Light conversion agent, light conversion composition and light conversion film

Abstract

The invention relates to a light conversion agent, a light conversion composition and a light conversion film. The light conversion agent provided by the invention comprises a compound as shown in a formula I. The light conversion agent provided by the invention can realize high absorption conversion rate and high spectral matching under the condition of low doping amount, does not need to depend on metal doping or complex post-treatment process, and shows remarkable technical advantages in the application of agricultural light conversion films.

Description

Technical Field

[0001] This application belongs to the technical field of light-converting agents and light-converting films, and particularly relates to a light-converting agent, a light-converting composition, and a light-converting film. Background Technology

[0002] In recent years, with the rapid development of facility agriculture, the demand for agricultural films in my country has continued to rise. As an important branch of agricultural photofunctional materials, light-converting film technology can optimize the efficiency of plant light energy utilization through spectral modulation, thus attracting widespread attention from the global agricultural research and industry. The core of this technology lies in converting light in the sunlight—wavelengths that plants cannot absorb or utilize, or that are harmful—into visible light that can be efficiently utilized by plants. Its functionality mainly depends on the performance optimization and process integration of the light-converting agent.

[0003] Studies have shown that the wavelength range of ultraviolet (UV) radiation in solar radiation covers 100-400 nm, with UV-A (315-400 nm) accounting for more than 95% of the total UV radiation reaching the Earth's surface. This type of long-wave UV radiation has strong penetrating power, and its induced accumulation of reactive oxygen species leads to lipid peroxidation and ion homeostasis imbalance in plant cell membranes. Higher-energy UV-B (280-315 nm) and UV-C (100-280 nm) can directly damage the base structure of DNA and the tertiary structure of proteins, inhibit chlorophyll biosynthesis, and trigger the degradation of photosynthetic system II reaction centers, resulting in a significant decrease in the accumulation of photosynthetic products. In contrast, plant photosynthetic pigments exhibit specific absorption characteristics for 400-480 nm blue-violet light and 600-680 nm red-orange light. Blue-violet light not only drives photochemical reactions but also regulates plant development through photomorphogenesis. Based on these spectral characteristics, light-converting films, by adding light-converting agents, convert ultraviolet light into 400-480nm blue-violet light, thus avoiding the physiological damage caused by ultraviolet radiation and increasing the energy proportion of photosynthetically active radiation (PAR). Current technology is focusing on developing novel light-converting agents that combine high quantum efficiency and excellent weather resistance to promote the sustainable development of facility agriculture.

[0004] Existing technologies often employ rare-earth fluorescent agents as the ultraviolet absorption functional unit, but their absorption bands do not match well with the ultraviolet spectra (such as UV-A and UV-B) that plants need to shield, making it difficult to achieve broad-spectrum and efficient absorption. In addition, traditional light-converting agents often improve their performance by increasing the doping concentration or introducing metal complexes, but the former is prone to causing molecular aggregation, leading to a decrease in transmittance, while the latter faces problems such as complex preparation processes and increased costs. Summary of the Invention

[0005] To address the problems in the prior art, this application provides a light-converting agent, a light-converting composition, and a light-converting film. The light-converting agent of this application possesses a high absorption conversion rate, enabling efficient energy conversion even with low doping levels.

[0006] In a first aspect, this application provides a light-converting agent comprising a compound of formula I.

[0007]

[0008] In Formula I, Ar1, Ar2, Ar3, and Ar4 may be the same or different, each independently selected from phenyl, and optionally phenyl substituted with a substituent selected from C1-C6 alkyl, C1-C6 alkoxy, halogen, hydroxyl, amino, amino substituted by C1-C6 alkyl, or cyano.

[0009] R1 to R 11 Whether the groups are the same or different, they are each independently selected from hydrogen, deuterium, C1-C6 alkyl, C1-C6 alkoxy, halogen, hydroxyl, amino, C1-C6 alkyl-substituted amino, and cyano.

[0010] The C1-C6 alkyl and C1-C6 alkoxy groups can be substituted with substituents selected from halogens, hydroxyl groups, amino groups, and cyano groups.

[0011] The light-converting agent of this application, through the synergistic design of fluorine atom substitution and terphenyl twisted configuration, regulates the intramolecular spatial conjugated charge transfer characteristics and frontier orbital energy level distribution, enabling its ultraviolet absorption to precisely cover the outer wavelength band sensitive to plants. Simultaneously, the presence of the twisted structure suppresses non-radiative transition channels, significantly improving energy conversion efficiency. Furthermore, the presence of the conjugated structure and the introduction of fluorine atoms enhance the thermal stability of the light-converting material. This effectively prevents thermal degradation or decomposition of the blue light absorber due to high temperatures during production and processing, thus preventing the loss of UV-A absorption function. Moreover, the light-converting agent of this application achieves high absorption conversion rate and high spectral matching even with low doping levels, without relying on metal doping or complex post-processing, demonstrating significant technical advantages in agricultural light conversion film applications.

[0012] In some embodiments, Ar1, Ar2, Ar3, and Ar4 are selected from C1-C6 alkyl-substituted phenyl groups (e.g., methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, or tert-butyl).

[0013] In some embodiments, Ar1, Ar2, Ar3, and Ar4 are selected from the structure shown in Formula II.

[0014]

[0015] In Equation II, R a R b and R c Whether the same or different, each is selected from C1-C6 alkyl groups.

[0016] In some implementations, R a R band R c Whether the groups are the same or different, each is selected from C1-C4 alkyl groups, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, or tert-butyl. In some embodiments, R a R b and R c Same. Both are methyl or ethyl.

[0017] In some implementations, R1 to R 11 They may be the same or different, and are each independently selected from hydrogen, deuterium, C1-C6 alkyl, and halogen.

[0018] In some implementations, R4 to R 11 They may be the same or different, each independently selected from hydrogen, deuterium, and C1-C4 alkyl groups (e.g., methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, or tert-butyl). In some embodiments, R4 to R 11 Both are hydrogen.

[0019] In some embodiments, R1 to R3 may be the same or different, each independently selected from hydrogen, deuterium, C1-C6 alkyl groups, or halogens. In some embodiments, R1 to R3 may be the same or different, selected from hydrogen or halogens (e.g., fluorine, chlorine, bromine, or iodine). In some embodiments, the halogen is fluorine.

[0020] In some embodiments, the light-converting agent comprises the following compounds:

[0021]

[0022] Among them, Mes is

[0023] Secondly, this application provides a compound represented by Formula III.

[0024]

[0025] R1 to R 11 They may be the same or different, and are each independently selected from hydrogen, deuterium, C1-C6 alkyl, C1-C6 alkoxy, halogen, hydroxyl, amino, C1-C6 alkyl-substituted amino, and cyano.

[0026] In some implementations, R4 to R 11 They may be the same or different, each independently selected from hydrogen, deuterium, and C1-C4 alkyl groups (e.g., methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, or tert-butyl). In some embodiments, R4 to R 11 The same amount of hydrogen is hydrogen.

[0027] In some embodiments, R1 to R3 may be the same or different, each independently selected from hydrogen, deuterium, C1-C6 alkyl groups, or halogens. In some embodiments, R1 to R3 may be the same or different, selected from hydrogen or halogens (e.g., fluorine, chlorine, bromine, or iodine). In some embodiments, the halogen is fluorine.

[0028] In some embodiments, the compound represented by Formula III is selected from:

[0029] In some embodiments, the compound represented by Formula III is selected from:

[0030] Thirdly, this application provides a method for preparing the compound represented by Formula III, which includes the following steps:

[0031] S1: The compound shown in Formula 1 undergoes a first reaction with the compounds shown in Formula II-1 and Formula II-2 to obtain the compound shown in Formula III.

[0032]

[0033] Among them, R1 to R 11 The definition is the same as that in Formula I, and each is independently selected from hydrogen, deuterium, C1-C6 alkyl, C1-C6 alkoxy, halogen, hydroxyl, amino, C1-C6 alkyl-substituted amino, and cyano;

[0034] The C1-C6 alkyl and C1-C6 alkoxy groups can be substituted with substituents selected from halogens, hydroxyl groups, amino groups, and cyano groups.

[0035] In some implementations, R1 to R 11 They may be the same or different, and are each independently selected from hydrogen, deuterium, C1-C6 alkyl, and halogen.

[0036] In some implementations, R4 to R 11 They may be the same or different, each independently selected from hydrogen, deuterium, and C1-C4 alkyl groups (e.g., methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, or tert-butyl). In some embodiments, R4 to R 11 Both are hydrogen.

[0037] In some embodiments, R1 to R3 may be the same or different, each independently selected from hydrogen, deuterium, C1-C6 alkyl groups, or halogens. In some embodiments, R1 to R3 may be the same or different, selected from hydrogen or halogens (e.g., fluorine, chlorine, bromine, or iodine). In some embodiments, the halogen is fluorine.

[0038] In some embodiments, the molar content of the compound shown in Formula 1 is in the ratio of the total molar content of the compounds shown in Formula II-1 and Formula II-2 to 1:(2-3), for example, 1:2.1, 1:2.2, 1:2.3, 1:2.4, 1:2.5, 1:2.6, 1:2.7, 1:2.8, 1:2.9 or any value between them.

[0039] In some embodiments, the first reaction is carried out in a mixed solvent of tetrahydrofuran and water.

[0040] In some embodiments, the first reaction is carried out under heating conditions, with the heating temperature being 50°C-100°C, for example 60°C, 70°C, 80°C or 90°C.

[0041] In some implementations, the time for the first reaction is 12h-60h, for example 16h, 24h, 30h, 36h, 40h, 48h, 52h or 58h.

[0042] In some embodiments, the first reaction is carried out in the presence of a base and a catalyst. In some embodiments, the base is selected from potassium carbonate. In some embodiments, the catalyst is selected from tetra(triphenylphosphine)palladium.

[0043] In some embodiments, the compounds shown in Formula II-1 and Formula II-2 are both 2-bromophenylboronic acid.

[0044] In some embodiments, the preparation method of the compound represented by Formula III includes the following specific steps:

[0045] Under an inert gas atmosphere, the compound shown in Formula 1, the compounds shown in Formula II-1 and Formula II-2, potassium carbonate, and tetra(triphenylphosphine)palladium are mixed, and a deoxygenated tetrahydrofuran / water mixed solvent is added. The mixture is heated under reflux for 24-48 hours to obtain the compound shown in Formula III.

[0046] Fourthly, this application provides a method for preparing the compound shown in Formula I, which includes the following steps:

[0047] S2: The compound shown in Formula III undergoes a second reaction with the compounds shown in Formula IV-1 and IV-2 to obtain the compound shown in Formula I.

[0048]

[0049] Among them, Ar1, Ar2, Ar3, Ar4, R1 to R 11 The definition is the same as that in Equation I.

[0050] Specifically, Ar1, Ar2, Ar3, and Ar4 may be the same or different, each independently selected from phenyl, and optionally substituted by a phenyl group selected from C1-C6 alkyl, C1-C6 alkoxy, halogen, hydroxyl, amino, amino group substituted by C1-C6 alkyl, or cyano group.

[0051] R1 to R 11 Whether the groups are the same or different, they are each independently selected from hydrogen, deuterium, C1-C6 alkyl, C1-C6 alkoxy, halogen, hydroxyl, amino, C1-C6 alkyl-substituted amino, and cyano.

[0052] The C1-C6 alkyl and C1-C6 alkoxy groups can be substituted with substituents selected from halogens, hydroxyl groups, amino groups, and cyano groups.

[0053] In some embodiments, Ar1, Ar2, Ar3, and Ar4 are selected from C1-C6 alkyl-substituted phenyl groups (e.g., methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, or tert-butyl).

[0054] In some embodiments, Ar1, Ar2, Ar3, and Ar4 are selected from the structure shown in Formula II.

[0055]

[0056] In Equation II, R a R b and R c Whether the same or different, each is selected from C1-C6 alkyl groups.

[0057] In some implementations, R a R b and R c Whether the groups are the same or different, each is selected from C1-C4 alkyl groups, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, or tert-butyl. In some embodiments, R a R b and R c Same. Both are methyl or ethyl.

[0058] In some implementations, R1 to R 11 They may be the same or different, and are each independently selected from hydrogen, deuterium, C1-C6 alkyl, and halogen.

[0059] In some implementations, R4 to R 11 They may be the same or different, each independently selected from hydrogen, deuterium, and C1-C4 alkyl groups (e.g., methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, or tert-butyl). In some embodiments, R4 to R 11 Both are hydrogen.

[0060] In some embodiments, R1 to R3 may be the same or different, each independently selected from hydrogen, deuterium, C1-C6 alkyl groups, or halogens. In some embodiments, R1 to R3 may be the same or different, selected from hydrogen or halogens (e.g., fluorine, chlorine, bromine, or iodine). In some embodiments, the halogen is fluorine.

[0061] In some embodiments, the molar content of the compound represented by Formula III is in the ratio of the total molar content of the compounds represented by Formulas IV-1 and IV-2 to 1:(2-3), for example, 1:2.1, 1:2.2, 1:2.3, 1:2.4, 1:2.5, 1:2.6, 1:2.7, 1:2.8, 1:2.9 or any value between them.

[0062] In some embodiments, the temperature of the second reaction is 5°C-35°C, for example, 10°C, 15°C, 20°C, 25°C, or 30°C. In some embodiments, the temperature of the second reaction is room temperature.

[0063] In some embodiments, the second reaction time is 1h-20h, for example 4h, 8h, 10h, 12h, 14h, 16h or 18h.

[0064] In some embodiments, the solvent for the second reaction is tetrahydrofuran.

[0065] In some embodiments, the second reaction is carried out in the presence of n-butyllithium or tert-butyllithium.

[0066] In some embodiments, the compounds shown in Formula IV-1 and Formula IV-2 are both Mes2BF.

[0067] In some embodiments, the preparation method of the compound represented by Formula I includes the following specific steps:

[0068] The reaction product containing the compound of formula I is obtained by dissolving the compound of formula III in a tetrahydrofuran solution, cooling to -78°C and stirring for 10-30 minutes, adding n-butyllithium or tert-butyllithium, stirring and reacting for 1-3 hours, then dissolving the compounds of formula IV-1 and IV-2 in a tetrahydrofuran solution and adding them to the reaction system, gradually raising the temperature to room temperature, and reacting for 8-12 hours.

[0069] Fifthly, this application provides a method for preparing a light-converting agent, which includes one or more of the following steps:

[0070] S1: The compound shown in Formula 1 is reacted with the second compounds shown in Formula II-1 and Formula II-2 to obtain the compound shown in Formula III;

[0071]

[0072] S2: React the compound shown in Formula III with the compounds shown in Formula IV-1 and Formula IV-2 in a second reaction to obtain a reaction product containing the compound shown in Formula I;

[0073]

[0074] Optionally, S3: recrystallize the reaction product containing the compound shown in Formula I;

[0075] Among them, Ar1, Ar2, Ar3, Ar4, R1 to R 11 The definition is the same as that in Equation I.

[0076] Specifically, Ar1, Ar2, Ar3, and Ar4 may be the same or different, each independently selected from phenyl, and optionally substituted by a phenyl group selected from C1-C6 alkyl, C1-C6 alkoxy, halogen, hydroxyl, amino, amino group substituted by C1-C6 alkyl, or cyano group.

[0077] R1 to R 11 Whether the groups are the same or different, they are each independently selected from hydrogen, deuterium, C1-C6 alkyl, C1-C6 alkoxy, halogen, hydroxyl, amino, C1-C6 alkyl-substituted amino, and cyano.

[0078] The C1-C6 alkyl and C1-C6 alkoxy groups can be substituted with substituents selected from halogens, hydroxyl groups, amino groups, and cyano groups.

[0079] The method for synthesizing the light conversion agent in this application is relatively simple. It can achieve high absorption conversion rate and high spectral matching with low doping amount, and does not rely on metal doping or complex post-processing, which reduces the amount of material used and lowers the cost. It shows significant technical advantages in agricultural light conversion film applications.

[0080] In some embodiments, Ar1, Ar2, Ar3, and Ar4 are selected from C1-C6 alkyl-substituted phenyl groups (e.g., methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, or tert-butyl).

[0081] In some embodiments, Ar1, Ar2, Ar3, and Ar4 are selected from the structure shown in Formula II.

[0082]

[0083] In Equation II, R a R b and R c Whether the same or different, each is selected from C1-C6 alkyl groups.

[0084] In some implementations, R a R b and Rc Whether the groups are the same or different, each is selected from C1-C4 alkyl groups, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, or tert-butyl. In some embodiments, R a R b and R c Same. Both are methyl or ethyl.

[0085] In some implementations, R1 to R 11 They may be the same or different, and are each independently selected from hydrogen, deuterium, C1-C6 alkyl, and halogen.

[0086] In some implementations, R4 to R 11 They may be the same or different, each independently selected from hydrogen, deuterium, and C1-C4 alkyl groups (e.g., methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, or tert-butyl). In some embodiments, R4 to R 11 Both are hydrogen.

[0087] In some embodiments, R1 to R3 may be the same or different, each independently selected from hydrogen, deuterium, C1-C6 alkyl groups, or halogens. In some embodiments, R1 to R3 may be the same or different, selected from hydrogen or halogens (e.g., fluorine, chlorine, bromine, or iodine). In some embodiments, the halogen is fluorine.

[0088] In some embodiments, in step S1, the molar content of the compound shown in Formula 1 is in the ratio of the total molar content of the compounds shown in Formula II-1 and Formula II-2 to 1:(2-3), for example, 1:2.1, 1:2.2, 1:2.3, 1:2.4, 1:2.5, 1:2.6, 1:2.7, 1:2.8, 1:2.9 or any value between them.

[0089] In some implementations, in step S1, the first reaction is carried out in a mixed solvent of deoxygenated tetrahydrofuran and water.

[0090] In some embodiments, the first reaction is carried out under heating conditions, with the heating temperature being 50°C-100°C, for example 60°C, 70°C, 80°C or 90°C.

[0091] In some implementations, the time for the first reaction in step S1 is 12h-60h, for example, 16h, 24h, 30h, 36h, 40h, 48h, 52h or 58h.

[0092] In some embodiments, in step S1, the first reaction is carried out in the presence of a base and a catalyst. In some embodiments, the base is selected from potassium carbonate. In some embodiments, the catalyst is selected from tetra(triphenylphosphine)palladium.

[0093] In some embodiments, in step S2, the molar content of the compound represented by Formula III is in the ratio of the total molar content of the compounds represented by Formula IV-1 and Formula IV-2 to 1:(2-3), for example, 1:2.1, 1:2.2, 1:2.3, 1:2.4, 1:2.5, 1:2.6, 1:2.7, 1:2.8, 1:2.9 or any value between them.

[0094] In some implementations, in step S2, the temperature of the second reaction is 5°C-35°C, for example, 10°C, 15°C, 20°C, 25°C or 30°C.

[0095] In some embodiments, the second reaction time is 1h-20h, for example 4h, 8h, 10h, 12h, 14h, 16h or 18h.

[0096] In some embodiments, in step S2, a second reaction is carried out by mixing a tetrahydrofuran solution containing compounds shown in Formula IV-1 and Formula IV-2 with a tetrahydrofuran solution containing compounds shown in Formula III.

[0097] In some embodiments, in step S2, a tetrahydrofuran solution containing the compound shown in Formula III is prepared using the following method:

[0098] The compound shown in Formula III and a tetrahydrofuran solution were mixed at -70°C to -85°C, and then n-butyllithium or tert-butyllithium was added to obtain the tetrahydrofuran solution containing the compound shown in Formula III.

[0099] In some embodiments, the preparation method of the light-converting agent includes the following specific steps:

[0100] (1) Under an inert gas atmosphere, the compound shown in Formula 1, the compounds shown in Formula II-1 and Formula II-2, potassium carbonate, and tetra(triphenylphosphine)palladium are mixed, and a deoxygenated tetrahydrofuran / water mixed solvent is added. The mixture is heated under reflux for 24-48 hours to obtain the compound shown in Formula III.

[0101] (2) The reaction product containing the light-converting agent is obtained by dissolving the compound shown in Formula III in a tetrahydrofuran solution, cooling to -78°C and stirring for 10-30 minutes, adding n-butyllithium or tert-butyllithium, stirring for 1-3 hours, then dissolving the compounds shown in Formula IV-1 and Formula IV-2 in a tetrahydrofuran solution and adding them to the reaction system, gradually raising the temperature to room temperature, and reacting for 8-12 hours.

[0102] In some embodiments, the compounds shown in Formula II-1 and Formula II-2 are both 2-bromophenylboronic acid.

[0103] In some embodiments, the compounds shown in Formula IV-1 and Formula IV-2 are both Mes2BF.

[0104] In a sixth aspect, this application provides a light-converting agent composition comprising the light-converting agent described in the first aspect, or the compound of formula I prepared by the preparation method described in the fourth aspect, or the light-converting agent prepared by the preparation method described in the fifth aspect, and a matrix resin.

[0105] In some embodiments, the light-converting agent is 0.1%-10% of the mass of the matrix resin, for example, 0.3%, 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, 5.5%, 6%, 6.5%, 7%, 7.5%, 8%, 8.5%, 9%, or 9.5%.

[0106] In some embodiments, the compound represented by Formula I is 0.1%-10% of the matrix resin by mass, for example, 0.3%, 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, 5.5%, 6%, 6.5%, 7%, 7.5%, 8%, 8.5%, 9%, or 9.5%.

[0107] In some embodiments, the matrix resin is selected from one or more of polymethyl methacrylate, polyethylene, polyvinyl chloride, and polypropylene.

[0108] In a seventh aspect, this application provides a light-converting film comprising the light-converting agent described in the first aspect, or the compound of formula I prepared by the preparation method described in the fourth aspect, or the light-converting agent prepared by the preparation method described in the fifth aspect, and a base film.

[0109] In some embodiments, the light-converting agent is 0.1%-10% of the mass of the base film, for example, 0.3%, 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, 5.5%, 6%, 6.5%, 7%, 7.5%, 8%, 8.5%, 9%, or 9.5%.

[0110] In some embodiments, the compound represented by Formula I is 0.1%-10% of the mass of the base film, for example, 0.3%, 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, 5.5%, 6%, 6.5%, 7%, 7.5%, 8%, 8.5%, 9%, or 9.5%.

[0111] In some embodiments, the raw material of the base film is selected from one or more of polymethyl methacrylate, polyethylene, polyvinyl chloride, and polypropylene.

[0112] In some embodiments, the preparation of the light-converting film includes: mixing the light-converting agent composition described in the sixth aspect with an organic solvent, followed by molding and drying.

[0113] In some embodiments, the organic solvent is selected from ethyl acetate.

[0114] In some embodiments, the drying temperature is 60°C-90°C, preferably 70°C-80°C.

[0115] Eighthly, this application provides the application of the light-converting agent described in the first aspect, or the compound of formula I prepared by the preparation method described in the fourth aspect, or the light-converting agent prepared by the preparation method described in the fifth aspect, or the light-converting agent composition described in the sixth aspect, or the light-converting film described in the seventh aspect in agricultural light conversion films.

[0116] Compared with the prior art, the beneficial effects of this application are as follows:

[0117] 1) The light conversion agent of this application reduces the harm of ultraviolet light to plants by precisely covering the ultraviolet light band (280-400nm) and efficiently converting it into blue-violet light (400-500nm), thereby significantly improving the light absorption and conversion efficiency.

[0118] 2) The light conversion agent of this application has excellent thermal stability, chemical stability and good solubility and dispersibility.

[0119] 3) The method for synthesizing the light conversion agent in this application is relatively simple. It can achieve high absorption conversion rate and high spectral matching with low doping amount, and does not rely on metal doping or complex post-processing, which reduces the amount of material used and lowers the cost. It shows significant technical advantages in agricultural light conversion film applications.

[0120] 4) The light-converting agent of this application removes harmful light while ensuring the transmittance of other light, achieving a balance between comprehensive protection and light transmittance, and has wide applicability. Attached Figure Description

[0121] Figure 1 For example, the light-converting agent BF in Example 1 1 H nuclear magnetic resonance spectrum.

[0122] Figure 2 For example, the light-converting agent BF in Example 1 13 C10 NMR spectrum.

[0123] Figure 3 For example, the light-converting agent BF in Example 1 11 B-NMR spectrum.

[0124] Figure 4 For example, the light-converting agent BF in Example 119 F nuclear magnetic resonance spectrum.

[0125] Figure 5 For example, the light-transfer agent BF2 in Example 2 1 H nuclear magnetic resonance spectrum.

[0126] Figure 6 For example, the light-transfer agent BF2 in Example 2 13 C10 NMR spectrum.

[0127] Figure 7 For example, the light-transfer agent BF2 in Example 2 11 B-NMR spectrum.

[0128] Figure 8 For example, the light-transfer agent BF2 in Example 2 19 F nuclear magnetic resonance spectrum.

[0129] Figure 9 For example, the light-converting agent BF4 in Example 3 1 H nuclear magnetic resonance spectrum.

[0130] Figure 10 For example, the light-converting agent BF4 in Example 3 13 C10 NMR spectrum.

[0131] Figure 11 For example, the light-converting agent BF4 in Example 3 11 B-NMR spectrum.

[0132] Figure 12 For example, the light-converting agent BF4 in Example 3 19 F nuclear magnetic resonance spectrum.

[0133] Figure 13 For the light transfer agent B0 in Comparative Example 1 1 H nuclear magnetic resonance spectrum.

[0134] Figure 14 For the light transfer agent B0 in Comparative Example 1 13 C10 NMR spectrum.

[0135] Figure 15 For the light transfer agent B0 in Comparative Example 1 11 B-NMR spectrum.

[0136] Figure 16 The single-crystal thermal vibration diagrams of the light-converting agents BF, BF2, and BF4 used in Examples 1-3 are shown.

[0137] Figure 17 The image shows the single-crystal thermal vibration diagram of the light-converting agent B0 in Comparative Example 1.

[0138] Figure 18The graphs show the thermal stability analysis of the light-converting agents BF, BF2, and BF4 used in Examples 1-3.

[0139] Figure 19 The graph shows the thermal stability analysis of the light-converting agent B0 in Comparative Example 1.

[0140] Figure 20 The UV-Vis absorption and fluorescence emission spectra of the light-transfer agents BF, BF2, and BF4 used in Examples 1-3 are shown.

[0141] Figure 21 The UV-Vis absorption and fluorescence emission spectra of the light-transfer agent B0 in Comparative Example 1 are shown.

[0142] Figure 22 The UV-Vis absorption and fluorescence emission spectra of the light-converting films BF-PMMA, BF2-PMMA, and BF4-PMMA used in Examples 4-6 are shown.

[0143] Figure 23 The UV transmittance test results are shown for the light-transmitting films BF-PMMA, BF2-PMMA, and BF4-PMMA used in Examples 4-6.

[0144] Figure 24 This is a weather resistance test diagram of the light-converting film BF-PMMA in Example 4.

[0145] Figure 25 This is a weather resistance test diagram of the light-converting film BF2-PMMA in Example 5.

[0146] Figure 26 The image shows the weather resistance test results of the light-converting film BF4-PMMA in Example 6. Detailed Implementation

[0147] To make the objectives, technical solutions, and advantages of this application clearer, the following detailed description is provided in conjunction with embodiments and accompanying drawings. The specific embodiments described herein are for illustrative purposes only and are not intended to limit the scope of this application. Furthermore, descriptions of well-known structures and technologies are omitted in the following description to avoid unnecessarily obscuring the concepts of this disclosure. Such structures and technologies have also been described in numerous publications.

[0148] The following provides further explanation of this application through specific implementations and comparative examples.

[0149] In the following examples and comparative examples, single-crystal X-ray diffraction was performed using Cu / Mo K2 refractometers. α radiation Data were collected using a SuperNova(Dual) X-ray diffractometer. Empirical absorption correction was performed using the SCALE3ABSPACK scaling algorithm from the CrysAlisPro dataset. The crystal structure was solved using the direct method of Olex2. Atomic positions were subsequently determined using Fourier analysis and least-squares optimization of the structure using the SHELXL-2014 / 7 package. The positions of all hydrogen atoms were determined by theoretical hydrogen addition and refined using a rigid model.

[0150] In the following examples and comparative examples, thermal stability analysis (TGA) was performed on a TGA / DSC3+ / Sartorius / MCA125S-2CCN-1 instrument (Mettler-Toledo) under argon atmosphere at a heating rate of 10 °C / min. Thermal decomposition temperature (T...) d The temperature was determined based on the recorded temperature at which a 5% weight loss occurred.

[0151] In the following examples and comparative examples, the ultraviolet-visible absorption spectra were tested on a Shimadzu UV-2600 ultraviolet spectrophotometer. During the test, dry potassium bromide was used as a substrate for mixing, grinding, and tableting.

[0152] In the following examples and comparative examples, the fluorescence emission photoluminescence (PL) spectra were measured using a HORIBA FL-3 variable-temperature steady-state / transient fluorescence spectrometer.

[0153] In the following examples and comparative examples, the ultraviolet transmittance test was conducted using a Dongru Optical transmittance tester DR82b. Three different locations were measured during the test, and the average value was taken.

[0154] In the following examples and comparative examples, the weather resistance test was performed using the same fluorescence emission spectrometer as the HORIBAFL-3 variable temperature steady-state / transient fluorescence spectrometer.

[0155] Example 1: Preparation of UV-A light conversion agent BF

[0156] In an inert gas atmosphere, 2-Bromophenylboronic acid, potassium carbonate, and tetra(triphenylphosphine)palladium are mixed, and a deoxygenated tetrahydrofuran / water mixed solvent is added. The mixture is heated under reflux for 24-48 hours to obtain the final product.

[0157] RF-2 was dissolved in tetrahydrofuran solution, cooled to -78°C, and stirred for 10-30 minutes. Then, n-butyllithium or tert-butyllithium was added, and the reaction was stirred for 1-3 hours. Then... Dissolve in tetrahydrofuran solution, add to the reaction system, gradually raise to room temperature, and react for 8-12 hours to obtain a UV-A light conversion agent. The reaction products.

[0158] The reaction product was recrystallized in a solution of hexane and chloroform to obtain a product with a purity of over 98%.

[0159] Example 2: Preparation of UV-A light conversion agent BF2

[0160] In an inert gas atmosphere, A mixture of 2-bromophenylboronic acid, potassium carbonate, and tetrakis(triphenylphosphine palladium) is added, followed by the addition of a deoxygenated tetrahydrofuran / water mixed solvent. The mixture is then heated under reflux for 24-48 hours to obtain the final product.

[0161] Dissolve RF2-2 in tetrahydrofuran solution, cool to -78℃ and stir for 10-30 minutes, add n-butyllithium or tert-butyllithium, stir and react for 1-3 hours, then... Dissolve in tetrahydrofuran solution, add to the reaction system, gradually raise to room temperature, and react for 8-12 hours to obtain the UV-A conversion agent. The reaction products.

[0162] The reaction product was recrystallized in a solution of hexane and chloroform to obtain a product with a purity of over 98%.

[0163] Example 3: Preparation of UV-A light conversion agent BF4

[0164] In an inert gas atmosphere, 2-Bromophenylboronic acid, potassium carbonate, and tetra(triphenylphosphine)palladium are mixed, and a deoxygenated tetrahydrofuran / water mixed solvent is added. The mixture is heated under reflux for 24-48 hours to obtain the compound.

[0165] Dissolve RF4-2 in tetrahydrofuran solution, cool to -78°C and stir for 10-30 minutes, then add n-butyllithium or tert-butyllithium, stir and react for 1-3 hours, then... Dissolve in tetrahydrofuran solution, add to the reaction system, gradually raise to room temperature, and react for 8-12 hours to obtain the UV-A conversion agent. The reaction products.

[0166] The reaction product was recrystallized in a solution of hexane and chloroform to obtain a product with a purity of over 98%.

[0167] Example 4: Preparation of light-converting film BF-PMMA

[0168] Weigh out 5 parts by weight of the light-converting agent BF prepared in Example 1 and 995 parts by weight of polymethyl methacrylate (PMMA). Dissolve the light-converting agent BF in ethyl acetate, then add the solution to PMMA and stir for 0.5 hours to obtain a mixture. Place the mixture in a mold and heat it in a forced-air drying oven to 70-80°C for 4-5 hours to obtain a light-converting film BF-PMMA with a doping ratio of 0.5 wt%.

[0169] Example 5: Preparation of light-converting film BF2-PMMA

[0170] Weigh out 5 parts by weight of the light-converting agent BF2 prepared in Example 2 and 995 parts by weight of polymethyl methacrylate (PMMA). Dissolve the light-converting agent BF2 in ethyl acetate, then add the solution to PMMA and stir for 0.5 hours to obtain a mixture. Place the mixture in a mold and heat it in a forced-air drying oven to 70-80°C for 4-5 hours to obtain a light-converting film BF2-PMMA with a doping ratio of 0.5 wt%.

[0171] Example 6: Preparation of light-converting film BF4-PMMA

[0172] Weigh out 5 parts by weight of the light-converting agent BF4 prepared in Example 3 and 995 parts by weight of polymethyl methacrylate (PMMA). Dissolve the light-converting agent BF4 in ethyl acetate, then add the solution to PMMA and stir to dissolve for 0.5 hours to obtain a mixture. Place the mixture in a mold and heat it in a forced-air drying oven to 70-80°C for 4-5 hours to obtain a light-converting film BF4-PMMA with a doping ratio of 0.5 wt%.

[0173] Comparative Example 1: Preparation of Comparative Compound B0

[0174] In an inert gas atmosphere, 2-Bromophenylboronic acid, potassium carbonate, and tetra(triphenylphosphine)palladium are mixed, and a deoxygenated tetrahydrofuran / water mixed solvent is added. The mixture is heated under reflux for 24-48 hours to obtain the final product.

[0175] The reaction is carried out by dissolving RH-2 in tetrahydrofuran solution, cooling to -78°C, stirring for 10-30 minutes, adding n-butyllithium or tert-butyllithium, and stirring for 1-3 hours. Then... Dissolved in tetrahydrofuran solution, added to the reaction system, and gradually heated to room temperature, the reaction was allowed to proceed for 8-12 hours to obtain the compound containing the comparative compound. The reaction products.

[0176] The reaction product was recrystallized in a solution of hexane and chloroform to obtain a product with a purity of over 98%.

[0177] Test case

[0178] (1) The NMR spectra of the light-transferring agents in Examples 1-3 are as follows: Figures 1-12 As shown.

[0179] like Figures 1-12 As shown, at 1.77-2.22 ppm 1 The H absorption peak is a characteristic peak of the -Mes group, indicating the presence of -B2Mes in the structure. The peak is located at 19.19-23.20 ppm. 13 The C absorption peak further confirms the presence of -B2Mes in the structure and the aromatic framework, while the concentration around 75 ppm... 11 B absorption peak and at -116 to -140 ppm 19 F absorption indicates the presence of boron and fluorine atoms in the structure.

[0180] (2) The NMR spectrum of the comparative substance in Comparative Example 1 is as follows: Figures 13-15 As shown.

[0181] like Figures 13-15 As shown, at 1.88 ppm and 2.16 ppm 1 The H absorption peak is a characteristic peak of the -Mes group, indicating the presence of -B2Mes in the structure. The peaks at 21.26 ppm and 23.35 ppm are also significant. 13 The C absorption peak further confirms the presence of -B2Mes in the structure and the aromatic framework, while the peak at 74.94 ppm... 11 The B absorption peak indicates the presence of boron atoms in the structure.

[0182] (3) The single-crystal X-ray diffraction patterns of the light-converting agents in Examples 1-3 are as follows: Figure 16 As shown.

[0183] from Figure 16 As can be seen, the light-converting agents BF, BF2, and BF4 have a distorted spatial structure, which can effectively prevent fluorescence quenching caused by aggregation.

[0184] (4) The single-crystal X-ray diffraction pattern of the comparative object in Comparative Example 1 is shown below. Figure 17 As shown.

[0185] from Figure 17 As can be seen, the comparative material, like the light-converting agents BF, BF2, and BF4, all have a distorted spatial structure.

[0186] (5) Thermal stability analysis diagrams of the light-transfer agents in Examples 1-3 are shown below. Figure 18 As shown.

[0187] from Figure 18As can be seen from the data, the framework collapse temperatures of the light-converting agents BF, BF2 and BF4 prepared in this application are 360℃, 367℃ and 389℃, respectively, indicating that the light-converting agent molecules have good thermal stability.

[0188] (6) The thermal stability analysis diagram of the comparative substance in Comparative Example 1 is shown below. Figure 19 As shown

[0189] from Figure 19 As can be seen from the data, the skeleton collapse temperature of the comparative compound B0 prepared in this application is 357℃.

[0190] (7) The UV-Vis absorption and fluorescence emission spectra of the light-transfer agents in Examples 1-3 are shown below. Figure 20 As shown, the solid line represents the ultraviolet-visible absorption spectrum, and the dashed line represents the fluorescence emission spectrum.

[0191] from Figure 20 As can be seen from the above, the light conversion agents BF, BF2 and BF4 prepared in this application can absorb ultraviolet light of 250nm-380nm very well and convert it into blue-violet light of 400nm-500nm.

[0192] (8) The UV-Vis absorption and fluorescence emission spectra of the comparative substance in Comparative Example 1 are shown below. Figure 21 As shown, the solid line represents the ultraviolet-visible absorption spectrum, and the dashed line represents the fluorescence emission spectrum.

[0193] from Figure 21 As can be seen, the UV-Vis absorption of the reference compound B0 is red-shifted compared to the light-converting agents BF, BF2, and BF4, indicating poorer absorption of ultraviolet light.

[0194] (9) The UV-Vis absorption and fluorescence emission spectra of the light-converting films in Examples 4-6 are shown below. Figure 22 As shown, the solid line represents the ultraviolet-visible absorption spectrum, and the dashed line represents the fluorescence emission spectrum.

[0195] from Figure 22 As can be seen, the light conversion films BF-PMMA, BF2-PMMA and BF4-PMMA can absorb ultraviolet light in the range of 280nm-380nm and convert it into blue-violet light in the range of 400nm-500nm. This indicates that the light conversion films BF-PMMA, BF2-PMMA and BF4-PMMA all have good ultraviolet absorption performance and blue-violet light emission performance.

[0196] The light-converting agents BF, BF2, and BF4 provided in this application have the advantages of simple synthesis, low cost, stable properties, and good dispersion in polymethyl methacrylate. Meanwhile, the light-converting films BF-PMMA, BF2-PMMA, and BF4-PMMA can reduce the ultraviolet content in sunlight, increase the amount of blue-violet light available to plants, promote plant photosynthesis, and increase crop yield.

[0197] (10) The ultraviolet transmittance test results of the light-transfer films in Examples 4-6 are shown below. Figure 23 As shown, the weather resistance test diagrams of the light-converting films in Examples 4-6 are as follows. Figures 24-26 As shown.

[0198] from Figure 23 As can be seen from the ultraviolet transmittance test, when the doping concentration of the 0.2mm thick PMMA light conversion film is 0.5%, more than 15% of the ultraviolet light is converted into blue light for plant photosynthesis.

[0199] from Figures 24-26 As can be seen, after 120 days, the luminescence intensity of the light-converting films BF-PMMA, BF2-PMMA and BF4-PMMA still remained above 85%, indicating that the light-converting films BF-PMMA, BF2-PMMA and BF4-PMMA all have good weather resistance.

[0200] The preferred embodiments of this application have been described in detail above; however, this application is not limited thereto. Within the scope of the technical concept of this application, various simple modifications can be made to the technical solution of this application, including combining various technical features in any other suitable manner. These simple modifications and combinations should also be considered as the content disclosed in this application and are all within the protection scope of this application.

Claims

1. A light-converting agent comprising the compound shown in Formula I, In Formula I, Ar1, Ar2, Ar3, and Ar4 may be the same or different, each independently selected from phenyl, and optionally phenyl substituted with a substituent selected from C1-C6 alkyl, C1-C6 alkoxy, halogen, hydroxyl, amino, amino substituted by C1-C6 alkyl, or cyano. R1 to R 11 Whether the groups are the same or different, they are each independently selected from hydrogen, deuterium, C1-C6 alkyl, C1-C6 alkoxy, halogen, hydroxyl, amino, C1-C6 alkyl-substituted amino, and cyano. in, The C1-C6 alkyl and C1-C6 alkoxy groups can be substituted with substituents selected from halogens, hydroxyl groups, amino groups, and cyano groups.

2. The light-converting agent according to claim 1, characterized in that, Ar1, Ar2, Ar3, and Ar4 are selected from C1-C6 alkyl-substituted phenyl groups; Preferably, Ar1, Ar2, Ar3, and Ar4 are selected from the structure shown in Formula II. In Equation II, R a R b and R c Whether the same or different, each is selected from C1-C6 alkyl groups, preferably methyl or ethyl.

3. The light-converting agent according to claim 1 or 2, characterized in that, R1 to R 11 Whether the elements are the same or different, they are each independently selected from hydrogen, deuterium, C1-C6 alkyl groups, and halogens; Preferably, R4 to R 11 Whether the elements are the same or different, each element is independently selected from hydrogen, deuterium, and C1-C4 alkyl groups, with hydrogen being preferred; Preferably, R1 to R3 are the same or different, and each is independently selected from hydrogen, deuterium, C1-C6 alkyl, halogen, preferably from hydrogen or halogen, and preferably the halogen is fluorine.

4. The light-converting agent according to any one of claims 1-3, characterized in that, The light conversion agent includes the following compounds: Among them, Mes is 5. The compound shown in Formula III, R1 to R 11 Whether the groups are the same or different, they are each independently selected from hydrogen, deuterium, C1-C6 alkyl, C1-C6 alkoxy, halogen, hydroxyl, amino, C1-C6 alkyl-substituted amino, and cyano. Preferably, R4 to R 11 Whether the elements are the same or different, each element is independently selected from hydrogen, deuterium, and C1-C4 alkyl groups, with hydrogen being preferred; Preferably, R1 to R3 may be the same or different, and each is independently selected from hydrogen, deuterium, C1-C6 alkyl groups, or halogens, preferably from hydrogen or halogens, and preferably the halogen is fluorine. Preferably, the compound represented by Formula III is selected from: Preferably, the compound represented by Formula III is selected from:

6. A method for preparing the compound of formula III according to claim 5, comprising the following steps: S1: The compound shown in Formula 1 undergoes a first reaction with the compounds shown in Formula II-1 and Formula II-2 to obtain the compound shown in Formula III. R1 to R 11 The definition is the same as that in Equation I; Preferably, the ratio of the molar content of the compound shown in Formula 1 to the total molar content of the compounds shown in Formula II-1 and Formula II-2 is 1:(2-3); And / or the first reaction is carried out in a mixed solvent of tetrahydrofuran and water; And / or the first reaction is carried out under heating conditions, with a heating temperature of 50℃-100℃; And / or the time for the first reaction is 12h-60h; And / or the first reaction is carried out in the presence of a base and a catalyst, preferably the base being selected from potassium carbonate and the catalyst being selected from tetra(triphenylphosphine)palladium.

7. A method for preparing the compound of formula I according to claim 1, comprising the following steps: S2: The compound shown in Formula III undergoes a second reaction with the compounds shown in Formula IV-1 and IV-2 to obtain the compound shown in Formula I. Among them, Ar1, Ar2, Ar3, Ar4, R1 to R 11 The definition is the same as that in Equation I; Preferably, the molar content of the compound represented by Formula III is in the ratio of the total molar content of the compounds represented by Formulas IV-1 and IV-2 to 1:(2-3); and / or The temperature of the second reaction is 5℃-35℃; and / or The second reaction takes 1-20 hours; and / or The solvent for the second reaction is tetrahydrofuran; and / or The second reaction is carried out in the presence of n-butyllithium or tert-butyllithium.

8. A light-converting agent composition comprising the light-converting agent according to any one of claims 1-4 or the compound of formula I prepared by the preparation method according to claim 7 and a matrix resin; Preferably, the light-converting agent or the compound represented by Formula I is 0.1%-10% of the mass of the matrix resin; Preferably, the matrix resin is selected from one or more of polymethyl methacrylate, polyethylene, polyvinyl chloride, and polypropylene.

9. A light-converting film comprising the light-converting agent according to any one of claims 1-4 or the compound of formula I prepared by the preparation method according to claim 7 and a base film; Preferably, the light-converting agent or the compound represented by Formula I is 0.1%-10% of the base film; Preferably, the raw material of the base film is selected from one or more of polymethyl methacrylate, polyethylene, polyvinyl chloride, and polypropylene.

10. The use of the light-converting agent according to any one of claims 1-4, or the compound of formula I prepared by the preparation method according to claim 7, or the light-converting agent composition according to claim 8, or the light-converting film according to claim 9, in agricultural light conversion films.

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