CN117247362B - Light conversion agent with asymmetric structure, light conversion adhesive film and preparation method thereof - Google Patents

Light conversion agent with asymmetric structure, light conversion adhesive film and preparation method thereof Download PDF

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CN117247362B
CN117247362B CN202311534569.1A CN202311534569A CN117247362B CN 117247362 B CN117247362 B CN 117247362B CN 202311534569 A CN202311534569 A CN 202311534569A CN 117247362 B CN117247362 B CN 117247362B
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light conversion
light
asymmetric
substituted
agent
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CN117247362A (en
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朱秀娟
茹正伟
周乐
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Changzhou Bbetter Film Technologies Co ltd
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Changzhou Bbetter Film Technologies Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/06—Non-macromolecular additives organic
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
    • C07D249/16—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms condensed with carbocyclic rings or ring systems
    • C07D249/18—Benzotriazoles
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
    • C07D409/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings
    • C07D409/04—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings directly linked by a ring-member-to-ring-member bond
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J123/00—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers
    • C09J123/02—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers not modified by chemical after-treatment
    • C09J123/04—Homopolymers or copolymers of ethene
    • C09J123/08—Copolymers of ethene
    • C09J123/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
    • C09J123/0853—Vinylacetate
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/02—Use of particular materials as binders, particle coatings or suspension media therefor
    • C09K11/025—Use of particular materials as binders, particle coatings or suspension media therefor non-luminescent particle coatings or suspension media
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
    • H01L31/054—Optical elements directly associated or integrated with the PV cell, e.g. light-reflecting means or light-concentrating means
    • H01L31/055—Optical elements directly associated or integrated with the PV cell, e.g. light-reflecting means or light-concentrating means where light is absorbed and re-emitted at a different wavelength by the optical element directly associated or integrated with the PV cell, e.g. by using luminescent material, fluorescent concentrators or up-conversion arrangements
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    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1018—Heterocyclic compounds
    • C09K2211/1025—Heterocyclic compounds characterised by ligands
    • C09K2211/1059—Heterocyclic compounds characterised by ligands containing three nitrogen atoms as heteroatoms
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1018—Heterocyclic compounds
    • C09K2211/1025—Heterocyclic compounds characterised by ligands
    • C09K2211/1092—Heterocyclic compounds characterised by ligands containing sulfur as the only heteroatom

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Abstract

The invention belongs to the technical field of light conversion adhesive films, and in particular relates to a light conversion agent with an asymmetric structure, a light conversion adhesive film and a preparation method thereof, wherein the light conversion adhesive film comprises the following components: the light conversion agent is benzotriazole as a matrix, and asymmetric aromatic rings are introduced at two sides of a benzene ring; the asymmetric aromatic ring comprises a heteroaryl group on one side and a benzene ring on the other side; according to the light conversion agent with an asymmetric structure, the light conversion adhesive film and the preparation method thereof, benzotriazole is used as a matrix, and asymmetric heteroaryl and benzene rings are introduced into two sides of the benzene ring, so that on one hand, the heteroaryl such as thiophene aromatic ring has higher electron density and excellent carrier mobility compared with the benzene ring; on the other hand, the asymmetric structure can enable the wavelength of the converted light of the light conversion agent to have wider regulation and control space, and meanwhile, light conversion in different wavelength ranges can be further realized by regulating and controlling the light emitting units at two sides, so that sunlight is efficiently utilized.

Description

Light conversion agent with asymmetric structure, light conversion adhesive film and preparation method thereof
Technical Field
The invention belongs to the technical field of light conversion adhesive films, and particularly relates to a light conversion agent with an asymmetric structure, a light conversion adhesive film and a preparation method of the light conversion adhesive film.
Background
In general, the visible light with medium wavelength and the near infrared light wave band are absorbed by the main body of the solar cell, and excited carriers easily enter an external circuit, so that the quantum efficiency is high; and for ultraviolet light wave bands with the wavelength smaller than 400nm, the utilization efficiency of the solar cell is lower. Furthermore, the presence of ultraviolet light in sunlight can also reduce the useful life of the photovoltaic device.
The light conversion adhesive film can effectively fully absorb ultraviolet light in sunlight, and avoid damage to the service life of the photovoltaic device; meanwhile, ultraviolet light can be converted into available visible light, so that the photoelectric conversion efficiency of the photovoltaic device is improved.
The luminous cores of the existing light conversion agents are of symmetrical structures, but the regulation and control range of molecules of the symmetrical structures on the wavelength of the converted light is narrow, and sunlight cannot be utilized efficiently.
Therefore, there is a need for a light conversion agent that can regulate a wider range of light conversion wavelengths.
Disclosure of Invention
The invention provides an asymmetric structure light conversion agent, a light conversion adhesive film and a preparation method thereof, which are used for solving the technical problem that the light conversion wavelength regulation range of the existing symmetric structure light conversion agent is too narrow.
In order to solve the technical problems, the invention provides an asymmetric structure light conversion agent, which comprises the following components: the light conversion agent is benzotriazole as a matrix, and asymmetric aromatic rings are introduced at two sides of a benzene ring; the asymmetric aromatic ring includes a heteroaryl group on one side and a benzene ring on the other side.
In still another aspect, the present invention further provides a method for preparing the light conversion agent with an asymmetric structure as described above, including the following steps: step S1, adding calcium carbonate into 1H-benzotriazole and organic iodide in N, N-dimethylformamide, heating, separating liquid, dehydrating, filtering and separating to obtain a first intermediate; step S2, stirring, heating and refluxing the first intermediate, liquid bromine and hydrobromic acid, extracting, separating liquid and separating to obtain a second intermediate; and step S3, heating the second intermediate, thiophene boric acid, phenylboric acid, potassium carbonate and tetrakis (triphenylphosphine) palladium in a nitrogen environment, cooling to room temperature after the reaction is completed, and removing water, filtering and separating to obtain the light conversion agent with an asymmetric structure.
In a third aspect, the present invention further provides a light conversion adhesive film, including: a base film and an asymmetric structured light conversion agent; wherein the asymmetric structured light transfer agent comprises a composition of any one or more of the asymmetric structured light transfer agents described previously; and the light conversion agent with the asymmetric structure is dispersed in the base film.
In a fourth aspect, the present invention further provides a method for preparing the light conversion adhesive film as described above, including: uniformly mixing matrix resin, an asymmetric structure light conversion agent and an auxiliary agent according to the raw material ratio; and (5) casting to form a film to obtain the light conversion adhesive film.
In a fifth aspect, the present invention further provides a photovoltaic module, which includes a light conversion film, where the light conversion film is a light conversion film as described above.
The light conversion agent with the asymmetric structure, the light conversion adhesive film and the preparation method thereof have the beneficial effects that benzotriazole is used as a matrix, and asymmetric aromatic rings (heteroaryl and benzene ring) are introduced into two sides of the benzene ring, so that on one hand, heteroaryl such as thiophene aromatic rings have higher electron density and excellent carrier mobility compared with the benzene ring; on the other hand, the asymmetric structure can enable the wavelength of the converted light of the light conversion agent to have wider regulation and control space, and meanwhile, light conversion in different wavelength ranges can be further realized by regulating and controlling the light emitting units at two sides, so that sunlight is efficiently utilized.
Additional features and advantages of the invention will be set forth in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention.
In order to make the above objects, features and advantages of the present invention more comprehensible, preferred embodiments accompanied with figures are described in detail below.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are needed in the description of the embodiments or the prior art will be briefly described, and it is obvious that the drawings in the description below are some embodiments of the present invention, and other drawings can be obtained according to the drawings without inventive effort for a person skilled in the art.
FIG. 1 is a step S1 reaction scheme of a preferred embodiment of an asymmetric light converter of the present invention;
FIG. 2 is a step S2 reaction scheme of a preferred embodiment of an asymmetric light converter of the present invention;
FIG. 3 is a step S3 reaction scheme of a preferred embodiment of an asymmetric light converter of the present invention;
FIG. 4 is a hydrogen spectrum of 4- (4- (tert-butyl) phenyl) -2-isobutyl-7- (thiophen-2-yl) -benzotriazol according to the invention;
FIG. 5 is a carbon spectrum of 4- (4- (tert-butyl) phenyl) -2-isobutyl-7- (thiophen-2-yl) -benzotriazol according to the invention;
FIG. 6 is a hydrogen spectrum of 4- (4- (tert-butyl) phenyl) -2-isobutyl-7- (benzothien-2-yl) -benzotriazol of the present invention;
FIG. 7 is a carbon spectrum of 4- (4- (tert-butyl) phenyl) -2-isobutyl-7- (benzothien-2-yl) -benzotriazol of the present invention;
FIG. 8 is a hydrogen spectrum of 4- (4- (tert-butyl) phenyl) -2-isobutyl-7- (5-alditothiophen-2-yl) -benzotriazol of the present invention;
FIG. 9 is a carbon spectrum of 4- (4- (tert-butyl) phenyl) -2-isobutyl-7- (5-alditothiophen-2-yl) -benzotriazol of the present invention.
Detailed Description
For the purpose of making the objects, technical solutions and advantages of the embodiments of the present invention more apparent, the technical solutions of the present invention will be clearly and completely described below with reference to the accompanying drawings, and it is apparent that the described embodiments are some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The benzotriazole compounds are used as light conversion agents by more and more light conversion adhesive films, but the conventional benzotriazole compounds are of symmetrical structures, the benzene rings are arranged on two sides of the conventional benzotriazole compounds for light conversion, and the thiophene with the same aromatic ring can have dark color after being introduced into a benzotriazole system and cannot be applied to the embarrassment in the packaging adhesive films.
The invention provides an asymmetric structure light conversion agent, which comprises the following components: the light conversion agent is benzotriazole as a matrix, and asymmetric aromatic rings are introduced at two sides of a benzene ring; the asymmetric aromatic ring includes a heteroaryl group on one side and a benzene ring on the other side.
In this embodiment, specifically, the structural general formula of the light conversion agent is as follows:
wherein
R1 is hydrogen, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted carboxyl, substituted or unsubstituted carbonyl, substituted or unsubstituted amino, substituted or unsubstituted amido;
r2 is substituted or unsubstituted heteroaryl;
r3 is a substituted or unsubstituted alkyl group, a substituted or unsubstituted amide group, a substituted or unsubstituted carboxyl group, or a substituted or unsubstituted carbonyl group.
The term "alkyl" refers to and includes straight and branched chain alkyl groups. Preferred alkyl groups are alkyl groups having from one to fifteen carbon atoms, more preferably from one to six carbon atoms; and includes methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, 1-methylethyl, 1-methylpropyl, 2-methylpropyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1-dimethylpropyl, 1, 2-dimethylpropyl, 2-dimethylpropyl, and the like. In addition, alkyl groups may be optionally substituted.
The term "alkenyl" refers to and includes both straight and branched alkenyl groups. Alkenyl is essentially an alkyl group comprising at least one carbon-carbon double bond in the alkyl chain. Preferred alkenyl groups contain those of from two to fifteen carbon atoms. Further preferred are one to six carbon atoms. In addition, alkenyl groups may be optionally substituted.
The term "alkynyl" refers to and includes both straight and branched chain alkynyl groups. Alkynyl is essentially an alkyl group that includes at least one carbon-carbon triple bond in the alkyl chain. Preferred alkynyl groups are those containing from two to fifteen carbon atoms. Further preferred are one to six carbon atoms. In addition, alkynyl groups may be optionally substituted.
The term "aryl" refers to and includes monocyclic aromatic hydrocarbon groups and polycyclic aromatic ring systems. The polycyclic ring may have two or more rings in common in which two carbons are two adjoining rings (the rings being "fused"), wherein at least one of the rings is an aromatic hydrocarbon group, e.g., the other rings may be cycloalkyl, cycloalkenyl, aryl, heterocyclic, and/or heteroaryl. Preferred aryl groups are those containing from six to thirty carbon atoms, preferably from six to twenty carbon atoms, more preferably from six to twelve carbon atoms. Particularly preferred are aryl groups having six carbons, ten carbons or twelve carbons. Suitable aryl groups include phenyl, biphenyl, triphenylene, tetraphenylene, naphthalene, anthracene, phenalene, phenanthrene, fluorene, pyrene, chrysene, perylene and azulene, preferably phenyl, biphenyl, triphenylene, fluorene and naphthalene. In addition, aryl groups may be optionally substituted.
The term "heteroaryl" refers to and includes monocyclic aromatic groups and polycyclic aromatic ring systems that include at least one heteroatom. Heteroatoms include, but are not limited to O, S, N, P, B, si and Se. In many cases O, S or N are preferred heteroatoms. The monocyclic heteroaromatic system is preferably a monocyclic ring having 5 or 6 ring atoms, and the ring may have one to six heteroatoms. The heteropolycyclic ring system may have two or more rings in which two atoms are common to two adjoining rings (the rings being "fused"), wherein at least one of the rings is heteroaryl, e.g., the other rings may be cycloalkyl, cycloalkenyl, aryl, heterocyclic, and/or heteroaryl. The heteropolycyclic aromatic ring system may have one to six heteroatoms in each ring of the polycyclic aromatic ring system. Preferred heteroaryl groups are those containing from three to thirty carbon atoms, preferably from three to twenty carbon atoms, more preferably from three to twelve carbon atoms. Suitable heteroaryl groups include dibenzothiophene, dibenzofuran, dibenzoselenophene, furan, thiophene, benzofuran, benzothiophene, benzoselenophene, carbazole, indolocarbazole, pyridylindole, pyrrolodipyridine, pyrazole, imidazole, triazole, oxazole, thiazole, oxadiazole, diazole, thiadiazole, pyridine, pyridazine, pyrimidine, pyrazine, triazine, oxazine, oxathiazine, oxadiazine, indole, benzimidazole, indazole, indolizine, benzoxazole, benzisoxazole, benzothiazole, quinoline, isoquinoline, cinnoline, quinazoline, quinoxaline, naphthyridine, phthalazine, pteridine, xanthene (xanthene), acridine, phenazine, phenothiazine, phenoxazine, benzofurandipyridine, benzothiophene pyridine, thienodipyridine, benzoselenophene dipyridine, dibenzofuran, dibenzoselenium, carbazole, indolocarbazole, benzimidazole, triazine, 1, 2-borazine, 1-boron-nitrogen, 1-nitrogen, 4-boron-nitrogen, boron-nitrogen-like compounds, and the like. In addition, heteroaryl groups may be optionally substituted.
The terms alkyl, alkenyl, alkynyl, aryl, and heteroaryl as used herein are independently unsubstituted or independently substituted with one or more common substituents.
In some cases, preferred general substituents are selected from the group consisting of: deuterium, fluoro, alkyl, cycloalkyl, heteroalkyl, alkoxy, aryloxy, halogen, nitro, amino, aldehyde, carboxyl, cyano, isocyano.
In some cases, more preferred general substituents are selected from the group consisting of: halogen, nitro, amino, aldehyde, carboxyl, cyano, isocyano, and combinations thereof.
In other cases, the most preferred general substituents are selected from the group consisting of: halogen, nitro, amino, aldehyde groups, and combinations thereof.
The term "halogen" refers to: F. cl, br, I.
In the embodiment, specifically, when benzotriazole is used as a parent, and asymmetric aryl hetero groups such as thiophene and benzene rings are introduced at two sides of the benzene ring, on one hand, 6 pi electrons are arranged on the thiophene aromatic ring, so that the thiophene aromatic ring has higher electron density, the HOMO orbital energy level is reduced, hole transport is facilitated, blue-green light can be generated, and the thiophene and derivatives thereof have good stability; on the other hand, the asymmetric structure can lead the wavelength of the light conversion agent to have wider regulation and control space, the thiophene group has larger influence on the light emission wavelength of the light emitting material, the light emission color can be regulated and controlled by regulating and controlling the length of a thiophene conjugated chain link, the type of substituent and the regularity of polythiophene, and the regulation and control range of the light emission wavelength can be between 400nm and 700 nm; more importantly, the thienyl heterocycle is introduced at one side only, and the benzene ring is reserved at the other side so as to adjust the light emitting wavelength of the light conversion agent to shift towards the blue light wave band.
In still another aspect, the present invention further provides a method for preparing the light conversion agent with an asymmetric structure as described above, including the following steps: step S1, adding calcium carbonate into 1H-benzotriazole and organic iodide in N, N-dimethylformamide, heating, separating liquid, dehydrating, filtering and separating to obtain a first intermediate; step S2, stirring, heating and refluxing the first intermediate, liquid bromine and hydrobromic acid, extracting, separating liquid and separating to obtain a second intermediate; and step S3, heating the second intermediate, thiophene boric acid, phenylboric acid, potassium carbonate and tetrakis (triphenylphosphine) palladium in a nitrogen environment, cooling to room temperature after the reaction is completed, and removing water, filtering and separating to obtain the light conversion agent with an asymmetric structure.
In this embodiment, specifically, the structural formula of the organic iodide is:
。
in this embodiment, specifically, the structural formula of the first intermediate is:
。
in this embodiment, specifically, the structural formula of the second intermediate is:
。
in this embodiment, specifically, the synthetic route reaction formula of the light conversion agent with an asymmetric structure is as follows:
in a third aspect, the present invention further provides a light conversion adhesive film, including: a base film and an asymmetric structured light conversion agent; wherein the asymmetric structured light transfer agent comprises a composition of any one or more of the asymmetric structured light transfer agents described previously; and the light conversion agent with the asymmetric structure is dispersed in the base film.
In this embodiment, the raw materials specifically include, by mass: 100 parts of matrix resin; 0.2 to 1.5 portions of cross-linking agent; 0.1-3 parts of auxiliary cross-linking agent; 0.1-1 part of light stabilizer; 0.01 to 0.3 part of antioxidant; 0.2-1 part of coupling agent; 0.01 to 10 parts of light conversion agent with an asymmetric structure.
In this embodiment, specifically, the base film includes any one or a combination of a plurality of EVA, PMMA, POE, PVB.
In this embodiment, the crosslinking agent comprises, in particular, one or more of tert-butyl peroxy-2-ethylhexyl carbonate, tert-amyl peroxy-2-ethylhexyl carbonate, tert-butyl peroxy-3, 5-trimethylhexanoate, 2, 5-dimethyl-2, 5-di (tert-butylperoxy) hexane.
In this embodiment, the auxiliary crosslinking agent includes one or more of triallyl isocyanurate TAIC and trimethylolpropane triacrylate TMPTA.
In this embodiment, the light stabilizers include, in particular, one or more combinations of light stabilizer 622, light stabilizer 770, light stabilizer 944, light stabilizer 783, light stabilizer 123, light stabilizer 765, light stabilizer 2908, light stabilizer 531, light stabilizer 327, light stabilizer 328.
In this embodiment, the antioxidant specifically includes one or a combination of more of aromatic amines, hindered phenols, and auxiliary antioxidants.
In this embodiment, the coupling agent comprises, in particular, one or more combinations of one or more of KH-550, KH-560, KH-570, A-174, KBM-503, Z-6030, KH-792, A-1120, Z-6020, KBM-603, KH-791, A-151, A-171.
In a fourth aspect, the present invention further provides a method for preparing the light conversion adhesive film as described above, including: uniformly mixing matrix resin, an asymmetric structure light conversion agent and an auxiliary agent according to the raw material ratio; and (5) casting to form a film to obtain the light conversion adhesive film.
In a fifth aspect, the present invention further provides a photovoltaic module, which includes a light conversion film, where the light conversion film is a light conversion film as described above.
Example 1
Step S1, as shown in fig. 1, 1H-benzotriazole (50 mmol,6.078 g,w =98%), potassium carbonate (150 mmol,20.924 g,w =99%) and iodoisobutane (60 mmol,11.041 g,w =97%) are taken, added into a round-bottomed flask, 100mL of N, N-dimethylformamide is added as a solvent, stirred and heated at 80 ℃ for 5 hours, the N, N-dimethylformamide is removed by multiple washing with saturated ammonium chloride solution, the upper liquid is left by extraction of ethyl acetate, anhydrous sodium sulfate is added to remove water, filtration and column separation are carried out to obtain 4.100g of 2-isobutylbenzotriazole, and the separation yield is 46.79%.
Step S2, as shown in FIG. 2, 2-isobutyl benzotriazole (23.394 mmol,4.100 g), liquid bromine (70.194 mmol,11.217 g,3.600 mL) and hydrobromic acid (206.428 mmol,34.825 g,w =48%, 23.4 mL) are sequentially added into a round-bottomed flask, stirred and heated at 130 ℃ for refluxing for 24 h, after the reaction is completed, a cold saturated potassium hydroxide solution is used for removing residual liquid bromine and hydrobromic acid, dichloromethane is used for extracting and separating liquid, anhydrous sodium sulfate is used for removing water, and the product is separated by a column, so that 6.658g of a product is obtained, and the separation yield is 85.44%.
Step S3, as shown in fig. 3, 2-thiopheneboronic acid (1 mmol,130.56 mg,w =98%), tert-butylphenylboronic acid (1 mmol,181.67 mg,w =98%), 4, 7-dibromo-2-isobutylbenzotriazol (1 mmol,333.03 mg), potassium carbonate (5.12 mmol,714.78m g,w =99%), tetrakis (triphenylphosphine) palladium (0.11 mmol,128.39 mg, w=99%). Firstly adding 2-thiophene boric acid, phenylboric acid and potassium carbonate into a three-neck flask, pumping air and filling nitrogen, uniformly mixing toluene (2.56 mL), n-butanol (5.12 mL), water (0.76 mL) and 4, 7-dibromo-2-isobutyl benzotriazole, transferring the mixture into the three-neck flask filled with nitrogen by using a syringe, heating and stirring at 100 ℃ for dissolving for 1h, removing dissolved oxygen contained in the solvent, stopping heating after 1h, cooling to below 50 ℃, adding tetra (triphenylphosphine) palladium under nitrogen atmosphere, sealing, heating to 100 ℃, and continuously stirring and heating for 8h. After the reaction is completed, cooling to room temperature, adding anhydrous sulfuric acid for dewatering, filtering, and separating by a column to obtain a solid, namely the light conversion agent with an asymmetric structure.
Example 2
In this example, specifically, the pre-reaction step in example 1 was adjusted to prepare a thiophene asymmetric structure.
2-isobutyl benzotriazole (17.623 mmol,3.088 g), hydrobromic acid (127.208 mmol,10.292 g,w =48%, 6.9 mL) and liquid bromine (19.358 mmol,3.098 g,0.993 mL) are sequentially added into a round-bottomed flask, stirring and heating are carried out at 130 ℃ for refluxing 18 h, after the reaction is finished, the residual liquid bromine and hydrobromic acid are removed by using cold saturated potassium hydroxide solution, dichloromethane is used for extraction and liquid separation, anhydrous sodium sulfate is added for water removal, and column separation is carried out, thus obtaining 2.225g (light yellow transparent viscous liquid) of 4-bromo-2-isobutyl-benzotriazole, and the separation yield is 49.58%.
The reaction formula is:
4-bromo-2-isobutyl-benzotriazole (7.635 mmol,1.940 g), p-tert-butylphenylboronic acid (11.453 mmol,2.080 g,w =98%), potassium carbonate (39.091 mmol,5.402 g,w =99%), tetrakis (triphenylphosphine) palladium (0.11 mmol,970.58 mg, w=99%). Adding p-tert-butylphenylboronic acid and potassium carbonate into a three-neck flask, pumping air and filling nitrogen, uniformly mixing toluene (19.55 mL), n-butanol (39.1 mL), water (5.8 mL) and 4-bromo-2-isobutyl-benzotriazole, transferring the mixture into the three-neck flask filled with nitrogen by using a syringe, stirring for 1h at 100 ℃, stopping heating, cooling to below 50 ℃, opening the three-neck flask mouth under nitrogen to remove oxygen in toluene, rapidly adding tetrakis (triphenylphosphine) palladium under nitrogen atmosphere, sealing, heating to 100 ℃, and continuing stirring and heating for 12h. After the reaction is completed, the temperature is reduced to room temperature, anhydrous sodium sulfate is added for water removal and filtration, and the product 4- (4- (tertiary butyl) phenyl) -2-isobutyl-benzotriazole 1.186 g (yellowish white transparent viscous liquid) is obtained after column separation, and the separation yield is 50.5 percent.
The reaction formula is:
4- (4- (tert-butyl) phenyl) -2-isobutyl-benzotriazole 1.186 g (3.858 mmol,1.186 g), hydrobromic acid (25.876 mmol,4.361 g,w =48%, 2.9 mL) and liquid bromine (3.858 mmol,616.51 mg,0.198 mL) are sequentially added into a round bottom flask, the mixture is stirred and heated at 130 ℃ for refluxing for 18 h, after the reaction is finished, the residual liquid bromine and hydrobromic acid are removed by using a cold saturated potassium hydroxide solution, dichloromethane is used for extraction and separation, anhydrous sodium sulfate is added for water removal, filtration and column separation are carried out, and the product 4-bromo-7- (4- (tert-butyl) phenyl) -2-isobutyl-benzotriazole 1.175g (white solid) is obtained, and the separation yield is 78.85%.
The reaction formula is:
4-bromo-7- (4- (tert-butyl) phenyl) -2-isobutyl-benzotriazole (0.579 mmol,223.9 mg), 2-thiopheneboronic acid (0.8685 mmol,111.12 mg), potassium carbonate (2.964 mmol,409.65 mg,w =99%) tetrakis (triphenylphosphine) palladium (0.0636 mmol,73.60 mg, w=99%).
4-bromo-7- (4- (tert-butyl) phenyl) -2-isobutyl-benzotriazole, 2-thiopheneboronic acid, potassium carbonate and tetrakis (triphenylphosphine) palladium are added into a reaction tube, air is pumped out, nitrogen is filled in, 1.48 mL toluene, 2.96 mL n-butanol and 0.44mL of water are added into a beaker and mixed uniformly, the mixture is injected into the reaction tube by a needle cylinder, the reaction tube is sealed for reaction for 12 hours at 100 ℃, anhydrous sodium sulfate is added for water removal, filtration and column separation are carried out after the solvent is rotationally evaporated, thus obtaining the product 4- (4- (tert-butyl) phenyl) -2-isobutyl-7- (thiophen-2-yl) -benzotriazole 194.19 mg (light yellow green solid) (absorption 310 nm emits 436 nm) with the separation yield of 86.1 percent.
The reaction formula is:
as shown in FIG. 4, the hydrogen spectrum of the obtained product was 1 H NMR (300 MHz, Chloroform-d) δ 8.01 (d,J= 3.4 Hz, 1H), 7.90 (d,J= 8.2 Hz, 2H), 7.57 (d,J= 7.5 Hz, 1H), 7.43 (d,J= 7.7 Hz, 3H), 7.25 (d,J= 5.0 Hz, 1H), 7.07 (t,J= 4.3 Hz, 1H), 4.49 (d,J= 7.3 Hz, 2H), 2.50 (dp,J= 13.6, 6.8 Hz, 1H), 1.28 (s, 9H), 0.91 (d,J= 6.7 Hz, 6H)。
As shown in FIG. 5, the carbon spectrum of the obtained product was 13 C NMR (75 MHz, Chloroform-d) δ 150.97, 143.36, 142.41, 140.19, 130.01, 128.22, 128.12, 126.97, 125.74, 125.43, 124.22, 123.56, 123.02, 63.84, 34.72, 31.43, 29.93, 20.10
Example 3
In this example, specifically, benzothiophene asymmetric structures were prepared.
4-bromo-7- (4- (tert-butyl) phenyl) -2-isobutyl-benzotriazole (0.700 mmol,270.44 mg), 2-benzothiophene boronic acid (1.05 mmol,190.73 mg,w =98%), potassium carbonate (3.584 mmol,495.82 mg,w =99%), tetrakis (triphenylphosphine) palladium (0.077 mmol,88.98 mg, w=99%).
4-bromo-7- (4- (tertiary butyl) phenyl) -2-isobutyl-benzotriazole, 2-benzothiophene boric acid, potassium carbonate and tetrakis (triphenylphosphine) palladium are added into a reaction tube to be sealed, air is pumped out, nitrogen is filled, 1.8 mL toluene, 3.6 mL n-butanol and 0.53 mL water are added into a beaker to be uniformly mixed, the mixture is injected into the reaction tube by a needle cylinder, the reaction tube is sealed to react for 12 hours at 100 ℃, anhydrous sodium sulfate is added to remove water, filtration and column separation are carried out after the solvent is rotationally evaporated, thus obtaining the product 4- (4- (tertiary butyl) phenyl) -2-isobutyl-7- (benzothiophen-2-yl) -benzotriazole 263.2 mg (light yellow green solid) (absorption 329 nm emission 444 nm) with the separation yield of 85.52 percent.
The reaction formula is:
as shown in FIG. 6, the hydrogen spectrum of the obtained product was 1 H NMR (400 MHz, Chloroform-d) δ 8.38 (s, 1H), 7.92 (d,J= 8.4 Hz, 2H), 7.78 (t,J= 7.2 Hz, 2H), 7.66 (d,J= 7.5 Hz, 1H), 7.47 (t,J= 7.9 Hz, 3H), 7.31 – 7.22 (m, 2H), 4.56 (d,J= 7.4 Hz, 2H), 2.57 (dp,J= 13.8, 6.9 Hz, 1H), 1.30 (s, 9H), 0.96 (d,J= 6.7 Hz, 6H)。
As shown in FIG. 7, the carbon spectrum of the obtained product was 13 C NMR (101 MHz, Chloroform-d) δ 151.26, 143.40, 142.62, 141.02, 140.09, 139.37, 134.36, 131.06, 128.35, 125.85, 124.75, 124.56, 124.48, 124.24, 124.23, 124.14, 123.44, 122.23, 63.95, 34.81, 31.47, 30.05, 20.16。
Example 4
In this example, in particular, a 5-aldehyde thiophene asymmetric structure was prepared.
4-bromo-7- (4- (tert-butyl) phenyl) -2-isobutyl-benzotriazole (0.200 mmol,77.27 mg), 5-aldehyde-2-thiopheneboronic acid (0.300 mmol,47.74 mg,w =98%), potassium carbonate (1.024 mmol,141.53 mg,w =99%), tetrakis (triphenylphosphine) palladium (0.022 mmol,25.42 mg, w=99%).
4-bromo-7- (4- (tert-butyl) phenyl) -2-isobutyl-benzotriazole, 5-aldehyde-2-thiopheneboronic acid, potassium carbonate and tetrakis (triphenylphosphine) palladium are added into a reaction tube, sealed, air is pumped out, nitrogen is filled, 0.52 mL toluene, 1.04 mL n-butanol and 0.15 mL water are added into a beaker and mixed uniformly, the mixture is injected into the reaction tube by a needle cylinder, the sealed reaction tube is reacted for 12 hours at 100 ℃, anhydrous sodium sulfate is added for water removal, filtration and column separation are carried out after the solvent is spirally evaporated, thus obtaining the product 4- (4- (tert-butyl) phenyl) -2-isobutyl-7- (5-aldehyde thiophene-2-yl) -benzotriazol 21.1 mg (yellow solid) (absorption 453 nm emits 484 nm) with the separation yield of 25.27 percent.
The reaction formula is:
as shown in figure 8 of the drawings,the hydrogen spectrum of the obtained product is 1 H NMR (400 MHz, Chloroform-d) δ 9.96 (s, 1H), 8.18 (d,J= 4.0 Hz, 1H), 8.02 (d,J= 8.5 Hz, 2H), 7.88 – 7.79 (m, 2H), 7.59 (dd,J= 17.7, 8.0 Hz, 3H), 4.64 (d,J= 7.3 Hz, 2H), 2.63 (dp,J= 13.8, 6.9 Hz, 1H), 1.39 (s, 9H), 1.04 (d,J= 6.7 Hz, 6H)。
As shown in FIG. 9, the carbon spectrum of the obtained product was 13 C NMR (101 MHz, Chloroform-d) δ 151.74, 150.04, 143.38, 142.61, 137.48, 134.03, 132.60, 128.45, 127.47, 125.94, 124.68, 124.12, 122.08, 64.10, 34.88, 31.46, 30.05, 20.15.
Further, light conversion films were prepared from the light conversion agents with asymmetric structures prepared in examples 1,3 and 4 according to different mass thousandths, and the test performances are shown in table 1:
the testing method comprises the following steps:
light conversion efficiency: and (3) performing absolute quantum efficiency test by using an integrating sphere at normal temperature by using the Horiba spectrometer FL-3.
Yellowing index: the yellowing index (ΔYI) of the pre-pressed components before and after the aging test was determined according to national standard GB 2409 test method for yellowness index of plastics.
TABLE 1
Examples Light conversion agent/mill Conversion efficiency/% Stability (yellowing index delta YI)
1-1 1 86.1 0.48
1-2 3 86.3 0.5
1-3 6 86.4 0.51
3-1 1 88.3 0.41
3-2 3 88.7 0.42
3-3 6 88.9 0.42
4-1 1 74.8 0.64
4-2 3 75.1 0.65
4-3 6 75.3 0.66
Wherein examples 1-1, 1-2, 1-3 are the performance data of the adhesive film group of example 1 4- (4- (tert-butyl) phenyl) -2-isobutyl-7- (thiophen-2-yl) -benzotriazole products under different light conversion agent addition amounts; examples 3-1, 3-2, 3-3 are film set performance data for example 3 4- (4- (tert-butyl) phenyl) -2-isobutyl-7- (benzothien-2-yl) -benzotriazol product at different amounts of light converting agent addition; examples 4-1, 4-2, 4-3 are performance data for the film set of example 4 4- (4- (tert-butyl) phenyl) -2-isobutyl-7- (5-alditothiophen-2-yl) -benzotriazol product at different amounts of light converting agent.
In this example, the matrix EVA resin is preferably DuPont 53071, the cross-linking agent is preferably tert-butyl 2-ethylhexyl carbonate 0.3 parts, the auxiliary cross-linking agent is preferably triallyl isocyanurate 0.2 parts, the light stabilizer is preferably light stabilizer 770.1 parts, the antioxidant is preferably hindered phenolic antioxidant 1010.1 parts, the silane coupling agent is preferably KH-570.2 parts, and the balance is the matrix EVA resin.
In summary, the light conversion agent with an asymmetric structure, the light conversion adhesive film and the preparation method thereof take benzotriazole as a matrix, and asymmetric aromatic rings (heteroaryl and benzene ring) are introduced at two sides of the benzene ring, so that on one hand, heteroaryl such as thiophene aromatic rings have higher electron density and excellent carrier mobility compared with the benzene ring; on the other hand, the asymmetric structure can enable the wavelength of the converted light of the light conversion agent to have wider regulation and control space, and meanwhile, light conversion in different wavelength ranges can be further realized by regulating and controlling the light emitting units at two sides, so that sunlight is efficiently utilized.
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.

Claims (8)

1. An asymmetric structure light conversion agent is characterized in that,
the structural general formula of the light conversion agent is as follows:
wherein the method comprises the steps of
R1 is hydrogen, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted carbonyl, substituted or unsubstituted amido;
r2 is substituted or unsubstituted heteroaryl;
r3 is a substituted or unsubstituted alkyl group, a substituted or unsubstituted amide group, a substituted or unsubstituted carboxyl group;
the heteroaryl is thiophene and benzothiophene;
the substituted optional group is selected from the group consisting of: alkyl, halogen, nitro, amino, aldehyde, carboxyl, cyano and isocyano, wherein the number of the substituents is as follows: 1.2, 3 or 4.
2. A method for preparing the light conversion agent with an asymmetric structure according to claim 1, comprising the following steps:
step S1, 1H-benzotriazol is reacted with an organic iodide I-R 3 Adding calcium carbonate into N, N-dimethylformamide, heating, separating liquid, removing water, filtering and separating to obtain a first intermediate, wherein the structural formula of the first intermediate is as follows:
step S2, stirring, heating and refluxing the first intermediate, liquid bromine and hydrobromic acid, extracting, separating liquid and separating to obtain a second intermediate, wherein the structural formula of the second intermediate is as follows:
step S3, the second intermediate is combined with R 2 -B(OH)2、Heating potassium carbonate and tetra (triphenylphosphine) palladium in a nitrogen environment, cooling to room temperature after the reaction is completed, and removing water, filtering and separating to obtain an asymmetric structure light conversion agent;
r1, R2 and R3 in the above structures are as defined in claim 1.
3. The asymmetric-structure light-converting agent according to claim 1 or the asymmetric-structure light-converting agent prepared by the preparation method according to claim 2, characterized by being selected from the following compounds:
4. the utility model provides a change light glued membrane which characterized in that includes:
a base film and an asymmetric structured light conversion agent; wherein the method comprises the steps of
The asymmetric structured light transfer agent comprising a composition of any one or more of the asymmetric structured light transfer agents of claims 1-3; and
the light conversion agent with the asymmetric structure is dispersed in the base film.
5. The light-converting adhesive film according to claim 4, wherein the raw materials comprise, in parts by weight:
6. the light-converting film of claim 4,
the base film is selected from any one or a combination of a plurality of EVA, PMMA, POE, PVB.
7. A method for preparing the light-converting adhesive film according to any one of claims 4 to 6, comprising:
uniformly mixing matrix resin, an asymmetric structure light conversion agent and an auxiliary agent according to the raw material ratio;
and (5) casting to form a film to obtain the light conversion adhesive film.
8. A photovoltaic module comprises a light conversion adhesive film, and is characterized in that,
the light conversion adhesive film is the light conversion adhesive film according to any one of claims 4 to 6.
CN202311534569.1A 2023-11-17 2023-11-17 Light conversion agent with asymmetric structure, light conversion adhesive film and preparation method thereof Active CN117247362B (en)

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JP2014185286A (en) * 2013-03-25 2014-10-02 Nitto Denko Corp Chromophore having benzotriazole structure and wavelength conversion light-emitting medium using the same
CN116769466A (en) * 2023-05-08 2023-09-19 上海海优威新材料股份有限公司 Coated light conversion powder and light Fu Jiaomo using same

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