CN117510421A - Fluorine-containing benzotriazolyl fluorescent compound for optical transfer film and synthesis method thereof - Google Patents
Fluorine-containing benzotriazolyl fluorescent compound for optical transfer film and synthesis method thereof Download PDFInfo
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- CN117510421A CN117510421A CN202410021184.3A CN202410021184A CN117510421A CN 117510421 A CN117510421 A CN 117510421A CN 202410021184 A CN202410021184 A CN 202410021184A CN 117510421 A CN117510421 A CN 117510421A
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- CN
- China
- Prior art keywords
- fluorine
- transfer film
- fluorescent compound
- benzotriazolyl
- light
- Prior art date
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- 238000012546 transfer Methods 0.000 title claims abstract description 80
- 229910052731 fluorine Inorganic materials 0.000 title claims abstract description 63
- 239000007850 fluorescent dye Substances 0.000 title claims abstract description 54
- 239000011737 fluorine Substances 0.000 title claims abstract description 53
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 title claims abstract description 52
- 230000003287 optical effect Effects 0.000 title claims abstract description 48
- 125000003354 benzotriazolyl group Chemical group N1N=NC2=C1C=CC=C2* 0.000 title claims abstract description 42
- 238000001308 synthesis method Methods 0.000 title abstract description 13
- 238000006243 chemical reaction Methods 0.000 claims abstract description 66
- -1 phenoxy, dimethylamino, diethylamino Chemical group 0.000 claims description 37
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- 239000011159 matrix material Substances 0.000 claims description 13
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 claims description 12
- 238000002360 preparation method Methods 0.000 claims description 11
- 239000012964 benzotriazole Substances 0.000 claims description 10
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Abstract
The invention relates to the technical field of photoelectric semiconductors, and particularly discloses a fluorine-containing benzotriazolyl fluorescent compound for optical transfer films and a synthesis method thereof. On the basis of a 4, 7-diphenyl-2-alkyl benzotriazole structure, the invention develops a material which has a wider ultraviolet absorption wavelength range and narrow spectrum blue light emission and has stronger selectivity on absorbed light through the special design of fluorine atom modification of 5, 6-positions and substituent groups on phenyl. When the fluorine-containing benzotriazolyl fluorescent compound for the optical transfer film is used for a photovoltaic module of a heterojunction solar cell, the power of the heterojunction module cannot be reduced, the half-width of spectrum of light is narrower after wavelength conversion, the utilization efficiency of the module is further improved, and the comprehensive performance of the crystalline silicon solar cell module can be obviously improved in various aspects.
Description
Technical Field
The invention relates to the technical field of photoelectric semiconductors, and particularly discloses a fluorine-containing benzotriazolyl fluorescent compound for optical transfer films and a synthesis method thereof.
Background
Solar cells are devices for converting solar energy into electric energy, and can be classified into silicon thin films, compound semiconductor thin films, and organic film solar cells according to materials, wherein silicon thin films are currently the dominant species. Currently, the main technologies of mass production of silicon thin film solar cells are PERC, TOPCon and the like. With the cost reduction and synergy of the industry, heterojunction (HJT) technology becomes the most potential next generation photovoltaic technology due to the ultrahigh battery efficiency, excellent power generation performance, simple production flow and lower product carbon footprint. The ultra-high photoelectric conversion efficiency of the heterojunction product is largely derived from the excellent surface passivation capability of intrinsic amorphous silicon on crystalline silicon, and the disadvantage is that the current of the battery is lower than that of a common battery because the transparent conductive oxide coating (TCO) film layer and the amorphous silicon film layer absorb ultraviolet rays. Heterojunction cells are multi-layer structures, wherein one layer uses amorphous or microcrystalline silicon, and the efficiency of the device decays faster under uv exposure due to the presence of surface Si-H groups compared to other types of cells.
The existing solution method firstly uses a cut-off adhesive film to filter ultraviolet rays, but the mode can lose the energy of the ultraviolet rays, and the initial power attenuation amplitude of the assembly is larger; and secondly, the red shift of the photon wavelength of the ultraviolet region harmful to the solar cell is realized by using the down-conversion luminescent material, and the wave band is converted into the visible light region available for the solar cell, so that the efficiency of the solar cell is improved. The down-converting luminescent material is called wavelength converting material or light converting agent, which requires that the conversion of harmful light (wavelength conversion of photons) is achieved before the light reaches the solar cell. The wavelength conversion material is made into the packaging material of the battery component, such as a EVA, EMMA, PVB light conversion film and the like, and is used for packaging a crystalline silicon battery, ultraviolet light in the range of 290-400 nm is converted into visible light of 440-650 nm, harmful ultraviolet light in sunlight can be effectively and fully absorbed, damage to the component is reduced, ultraviolet energy can be converted into usable wavelength of the battery component, and the photoelectric conversion efficiency is further improved while the service life of the component is prolonged. Generally, the wavelength of the photovoltaic cell made of the silicon material is 350-1200 nm, and the response of the solar cell to light with middle wavelength (such as blue light, green light and red light) is relatively good, so that if ultraviolet rays can be efficiently converted into blue-green light with the wavelength of 440-520 nm, the improvement of the photoelectric conversion efficiency of the cell is most remarkable.
The wavelength conversion materials currently used on photo-adhesive films mainly comprise rare earth organic ligand complexes, semiconductor quantum dots and small molecule organic materials. The rare earth element-containing material has higher cost, the rare earth organic ligand compound serving as the light conversion agent of the adhesive film has the problems of uneven dispersion, narrower absorption band, low conversion efficiency, easy color change of the organic ligand after long-term use and the like; the semiconductor quantum dots (such as CdS, cdTe, znS) are used as the photovoltaic adhesive film conversion agent, have potential induced attenuation phenomenon caused by hidden environmental protection and metal particle precipitation, and meanwhile, the mass industrialization of the stable quality of the quantum dots is not perfect. In addition, the two light conversion agents can only convert the absorbed ultraviolet light into red light or blue light with a narrower specific wavelength range, so that the utilization efficiency of the battery is lower. The organic compound is easy to design molecules, and has the advantages of easy performance and synthesis cost.
Triazole is a classical electron-deficient five-membered heterocyclic unit, and a polymer donor material, a small molecule donor material, a non-fullerene small molecule and a polymer acceptor based on the triazole unit are continuously designed and synthesized, so that the triazole is an excellent parent structure. Although organic photovoltaic materials based on triazole units have been developed for decades, donor-acceptor photovoltaic materials with rich structural types are constructed, and have wide research prospects at present. The existing inorganic or organic light conversion agent has the defects of overlarge light absorption range, limited light conversion efficiency, poor stability, poor film forming property, easy precipitation and the like, and has no obvious comprehensive improvement on the efficiency of the component. When a plurality of materials are combined, the problems of high cost, complex manufacture and the like exist, the optimal spectrum superposition effect is difficult to combine, and the adverse result that the battery efficiency is not increased or reduced easily occurs.
Disclosure of Invention
In view of the above problems, the present invention provides a fluorine-containing benzotriazolyl fluorescent compound for optical transfer film and a synthesis method thereof, wherein the molecular structure of an organic compound is designed to realize the photoelectric performance of high-selectivity narrow-band emission, and the film forming property and stability can be considered.
In order to solve the technical problems, the technical scheme provided by the invention is as follows:
a fluorine-containing benzotriazolyl fluorescent compound for optical transfer films has a structural formula of at least one of structures shown in a formula I:
I；
wherein R is 1 Is taken from: C1-C10 alkyl, C3-C11 cycloalkyl or C3-C11 substituted cycloalkyl;
R 2 is taken from: -H, -F, phenoxy, dimethylamino, diethylamino, 4-alkylphenyl, C1-C6 alkyl, C1-C6 alkoxy, C3-C11 cycloalkyl, C3-C11 substituted cycloalkyl or 1-adamantyl;
R 3 is taken from: -H, -F or phenoxy;
x is-H or-F; x is X 1 And X 2 is-H or-F, and is not simultaneously-H.
Compared with the prior art, the fluorine-containing benzotriazole fluorescent compound for the optical transfer film provided by the invention has the advantages that on the basis of a 4, 7-diphenyl-2-alkyl benzotriazole structure, through the special design of fluorine atom modification of 5, 6-positions and substituent groups on phenyl, the fluorine-containing benzotriazole fluorescent compound has stronger selectivity on light absorption than the existing rare earth element organic complex or quantum dot material, has redshift than the emission spectrum of fluorine-free benzotriazole compounds, has narrower half-peak width of the emission spectrum, and greatly improves the quantum efficiency. The fluorine-containing benzotriazole fluorescent compound for the optical transfer film has the characteristics of wide ultraviolet absorption wavelength range, narrow spectrum blue light emission and stronger selectivity on absorbed light. The example results show that the fluorine-containing benzotriazole-based fluorescent compound for the optical transfer film has the characteristics that the maximum absorption wavelength is in an ultraviolet region and the maximum emission wavelength is in a visible light region, the absorption spectrum is between 310 and 390nm, the emission spectrum is between 440 and 600nm, the half-peak width of the emission spectrum is between 40 and 60nm, the melting point is between 130 and 225 ℃, and the molar absorption coefficient at the maximum absorption wavelength is more than 20000; the film has proper melting point, good film forming property, difficult crystallization and solidification after melting, suitability for the working temperature of a solar cell and good stability to light and heat. When the fluorine-containing benzotriazolyl fluorescent compound for the light transfer film is used for a photovoltaic module of a heterojunction solar cell, the comprehensive performance of the crystalline silicon solar cell module can be obviously improved in many aspects.
Halogen substituted materials are widely applied to the field of organic photoelectricity due to unique properties, fluorine, chlorine and bromine atoms with induction effect and conjugation effect are introduced into organic molecules, and the highest occupied molecular orbital and lowest unoccupied molecular orbital (HOMO/LUMO) energy levels and luminescent colors of the materials can be regulated, so that the electron transmission performance and the like are improved. The inventor finds out through a large number of experiments that the fluorine atom is the most special, the radius of the fluorine atom is similar to that of hydrogen, the size is smaller, and the characteristic of the small size can enable a molecular skeleton to have stronger coplanarity, so that charge transmission is promoted; the fluorine atom is a strong electron-withdrawing group, has stronger electronegativity, has an induction effect of providing electrons, can regulate the polarity of the whole molecule and has influence on the polarization rate, the melting point and the like; in addition, the C-F bond has high stability, compared with chlorine and bromine, fluorine atoms can induce inter-chain arrangement, so that a more ordered structure is formed, the material has higher thermal decomposition temperature, and the fluorine substituted compound has higher stability; in addition, the non-covalent bond formed by introducing fluorine atoms can strengthen the interaction force and aggregation among molecules, thereby improving the morphology of the polymer film.
The invention introduces fluorine atoms into the 5, 6-position of the main core, thereby enhancing the transfer of electronsA speed; the 4, 7-benzene ring is introduced with unequal number of fluorine atoms, a plurality of fluorine atoms and hetero atoms on the benzene ring have the adjusting effect on the maximum absorption wavelength and the maximum fluorescence luminescence wavelength, and the wavelength of fluorescence emission can be adjusted by combining other substituent groups, so that the wavelength most suitable for the solar cell is found; meanwhile, a plurality of fluorine atoms have an adjusting effect on the half-width of fluorescence, so that the ratio of wavelength photons can be maximized; the fluorine atom energy with high polarity forms hydrogen bond action with polar groups in materials such as EVA, PMMA and the like, so that the stability is enhanced; in addition, the benzotriazol mother nucleus and the benzene ring have stronger coplanarity under the action of fluorine atoms, the energy loss in the molecular luminescence process is small, and the light conversion efficiency is improved. In the present invention, R 1 The arrangement of the groups can improve the solubility of the compound; r is R 2 And R is 3 The placement of the groups can adjust the position of the absorption and emission spectra.
Preferably, R of formula I 1 Wherein the C3-C11 substituted cycloalkyl comprises 4-cyclopropyl cyclohexyl, 4-cyclopentyl cyclohexyl, 4-ethyl cyclohexyl, 4-propyl cyclohexyl, 4-butyl cyclohexyl or 4-amyl cyclohexyl.
Preferably, the structural formula comprises at least one of structures shown in formulas II-XXXIX:
the invention provides a method for synthesizing the fluorine-containing benzotriazolyl fluorescent compound for optical transfer film, when X 1 、X 2 When the reaction formula is F, the reaction formula is shown as formula 1, and the method comprises the following steps:
s1, taking 3, 4-difluoroaniline (A) as a raw material, and sequentially performing nitration reaction, reduction reaction and bromination reaction to obtain 4, 5-difluoro-3, 6-dibromo-1, 2-phenylenediamine (D);
s2, carrying out cyclization reaction on the 4, 5-difluoro-3, 6-dibromo-1, 2-phenylenediamine (D) and sodium nitrite, and carrying out alkylation to obtain 2-alkyl-4, 7-dibromo-5, 6-difluoro benzotriazol (F);
s3, performing a coupling reaction on the 2-alkyl-4, 7-dibromo-5, 6-difluoro benzotriazol (F) and aryl boric acid (G) to obtain a fluorine-containing benzotriazol fluorescent compound (H) for optical transfer films;
formula 1.
The invention provides a method for synthesizing the fluorine-containing benzotriazolyl fluorescent compound for optical transfer film, when X 1 、X 2 When only one of them is F, the reaction equation is shown in formula 2, and the method comprises the following steps:
s1', taking 4-fluoro-1, 2-phenylenediamine (A ') as a raw material, and sequentially carrying out cyclization reaction, double bromination reaction and reduction reaction to obtain 3, 6-dibromo-4-fluoro-1, 2-phenylenediamine (D ');
s2', carrying out cyclization reaction on the 3, 6-dibromo-4-fluoro-1, 2-phenylenediamine (D ') and sodium nitrite, and carrying out alkylation to obtain 2-alkyl-4, 7-dibromo-5-fluorobenzotriazole (F ');
s3', carrying out coupling reaction on the 2-alkyl-4, 7-dibromo-5-fluorobenzotriazole (F') and an aryl compound (G ') to obtain a fluorine-containing benzotriazolyl fluorescent compound (H') for optical transfer film;
formula 2.
The synthesis method of the fluorine-containing benzotriazolyl fluorescent compound for the optical transfer film is simple to operate, good in batch uniformity, low in cost and suitable for large-scale production.
The invention provides a light transfer film, which comprises the fluorine-containing benzotriazolyl fluorescent compound for the light transfer film.
The compound provided by the invention can be used for manufacturing solar cell packaging adhesive film materials independently or mutually mixed or combined with other ultraviolet absorbers, quantum dot materials, inorganic light conversion materials, organic light conversion materials and the like.
Preferably, the light transfer film comprises the following raw materials in parts by weight: 100 parts of polymer matrix, 0.001-1 part of fluorine-containing benzotriazole fluorescent compound for optical transfer film, 0-2 parts of alkoxy silane, 0-5 parts of cross-linking agent and 0-1 part of cross-linking auxiliary agent.
The invention takes the fluorine-containing benzotriazolyl fluorescent compound for the light transfer film as the packaging material (namely the light transfer film) of the wavelength conversion type solar cell module prepared by a single light transfer agent, the light transfer agent is dispersed in a transparent polymer resin matrix, the fluorine-containing benzotriazolyl fluorescent compound for the light transfer film and the polymer matrix can be subjected to hydrogen bonding, the compatibility of the fluorine-containing benzotriazolyl fluorescent compound for the light transfer film and the polymer matrix is good, the stability is high, the expected performance can be obtained without complex composition or additive mixing, and the use amount of additives such as a stabilizer, a cross-linking agent and the like can be reduced. The light transfer film provided by the invention has ideal optical characteristics and good light stability, improves the sunlight collection efficiency of the solar cell module, and improves the photoelectric conversion efficiency of the solar cell; meanwhile, the power of the solar cell module is improved, the attenuation degree of the power of the module after long-term UV irradiation is reduced, and the service life of the photovoltaic module is prolonged; the precipitation phenomenon after long-time working in the outdoor environment can be restrained, and stable environmental protection is provided for the battery assembly. Especially, the heterojunction battery pack is matched with the heterojunction battery pack for use, and the service life and the photoelectric conversion efficiency can be effectively prolonged.
Preferably, the polymer matrix comprises at least one of Ethylene Vinyl Acetate (EVA), polyvinyl alcohol (PVA), polymethyl methacrylate (PMMA) or polyolefin elastomer (POE).
Preferably, the crosslinking agent comprises t-butylperoxy-2-ethylhexyl carbonate (TBEC).
Preferably, the crosslinking aid comprises triallyl isocyanurate (TAIC).
Preferably, the alkoxysilane comprises gamma-glycidoxypropyl trimethoxysilane (KH-560).
Preferably, the thickness of the light transfer film is 100-1000 μm.
The invention provides a preparation method of a light transfer film, which comprises the following steps:
weighing the raw materials according to parts by weight, uniformly mixing a polymer matrix, a fluorine-containing benzotriazolyl fluorescent compound for the optical transfer film, alkoxy silane, a cross-linking agent and a cross-linking auxiliary agent, and carrying out melt extrusion and tape casting at 75-95 ℃ to obtain the optical transfer film.
The optical transfer film of the invention does not need complex additive compounding, can realize that a single optical transfer agent component is matched with a simple composition, can form a film by melt blending and tape casting, has simple and efficient film forming process, and has stable performance, slow performance attenuation and lasting service life.
The invention also provides application of the light conversion film in a photovoltaic module, an agricultural film or building glass.
Preferably, the photovoltaic module is a double-glass module and sequentially comprises upper glass, an upper light transfer film, a heterojunction cell, a lower light transfer film and lower glass from top to bottom.
When the light transfer film is used for the photovoltaic module of the heterojunction solar cell, the utilization efficiency of the module is further improved, the power of the photovoltaic module can be remarkably improved, the attenuation degree of the power of the module after long-term UV irradiation can be reduced, the service life of the photovoltaic module is prolonged, the comprehensive performance of the crystalline silicon solar cell module can be remarkably improved in various aspects, and the material is superior to the existing material in the aspect of relevant synergy index.
Detailed Description
The present invention will be described in further detail with reference to the following examples in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
In the examples and comparative examples of the present invention, the specific conditions were not specified, and the treatment was performed according to the conventional conditions or the conditions recommended by the manufacturer; the reagents or apparatus used were conventional products commercially available without the manufacturer's attention. The purity of the intermediate and the final product in the synthesis process and the detection of related impurities can be carried out by adopting a gas chromatograph GC or a high performance liquid chromatograph HPLC, and the models used in the invention are Agilent 8890 GC and Agilent 1260II HPLC respectively; the structures of the intermediates or the end products are all hydrogen nuclear magnetic resonance spectra 1 HNMR or carbon Spectrometry 13 CNMR confirms.
In order to better illustrate the present invention, the following examples are provided for further illustration.
Example 1
The present example provides a fluorine-containing benzotriazolyl fluorescent compound (Ia) for optical transfer films.
Ia
The synthetic method of the Ia comprises the following steps (the reaction equation is shown in formula 3):
s1, adding 25.8g (0.2 mol) of 3, 4-difluoroaniline and 200ml of acetic acid solution into a reaction bottle, uniformly mixing, dropwise adding 39.4g (0.6 mol) of fuming nitric acid with the concentration of 96wt%, naturally stirring for 3 hours after the dropwise adding, heating in a water bath, and reacting at 50 ℃ until the raw material is less than 0.5%; the reaction solution was quenched by pouring into ice water, stirred well, extracted with dichloromethane, washed to neutrality with 5wt% sodium bicarbonate solution and water, and concentrated under reduced pressure to give 3, 4-difluoro-6-nitroaniline (GC > 99%) which was used directly for hydrogenation reduction.
S2, dissolving the 3, 4-difluoro-6-nitroaniline in 300ml of ethanol, adding 3.5g of 5wt% palladium-carbon catalyst, uniformly mixing, and carrying out hydrogenation reduction for 4-6 h at 30 ℃ under the hydrogen pressure of 0.3MPa until the reaction is complete; decompression, filtering out catalyst, concentrating ethanol, re-crystallizing with 100mL toluene (heating to boiling point, cooling to-5 deg.c for crystallization, filtering) to obtain 23.0g (0.16 mol) 4, 5-difluoro-1, 2-phenylenediamine with GC > 99% and the first two steps yield of 80.0%;
s3, dissolving the 4, 5-difluoro-1, 2-phenylenediamine in a mixed solution of acetic acid (200 ml) and dichloromethane (100 ml), uniformly mixing, dropwise adding 64g (0.4 mol) of bromine, and completely reacting at 50-60 ℃; cooling to room temperature, quenching with an excess of 5wt% sodium bisulphite solution, extracting with dichloromethane, washing the organic layer with water, drying, concentrating, recrystallizing with 200mL ethanol (heating to boiling point, cooling to-5 ℃ C. After complete dissolution, crystallizing, filtering), drying to obtain 42.3g (0.14 mol) 4, 5-difluoro-3, 6-dibromo-1, 2-phenylenediamine (GC > 99%) with a yield of 87.5%.
S4, adding the 4, 5-difluoro-3, 6-dibromo-1, 2-phenylenediamine and 400ml glacial acetic acid into a reaction bottle, uniformly mixing, dropwise adding 100ml of sodium nitrite aqueous solution (the mass of sodium nitrite is 27.6g (0.4 mol)) at room temperature, and reacting for 3 hours after 1 hour; the mixture was poured into ice water, and the precipitated crude solid was collected and recrystallized from 400mL of toluene (heated to boiling point, after complete dissolution, cooled to-5 ℃ C. For crystallization, filtration) to give 37.6g (0.12 mol) of 4, 7-dibromo-5, 6-difluorobenzotriazole (GC > 99%) in a yield of 85.7%.
S5, adding the 4, 7-dibromo-5, 6-difluorobenzotriazole, 24.7g (0.18 mol) bromoisobutane, 400ml DMF and 24.8g (0.18 mol) anhydrous potassium carbonate into a reaction bottle, uniformly mixing, adding 1g tetrabutylammonium bromide, stirring and heating to 105 ℃ until the raw materials are completely converted (the peak area ratio of a target product and an isomer is 1:0.7 detected by GC); cooling to room temperature, filtering, washing the solid with 600ml toluene at 50deg.C for three times, and mixing filtrates; washing with water to neutrality, mixing water layers, extracting with 200ml toluene, and discarding; concentrating the solvent, adding 800ml of n-heptane, stirring and suction filtering; the filtrate was subjected to column chromatography to remove the solvent, and 200mL of ethanol was added for recrystallization (heating to boiling point, cooling to-5 ℃ C. After complete dissolution, crystallization, filtration) to give 22.1g (0.060 mol) of 2-isobutyl-4, 7-dibromo-5, 6-difluorobenzotriazol (GC > 99%) with a yield of 50.0%.
S6, adding the 2-isobutyl-4, 7-dibromo-5, 6-difluorobenzotriazole, 26.3g (0.13 mol) of 2, 3-difluoro-4-ethoxyphenylboric acid, 200ml of toluene, 300ml of ethanol, 16.6g (0.12 mol) of potassium carbonate and 100ml of water into a reaction bottle, uniformly stirring, replacing air with nitrogen, adding 0.1g of di-tert-butyl- (4-dimethylaminophenyl) phosphine palladium, heating the reaction bottle to reflux, and stirring for reacting for 5-6 hours until the conversion is complete; cooling the reaction bottle to room temperature, adding 300ml of water, stirring, standing and separating liquid; extracting the water phase with 200ml toluene for three times, combining organic phases, and washing with deionized water to neutrality; the organic phase was passed through a silica gel column, the solvent was distilled off under reduced pressure, 400mL of ethanol was added for recrystallization (heating to boiling point, cooling to-5 ℃ C. After complete dissolution, crystallization, filtration) and drying to give 26.2g (0.050 mol) of Compound Ia (GC > 99%, HPLC > 99%) in 83.3% yield.
1 H NMR (400 MHz, Chloroform-d) δ 7.52 (dd,J= 9.2, 5.0 Hz, 2H), 7.01 (dd,J= 9.2, 5.0 Hz, 2H), 4.14 (q,J= 6.2 Hz, 4H), 3.79 (d,J= 4.3 Hz, 2H), 2.28 – 2.14 (m, 1H), 1.43 (t,J= 6.3 Hz, 6H), 1.02 (d,J= 7.4 Hz, 6H).
The compound Ia is detected to be non-absorbing to light with the wavelength of more than 410nm, which shows that the compound Ia can not absorb visible light after being used as an encapsulation material of a solar cell, and further can not adversely affect the photoelectric conversion efficiency of the solar cell.
Formula 3.
Example 2
This example provides a fluorine-containing benzotriazolyl fluorescent compound (Ib) for optical transfer films.
Ib
The synthesis method of the Ib comprises the following steps (the reaction equation is shown in the formula 4):
s1, adding 25.2g (0.2 mol) of 4-fluoro-1, 2-phenylenediamine and 200ml of methylene dichloride into a reaction bottle, uniformly mixing, dropwise adding 35.7g (0.3 mol) of thionyl chloride, naturally stirring for 3 hours after the dropwise adding, heating in a water bath, and reacting at 35 ℃ until the raw material is less than 0.2%; concentrating to remove excessive thionyl chloride and dichloromethane; 100ml of 5wt% sodium bicarbonate aqueous solution was added, stirred well, extracted with dichloromethane, washed with water to neutrality, and the solvent was concentrated under reduced pressure to give 5-fluorobenzothiadiazole compound (GC > 99%) which was used directly for bromination.
S2, uniformly mixing the 5-fluorobenzothiadiazole compound with 300ml of 48wt% hydrobromic acid solution, dropwise adding 96g (0.6 mol) of bromine at 100 ℃, and keeping the temperature of 100-110 ℃ for stirring reaction until the conversion of dibromo is detected to be more than 98%; cooling to 40deg.C, adding 300ml of dichloromethane, extracting, separating out organic layer, and extracting water layer with 300ml of dichloromethane again; the organic layers were combined, washed with 300ml of 5wt% aqueous sodium bicarbonate and water, respectively, to neutrality and dried; the solvent was concentrated and recrystallized from 150mL of ethanol (the procedure for recrystallization was the same as in example 1 and will not be repeated) to give 49.9g (0.16 mol) of 4, 7-dibromo-5-fluorobenzothiadiazole as a pale brown solid (GC > 99%) in 80.0% yield in the first two steps.
S3, dissolving the 4, 7-dibromo-5-fluorobenzothiadiazole in 500ml of ethanol, uniformly mixing, adding 37.8g (1.0 mol) of sodium borohydride in batches, stirring at room temperature for 20h, and reacting at 40 ℃ until the raw material is less than 0.5%; concentrating the solvent under reduced pressure, adding 600ml of ammonium chloride aqueous solution, and stirring uniformly; extraction with ethyl acetate, washing with brine, drying and evaporation of the solvent gave 34.1g (0.12 mol) of 3, 6-dibromo-4-fluoro-1, 2-phenylenediamine as a pale yellow solid (GC > 99%) in 75.0% yield.
S4, dissolving the 3, 6-dibromo-4-fluoro-1, 2-phenylenediamine in 500ml of acetic acid, uniformly mixing, dropwise adding 100ml of sodium nitrite aqueous solution (the mass of sodium nitrite is 27.6g (0.4 mol)) at room temperature, and reacting for 3 hours after 1 hour; the mixture was poured into ice water, and the precipitated crude solid was collected and recrystallized from 300mL of toluene to give 29.5g (0.10 mol) of 4, 7-dibromo-5-fluorobenzotriazol (GC > 99%) in 83.3% yield.
S5, adding the 4, 7-dibromo-5-fluorobenzotriazole, 29.0g (0.15 mol) of n-octyl bromide, 400ml of DMF and 24.8g (0.18 mol) of anhydrous potassium carbonate into a reaction bottle, uniformly mixing, adding 2g of tetrabutylammonium bromide, stirring and heating to 110 ℃ until the raw materials are completely converted (the peak area ratio of a target product and an isomer is 1:0.6); cooling to room temperature, filtering, washing the solid with 600ml toluene at 50 ℃ for three times, and combining the filtrates; washing with water to neutrality, mixing water layers, extracting with 200ml toluene, and discarding; concentrating the solvent, adding 800ml of n-heptane, stirring and suction filtering; the filtrate was desolventized by column chromatography and recrystallized from 200mL of ethanol to give 20.4g (0.05 mol) of 2-n-octyl-4, 7-dibromo-5-fluorobenzotriazole (GC > 99%) in a yield of 50.0%.
S6, adding 5g of magnesium chips, 2 pieces of iodine and 25ml of tetrahydrofuran into a Grignard reaction bottle, uniformly mixing, and dropwise adding 100ml of tetrahydrofuran solution containing 4- (1-adamantyl) bromobenzene (the mass of the 4- (1-adamantyl) bromobenzene is 43.7g (0.15 mol)) to obtain a Grignard reagent;
adding 27.2g (0.2 mol) anhydrous zinc chloride and 125ml tetrahydrofuran into a main reaction bottle, stirring for complete dissolution, cooling to-15 ℃, dripping the Grignard reagent solution, stirring for 1h after dripping, and returning to room temperature; adding 20.4g (0.05 mol) of the 2-n-octyl-4, 7-dibromo-5-fluorobenzotriazole, uniformly stirring, replacing air with nitrogen, adding 0.1g of dichloro di-tert-butyl- (4-dimethylaminophenyl) phosphine palladium, heating a reaction bottle to reflux, and stirring for reacting for 5-6 hours until the conversion is complete; concentrating under reduced pressure to evaporate 150ml tetrahydrofuran, adding 300ml toluene, stirring and cooling to room temperature, adding 300ml water, stirring uniformly, standing and separating liquid; extracting the water phase twice with 200ml toluene, combining the organic phases, and washing with deionized water to neutrality; the organic phase is passed through a silica gel column, the solvent is distilled off under reduced pressure, 400mL of ethanol are added for recrystallization and drying, 26.8g (0.040 mol) of compound Ib (GC > 99%, HPLC > 99%) are obtained, the yield being 80.0%.
1 H NMR (400 MHz, Chloroform-d) δ 7.81 – 7.74 (m, 2H), 7.65 (d,J= 8.1 Hz, 1H), 7.56 – 7.49 (m, 2H), 7.43 (dd,J= 8.0, 1.1 Hz, 4H), 4.23 (t,J= 5.3 Hz, 2H), 2.15 – 2.05 (m, 6H), 1.95 (d,J= 4.8 Hz, 12H), 1.86 (q,J= 5.3 Hz, 14H), 1.45 – 1.35 (m, 2H), 1.35 – 1.24 (m, 8H), 0.93 – 0.85 (m, 3H).
Compound Ib was detected to be non-absorbing for light having a wavelength greater than 415 nm.
Formula 4.
Example 3
This example provides a fluorine-containing benzotriazolyl fluorescent compound (Ic) for optical transfer films.
Ic
The above-mentioned synthetic method of Ic includes the following step (equation of reaction is shown in formula 5):
s1 to S4 are the same as in embodiment 1, and will not be described again.
S5, adding the 4, 7-dibromo-5, 6-difluorobenzotriazole, 24.7g (0.18 mol) of 1-bromobutane, 400ml of DMF and 24.8g (0.18 mol) of anhydrous potassium carbonate into a reaction bottle, uniformly mixing, adding 1g of tetrabutylammonium bromide, stirring and heating to 105 ℃ until the raw materials are completely converted (the peak area ratio of a target product and an isomer is 1:0.74); cooling to room temperature, filtering, washing the solid with 600ml toluene at 50deg.C for three times, and mixing filtrates; washing with water to neutrality, mixing water layers, extracting with 200ml toluene, and discarding; concentrating the solvent, adding 800ml of n-heptane, stirring and suction filtering; the filtrate was desolventized by column chromatography, and recrystallized by adding 200mL of ethanol to give 24.4g (0.066 mol) of 2-n-butyl-4, 7-dibromo-5, 6-difluorobenzotriazol (GC > 99%) in a yield of 55.0%.
S6, adding the 2-n-butyl-4, 7-dibromo-5, 6-difluorobenzotriazole (22.1 g,0.06 mol), 23.3g (0.12 mol) of 4-tert-butoxyphenylboric acid, 200ml of toluene, 300ml of ethanol, 16.6g (0.12 mol) of potassium carbonate and 100ml of water into a reaction bottle, uniformly stirring, replacing air with nitrogen, then adding 0.1g of dichloro-di-tert-butyl- (4-dimethylaminophenyl) phosphine palladium, heating the reaction bottle to reflux, and stirring for reaction for 5-6 hours until complete conversion; cooling the reaction bottle to room temperature, adding 300ml of water, stirring, standing and separating liquid; extracting the water phase with 200ml toluene for three times, combining organic phases, and washing with deionized water to neutrality; the organic phase was passed through a silica gel column, the solvent was distilled off under reduced pressure, and 300mL of ethanol was added for recrystallization and drying to give 23.4g (0.046 mol) of compound Ic (GC > 99%, HPLC > 99%) in a yield of 76.7%.
1 H NMR (400 MHz, Chloroform-d) δ 7.46 – 7.38 (m, 4H), 7.07 – 7.00 (m, 4H), 4.24 (t,J= 5.7 Hz, 2H), 1.88 (tt,J= 7.1, 5.6 Hz, 2H), 1.46 (q,J= 7.0 Hz, 2H), 1.30 (s, 18H), 0.94 (t,J= 6.8 Hz, 3H).
The compound Ic was detected to be non-absorbing for light having a wavelength greater than 405 nm.
Formula 5.
Example 4
This example provides a fluorine-containing benzotriazolyl fluorescent compound (Id) for optical transfer films.
Id
The synthesis of Id was similar to example 1, except that in step S6, the same molar amount of 3,4, 5-trifluorophenylboronic acid was used instead of 2, 3-difluoro-4-ethoxyphenylboronic acid in example 1, and 24.0g (0.051 mol) of compound Id (GC > 99%, HPLC > 99%) was finally obtained in a yield of 85.0% and will not be described again.
1 H NMR (400 MHz, Chloroform-d) δ 7.50 (ddt,J= 8.0, 5.1, 0.7 Hz, 4H), 3.79 (d,J= 4.3 Hz, 2H), 2.28 – 2.13 (m, 1H), 1.02 (d,J= 7.4 Hz, 6H).
The compound Id was detected as non-absorbing for light having a wavelength greater than 400 nm.
Example 5
This example provides a fluorine-containing benzotriazolyl fluorescent compound (Ie) for optical transfer films.
Ie
The above-described synthetic method of Ie is similar to example 1, except that: in step S5, the bromoisobutane in example 1 was replaced with the same molar amount of cyclopentylbromomethane to give 30.8g (0.078 mol) of intermediate 2-cyclopentylmethyl-4, 7-dibromo-5, 6-difluorobenzotriazol (GC > 99%) in a yield of 65.0%; in step S6, 23.7g (0.06 mol) of the above 2-cyclopentylmethyl-4, 7-dibromo-5, 6-difluorobenzotriazole was taken, and the 2, 3-difluoro-4-ethoxyphenylboronic acid in example 1 was replaced with 4-dimethylaminophenylboronic acid in the same molar amount, to finally obtain 26.2g (0.055 mol) of compound Ie (GC > 99%, HPLC > 99%) in a yield of 91.7% without further description.
1 H NMR (400 MHz, Chloroform-d) δ 7.45 – 7.38 (m, 4H), 6.75 – 6.67 (m, 4H), 3.85 (dd,J= 13.1, 3.6 Hz, 1H), 3.78 (dd,J= 13.1, 3.6 Hz, 1H), 2.98 (s, 12H), 1.92 – 1.81 (m, 1H), 1.74 – 1.62 (m, 4H), 1.62 – 1.44 (m, 4H).
The compound Ie was detected to be non-absorbing for light having a wavelength greater than 400 nm.
Example 6
This example provides a fluorine-containing benzotriazolyl fluorescent compound (If) for optical transfer films.
If
The synthesis method of If is similar to that of example 2, except that: in step S5, the bromo-n-octane of example 2 was replaced with equal molar amount of cyclopentylbromomethane to give 22.6g (0.06 mol) of intermediate 2-cyclopentylmethyl-4, 7-dibromo-5-fluorobenzotriazole (GC > 99%) in a yield of 60.0%; in the step S6, 18.9g (0.05 mol) of the 2-cyclopentylmethyl-4, 7-dibromo-5-fluorobenzotriazole is taken, and the 4- (1-adamantyl) bromobenzene in the example 2 is replaced by 4-bromodiphenyl ether with the same molar quantity, so that 25g (0.045 mol) of a compound If (GC > 99% and HPLC > 99%) is finally obtained, and the yield is 90.0% and is not described again.
1 H NMR (400 MHz, Chloroform-d) δ 7.59 (d,J= 8.1 Hz, 1H), 7.52 – 7.40 (m, 4H), 7.40 – 7.31 (m, 4H), 7.24 – 7.06 (m, 6H), 7.03 – 6.96 (m, 4H), 3.85 (dd,J= 13.1, 3.6 Hz, 1H), 3.78 (dd,J= 13.1, 3.6 Hz, 1H), 1.86 (dtt,J= 7.4, 4.6, 1.3 Hz, 1H), 1.73 – 1.65 (m, 2H), 1.65 – 1.59 (m, 3H), 1.59 – 1.54 (m, 1H), 1.51 (m, 2H).
The compound If is detected to have no absorption to light with the wavelength of more than 416 nm.
Example 7
This example provides a fluorine-containing benzotriazolyl fluorescent compound (Ig) for optical transfer films.
Ig
The Ig synthesis method is similar to example 1, except that in step S6, the 2, 3-difluoro-4-ethoxyphenylboronic acid in example 1 is replaced with an equivalent molar amount of 4-tert-butylphenylboronic acid, so that 25.2g (0.053 mol) of compound Ig (GC > 99%, HPLC > 99%) is finally obtained, and the yield is 88.3%, which is not described again.
1 H NMR (400 MHz, Chloroform-d) δ 7.61 – 7.38 (m, 4H), 7.38 – 7.23 (m, 4H), 3.79 (d,J= 4.3 Hz, 2H), 2.43 – 2.04 (m, 1H), 1.34 (s, 18H), 1.02 (d,J= 7.4 Hz, 6H).
The compound Ig was detected to have no absorption of light having a wavelength of greater than 419 nm.
Example 8
This example provides a fluorine-containing benzotriazolyl fluorescent compound (Ih) for optical transfer films.
Ih
The synthesis of Ih was similar to example 3, except that in step S6, the same molar amount of 2-fluoro-4- (4-ethylcyclohexyl) phenylboronic acid was used instead of 4-tert-butoxyphenylboronic acid in example 3, and 34.7g (0.056 mol) of compound Ih (GC > 99%, HPLC > 99%) was finally obtained, with a yield of 93.3%, which was not described again.
1 H NMR (400 MHz, Chloroform-d) δ 7.65 (dd,J= 8.0, 5.0 Hz, 2H), 7.17 – 7.10 (m, 2H), 7.08 (dd,J= 8.0, 2.1 Hz, 2H), 4.24 (t,J= 5.7 Hz, 2H), 2.74 – 2.64 (m, 2H), 1.88 (m, 2H), 1.83 – 1.73 (m, 4H), 1.73 – 1.26 (m, 20H), 0.98 – 0.86 (m, 9H).
The compound Ih was detected to be non-absorbing for light having a wavelength greater than 419 nm.
Example 9
This example provides a fluorine-containing benzotriazolyl fluorescent compound (Ii) for optical transfer films.
Ii
The synthesis of Ii above was similar to that of example 5, except that: in the step S6, the 4-dimethylaminophenylboronic acid in example 5 was replaced with an equivalent molar amount of 2-fluoro-4- (4-propylphenyl) phenylboronic acid, and 34.4g (0.052 mol) of the compound Ii (GC > 99%, HPLC > 99%) was finally obtained in a yield of 86.7% without further description.
1 H NMR (400 MHz, Chloroform-d) δ 7.77 (dd,J= 7.9, 5.0 Hz, 2H), 7.57 – 7.50 (m, 5H), 7.49 (d,J= 2.0 Hz, 1H), 7.42 (dd,J= 7.8, 2.0 Hz, 2H), 7.20 (dt,J= 8.2, 1.0 Hz, 4H), 3.90 – 3.73 (m, 2H), 2.61 (m, 4H), 1.86 (m, 1H), 1.74 – 1.56 (m, 10H), 1.51 (m, 2H), 0.96 (t,J= 7.5 Hz, 6H).
The compound Ii was detected as non-absorbing for light having a wavelength greater than 423 nm.
Example 10
This example provides a fluorine-containing benzotriazolyl fluorescent compound (Ij) for optical transfer films.
Ij
The synthesis method of Ij is similar to example 6, except that: in the step S6, the 4-bromodiphenyl ether in the example 6 is replaced by 4-cyclopentyl bromobenzene with the same molar quantity, and 21.8g (0.043 mol) of a compound Ij (GC > 99%, HPLC > 99%) is finally obtained, and the yield is 86.0%, and is not repeated.
1 H NMR (400 MHz, Chloroform-d) δ 7.84 – 7.76 (m, 2H), 7.53 (dq,J= 8.7, 1.7 Hz, 2H), 7.29 – 7.18 (m, 4H), 3.90 – 3.73 (m, 2H), 2.92 (p,J= 4.7 Hz, 2H), 1.92 – 1.44 (m, 26H).
The compound Ij was detected as non-absorbing for light having a wavelength greater than 416 nm.
Example 11
This example provides a fluorine-containing benzotriazolyl fluorescent compound (Ik) for optical transfer films.
Ik
The above-described method of synthesizing Ik differs from example 1 only in that: in the step S6, the 2, 3-difluoro-4-ethoxyphenylboronic acid in example 1 is replaced by 3-phenoxyphenylboronic acid with the same molar amount, and 29.6g (0.054 mol) of the compound Ik (GC > 99%, HPLC > 99%) is finally obtained, and the yield is 90.0% and is not repeated.
1 H NMR (400 MHz, Chloroform-d) δ 7.51 – 7.40 (m, 4H), 7.40 – 7.31 (m, 4H), 7.26 (t,J= 2.0 Hz, 2H), 7.10 (m, 2H), 7.07 – 6.96 (m, 6H), 3.79 (d,J= 4.3 Hz, 2H), 2.21 (m, 1H), 1.02 (d,J= 7.4 Hz, 6H).
The compound Ik was detected as non-absorbing for light having a wavelength greater than 412 nm.
Comparative example 1
This comparative example provides a benzotriazole-based fluorescent compound (Ix) for use in optical transfer films.
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Ix
The above Ix is a known compound in the prior art, and the synthesis method can be referred to the related preparation method in https:// doi.org/10.1016/j.tet.2014.05.016.
Comparative example 2
This comparative example provides a benzotriazole-based fluorescent compound (Iy) for optical transfer film.
Iy
The above Iy is a known compound in the prior art, and the synthesis method thereof can be referred to the preparation method of paragraph 0201 in the specification of patent application CN103562323 a.
Comparative example 3
This comparative example provides a benzotriazole-based fluorescent compound (Iz) for optical transfer film.
Iz
The above-mentioned Iz is a known compound in the prior art, and the synthesis method thereof can refer to the preparation method of paragraphs 0030 to 0031 of the specification of the patent application CN 116426227A.
Performance test 1
Referring to IEC61215, ultraviolet-visible light absorbance spectra and fluorescence spectra were tested for the compounds provided in examples 1 to 11 and comparative examples 1 to 3 of the present invention. In the invention, an absorption spectrum is tested by adopting a UV-6100S type ultraviolet visible spectrophotometer (the solvent is methylene dichloride solution), and the result is shown in table 1; the fluorescence spectrum was measured by using a Hitachi F7100 fluorescence spectrophotometer, and the results are shown in Table 1. Melting point tests were performed on the compounds provided in examples 1 to 11 and comparative examples 1 to 3 of the present invention, and the results are shown in Table 1. As can be seen from table 1, the fluorine-containing benzotriazolyl fluorescent compound for optical transfer film provided by the invention has the following advantages: (1) the absorption spectrum covers the ultraviolet region, and the spectrum range is wider; (2) the emission spectrum is positioned in a dominant wavelength region utilized by the solar cell, and the half-peak width of the emission spectrum is narrow; (3) the melting point is proper, the film forming property is good, the crystallization and solidification are difficult to be carried out after the melting, and the solar cell can adapt to the working temperature of the solar cell. In addition, the invention is acted by fluorine atoms, so that the thermal stability of the material is improved; under the action of fluorine electronegativity and non-covalent bond, the compatibility of the material and the polymer matrix is good, and the stability is excellent.
Table 1 characterization of the properties such as the spectra of the Compounds of examples 1 to 11 and comparative examples 1 to 3
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Example 12
The embodiment provides a light transfer film which comprises the following raw materials in parts by weight: 100 parts of polymer matrix EVA, 0.2 part of fluorine-containing benzotriazolyl fluorescent compound Ia for optical transfer film, 0.4 part of gamma-glycidol ether oxypropyl trimethoxy silane (KH-560), 1 part of tert-butyl peroxy-2-ethylhexyl carbonate (TRPEHC) and 0.4 part of triallyl isocyanurate (TAIC).
The preparation method of the light transfer film comprises the following steps: the raw materials are weighed according to the weight portions, evenly mixed, melted and extruded at 90 ℃ and cast to obtain the light transfer film with the thickness of 300 mu m (the thickness difference is less than 5%).
Example 13
The embodiment provides a light transfer film which comprises the following raw materials in parts by weight: 100 parts of polymer matrix PVA, 0.02 part of fluorine-containing benzotriazolyl fluorescent compound Ib for optical transfer film, 1 part of gamma-glycidol ether oxypropyl trimethoxy silane (KH-560), 3 parts of tert-butyl peroxy-2-ethylhexyl carbonate (TRPEHC) and 0.6 part of triallyl isocyanurate (TAIC).
The preparation method of the light transfer film comprises the following steps: the raw materials are weighed according to the weight portions, evenly mixed, melted and extruded at 80 ℃ and cast to obtain the light transfer film with the thickness of 300 mu m (the thickness difference is less than 5%).
Example 14
The embodiment provides a light transfer film which comprises the following raw materials in parts by weight: 100 parts of polymer matrix PMMA, 0.8 part of fluorine-containing benzotriazolyl fluorescent compound Ic for optical transfer film, 1.5 parts of gamma-glycidol ether oxypropyl trimethoxy silane (KH-560), 4 parts of tert-butyl peroxy-2-ethylhexyl carbonate (TRPEHC) and 0.8 part of triallyl isocyanurate (TAIC).
The preparation method of the light transfer film comprises the following steps: the raw materials are weighed according to the weight portions, evenly mixed, melted and extruded at 85 ℃, and cast to obtain the light transfer film with the thickness of 300 mu m (the thickness difference is less than 5%).
Examples 15 to 22
The present embodiment provides a light conversion film and a preparation method thereof, similar to embodiment 12, except that the compound Ia is replaced by Id to Ik, respectively, and the description is omitted.
Comparative examples 4 to 6
The comparative examples all provide a light conversion film and a preparation method thereof, similar to example 12, except that the compound Ia was replaced with Ix to Iz, respectively, and no description is repeated.
Comparative example 7
The comparative examples all provide a light-transmitting film and a method for preparing the same, which are similar to example 12, except that the compound Ia is omitted and the description is omitted.
Examples 23 to 33
The embodiment provides a dual-glass photovoltaic module, which sequentially comprises upper glass, an upper light transfer film, a heterojunction battery piece, a lower light transfer film and lower glass from top to bottom, wherein the silicon wafer size of the heterojunction battery piece is 210mm. The light conversion films (including the upper light conversion film and the lower light conversion film) are the light conversion films provided in examples 12 to 22 in order.
Comparative examples 8 to 11
The comparative examples all provide a dual-glass photovoltaic module, similar to examples 23 to 33, except that the light conversion films were replaced with those provided in comparative examples 4 to 7, respectively, and the description thereof is omitted.
Performance test 2
In order to evaluate the light conversion performance of the photovoltaic module, the dual-glass photovoltaic modules provided in examples 23 to 33 and comparative examples 8 to 11 of the present invention were subjected to a power test, a UV aging test of 120kWh and a module attenuation rate test with reference to IEC61215, and the results are shown in table 2. As can be seen from table 2, when the light conversion film was used as a packaging material for HJT solar cells, the light conversion film prepared by adding the compound of the present invention significantly improved the overall efficiency and good stability of the photovoltaic module when the amount and the preparation conditions were the same.
Table 2 comprehensive properties of the double-glass photovoltaic modules of examples 23 to 33 and comparative examples 8 to 11
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, or alternatives falling within the spirit and principles of the invention.
Claims (10)
1. The fluorine-containing benzotriazolyl fluorescent compound for the optical transfer film is characterized in that the structural formula of the fluorine-containing benzotriazolyl fluorescent compound is at least one of the structures shown in the formula I:
I；
wherein R is 1 Is taken from: C1-C10 alkyl, C3-C11 cycloalkyl or C3-C11 substituted cycloalkyl;
R 2 is taken from: -H, -F, phenoxy, dimethylamino, diethylamino, 4-alkylphenyl, C1-C6 alkyl, C1-C6 alkoxy, C3-C11 cycloalkyl, C3-C11 substituted cycloalkyl or 1-adamantyl;
R 3 is taken from: -H, -F or phenoxy;
x is-H or-F; x is X 1 、X 2 is-H or-F, and is not simultaneously-H.
2. The fluorine-containing benzotriazolyl fluorescent compound for optical transfer film according to claim 1, wherein R of formula I 1 Wherein the C3-C11 substituted cycloalkyl comprises 4-cyclopropyl cyclohexyl, 4-cyclopentyl cyclohexyl, 4-ethyl cyclohexyl, 4-propyl cyclohexyl, 4-butyl cyclohexyl or 4-amyl cyclohexyl.
3. The fluorine-containing benzotriazole-based fluorescent compound for optical transfer film according to claim 1, wherein the structural formula thereof comprises at least one of the structures represented by formulas II to XXXIX:
4. the method for producing a fluorine-containing benzotriazolyl fluorescent compound for optical transfer film according to any one of claims 1 to 3, wherein when X 1 、X 2 When the total F is the F, the method comprises the following steps:
s1, using 3, 4-difluoroaniline as a raw material, and sequentially performing nitration reaction, reduction reaction and bromination reaction to obtain 4, 5-difluoro-3, 6-dibromo-1, 2-phenylenediamine;
s2, carrying out cyclization reaction on the 4, 5-difluoro-3, 6-dibromo-1, 2-phenylenediamine and sodium nitrite, and carrying out alkylation to obtain 2-alkyl-4, 7-dibromo-5, 6-difluoro benzotriazol shown in a formula (F);
s3, performing a coupling reaction on the 2-alkyl-4, 7-dibromo-5, 6-difluoro benzotriazol shown in the formula (F) and aryl boric acid shown in the formula (G) to obtain a fluoro benzotriazol fluorescent compound for optical transfer film shown in the formula (H);
。
5. the method for producing a fluorine-containing benzotriazolyl fluorescent compound for optical transfer film according to any one of claims 1 to 3, wherein when X 1 、X 2 When only one of them is F, the method comprises the following steps:
s1', taking 4-fluoro-1, 2-phenylenediamine as a raw material, and sequentially carrying out cyclization reaction, double bromination reaction and reduction reaction to obtain 3, 6-dibromo-4-fluoro-1, 2-phenylenediamine;
s2', carrying out cyclization reaction on the 3, 6-dibromo-4-fluoro-1, 2-phenylenediamine and sodium nitrite, and carrying out alkylation to obtain 2-alkyl-4, 7-dibromo-5-fluorobenzotriazole shown in a formula (F');
s3', carrying out coupling reaction on the 2-alkyl-4, 7-dibromo-5-fluorobenzotriazole shown in the formula (F') and an aryl compound shown in the formula (G '), so as to obtain a fluorine-containing benzotriazolyl fluorescent compound shown in the formula (H');
。
6. the fluorine-containing benzotriazolyl fluorescent compound for a light transfer film according to any one of claims 1 to 3 or the fluorine-containing benzotriazolyl fluorescent compound for a light transfer film prepared by the method for preparing the fluorine-containing benzotriazolyl fluorescent compound for a light transfer film according to claim 4 or 5.
7. The light conversion film according to claim 6, comprising the following raw materials in parts by weight: 100 parts of polymer matrix, 0.001-1 part of fluorine-containing benzotriazole fluorescent compound for optical transfer film, 0-2 parts of alkoxy silane, 0-5 parts of cross-linking agent and 0-1 part of cross-linking auxiliary agent.
8. The light transfer film of claim 7, wherein the polymer matrix comprises at least one of an ethylene vinyl acetate copolymer, a polyvinyl alcohol, a polymethyl methacrylate, or a polyolefin elastomer; and/or
The cross-linking agent comprises tert-butyl peroxy-2-ethylhexyl carbonate; and/or
The crosslinking aid comprises triallyl isocyanurate; and/or
The alkoxy silane comprises gamma-glycidyl ether oxypropyl trimethoxy silane; and/or
The thickness of the light transfer film is 100-1000 mu m.
9. The method for producing a light-transmitting film according to claim 7 or 8, comprising the steps of:
weighing the raw materials according to parts by weight, uniformly mixing a polymer matrix, a fluorine-containing benzotriazolyl fluorescent compound for the optical transfer film, alkoxy silane, a cross-linking agent and a cross-linking auxiliary agent, and carrying out melt extrusion and tape casting at 75-95 ℃ to obtain the optical transfer film.
10. The use of the light conversion film according to any one of claims 6 to 8 or the light conversion film prepared by the preparation method of the light conversion film according to claim 9 in photovoltaic modules, agricultural films or architectural glass.
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