Detailed Description
The present invention will be described in detail with reference to examples. It is to be understood that the following examples are illustrative of embodiments of the present invention and are not intended to limit the scope of the invention.
The existing organic light conversion agent has narrow and single absorption peak, and meanwhile, the novel organic light conversion agent is not good in stability due to a small molecular structure, and therefore, the novel organic light conversion agent is required to be designed, and has the structure and molecular weight similar to those of a high polymer matrix, so that the dispersibility and compatibility of the novel organic light conversion agent are enhanced.
The invention aims to develop a macromolecule light conversion agent for photovoltaic and a photovoltaic packaging light conversion adhesive film so as to meet the application requirements of the existing photovoltaic packaging materials. The realization thinking is that a benzotriazole-based macromolecule light conversion agent is self-made, so that the compatibility and the dispersibility of the benzotriazole-based macromolecule light conversion agent in a photovoltaic packaging material are ensured, and meanwhile, the benzotriazole-based macromolecule light conversion agent has high stability and light conversion efficiency. The method comprises the steps of carrying out asymmetric modification and electron-rich structure benzene ring bonding modification by taking benzotriazole as a matrix, and carrying out free radical copolymerization with fluorene to form a macromolecular chain structure taking a core light conversion structure as a side group while enlarging the absorption peak width. The preparation method is characterized by comprising the following steps of carrying out liquid bromine substitution reaction on benzotriazole, then carrying out substitution reaction on benzotriazole with bromoester, then carrying out coupling reaction on benzotriazole with phenylboronic acid, carrying out substitution reaction on fluorene with bromoalkane, then carrying out coupling reaction on fluorene with phenylboronic acid, and finally carrying out free radical polymerization on the two intermediates to obtain the macromolecular light conversion agent. The macromolecular light conversion agent is a copolymer of fluorene and benzotriazole, contains chemical structures such as long-chain ester groups, long-chain hydrocarbon groups, benzene rings and the like, has larger absorption peaks, has excellent compatibility and stability with a matrix, has higher light conversion efficiency and the like, and does not migrate and separate out. The implementation method of the invention is as follows:
the invention provides a preparation method of a macromolecular light conversion agent, which comprises the following steps:
S11, adding benzotriazole into hydrobromic acid, stirring, slowly adding dropwise bromine into a reaction system, heating and refluxing for 18-24 hours, adding saturated sodium bisulphite aqueous solution for quenching, extracting with dichloromethane, separating liquid, taking an organic phase, adding anhydrous sodium sulfate for drying, filtering, taking a solution, separating by column chromatography (eluent: petroleum ether/dichloromethane=1/10, V/V), and vacuum-drying at 40 ℃ for 8 hours to obtain an intermediate product I;
Preferably, the dosage ratio of benzotriazole, hydrobromic acid, liquid bromine, saturated aqueous sodium bisulfite solution, methylene chloride and anhydrous sodium sulfate in the step is 0.1mol:0.75mol (0.12-0.15) mol:400mL:300mL:5g.
S12, adding the intermediate product I, potassium carbonate and bromoester into N, N-dimethylformamide, stirring and heating for 40-48h at 40-60 ℃, cooling to room temperature after the reaction is finished, washing with saturated ammonium chloride solution for 3 times, extracting with ethyl acetate, separating liquid, taking an organic phase, adding anhydrous sodium sulfate for drying, filtering, taking a solution, separating by column chromatography (eluent: petroleum ether/dichloromethane=1/5, V/V), and drying in vacuum for 8h at 40 ℃ to obtain an intermediate product II.
Preferably, the intermediate I, potassium carbonate, bromoester, N-dimethylformamide, saturated ammonium chloride solution, ethyl acetate and anhydrous sodium sulfate are used in the amount ratio of 0.1mol to 0.25mol (0.12-0.15) mol to 200mL to 300mL to 400mL to 5g.
The bromoester has preferably C6-C10 to avoid the influence of C10, low reactivity, adverse effect on the subsequent reaction efficiency, and C6 with smaller molecular chain, and no good compatibility with matrix resin, and the product performance is affected, so the bromoester can be 4-bromovalerate ethyl ester, 5-bromovalerate ethyl ester, 6-bromohexanoate ethyl ester, 7-bromoheptanoate ethyl ester, 5-bromovalerate tert-butyl ester, 8-bromooctanoate ethyl ester and the like, and is preferably 5-bromovalerate tert-butyl ester.
S13, mixing an intermediate product II, a vinylphenylboronic acid derivative, potassium carbonate and tetra (triphenylphosphine) palladium, adding the mixture into a reactor, carrying out N2 replacement protection, adding a mixed solvent, stirring, heating and refluxing for 12-24 hours, adding deionized water, oscillating, extracting with dichloromethane, separating liquid, taking an organic phase, adding anhydrous sodium sulfate for drying, filtering, taking a solution, and carrying out column chromatography separation (eluent: petroleum ether/dichloromethane=1/10, V/V), and carrying out vacuum drying at 40 ℃ for 8 hours to obtain a benzotriazole-containing monomer, namely the intermediate product III.
The dosage ratio of the intermediate product II, the vinylphenylboronic acid derivative, the potassium carbonate, the tetra (triphenylphosphine) palladium, the mixed solvent, the deionized water, the methylene dichloride and the anhydrous sodium sulfate is 0.1mol (0.12-0.16) mol, 0.5mol, 0.005-0.01mol, 150mL, 200mL, 300mL, 5g;
The mixed solvent is toluene, n-butanol and deionized water which are mixed according to the volume ratio of 3:5:1.
The vinylphenylboronic acid derivative may be 4-vinylphenylboronic acid, 3-vinylphenylboronic acid, 2-vinylphenylboronic acid, benzocyclobutene-4-boronic acid, 3-vinyl-5-fluorobenzeneboronic acid, 3-vinyl-4-fluorobenzeneboronic acid, 3-vinyl-5-chlorobenzeneboronic acid, etc., and is preferably 4-vinylphenylboronic acid.
S14, adding bromofluorene, alkyl bromide, tetrabutylammonium bromide and dimethyl sulfoxide into a 50wt% sodium hydroxide solution, stirring, heating to 75-85 ℃ for reaction for 6-10h, adding deionized water after the reaction is finished, oscillating, adding petroleum ether for extraction, separating liquid, taking an upper organic phase, separating by column chromatography (eluent: petroleum ether), and vacuum drying at 40 ℃ for 8h to obtain an intermediate product IV.
Bromofluorene, alkyl bromide, dimethyl sulfoxide, 50wt% sodium hydroxide solution, deionized water and petroleum ether with the dosage ratio of 0.1mol (0.24-0.30 mol) 10mL:40mL:100mL:150mL;
The dosage of tetrabutylammonium bromide is 2.0 percent of the mole number of bromofluorene;
Bromofluorene is monobromo substituent fluorene, and may be 1-bromo-9H-fluorene, 2-bromo-9H-fluorene, 3-bromo-9H-fluorene, 4-bromo-9H-fluorene, etc., and is preferably 2-bromo-9H-fluorene.
The alkyl bromide is aliphatic hydrocarbon bromide with a certain chain length, and the carbon number of the alkyl bromide is C6-C10, and can be 1-bromohexane, 1-bromoheptane, 1-bromooctane, 1-bromononane, 1-bromodecane and the like, and is preferably 1-bromooctane.
S15, mixing an intermediate product IV, a vinylphenylboronic acid derivative, potassium carbonate and tetra (triphenylphosphine) palladium, adding the mixture into a reactor, carrying out N2 replacement protection, adding a mixed solvent, stirring, heating and refluxing for 12-24 hours, adding deionized water, oscillating, extracting with dichloromethane, separating liquid, taking an organic phase, adding anhydrous sodium sulfate for drying, filtering, taking a solution, and carrying out column chromatography separation (eluent: petroleum ether/dichloromethane=1/10, V/V), and carrying out vacuum drying at 40 ℃ for 8 hours to obtain a fluorene-containing monomer, namely the intermediate product V.
The dosage ratio of the intermediate product IV, the vinylphenylboronic acid derivative, the potassium carbonate, the tetra (triphenylphosphine) palladium, the mixed solvent, the deionized water, the methylene dichloride and the anhydrous sodium sulfate is 0.1mol (0.12-0.16) mol, 0.5mol, 0.005-0.01mol, 150mL, 200mL, 300mL, 5g;
The mixed solvent is toluene, n-butanol and deionized water which are mixed according to the volume ratio of 3:5:1.
The vinylphenylboronic acid derivative may be 4-vinylphenylboronic acid, 3-vinylphenylboronic acid, 2-vinylphenylboronic acid, benzocyclobutene-4-boronic acid, 3-vinyl-5-fluorobenzeneboronic acid, 3-vinyl-4-fluorobenzeneboronic acid, 3-vinyl-5-chlorobenzeneboronic acid, etc., and is preferably 4-vinylphenylboronic acid.
S16, adding an intermediate product III, an intermediate product V and benzoyl peroxide into anhydrous toluene, vacuumizing, filling nitrogen for protection, heating to 75-85 ℃ for reaction for 20-28 hours, adding methanol after the reaction is finished to obtain an insoluble substance, adding the insoluble substance into acetone, oscillating for 6 hours, filtering, taking the insoluble substance, and vacuum-drying for 8 hours at 40 ℃ to obtain a target product, namely the macromolecular light conversion agent.
The dosage ratio of the intermediate product III to the intermediate product V to the anhydrous toluene to the methanol to the acetone is (0.2-0.5) mol (0.5-0.8) mol 1000mL:3000 mL;
The amount of benzoyl peroxide was 1.0wt% based on the total mass of the reactants.
The preparation process of the macromolecular light conversion agent comprises the following steps:
;
wherein m and n are natural numbers greater than 1.
Another object of the present invention is to provide a macromolecular light-converting agent prepared by the preparation method as described above.
The macromolecular light conversion agent is a copolymer of fluorene and benzotriazole, long-chain ester groups and long-chain hydrocarbon groups in molecules of the copolymer can improve dispersibility with a matrix, a macromolecular structure can form chain entanglement with the matrix, compatibility with matrix resin is effectively improved, fluorene, benzene rings, benzotriazole and the like form a conjugated structure, electron transmission capacity is improved, light conversion efficiency is improved, meanwhile, the benzotriazole is asymmetrically modified and copolymerized with the fluorene, absorption peak width in an ultraviolet region is effectively widened, molecular structure design is further carried out, a core light conversion structure is arranged in a side chain, adverse effects caused by conjugated extension are reduced, and luminous efficiency is improved. The macromolecular light conversion agent structure has the function of promoting the light conversion efficiency by mutual cooperation of all chemical structures.
Still another object of the present invention is to provide a photovoltaic packaging light conversion film, which includes the above macromolecular light conversion agent.
Specifically, the photovoltaic packaging light conversion adhesive film disclosed by the invention comprises the following raw materials in parts by weight:
100 parts of polyolefin resin;
0.5-1.5 parts of cross-linking agent;
1.0-1.5 parts of auxiliary cross-linking agent;
0.5-8.0 parts of macromolecular light conversion agent;
0.05-0.25 part of antioxidant;
0.05-0.3 part of light stabilizer;
0.3-0.8 part of coupling agent.
Further, it is preferable that the polyolefin resin is at least one selected from EVA resin and POE resin.
When the polyolefin resin is EVA resin, the photovoltaic packaging light conversion adhesive film preferably comprises the following raw materials in parts by weight:
100 parts of EVA resin;
0.5-1.5 parts of cross-linking agent;
1.0-1.5 parts of auxiliary cross-linking agent;
0.5-8.0 parts of macromolecular light conversion agent;
0.1-0.25 part of antioxidant;
0.1-0.3 part of light stabilizer;
0.3-0.5 part of coupling agent.
When the polyolefin resin is POE resin, the photovoltaic packaging light conversion adhesive film preferably comprises the following raw materials in parts by weight:
100 parts of POE resin;
0.5-1.5 parts of cross-linking agent;
1.0-1.5 parts of auxiliary cross-linking agent;
0.5-8.0 parts of macromolecular light conversion agent;
0.05-0.20 part of antioxidant;
0.05-0.20 parts of light stabilizer;
0.4-0.8 part of coupling agent.
The EVA resin has the VA mass content of 28-33%. Without particular explanation, the EVA resins having a Melt Index (MI) of 31, obtained from DuPont, U.S. and having a VA mass content of 33%, are preferred in the following examples and comparative examples of the present invention.
The POE resins of the following examples and comparative examples of the present invention, model XUS38660, were purchased from Dow chemical company, USA, unless otherwise specified.
The crosslinking agent in the present invention is preferably an organic peroxide, and specifically benzoyl peroxide, 2, 5-dimethyl-2, 5-bis (benzoylperoxy) hexane, dicyclohexyl peroxycarbonate, dicumyl peroxide or the like, and the crosslinking agent in the following examples and comparative examples of the present invention is benzoyl peroxide unless otherwise specified.
The auxiliary crosslinking agent in the invention is polyfunctional allyl and/or acryloxy.
The allyl auxiliary cross-linking agent can be triallyl cyanurate or triallyl isocyanurate and the like.
The acryloyloxy auxiliary crosslinking agent can be any one or a plurality of compositions of trimethylol propane trimethacrylate, ethoxylated trimethylol propane triacrylate, propoxylated neopentyl glycol diacrylate and pentaerythritol triacrylate.
Without any particular explanation, the auxiliary crosslinking agents in the following examples and comparative examples of the present invention were triallyl isocyanurate, trimethylolpropane trimethacrylate, trimethylolpropane propoxylate triacrylate and pentaerythritol triacrylate in a mass ratio of 7:2:4:2.
The antioxidant is formed by compounding hindered phenols and phosphites. The hindered phenol antioxidant may be antioxidant 1010, antioxidant 1076, antioxidant 264, antioxidant 2246, etc., and is preferably antioxidant 1010. The phosphite antioxidant may be antioxidant 168, antioxidant 242, antioxidant TPP, etc., and is preferably antioxidant 168. In the following examples and comparative examples, the antioxidant was added as an antioxidant 1010 and an antioxidant 168 in a mass ratio of 1:2, unless otherwise specified.
In the present invention, a hindered amine type light stabilizer is used in order to avoid competition with the light converting agent for ultraviolet rays. The hindered amine light stabilizer may be UV-292, UV-770, GW540, or the like, and is preferably UV-292. The light stabilizer in the following examples and comparative examples of the present invention was UV-292, unless otherwise specified.
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, and may be KH151, KH171, KH172, or the like, and the coupling agent in the following examples and comparative examples is KH172 without particular description.
In order to better understand the invention, the invention also provides a preparation method of the photovoltaic packaging light conversion adhesive film, which comprises the following steps:
S21, mixing, namely
Mixing and stirring raw materials in a formula proportion in a mixer for 2 hours at the temperature of 40 ℃ and the rotating speed of 80rpm to obtain a mixed raw material;
S22, extruding;
Specifically, the EVA extrusion process is as follows:
Placing the mixed raw materials in the step S21 into a double-screw extruder, melting, blending and extruding the mixed raw materials at the temperature of 80 ℃ in a first area, 90 ℃ in a second area and 98 ℃ in a third area at the temperature of 102 ℃ in a die head, discharging and casting the mixed raw materials through a casting film die head, and cooling the mixed raw materials through a casting roller;
the POE extrusion process is as follows:
Placing the mixed raw materials in the step S21 into a double-screw extruder, melting, blending and extruding the mixed raw materials at the temperature of a first area of 90 ℃, the temperature of a second area of 100 ℃ and the temperature of a third area of 105 ℃ at the temperature of a die head of 110 ℃ at the rotating speed of 50rpm, discharging and casting the mixed raw materials through a casting film die head, and cooling the mixed raw materials through a casting roller;
the EPE coextrusion process is as follows:
placing the EVA layer raw material in the S21 into a double-screw extruder, melting and blending the EVA layer raw material in the S21 at the temperature of 80 ℃ in a first area, the temperature of 90 ℃ in a second area and the temperature of 98 ℃ in a third area, the temperature of a die head of 102 ℃ and the rotating speed of 50rpm, placing the POE layer raw material in the S21 into the double-screw extruder, melting and blending the POE layer raw material at the temperature of 90 ℃ in the first area, the temperature of 100 ℃ in the second area and the temperature of 105 ℃ in the third area, the die head of 110 ℃ and the rotating speed of 50rpm, discharging and casting through a co-extrusion casting film die head, and cooling through a casting roller;
s23, film formation, i.e
Measuring thickness, pressing edges, shaping, trimming edges and rolling to obtain the photovoltaic packaging light-converting adhesive film with the thickness of 500 mu m;
Wherein, relates to an EPE packaging light conversion adhesive film, and the total thickness of the film is 500 mu m.
In order to further understand the present invention, the following specific examples are provided to illustrate the macromolecule light conversion agent for photovoltaic and the photovoltaic packaging light conversion adhesive film in detail, and the protection scope of the present invention is not limited by the following examples.
Example 1
The preparation method of the macromolecular light conversion agent comprises the following steps:
s11, adding benzotriazole into hydrobromic acid, stirring, slowly adding dropwise bromine into a reaction system, heating and refluxing for 20 hours, adding saturated sodium bisulphite aqueous solution for quenching, extracting with dichloromethane, separating liquid, taking an organic phase, adding anhydrous sodium sulfate for drying, filtering, taking a solution, separating by column chromatography (eluent: petroleum ether/dichloromethane=1/10, V/V), and vacuum-drying at 40 ℃ for 8 hours to obtain an intermediate product I;
The dosage ratio of benzotriazole, hydrobromic acid, liquid bromine, saturated sodium bisulfite aqueous solution, methylene dichloride and anhydrous sodium sulfate is 0.1mol:0.75mol:0.14mol:400mL:300mL:5g.
The nuclear magnetic resonance hydrogen spectrum is shown in figure 1, and the nuclear magnetic resonance hydrogen spectrum data is1H NMR(400MHz, CDCl3, delta ppm, 7.2-7.8 (3H, benzene ring) and 10.22 (1H, -NH-).
S12, taking an intermediate product I, potassium carbonate and 5-bromovalerate, adding the intermediate product I, potassium carbonate and 5-bromovalerate into N, N-dimethylformamide, stirring and heating for 46h at 50 ℃, cooling to room temperature after the reaction is finished, washing 3 times with saturated ammonium chloride solution, extracting with ethyl acetate, separating liquid, taking an organic phase, adding anhydrous sodium sulfate for drying, filtering, taking a solution, separating by column chromatography (eluent: petroleum ether/dichloromethane=1/5, V/V), and drying in vacuum for 8h at 40 ℃ to obtain an intermediate product II.
The dosage ratio of the intermediate product I, potassium carbonate, 5-bromovaleric acid tert-butyl ester, N-dimethylformamide, saturated ammonium chloride solution, ethyl acetate and anhydrous sodium sulfate is 0.1mol:0.25mol:0.15mol:200mL:300mL:400mL:5g.
The nuclear magnetic hydrogen spectrum is shown in figure 2, and the nuclear magnetic hydrogen spectrum data is1H NMR(400MHz, CDCl3, delta 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).
S13, mixing an intermediate product II, 4-vinylphenylboronic acid, potassium carbonate and tetra (triphenylphosphine) palladium, adding the mixture into a reactor, carrying out N2 replacement protection, adding a mixed solvent, stirring, heating and refluxing for 18 hours, adding deionized water, oscillating, extracting with dichloromethane, separating liquid, taking an organic phase, adding anhydrous sodium sulfate for drying, filtering, taking a solution, and carrying out column chromatography separation (eluent: petroleum ether/dichloromethane=1/10, V/V), and carrying out vacuum drying at 40 ℃ for 8 hours to obtain an intermediate product III.
The dosage ratio of the intermediate product II, 4-vinylphenylboronic acid, potassium carbonate, tetra (triphenylphosphine) palladium, mixed solvent, deionized water, methylene dichloride and anhydrous sodium sulfate is 0.1mol:0.15mol:0.5mol:0.008mol:150mL:200mL:300mL:5g;
The mixed solvent is toluene, n-butanol and deionized water which are mixed according to the volume ratio of 3:5:1.
The nuclear magnetic hydrogen spectrum is shown in figure 3, and the nuclear magnetic hydrogen spectrum data is1H NMR(400MHz, CDCl3, delta 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).
S14, adding 2-bromo-9H-fluorene, 1-bromooctane, tetrabutylammonium bromide and dimethyl sulfoxide into a 50wt% sodium hydroxide solution, stirring, heating to 80 ℃ for reaction for 8.5 hours, adding deionized water after the reaction is finished, oscillating, adding petroleum ether for extraction, separating liquid, taking an upper organic phase, separating by column chromatography (eluent: petroleum ether), and vacuum drying at 40 ℃ for 8 hours to obtain an intermediate product IV.
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;
The dosage of tetrabutylammonium bromide is 2.0 percent of the mole number of 2-bromo-9H-fluorene;
The nuclear magnetic resonance hydrogen spectrum is shown in FIG. 4, and the nuclear magnetic resonance hydrogen spectrum data is1H NMR(400MHz, CDCl3, delta ppm, 7.2-7.8 (7H, benzene ring) and 1.27 (28H, -CH2-); 0.93(6H, -CH3).
S15, mixing an intermediate product IV, 4-vinylphenylboronic acid, potassium carbonate and tetra (triphenylphosphine) palladium, adding the mixture into a reactor, carrying out N2 replacement protection, adding a mixed solvent, stirring, heating and refluxing for 18 hours, adding deionized water, oscillating, extracting with dichloromethane, separating liquid, taking an organic phase, adding anhydrous sodium sulfate for drying, filtering, taking a solution, and carrying out column chromatography separation (eluent: petroleum ether/dichloromethane=1/10, V/V), and carrying out vacuum drying at 40 ℃ for 8 hours to obtain the intermediate product V.
The dosage ratio of the intermediate product IV, 4-vinylphenylboronic acid, potassium carbonate, tetra (triphenylphosphine) palladium, mixed solvent, deionized water, methylene dichloride and anhydrous sodium sulfate is 0.1mol:0.14mol:0.5mol:0.008mol:150mL:200mL:300mL:5g;
The mixed solvent is toluene, n-butanol and deionized water which are mixed according to the volume ratio of 3:5:1.
The nuclear magnetic hydrogen spectrum is shown in figure 5, and the nuclear magnetic hydrogen spectrum data is1H NMR(400MHz, CDCl3, delta 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).
S16, adding the intermediate product III, the intermediate product V and benzoyl peroxide into anhydrous toluene, vacuumizing, filling nitrogen for protection, heating to 80 ℃ for reaction for 22 hours, adding methanol after the reaction is finished to obtain insoluble substances, adding the insoluble substances into acetone, oscillating for 6 hours, filtering, taking the insoluble substances, and vacuum drying for 8 hours at 40 ℃ to obtain a target productNamely a macromolecular light conversion agent.
The dosage ratio of the intermediate product III to the intermediate product V to the anhydrous toluene to the methanol to the acetone is 0.7mol to 0.3mol to 1000mL to 3000mL;
The amount of benzoyl peroxide was 1.0wt% based on the total mass of the reactants.
The nuclear magnetic hydrogen spectrum is shown in FIG. 6.
An EVA (ethylene vinyl acetate) packaging light conversion adhesive film comprises the following raw materials in parts by weight:
100 parts of EVA resin;
1.0 part of cross-linking agent;
1.2 parts of auxiliary cross-linking agent;
5.0 parts of macromolecular light conversion agent;
0.2 parts of antioxidant;
0.2 parts of light stabilizer;
0.4 parts of coupling agent.
Example 2
The preparation method of the macromolecular light conversion agent comprises the following steps:
s11, adding benzotriazole into hydrobromic acid, stirring, slowly adding dropwise bromine into a reaction system, heating and refluxing for 18 hours, adding saturated sodium bisulphite aqueous solution for quenching, extracting with dichloromethane, separating liquid, taking an organic phase, adding anhydrous sodium sulfate for drying, filtering, taking a solution, separating by column chromatography (eluent: petroleum ether/dichloromethane=1/10, V/V), and vacuum-drying at 40 ℃ for 8 hours to obtain an intermediate product I;
the dosage ratio of benzotriazole, hydrobromic acid, liquid bromine, saturated sodium bisulfite aqueous solution, methylene dichloride and anhydrous sodium sulfate is 0.1mol:0.75mol:0.15mol:400mL:300mL:5g.
S12, taking an intermediate product I, potassium carbonate and 5-bromovalerate, adding the intermediate product I, potassium carbonate and 5-bromovalerate into N, N-dimethylformamide, stirring and heating for 40h at 60 ℃, cooling to room temperature after the reaction is finished, washing with saturated ammonium chloride solution for 3 times, extracting with ethyl acetate, separating liquid, taking an organic phase, adding anhydrous sodium sulfate for drying, filtering, taking a solution, separating by column chromatography (eluent: petroleum ether/dichloromethane=1/5, V/V), and drying in vacuum for 8h at 40 ℃ to obtain an intermediate product II.
The dosage ratio of the intermediate product I, potassium carbonate, 5-bromovaleric acid tert-butyl ester, N-dimethylformamide, saturated ammonium chloride solution, ethyl acetate and anhydrous sodium sulfate is 0.1mol:0.25mol:0.12mol:200mL:300mL:400mL:5g.
S13, mixing an intermediate product II, 4-vinylphenylboronic acid, potassium carbonate and tetrakis (triphenylphosphine) palladium, adding the mixture into a reactor, performing N2 replacement protection, adding a mixed solvent, stirring, heating and refluxing for 12 hours, adding deionized water, oscillating, extracting with dichloromethane, separating liquid, taking an organic phase, adding anhydrous sodium sulfate for drying, filtering, taking a solution, and performing column chromatography separation (eluent: petroleum ether/dichloromethane=1/10, V/V), and vacuum drying at 40 ℃ for 8 hours to obtain an intermediate product III.
The dosage ratio of the intermediate product II, 4-vinylphenylboronic acid, potassium carbonate, tetra (triphenylphosphine) palladium, mixed solvent, deionized water, methylene dichloride and anhydrous sodium sulfate is 0.1mol:0.16mol:0.5mol:0.01mol:150mL:200mL:300mL:5g;
The mixed solvent is toluene, n-butanol and deionized water which are mixed according to the volume ratio of 3:5:1.
S14, adding 2-bromo-9H-fluorene, 1-bromooctane, tetrabutylammonium bromide and dimethyl sulfoxide into a 50wt% sodium hydroxide solution, stirring, heating to 75 ℃ for reaction for 10 hours, adding deionized water after the reaction is finished, oscillating, adding petroleum ether for extraction, separating liquid, taking an upper organic phase, separating by column chromatography (eluent: petroleum ether), and vacuum drying at 40 ℃ for 8 hours to obtain an intermediate product IV.
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;
The dosage of tetrabutylammonium bromide is 2.0 percent of the mole number of 2-bromo-9H-fluorene;
s15, mixing an intermediate product IV, 4-vinylphenylboronic acid, potassium carbonate and tetra (triphenylphosphine) palladium, adding the mixture into a reactor, carrying out N2 replacement protection, adding a mixed solvent, stirring, heating and refluxing for 24 hours, adding deionized water, oscillating, extracting with dichloromethane, separating liquid, taking an organic phase, adding anhydrous sodium sulfate for drying, filtering, taking a solution, and carrying out column chromatography separation (eluent: petroleum ether/dichloromethane=1/10, V/V), and carrying out vacuum drying at 40 ℃ for 8 hours to obtain the intermediate product V.
The dosage ratio of the intermediate product IV, 4-vinylphenylboronic acid, potassium carbonate, tetra (triphenylphosphine) palladium, mixed solvent, deionized water, methylene dichloride and anhydrous sodium sulfate is 0.1mol:0.12 mol:0.005mol:150mL:200mL:300mL:5g;
The mixed solvent is toluene, n-butanol and deionized water which are mixed according to the volume ratio of 3:5:1.
S16, adding the intermediate product III, the intermediate product V and benzoyl peroxide into anhydrous toluene, vacuumizing, filling nitrogen for protection, heating to 75 ℃ for reaction for 28 hours, adding methanol after the reaction is finished to obtain insoluble substances, adding the insoluble substances into acetone, oscillating for 6 hours, filtering, taking the insoluble substances, and vacuum drying for 8 hours at 40 ℃ to obtain a target productNamely a macromolecular light conversion agent.
The dosage ratio of the intermediate product III to the intermediate product V to the anhydrous toluene to the methanol to the acetone is 0.7mol to 0.3mol to 1000mL to 3000mL;
The amount of benzoyl peroxide was 1.0wt% based on the total mass of the reactants.
An EVA (ethylene vinyl acetate) packaging light conversion adhesive film comprises the following raw materials in parts by weight:
100 parts of EVA resin;
05 parts of a cross-linking agent;
1.5 parts of auxiliary cross-linking agent;
5.0 parts of macromolecular light conversion agent;
0.2 parts of antioxidant;
0.2 parts of light stabilizer;
0.3 parts of coupling agent.
Example 3
The preparation method of the macromolecular light conversion agent comprises the following steps:
S11, adding benzotriazole into hydrobromic acid, stirring, slowly adding dropwise bromine into a reaction system, heating and refluxing for 24 hours, adding saturated sodium bisulphite aqueous solution for quenching, extracting with dichloromethane, separating liquid, taking an organic phase, adding anhydrous sodium sulfate for drying, filtering, taking a solution, separating by column chromatography (eluent: petroleum ether/dichloromethane=1/10, V/V), and vacuum-drying at 40 ℃ for 8 hours to obtain an intermediate product I;
the dosage ratio of benzotriazole, hydrobromic acid, liquid bromine, saturated sodium bisulfite aqueous solution, methylene chloride and anhydrous sodium sulfate is 0.1mol:0.75mol:0.12mol:400mL:300mL:5g.
S12, taking an intermediate product I, potassium carbonate and 5-bromovalerate, adding the intermediate product I, potassium carbonate and 5-bromovalerate into N, N-dimethylformamide, stirring and heating for 48 hours at 40 ℃, cooling to room temperature after the reaction is finished, washing 3 times with saturated ammonium chloride solution, extracting with ethyl acetate, separating liquid, taking an organic phase, adding anhydrous sodium sulfate for drying, filtering, taking a solution, separating by column chromatography (eluent: petroleum ether/dichloromethane=1/5, V/V), and drying in vacuum for 8 hours at 40 ℃ to obtain an intermediate product II.
The dosage ratio of the intermediate product I, potassium carbonate, 5-bromovaleric acid tert-butyl ester, N-dimethylformamide, saturated ammonium chloride solution, ethyl acetate and anhydrous sodium sulfate is 0.1mol:0.25mol:0.15mol:200mL:300mL:400mL:5g.
S13, mixing an intermediate product II, 4-vinylphenylboronic acid, potassium carbonate and tetra (triphenylphosphine) palladium, adding the mixture into a reactor, carrying out N2 replacement protection, adding a mixed solvent, stirring, heating and refluxing for 24 hours, adding deionized water, oscillating, extracting with dichloromethane, separating liquid, taking an organic phase, adding anhydrous sodium sulfate for drying, filtering, taking a solution, and carrying out column chromatography separation (eluent: petroleum ether/dichloromethane=1/10, V/V), and carrying out vacuum drying at 40 ℃ for 8 hours to obtain an intermediate product III.
The dosage ratio of the intermediate product II, 4-vinylphenylboronic acid, potassium carbonate, tetrakis (triphenylphosphine) palladium, mixed solvent, deionized water, methylene dichloride and anhydrous sodium sulfate is 0.1mol:0.12 mol:0.005mol:150mL:200mL:300mL:5g;
The mixed solvent is toluene, n-butanol and deionized water which are mixed according to the volume ratio of 3:5:1.
S14, adding 2-bromo-9H-fluorene, 1-bromooctane, tetrabutylammonium bromide and dimethyl sulfoxide into a 50wt% sodium hydroxide solution, stirring, heating to 85 ℃ for reaction for 6 hours, adding deionized water after the reaction is finished, oscillating, adding petroleum ether for extraction, separating liquid, taking an upper organic phase, separating by column chromatography (eluent: petroleum ether), and vacuum drying at 40 ℃ for 8 hours to obtain an intermediate product IV.
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;
The dosage of tetrabutylammonium bromide is 2.0 percent of the mole number of 2-bromo-9H-fluorene;
S15, mixing an intermediate product IV, 4-vinylphenylboronic acid, potassium carbonate and tetra (triphenylphosphine) palladium, adding the mixture into a reactor, carrying out N2 replacement protection, adding a mixed solvent, stirring, heating and refluxing for 12 hours, adding deionized water, oscillating, extracting with dichloromethane, separating liquid, taking an organic phase, adding anhydrous sodium sulfate for drying, filtering, taking a solution, and carrying out column chromatography separation (eluent: petroleum ether/dichloromethane=1/10, V/V), and carrying out vacuum drying at 40 ℃ for 8 hours to obtain the intermediate product V.
The dosage ratio of the intermediate product IV, 4-vinylphenylboronic acid, potassium carbonate, tetra (triphenylphosphine) palladium, mixed solvent, deionized water, methylene dichloride and anhydrous sodium sulfate is 0.1mol:0.16mol:0.5mol:0.01mol:150mL:200mL:300mL:5g;
The mixed solvent is toluene, n-butanol and deionized water which are mixed according to the volume ratio of 3:5:1.
S16, adding the intermediate product III, the intermediate product V and benzoyl peroxide into anhydrous toluene, vacuumizing, filling nitrogen for protection, heating to 85 ℃ for reaction for 20 hours, adding methanol after the reaction is finished to obtain insoluble substances, adding the insoluble substances into acetone, oscillating for 6 hours, filtering, taking the insoluble substances, and vacuum drying for 8 hours at 40 ℃ to obtain a target productNamely a macromolecular light conversion agent.
The dosage ratio of the intermediate product III to the intermediate product V to the anhydrous toluene to the methanol to the acetone is 0.7mol to 0.3mol to 1000mL to 3000mL;
The amount of benzoyl peroxide was 1.0wt% based on the total mass of the reactants.
An EVA (ethylene vinyl acetate) packaging light conversion adhesive film comprises the following raw materials in parts by weight:
100 parts of EVA resin;
1.5 parts of cross-linking agent;
1.0 parts of auxiliary cross-linking agent;
5.0 parts of macromolecular light conversion agent;
0.2 parts of antioxidant;
0.2 parts of light stabilizer;
0.5 part of coupling agent.
Example 4
Otherwise, the embodiment 1 is different in that:
A preparation method of macromolecular light conversion agent, in S16,
The ratio of the amount of intermediate III, intermediate V, anhydrous toluene, methanol, and acetone was 0.8mol:0.2mol:1000mL:3000 mL.
Example 5
Otherwise, the embodiment 1 is different in that:
A preparation method of macromolecular light conversion agent, in S16,
The ratio of the amount of intermediate III, intermediate V, anhydrous toluene, methanol, and acetone was 0.5mol:0.5mol:1000mL:3000 mL.
Example 6
Otherwise, the embodiment 1 is different in that:
An EVA (ethylene vinyl acetate) packaging light conversion adhesive film comprises the following raw materials in parts by weight:
100 parts of EVA resin;
1.0 part of cross-linking agent;
1.2 parts of auxiliary cross-linking agent;
5.0 parts of macromolecular light conversion agent;
0.1 part of antioxidant;
0.3 parts of light stabilizer;
0.4 parts of coupling agent.
Example 7
Otherwise, the embodiment 1 is different in that:
An EVA (ethylene vinyl acetate) packaging light conversion adhesive film comprises the following raw materials in parts by weight:
100 parts of EVA resin;
1.0 part of cross-linking agent;
1.2 parts of auxiliary cross-linking agent;
5.0 parts of macromolecular light conversion agent;
0.25 parts of antioxidant;
0.1 part of light stabilizer;
0.4 parts of coupling agent.
Example 8
Otherwise, the embodiment 1 is different in that:
An EVA (ethylene vinyl acetate) packaging light conversion adhesive film comprises the following raw materials in parts by weight:
100 parts of EVA resin;
1.0 part of cross-linking agent;
1.2 parts of auxiliary cross-linking agent;
0.5 part of macromolecular light conversion agent;
0.2 parts of antioxidant;
0.2 parts of light stabilizer;
0.4 parts of coupling agent.
Example 9
Otherwise, the embodiment 1 is different in that:
An EVA (ethylene vinyl acetate) packaging light conversion adhesive film comprises the following raw materials in parts by weight:
100 parts of EVA resin;
1.0 part of cross-linking agent;
1.2 parts of auxiliary cross-linking agent;
1.0 part of macromolecular light conversion agent;
0.2 parts of antioxidant;
0.2 parts of light stabilizer;
0.4 parts of coupling agent.
Example 10
Otherwise, the embodiment 1 is different in that:
An EVA (ethylene vinyl acetate) packaging light conversion adhesive film comprises the following raw materials in parts by weight:
100 parts of EVA resin;
1.0 part of cross-linking agent;
1.2 parts of auxiliary cross-linking agent;
2.0 parts of macromolecular light conversion agent;
0.2 parts of antioxidant;
0.2 parts of light stabilizer;
0.4 parts of coupling agent.
Example 11
Otherwise, the embodiment 1 is different in that:
An EVA (ethylene vinyl acetate) packaging light conversion adhesive film comprises the following raw materials in parts by weight:
100 parts of EVA resin;
1.0 part of cross-linking agent;
1.2 parts of auxiliary cross-linking agent;
8.0 parts of macromolecular light conversion agent;
0.2 parts of antioxidant;
0.2 parts of light stabilizer;
0.4 parts of coupling agent.
Example 12
Otherwise, the embodiment 1 is different in that:
A POE packaging light conversion adhesive film comprises the following raw materials in parts by weight:
100 parts of POE resin;
1.0 part of cross-linking agent;
1.2 parts of auxiliary cross-linking agent;
5.0 parts of macromolecular light conversion agent;
0.05 parts of antioxidant;
0.05 parts of light stabilizer;
0.8 parts of coupling agent.
Example 13
Otherwise, the embodiment 1 is different in that:
An EPE packaging light conversion adhesive film comprises an EVA layer (thickness 100 μm) and a POE layer (thickness 300 μm),
The EVA layer comprises the following raw materials in parts by weight:
100 parts of EVA resin;
1.0 part of cross-linking agent;
1.2 parts of auxiliary cross-linking agent;
5.0 parts of macromolecular light conversion agent;
0.2 parts of antioxidant;
0.2 parts of light stabilizer;
0.4 parts of coupling agent.
The POE layer comprises the following raw materials in parts by weight:
100 parts of POE resin;
1.0 part of cross-linking agent;
1.2 parts of auxiliary cross-linking agent;
5.0 parts of macromolecular light conversion agent;
0.05 parts of antioxidant;
0.05 parts of light stabilizer;
0.8 parts of coupling agent.
The following comparative examples are all compared to example 1:
Comparative example 1
Otherwise, the embodiment 1 is different in that:
the macromolecule light conversion agent is not added in the formula of the photovoltaic packaging light conversion adhesive film.
Comparative example 2
Otherwise, the embodiment 1 is different in that:
In the formula of the photovoltaic packaging light conversion adhesive film, a macromolecular light conversion agent is replaced by benzotriazole.
Comparative example 3
The other embodiments are the same as those of comparative example 1, except that:
in the formula of the photovoltaic packaging light conversion adhesive film, a macromolecular light conversion agent is replaced by a mixture of benzotriazole and an intermediate product V according to a molar ratio of 7:3.
Comparative example 4
Otherwise, the embodiment 1 is different in that:
in the formula of the photovoltaic packaging light conversion adhesive film, a macromolecular light conversion agent is replaced by a mixture of an intermediate product III and an intermediate product V according to a molar ratio of 7:3.
Comparative example 5
Otherwise, the embodiment 1 is different in that:
In the preparation method of the macromolecular light conversion agent, in S11, the dosage ratio of benzotriazole, hydrobromic acid, liquid bromine, saturated sodium bisulfite aqueous solution, methylene dichloride and anhydrous sodium sulfate is 0.1mol:0.75mol:0.28mol:400mL:300mL:5g.
In S13, mixing the intermediate product II, 4-vinylphenylboronic acid, potassium carbonate and tetra (triphenylphosphine) palladium, adding the mixture into a reactor, carrying out N2 replacement protection, adding a mixed solvent, stirring, heating and refluxing for 18 hours, adding phenylboronic acid, continuously heating and refluxing for 18 hours, adding deionized water, oscillating, extracting with dichloromethane, separating liquid, taking an organic phase, adding anhydrous sodium sulfate for drying, filtering, taking a solution, separating by column chromatography (eluent: petroleum ether/dichloromethane=1/10, V/V), and carrying out vacuum drying at 40 ℃ for 8 hours to obtain an intermediate product III.
The dosage ratio of the intermediate II, 4-vinylphenylboronic acid, potassium carbonate, tetra (triphenylphosphine) palladium, mixed solvent, phenylboronic acid, deionized water, methylene dichloride and anhydrous sodium sulfate is 0.1mol:0.15mol:0.5mol:0.008mol:150mL:0.15mol:200mL:300mL:5g.
Comparative example 6
Otherwise, the embodiment 1 is different in that:
in S11, the dosage ratio of benzotriazole, hydrobromic acid, liquid bromine, saturated sodium bisulfite aqueous solution, methylene dichloride and anhydrous sodium sulfate is 0.1mol:0.75mol:0.28mol:400mL:300mL:5g.
In S13, the dosage ratio of the intermediate II, 4-vinylphenylboronic acid, potassium carbonate, tetrakis (triphenylphosphine) palladium, mixed solvent, deionized water, methylene chloride and anhydrous sodium sulfate is 0.1mol:0.30mol:0.5mol:0.008mol:150mL:200mL:300mL:5g.
Comparative example 7
Otherwise, the embodiment 1 is different in that:
in the preparation method of the macromolecular light conversion agent, in S13 and S15, 4-vinylphenylboronic acid is replaced by 4-penteneboronic acid.
Comparative example 8
Otherwise, the embodiment 1 is different in that:
Preparation method of macromolecular light conversion agent, S12, replacing tert-butyl 5-bromopentanoate with bromobutane, and
In S14, 1-bromooctane is replaced with bromobutane.
Physical properties of the photovoltaic packaging light conversion adhesive films prepared in the examples and the comparative examples of the present invention were measured respectively, and the results are shown in table 1.
Firstly, it can be obtained from examples 1-13 in table 1 that the macromolecule light conversion agent for photovoltaic and the photovoltaic packaging light conversion adhesive film have obvious advantages in improving performances such as photoelectric conversion efficiency and the like, and have better ageing resistance (stability).
Second, it can be observed from example 1 and comparative example 1 that the photovoltaic packaging light conversion film of the present invention has excellent light conversion efficiency using the self-made macromolecular light conversion agent. It can be observed from examples 1 and comparative examples 2 to 4 that the photovoltaic film of the invention uses the self-made macromolecular light conversion agent, has higher half-width and light conversion efficiency compared with a small molecular structure, and also has low migration performance, and the asymmetric substitution structure, the core light conversion structure positioned at a side chain and an electron-rich benzene ring in the macromolecular light conversion agent are used as a linking structure, so that the photovoltaic film has remarkable positive effects on improving the light conversion efficiency, and the long-fatty chain and long-chain ester structure in the macromolecular light conversion agent structure are beneficial to effectively improving the compatibility, so that the light conversion efficiency is improved.
Thirdly, it can be observed from the examples that the photovoltaic packaging light conversion adhesive film has lasting high-efficiency light conversion efficiency, and therefore has excellent optical performance and stability.
In conclusion, the macromolecule light conversion agent for the photovoltaic and the photovoltaic packaging light conversion adhesive film provided by the invention use the self-made light conversion agent, and have excellent light conversion performance, low mobility, high stability, power gain function and the like.
The test method comprises the following steps:
(1) And (5) measuring the fluorescence excitation spectrum of the light conversion adhesive film.
(2) Light conversion efficiency is that the Horiba spectrometer FL-3 is used for absolute quantum efficiency test at normal temperature.
(3) And (3) wet heat aging resistance, namely performing a wet heat aging test on the photovoltaic adhesive film. The test conditions are +85 ℃ and the relative humidity is 85%.
The measurement was performed before and after the test, and the retention was calculated as follows:
retention = average after test/average before test x 100%.
(4) Ultraviolet aging resistance, namely performing ultraviolet irradiation aging test on the obtained photovoltaic adhesive film according to the requirements specified by International Electrotechnical Commission (IEC) 61345. The test conditions are that the surface temperature of the test piece is 60+/-5 ℃, the ultraviolet wavelength range is 280-400nm, the irradiation intensity is 15 kW.h/m2, and the ultraviolet irradiation test time is 2000hr.
The measurement was performed before and after the test, and the retention was calculated as follows:
retention = average after test/average before test x 100%.
(5) The mobility test method comprises the steps of carrying out quick aging migration test on the module end, wherein the front surface of the photovoltaic module is a light conversion film doped with a light conversion agent, the back surface of the module is a blank film without the light conversion agent (only the light conversion agent is a variable), and after the module is subjected to UV300 aging test in an aging box, respectively removing the adhesive film on the front surface of the module, and carrying out heating soaking treatment (stirring and heating soaking for 24H at 60 ℃) by using an organic solvent (methanol). HPLC analysis was performed on the solution after soaking to obtain the content (A) of one example. The adhesive film on the front side of the module which had not been aged was removed, subjected to the same heat soaking treatment, and the soaked solution was subjected to HPLC analysis to obtain the content (B) of another example. The mobility is a/B100%.
(6) The photoelectric gain is measured by an EL tester. Orderly stacking photovoltaic glass, a glue film, a battery piece, a glue film and a photovoltaic backboard from top to bottom, laminating for 15min at 140 ℃, taking out, cooling, testing the power of a bare chip, recording as P0.1, laminating the photovoltaic glue film without an adsorbent to obtain a component, testing the power of the component, recording as P1, testing the power of a new bare chip, recording as P0.2, testing the power of the component, recording as P2, and obtaining the power gain as Pm=（P2/P0.2）/（P1/P0.1.
With the above-described preferred embodiments according to the present invention as an illustration, the above-described descriptions can be used by persons skilled in the relevant art to make various changes and modifications without departing from the scope of the technical idea of the present invention. The technical scope of the present invention is not limited to the description, but must be determined according to the scope of claims.