] Retention rate = average value after the test / average value before the test × 100%.

[0347] (5) Mobility test method: A rapid aging migration test is performed at the module end. The front of the photovoltaic module is a light-converting film doped with a light-converting agent, and the back of the module is a blank film without a light-converting agent (only the light-converting agent is a variable). After the module undergoes a UV300 aging test in the aging box, the film on the front of the module is removed and heated and soaked in an organic solvent (methanol) (stirring at 60°C, heating and soaking for 24 hours). The solution after soaking is analyzed by HPLC to obtain the content (A) of one embodiment. The film on the front of the module that has not been aged is removed, and the same heating and soaking treatment is performed. The solution after soaking is analyzed by HPLC to obtain the content (B) of another embodiment. The mobility is: A / B*100%.

[0348] (6) Photoelectric gain: Measured using an EL tester. Stack the photovoltaic glass, film, cell, film and photovoltaic backplane neatly from top to bottom, laminate at 140°C for 15 minutes, take out and cool, first test the bare chip power and record it as P 0.1 ; The power of the new bare chip is recorded as P1. 0.2 , the photovoltaic film of the present invention is used for lamination, and its power is tested and recorded as P2, then the power gain P m =(P2 / P 0.2 ) / (P1 / P 0.1 ).

[0349] 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. A method for preparing a macromolecular light conversion agent, characterized in that: The following steps are involved: S11, subjecting benzotriazole to a substitution reaction with liquid bromine to obtain an intermediate product I; S12, subjecting the intermediate product I to a substitution reaction with a bromoester to obtain an intermediate product II; S13, coupling the intermediate product II with a vinylbenzene boronic acid derivative to obtain an intermediate product III; S14, subjecting bromofluorene to a substitution reaction with an alkyl bromide to obtain an intermediate product IV; S15, coupling the intermediate product IV with a vinylbenzene boronic acid derivative to obtain an intermediate product V; S16, subjecting the intermediate product III to a free radical polymerization reaction with the intermediate product V to obtain a macromolecular light conversion agent; The molar ratio of the benzotriazole to the liquid bromine is 1:(1.2-1.5); the molar ratio of the intermediate product I to the bromoester is 1:(1.2-1.5); the molar ratio of the intermediate product II to the vinylbenzene boronic acid derivative is 1:(1.2-1.6); the molar ratio of the bromofluorene to the alkyl bromide is 1:(2.4-3.0); the molar ratio of the intermediate product IV to the vinylbenzene boronic acid derivative is 1:(1.2-1.6); the molar ratio of the intermediate product III to the intermediate product V is (0.5-0.8):(0.2-0.5); The carbon number of the alkyl bromide is C6-C 10 .

2. A macromolecular light conversion agent, characterized in that: The macromolecular light conversion agent is prepared by the preparation method of claim 1.

3. A photovoltaic encapsulation light-converting adhesive film, characterized in that: It comprises the macromolecular light conversion agent as described in claim 2.

4. The photovoltaic encapsulation light-converting adhesive film according to claim 3, characterized in that: The invention comprises the following raw materials in parts by weight: 100 parts of polyolefin resin; Cross-linking agent 0.5-1.5 parts; 1.0-1.5 parts of auxiliary cross-linking agent; 0.5-8.0 parts of the macromolecular light conversion agent; Antioxidant 0.05-0.25 parts; Light stabilizer 0.05-0.3 parts; Coupling agent 0.3-0.8 parts.

5. The photovoltaic encapsulation light-converting adhesive film according to claim 4, characterized in that: The polyolefin resin is selected from at least one of EVA resin and POE resin.

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