A naphthalimide compound and a preparation method and application thereof

Abstract

The application provides a naphthalimide compound and a preparation method and application thereof, and belongs to the technical field of organic compounds. The application takes N-(4-tert-butylphenyl) naphthalimide as an acceptor unit (A group), takes 9,9-dimethylacridine, 9,9-diphenylacridine, phenoxazine, phenothiazine, 7H-benzo[c]carbazole or 9H-dibenzo[a,c]carbazole as an electron donor unit (D group), and the donor unit and the acceptor unit are connected through the ortho position or the meta position of a benzene bridge or a derivative thereof; 3 The formation of the CT state depends on the CT interaction between the D group and the A group, the benzene bridge unit is used for controlling the distance and the dihedral angle between the D unit and the A unit by selecting a specific D group, so that the CT state lifetime is controlled, and the CT state energy is fine-tuned through the substituents on the benzene bridge unit, so that the naphthalimide compound has a long charge transfer triplet state lifetime in a single molecule state. 3 The formation of the CT state depends on the CT interaction between the D group and the A group, the benzene bridge unit is used for controlling the distance and the dihedral angle between the D unit and the A unit by selecting a specific D group, so that the CT state lifetime is controlled, and the CT state energy is fine-tuned through the substituents on the benzene bridge unit, so that the naphthalimide compound has a long charge transfer triplet state lifetime in a single molecule state. 3 The formation of the CT state depends on the CT interaction between the D group and the A group, the benzene bridge unit is used for controlling the distance and the dihedral angle between the D unit and the A unit by selecting a specific D group, so that the CT state lifetime is controlled, and the CT state energy is fine-tuned through the substituents on the benzene bridge unit, so that the naphthalimide compound has a long charge transfer triplet state lifetime in a single molecule state.

Description

Technical Field

[0001] This invention belongs to the field of organic compound technology, specifically relating to a naphthalimide compound, its preparation method, and its application. Background Technology

[0002] Organic room temperature phosphorescence (ORTP) compounds can achieve afterglow emission of single organic compounds. Due to the spin-forbidden nature of their phosphorescence emission process, their triplet state lifetimes can reach milliseconds or even seconds, thus providing afterglow emission capability. Based on the transition properties between the molecular triplet state and the ground state, phosphorescence emission can generally be divided into local excited states (Triplet Local Excited State). 3 LE) and Triplet Charge Transfer State 3 There are two types: CT and CT. Currently, the phosphorescence emission of the vast majority of ORTP materials belongs to... 3 LE transition properties. The LE state is essentially a tightly bound electron-hole pair. Its highly localized nature implies a strong Coulomb interaction between electrons and holes, resulting in a high exciton binding energy (0.5–1.0 eV), making charge separation difficult. In contrast, the CT-type excited state has holes / electrons distributed separately on the D / A units, leading to a lower exciton binding energy (0.1–0.5 eV), making electron transfer more likely than in the LE state. Furthermore, compared to the LE process, the CT process can participate in unique reactions. For example, key steps in photosynthesis in chloroplasts rely on the CT state between the cell membrane and protein assemblies to obtain the potential difference required for electrochemical reactions. In organic photovoltaic devices, CT states also need to be formed at the interface of D and A materials to generate current. Therefore, it has a long lifetime. 3 Room-temperature phosphorescent materials with CT properties have greater advantages in improving photocatalytic reaction efficiency, promoting artificial photosynthesis, and enhancing the performance of photovoltaic materials. However, existing... 3 CT-ORTP material lifespan is much shorter than 3 LE-ORTP material. Therefore, it is necessary to improve... 3 Improving the lifespan of CT-ORTP materials, thereby expanding their applications, has become a pressing technical challenge in this field. Summary of the Invention

[0003] The purpose of this invention is to provide a naphthalene imide compound, its preparation method, and its application. The naphthalene imide compound provided by this invention has long... 3CT lifetime, can be used as organic photoinitiator, and can emit room temperature phosphorescence, so the photopolymerization initiated by the photopolymerization initiator can emit fluorescence under the condition of dark field ultraviolet light irradiation, and after the violet light is turned off, there is a long afterglow, so that the fine pattern of the coating can be clearly, completely and quickly evaluated, thereby being applied to photoresist, three-dimensional printing and other fields, and having important significance for expanding the application field of photopolymerization technology; meanwhile, the compound can also be used as an afterglow material in the field of anti-counterfeiting.

[0004] In order to achieve the above-mentioned purpose of the application, the application provides the following technical solutions.

[0005] The application provides a naphthalimide compound having a chemical structure shown in formula I.

[0006]

[0007] In formula I, R is

[0008] R1, R2, R3 and R4 are independently hydrogen, halogen, cyano, alkoxy, unsubstituted C1-20 straight chain alkyl, substituted C1-20 straight chain alkyl, unsubstituted C1-20 branched alkyl or substituted C1-20 branched alkyl;

[0009] D has any one of the following structures.

[0010]

[0011] Preferably, R1, R2, R3 and R4 are independently any one of hydrogen, fluorine, cyano, methoxy, methyl and isopropyl.

[0012] Preferably, the naphthalimide compound has any one of the following structures.

[0013]

[0014]

[0015] The application further provides a preparation method of the naphthalimide compound.

[0016] Compound 1, compound 2, a palladium catalyst, an acid binding agent and a polar solvent are mixed to perform a nucleophilic substitution reaction, so as to obtain the naphthalimide compound.

[0017] The compound 1 has a chemical structure shown in formula II.

[0018]

[0019] The chemical structure of the compound 2 is

[0020] Preferably, the preparation method of the compound 1 comprises the following steps:

[0021] (1) mixing 4-bromo-1,8-naphthalic anhydride, 4-tert-butylaniline and an organic solvent to perform a first nucleophilic substitution reaction to obtain a compound 3; the chemical structure of the compound 3 is

[0022] (2) mixing the compound 3 obtained in the step (1), pinacol diboronic acid, an organic palladium catalyst, an acid binding agent and an organic solvent to perform a second nucleophilic substitution reaction to obtain the compound 1.

[0023] Preferably, the preparation method of the compound 2 comprises the following steps:

[0024] mixing the compound 4, the compound D, an organic palladium catalyst, an acid binding agent and an organic solvent to perform a nucleophilic substitution reaction, and then performing a post-treatment to obtain the compound 2;

[0025] the compound 4 has the following structural formula

[0026] the compound D is any one of compounds D1 to D6:

[0027]

[0028] The application further provides application of the naphthalimide compound in the technical solution or the naphthalimide compound prepared by the preparation method in the technical solution as an organic photoinitiator.

[0029] The application further provides application of the naphthalimide compound in the technical solution or the naphthalimide compound prepared by the preparation method in the technical solution as a residual glow material.

[0030] The application further provides a photocuring material, raw materials of which include a prepolymerized photosensitive resin, an active monomer, an organic photoinitiator and a solvent, and the organic photoinitiator is the naphthalimide compound in the technical solution or the naphthalimide compound prepared by the preparation method in the technical solution.

[0031] Preferably, the prepolymerized photosensitive resin is a resin with a vinyl group; and the active monomer is a monomer with a vinyl group.

[0032] This invention provides a naphthalene imide compound having the chemical structure shown in Formula I. The naphthalene imide compound provided by this invention uses N-(4-tert-butylphenyl)naphthalene imide as the acceptor unit (A group) and 9,9-dimethylacridinium, 9,9-diphenylacridinium, phenoxazine, phenothiazine, 7H-benzo[c]carbazole, or 9H-dibenzo[a,c]carbazole as the electron donor unit (D group). The donor and acceptor units are connected by a benzene bridge or its derivatives at the ortho or meta position. 3 The formation of the CT state depends on the CT interaction between the D group and the A group, and can be modulated by replacing the D group or the A group. 3 The energy of the CT state can be controlled by selecting specific D groups; the benzene bridging unit is used to control the distance and dihedral angle between the D and A units, thereby achieving control over the CT state. 3 The regulation of CT state lifetime is achieved through substituents on the benzene-bridged unit. 3 Fine-tuning of the CT state energy enables naphthalimide compounds to possess a long charge-transfer triplet lifetime in the single-molecule state. The naphthalimide compounds provided by this invention can be used as single-component photoinitiators for photopolymerization. These compounds exhibit fluorescence properties; as photocuring agents, their molecular framework remains intact after photoinitiation, resulting in a cured layer that fluoresces under dark-field ultraviolet irradiation, allowing for clear, complete, and rapid evaluation of the coating's fine patterns. Simultaneously, they possess room-temperature phosphorescence properties; the cured layer emits room-temperature phosphorescence after a certain period of dark-field ultraviolet irradiation, with a long afterglow time, enabling clear, complete, and rapid evaluation of the coating's fine patterns. As raw materials for luminescent materials (fluorescence or phosphorescence), the naphthalimide compounds provided by this invention can form a pure organic system without causing metal contamination, thus making them suitable for applications such as photoresists where strict control of metal ions is required. Experimental results show that the naphthalimide compounds A1 and A3 provided in this invention, under vacuum conditions, have fluorescence lifetimes of only about 20 ns in their 1.5 wt% PMMA-doped films (19.2 ns and 27.6 ns, respectively), while the lifetimes of long-lived excited species are 152 ms and 217 ms, respectively. The cured coating prepared with naphthalimide compound A3 is colorless and transparent under natural light, with no visible abnormalities. It fluoresces under dark-field ultraviolet light, allowing for clear observation of the pattern. After the ultraviolet light is turned off after 5 seconds of irradiation, the coating emits room-temperature phosphorescence with an afterglow time of 4 seconds. Attached Figure Description

[0033] Figure 1 The photoluminescence decay curve of naphthalimide compound A1 prepared in Example 1;

[0034] Figure 2 The photoluminescence decay curve of the naphthalene imide compound A3 prepared in Example 3 is shown.

[0035] Figure 3 Phosphorescence spectra of naphthalimide compound A1 prepared for Example 1 in PS and PMMA;

[0036] Figure 4 Phosphorescence spectra of naphthalimide compound A3 prepared for Example 3 in PS and PMMA;

[0037] Figure 5 Pattern of photocured coating prepared from naphthalimide compound A3 prepared for Example 1 under sunlight;

[0038] Figure 6 Pattern of photocured coating prepared from naphthalimide compound A3 prepared for Example 1 under UV light;

[0039] Figure 7 Afterglow pattern of photocured coating prepared from naphthalimide compound A3 prepared for Example 1 after UV light irradiation for 5s and then turned off. DETAILED DESCRIPTION

[0040] The present application provides a naphthalimide compound having a chemical structure shown in Formula I:

[0041]

[0042] In the present application, the R is

[0043] In the present application, the R preferably has any one of the following structures:

[0044]

[0045] In the present application, the R1, R2, R3and R4are independently hydrogen, halogen, cyano, alkoxy, unsubstituted C1-20 straight chain alkyl, substituted C1-20 straight chain alkyl, unsubstituted C1-20 branched alkyl or substituted C1-20 branched alkyl; and the D has any one of the following structures:

[0046]

[0047] As an embodiment, the R1, R2, R3and R4may be independently any one of hydrogen, fluorine, cyano, methoxy, methyl and isopropyl.

[0048] In the present application, the naphthalimide compound has any one of the following structures:

[0049]

[0050]

[0051] The naphthalene imide compounds provided by this invention use N-(4-tert-butylphenyl)naphthalene imide as the acceptor unit (A group) and 9,9-dimethylacridinium, 9,9-diphenylacridinium, phenoxazine, phenothiazine, 7H-benzo[c]carbazole, or 9H-dibenzo[a,c]carbazole as the electron donor unit (D group). The donor and acceptor units are connected by a benzene bridge or its derivatives at the ortho or meta position. 3 The formation of the CT state depends on the CT interaction between the D group and the A group, and can be modulated by replacing the D group or the A group. 3 The energy of the CT state can be controlled by selecting specific D groups; the benzene bridging unit is used to control the distance and dihedral angle between the D and A units, thereby achieving control over the CT state. 3 The regulation of CT state lifetime is achieved through substituents on the benzene-bridged unit. 3 Fine-tuning of the CT state energy enables naphthalimide compounds to possess a long charge-transfer triplet lifetime in the single-molecule state. The naphthalimide compounds provided by this invention can be used as single-component photoinitiators for photopolymerization. These compounds exhibit fluorescence properties; as photocuring agents, their molecular framework remains intact after photoinitiation, resulting in a cured layer that fluoresces under dark-field ultraviolet irradiation, allowing for clear, complete, and rapid evaluation of the coating's fine patterns. Simultaneously, they possess room-temperature phosphorescence properties; the cured layer emits room-temperature phosphorescence after a certain period of dark-field ultraviolet irradiation, with a long afterglow time, enabling clear, complete, and rapid evaluation of the coating's fine patterns. As raw materials for luminescent materials (fluorescence or phosphorescence), the naphthalimide compounds provided by this invention can form a pure organic system without causing metal contamination, thus making them suitable for applications such as photoresists where strict control of metal ions is required.

[0052] The naphthalimide compounds provided by this invention possess a long charge-transfer triplet lifetime, and their triplet excitons can be used to initiate photopolymerization. Therefore, these compounds can be used as single-component photoinitiators added to ordinary photocuring systems. The added system can effectively initiate photocuring under an LED light source, forming a pure organic photocurable coating that emits light under ultraviolet illumination and exhibits afterglow properties after the light is turned off. Furthermore, naphthalimide compounds can also be directly added to coatings to form afterglow coatings in pure organic systems. These compounds have wide applications, including but not limited to photoresists, 3D printing, and anti-counterfeiting fields.

[0053] Among the naphthalimide compounds provided by this invention, A1, A3, A5, A7, A9, A11, A13, A15, A17, A19, A21, and A23 have longer lifespans than other naphthalimide compounds.

[0054] This invention also provides a method for preparing the naphthalimide compounds described in the above technical solution, comprising the following steps:

[0055] Compound 1, Compound 2, palladium catalyst, acid-binding agent, and polar solvent were mixed and subjected to a nucleophilic substitution reaction to obtain naphthalimide compounds.

[0056] This invention does not impose any special restrictions on the source of the raw materials; commercially available products familiar to those skilled in the art can be used.

[0057] In this invention, compound 1 has the chemical structure shown in Formula II:

[0058]

[0059] In this invention, the preparation method of compound 1 preferably includes the following steps:

[0060] (1) 4-bromo-1,8-naphthalenedicarboxylic anhydride, 4-tert-butylaniline and organic solvent were mixed and subjected to a first nucleophilic substitution reaction to obtain compound 3;

[0061] (2) The compound 3 obtained in step (1), pinacol diboronic acid ester, organopalladium catalyst, acid-binding agent and organic solvent are mixed and subjected to a second nucleophilic substitution reaction to obtain compound 1.

[0062] In this invention, 4-bromo-1,8-naphthalenedicarboxylic anhydride, 4-tert-butylaniline and an organic solvent are mixed to carry out a first nucleophilic substitution reaction to obtain compound 3.

[0063] In this invention, the preferred molar ratio of 4-bromo-1,8-naphthoic anhydride to 4-tert-butylaniline is (1-2.25):(2-7).

[0064] In one embodiment, the molar ratio of 4-bromo-1,8-naphthoic anhydride and 4-tert-butylaniline can be (1.4-2.0):(2.5-3.5), or it can be 1.45:2.88.

[0065] In this invention, the organic solvent is preferably one or more selected from N-methylpyrrolidone, dimethylformamide, dimethylacetamide, dimethyl sulfoxide, hexamethylphosphoramide, sulfolane, acetonitrile, ethanol, and benzonitrile, more preferably ethanol. This invention does not have special requirements on the amount of the organic solvent used, as long as the first nucleophilic substitution reaction proceeds smoothly.

[0066] The present invention does not have any special limitations on the operation of mixing the 4-bromo-1,8-naphthalenedicarboxylic anhydride, 4-tert-butylaniline and organic solvent, and any technical solution for preparing the mixture can be prepared by means of operations well known to those skilled in the art.

[0067] In this invention, the temperature of the first nucleophilic substitution reaction is preferably 80–140°C, more preferably 80–120°C, and most preferably 80–100°C; the holding time of the first nucleophilic substitution reaction is preferably 12–24 h, more preferably 16–24 h, and even more preferably 20–24 h; the first nucleophilic substitution reaction is preferably carried out under magnetic stirring. This invention does not impose any special limitations on the operation of the magnetic stirring; any operation well-known to those skilled in the art can be used.

[0068] After the first nucleophilic substitution reaction is completed, the product obtained from the first nucleophilic substitution reaction is preferably post-processed to obtain compound 3. This post-processing method allows for the purification of compound 3.

[0069] In this invention, the post-processing preferably includes cooling, solid-liquid separation and washing performed sequentially.

[0070] The present invention does not impose any special limitations on the cooling operation; cooling to room temperature is sufficient.

[0071] In this invention, the solid-liquid separation is preferably performed by pressure filtration. The operation of the pressure filtration is not particularly limited in this invention; any operation well-known to those skilled in the art can be used.

[0072] In this invention, the washing agent used is preferably ethanol. The washing procedure is not particularly limited in this invention; it can be performed until the filtrate is colorless.

[0073] In this invention, the chemical structure of compound 3 is preferably...

[0074] After obtaining compound 3, the present invention preferably mixes compound 3, pinacol diboronic acid ester, organopalladium catalyst, acid-binding agent and organic solvent to carry out a second nucleophilic substitution reaction to obtain compound 1.

[0075] In this invention, the organopalladium catalyst is preferably [1,1'-bis(diphenylphosphino)ferrocene]palladium dichloride.

[0076] In this invention, the acid-binding agent is preferably potassium carbonate or potassium acetate.

[0077] In this invention, the organic solvent is preferably one or more of benzene, toluene, xylene, chlorobenzene, dichlorobenzene, tetrahydrofuran, 1,4-dioxane, N-methylpyrrolidone, dimethylformamide, dimethylacetamide, dimethyl sulfoxide, hexamethylphosphoramide, sulfolane, acetonitrile, and benzonitrile, more preferably 1,4-dioxane.

[0078] In this invention, the preferred molar ratio of compound 3 to pinacol diboronate is (4.24-10):(5.08-12); the preferred molar ratio of compound 3 to organopalladium catalyst is (4.24-10):(0.2-0.5); and the preferred molar ratio of compound 3 to acid-binding agent is (4.24-10):(12.7-30).

[0079] In one embodiment, the molar ratio of compound 3 to pinacol diboronic acid ester can be (4.24-5):(10-12), or 4.41:11.034; the molar ratio of compound 3 to organopalladium catalyst can be (4.24-5):(0.2-0.3), or 4.9:0.24; the molar ratio of compound 3 to acid-binding agent can be (4.5-5):(13-15), or 4.9:14.7.

[0080] The present invention does not have special requirements on the amount of the organic solvent used, as long as the second nucleophilic substitution reaction proceeds smoothly.

[0081] The present invention does not have any special limitations on the operation of mixing compound 3, pinacol diboronate, organopalladium catalyst, acid-binding agent and organic solvent. Any technical solution for preparing the mixture can be prepared by means of operations well known to those skilled in the art.

[0082] In this invention, the temperature of the second nucleophilic substitution reaction is preferably 90–110°C, more preferably 95–105°C, and most preferably 100°C; the time of the second nucleophilic substitution reaction is preferably 6–12 h, more preferably 6–10 h, and most preferably 6–8 h; the second nucleophilic substitution reaction is preferably carried out in a protective gas atmosphere; the protective gas is preferably argon or nitrogen; the second nucleophilic substitution reaction is preferably carried out under magnetic stirring. This invention does not impose any special limitations on the operation of the magnetic stirring; any operation well known to those skilled in the art can be used.

[0083] After the second nucleophilic substitution reaction is completed, the product obtained from the second nucleophilic substitution reaction is preferably post-processed to obtain compound 1. This post-processing method allows for the purification of compound 1.

[0084] In this invention, the post-processing preferably includes sequential cooling, solid-liquid separation, water washing, extraction, drying, vacuum rotary evaporation, and column chromatography purification.

[0085] The present invention does not impose any special limitations on the cooling operation; cooling to room temperature is sufficient.

[0086] In this invention, the solid-liquid separation is preferably performed by pressure filtration. This invention does not impose any particular limitations on the operation of the pressure filtration; any operation well-known to those skilled in the art can be used.

[0087] The present invention does not impose any special limitations on the water washing operation; any operation well known to those skilled in the art can be used. The water washing method used in this invention can effectively remove the added salt.

[0088] In this invention, the extractant used for extraction is preferably dichloromethane; and the number of extractions is preferably three.

[0089] In this invention, the reagent used for drying is preferably anhydrous sodium sulfate. There is no particular limitation on the amount of anhydrous sodium sulfate used; it can be determined based on common sense.

[0090] The present invention does not impose any special limitations on the operation of the reduced pressure rotary evaporation; any operation known to those skilled in the art can be used.

[0091] In this invention, the eluent used for column chromatography purification is preferably a mixed solvent of petroleum ether (PE) and dichloromethane (DCM), and the volume ratio of PE to DCM is preferably (1-5):1.

[0092] In one implementation, the volume ratio of PE to DCM can be (1-2):1.

[0093] In this invention, the chemical structure of compound 2 is preferably...

[0094] In this invention, R1, R2, R3, and R4 are independently preferably hydrogen, halogen, cyano, alkoxy, unsubstituted C1-20 straight-chain alkyl, substituted C1-20 straight-chain alkyl, unsubstituted C1-20 branched alkyl, or substituted C1-20 branched alkyl; and D preferably has any one of the following structures:

[0095]

[0096] In one embodiment, R1, R2, R3 and R4 can independently be any one of hydrogen, fluorine, cyano, methoxy, methyl and isopropyl.

[0097] In this invention, compound 2 is preferably any one of the following structures:

[0098]

[0099]

[0100] In this invention, the preparation method of compound 2 preferably includes the following steps:

[0101] Compound 4, compound D, an organopalladium catalyst, an acid-binding agent, and an organic solvent were mixed and subjected to a nucleophilic substitution reaction, followed by post-treatment to obtain compound 2.

[0102] In this invention, the preferred structural formula of compound 4 is... R1, R2, R3 and R4 are independently preferably hydrogen, halogen, cyano, alkoxy, unsubstituted C1-20 straight-chain alkyl, substituted C1-20 straight-chain alkyl, unsubstituted C1-20 branched alkyl or substituted C1-20 branched alkyl.

[0103] In one embodiment, R1, R2, R3 and R4 can independently be any one of hydrogen, fluorine, cyano, methoxy, methyl and isopropyl.

[0104] In this invention, compound D is preferably any one of compounds D1 to D6:

[0105]

[0106] In this invention, the organic palladium catalyst is preferably tetra(triphenylphosphine)palladium or [1,1'-bis(diphenylphosphine)ferrocene]palladium dichloride.

[0107] In this invention, the acid-binding agent is preferably potassium carbonate, potassium acetate, or potassium tert-butoxide.

[0108] In this invention, the organic solvent is preferably one or more of benzene, toluene, xylene, chlorobenzene, dichlorobenzene, tetrahydrofuran, 1,4-dioxane, N-methylpyrrolidone, dimethylformamide, dimethylacetamide, dimethyl sulfoxide, hexamethylphosphoramide, sulfolane, acetonitrile, and benzonitrile, more preferably toluene.

[0109] In this invention, the preferred molar ratio of compound D to compound 4 is (5.15–10.98):(5.49–16.86).

[0110] In one embodiment, the molar ratio of compound D to compound 4 can be (6-8):(8-12), or it can be 6:9.

[0111] In this invention, the preferred molar ratio of compound D to the organopalladium catalyst is (5.15–10.98):(0.1–0.5).

[0112] In one embodiment, the molar ratio of compound D to the organopalladium catalyst can be (10-10.98):(0.1-0.2), or it can be 10:0.2.

[0113] In this invention, the preferred molar ratio of compound D to the acid-binding agent is (5.15–10.98):(5.49–43.92).

[0114] In one embodiment, the molar ratio of compound D to the acid-binding agent can be (5.15-6):(5.49-6.5), or it can be 5.15:6.18.

[0115] The present invention does not have special requirements on the amount of the organic solvent used, as long as the nucleophilic substitution reaction proceeds smoothly.

[0116] In this invention, the temperature of the nucleophilic substitution reaction is preferably 80–110°C; the time of the nucleophilic substitution reaction is preferably 6–24 hours; the nucleophilic substitution reaction is preferably carried out in a protective gas atmosphere; the protective gas is preferably argon or nitrogen; the nucleophilic substitution reaction is preferably carried out under magnetic stirring. This invention does not impose any special limitations on the operation of the magnetic stirring; any operation well known to those skilled in the art can be used.

[0117] In one embodiment, the temperature of the nucleophilic substitution reaction can be 100–110°C; the time of the nucleophilic substitution reaction can be 8–12 h.

[0118] In this invention, the post-processing preferably includes sequential cooling, water washing, extraction, drying, vacuum rotary evaporation, and column chromatography purification.

[0119] The present invention does not impose any special limitations on the cooling operation; cooling to room temperature is sufficient.

[0120] The present invention does not impose any special limitations on the water washing operation; any operation known to those skilled in the art can be used.

[0121] In this invention, the extractant used for extraction is preferably dichloromethane; and the number of extractions is preferably three.

[0122] In this invention, the reagent used for drying is preferably anhydrous sodium sulfate. There is no particular limitation on the amount of anhydrous sodium sulfate used; it can be determined based on common sense.

[0123] The present invention does not impose any special limitations on the operation of the reduced pressure rotary evaporation; any operation known to those skilled in the art can be used.

[0124] In this invention, the eluent used for column chromatography purification is preferably petroleum ether. This invention does not impose any special limitation on the amount of eluent used; it can be determined based on common sense.

[0125] In this invention, the palladium catalyst is preferably tetra(triphenylphosphine)palladium.

[0126] In this invention, the acid-binding agent is preferably cesium carbonate or potassium carbonate.

[0127] In this invention, the polar solvent is preferably a mixed solution of an organic solvent and water; the organic solvent preferably includes one or more of benzene, toluene, xylene, chlorobenzene, dichlorobenzene, tetrahydrofuran, 1,4-dioxane, N-methylpyrrolidone, dimethylformamide, dimethylacetamide, dimethyl sulfoxide, hexamethylphosphoramide, sulfolane, acetonitrile, and benzonitrile, more preferably toluene; the volume ratio of the first organic solvent to water is preferably 2:1.

[0128] In this invention, the preferred molar ratio of compound 1 to compound 2 is (10.66-11.34):(3.53-7.57); the preferred molar ratio of compound 1 to palladium catalyst is (3.53-3.77):(0.09-0.19); and the preferred molar ratio of compound 1 to acid-binding agent is (3.53-3.77):(5.29-20.74).

[0129] In one embodiment, the molar ratio of compound 1 to compound 2 can be (10.66–11.00):(7–7.57), or 10.695:7.13; the molar ratio of compound 1 to palladium catalyst can be (3.7–3.77):(0.1–0.15), or 3.72:0.1; the molar ratio of compound 1 to acid-binding agent can be (3.7–3.77):(19–20.5), or 3.72:19.84.

[0130] The present invention does not have special requirements on the amount of the polar solvent used, as long as the nucleophilic substitution reaction proceeds smoothly.

[0131] In this invention, the temperature of the nucleophilic substitution reaction is preferably 100–110°C; the time of the nucleophilic substitution reaction is preferably 12–36 h; the nucleophilic substitution reaction is preferably carried out in a protective gas atmosphere; the protective gas is preferably argon or nitrogen; the nucleophilic substitution reaction is preferably carried out under stirring conditions. This invention does not impose any special limitations on the stirring operation; any operation well-known to those skilled in the art can be used.

[0132] In one embodiment, the temperature of the nucleophilic substitution reaction can be 100–105°C; the time of the nucleophilic substitution reaction can be 12–16 h.

[0133] After the nucleophilic substitution reaction is completed, the present invention preferably performs post-processing on the product obtained by the nucleophilic substitution reaction to obtain a naphthalimide compound.

[0134] In this invention, the post-processing preferably includes sequential cooling, washing, extraction, drying, and purification by rotary evaporation under reduced pressure or column chromatography. This post-processing method improves the purity of naphthalimide compounds.

[0135] The present invention does not impose any special limitations on the cooling operation; cooling to room temperature is sufficient.

[0136] The present invention does not impose any special limitations on the water washing operation; any operation known to those skilled in the art can be used.

[0137] In this invention, the extractant used for extraction is preferably dichloromethane; and the number of extractions is preferably three.

[0138] In this invention, the reagent used for drying is preferably anhydrous sodium sulfate. There is no particular limitation on the amount of anhydrous sodium sulfate used; it can be determined based on common sense.

[0139] The present invention does not impose any special limitations on the operation of the reduced pressure rotary evaporation; any operation known to those skilled in the art can be used.

[0140] In this invention, the eluent used for column chromatography purification is preferably a mixed solvent of petroleum ether (PE) and dichloromethane (DCM), and the volume ratio of PE to DCM is preferably (1-50):1.

[0141] In one implementation, the volume ratio of PE to DCM can be 2:1 or 3:1.

[0142] The preparation method provided by this invention is simple.

[0143] This invention also provides the application of the naphthalimide compounds described in the above technical solutions or the naphthalimide compounds prepared by the above technical solutions as organic photoinitiators.

[0144] The naphthalimide compounds provided by this invention have afterglow properties and can be used as organic photoinitiators.

[0145] The present invention also provides the application of the naphthalimide compounds described in the above technical solutions or the naphthalimide compounds prepared by the preparation methods described in the above technical solutions as afterglow materials.

[0146] The present invention also provides a photocurable material, the raw materials of which include a prepolymerized photosensitive resin, an active monomer, an organic photoinitiator and a solvent, wherein the organic photoinitiator is a naphthalimide compound as described in the above technical solution or a naphthalimide compound prepared by the preparation method described in the above technical solution.

[0147] As one implementation method, the photocurable material can be a photocurable coating.

[0148] In this invention, the prepolymerized photosensitive resin is preferably a resin containing vinyl groups; the prepolymerized photosensitive resin is preferably a copolymer of methacrylate / methacrylic acid / methyl methacrylate; the molar ratio of methacrylate, methacrylic acid, and methyl methacrylate is preferably 50:15:30; the M of the prepolymerized photosensitive resin... w Preferably, it is 70000. In this invention, the prepolymerized photosensitive resin is a matrix resin.

[0149] In this invention, the active monomer is preferably a monomer having a vinyl group; the active monomer is preferably one or more of tripropylene glycol diacrylate (TPGDA), 1,6-hexanediol diacrylate (HDDA), and trimethylolpropane triacrylate (TMPTA).

[0150] In this invention, the organic photoinitiator is preferably one or two of the naphthalimide compounds; when the organic photoinitiator is two of the naphthalimide compounds, the organic photoinitiator is preferably A1 and A9, A3 and A4, A5 and A21, A11 and A16 or A18 and A24.

[0151] In this invention, when the organic photoinitiator is two of the naphthalimide compounds, the mass ratio of the two naphthalimide compounds is preferably 1:1.

[0152] In this invention, the solvent is preferably an organic solvent; the organic solvent is preferably acetone or chloroform. This invention does not have special requirements on the amount of the organic solvent used; it is sufficient to dissolve the raw materials.

[0153] In this invention, the raw materials of the photocurable material preferably include 60-69.999% prepolymerized photosensitive resin, 30% active monomer, and 0.001-10% organic photoinitiator by mass percentage.

[0154] In one embodiment, the raw materials of the photocurable material may be 62-69.995% prepolymerized photosensitive resin, 30% active monomer, and 0.005-8% organic photoinitiator by weight percentage. Alternatively, the raw materials of the photocurable material may preferably include 65-69.99% prepolymerized photosensitive resin, 30% active monomer, and 0.01-5% organic photoinitiator by weight percentage.

[0155] In this invention, the method for preparing the photocurable material preferably includes the following steps:

[0156] 1) Mix the prepolymerized photosensitive resin, reactive monomer, organic photoinitiator and solvent to obtain a mixture;

[0157] 2) Coat the mixture obtained in step 1) onto the surface of a PET template, and then dry it to obtain a dry film;

[0158] 3) The dry film obtained in step 2) is subjected to photocuring, developing, washing, drying and baking in sequence to obtain a photocurable material.

[0159] The present invention preferably involves mixing a prepolymerized photosensitive resin, an active monomer, an organic photoinitiator, and a solvent to obtain a mixture.

[0160] The present invention does not impose any special limitations on the operation of mixing the prepolymerized photosensitive resin, active monomer, organic photoinitiator and solvent, and any technical solution for preparing the mixture well known to those skilled in the art can be used.

[0161] After obtaining the mixture, the present invention preferably coats the mixture onto the surface of a PET template and then dries it to obtain a dry film.

[0162] In this invention, the coating thickness is preferably 200 μm; the drying temperature is preferably 90°C. This invention does not impose any special limitations on the coating operation; any operation well-known to those skilled in the art can be used. This invention does not impose any special limitations on the drying time; complete removal of the solvent is sufficient.

[0163] After obtaining the dry film, the present invention preferably performs photocuring, developing, washing, drying and baking sequentially on the dry film to obtain a photocurable material.

[0164] In this invention, during photocuring, it is preferable to attach a mask to the dry film; the light source for exposure is preferably a 365nm LED surface light source; the power of the 365nm LED surface light source is preferably 100mW; the exposure time is preferably 120-240s; the solvent used for development is preferably an aqueous sodium hydroxide solution; the mass percentage of the aqueous sodium hydroxide solution is preferably 1%; the liquid used for washing is preferably ultrapure water; the drying is preferably air drying; the baking temperature is preferably 220℃, and the baking time is preferably 30min.

[0165] The technical solutions of this invention will be clearly and completely described below with reference to the embodiments thereof. Obviously, the described embodiments are only a part of the embodiments of this invention, and not all of them. All other embodiments obtained by those skilled in the art based on the embodiments of this invention without creative effort are within the scope of protection of this invention.

[0166] Example 1

[0167] The structural formula of naphthalimide compound A1 is:

[0168]

[0169] The preparation method of the naphthimide compound A1 is as follows:

[0170] (1) In a 250 mL three-necked flask, 4-bromo-1,8-naphthalenedicarboxylic anhydride (2.0 g, 7.25 mmol), 4-tert-butylaniline (2.2 g / 3 mL, 14.40 mmol), and ethanol (100 mL) were added. The mixture was heated under reflux at 80 °C for 24 h to carry out a nucleophilic substitution reaction. After the reaction was completed, the mixture was cooled to room temperature and then filtered to obtain a solid crude product. The product was then washed repeatedly with ethanol (25 mL × 5) until the filtrate was colorless to obtain compound 3. The chemical structure of compound 3 is as follows:

[0171] (2) Compound 3 (1.0 g, 2.45 mmol), pinacol diboronate (1.6 g, 6.13 mmol), potassium carbonate (720 mg, 7.35 mmol), [1,1'-bis(diphenylphosphine)ferrocene]palladium dichloride (88 mg, 0.12 mmol), and 1,4-dioxane (15 mL) were added to a 100 mL pressure-resistant branch tube. The nucleophilic substitution reaction was carried out under an argon atmosphere at 100 °C with stirring for 6 h. After the reaction system cooled to room temperature, it was washed with 20 mL of water and extracted with DCM (10 mL × 3). The extracted organic phase was dried over anhydrous sodium sulfate, and the solvent was removed by rotary evaporation under reduced pressure. The mixture was then purified by rapid column chromatography. PE and DCM (V PE V DCM Using a ratio of 2:1 as the eluent, compound 1 is obtained;

[0172] (3) Compound D1 (418 mg, 2.00 mmol), 1-bromo-2-iodobenzene (846 mg / 0.4 mL, 3.00 mmol), tetra(triphenylphosphine)palladium (46 mg, 0.04 mmol), potassium tert-butoxide (269 mg, 2.40 mmol) and anhydrous Tol (10 mL) were added to a 100 mL three-necked flask and stirred at 110 °C under an argon atmosphere for a nucleophilic substitution reaction for 6 h. After the reaction system cooled, it was washed with 20 mL of water and extracted with DCM (10 mL × 3). The organic phase was dried with anhydrous sodium sulfate and the organic solvent was removed by vacuum rotation. Then, rapid column chromatography was performed with petroleum ether as the eluent to obtain compound 2.

[0173] (4) Add compound 2 (450 mg, 1.24 mmol), compound 1 (846 mg, 1.86 mmol), tetrakis(triphenylphosphine)palladium (58 mg, 0.05 mmol), potassium carbonate (1.4 g, 9.92 mmol), and Tol-water mixed solvent (V) to a 100 mL pressure-resistant branch tube. Tol V H2O= 2:1 (total 15 mL), nucleophilic substitution reaction was carried out under argon atmosphere and stirred at 100 °C for 12 h. After the reaction system cooled, it was washed with 20 mL of water and extracted with DCM (10 mL × 3). The extracted organic phase was dried over anhydrous sodium sulfate and the solvent was removed by rotary evaporation under reduced pressure. Then it was purified by rapid column chromatography. PE and DCM (V PE V DCM Using a ratio of 2:1 as the eluent, we obtained a naphthalimide compound A1.

[0174] The characterization data of compound 3 in Example 1 are as follows: 1 H NMR (400MHz, CDCl3) δ8.71(dd,1H),8.64(dd,1H),8.47(d,1H),8.09(d,1H),7.90(td,1H),7.59-7.50(m,2H),7.25-7.22(m,2H),1.38(s,9H).HRMS found: 407.0521;

[0175] The characterization data of compound 1 in Example 1 are as follows: 1 HNMR(400MHz, CDCl3)δ9.17(dd,1H),8.64(dd,1H),8.60(d,1H),8.32(d,1H),7.8 1(td,1H),7.58-7.54(m,2H),7.27-7.23(m,2H),1.38(s,12H),1.26(s,9H).HRMS found: 455.2268;

[0176] The characterization data of the naphthalene imide compound A1 prepared in Example 1 are as follows: 1 HNMR(400MHz, CDCl3)δ8.48(dd,1H),8.33(d,1H),8.03(dd,1H),7.81(td,1H) ,7.71(td,1H),7.65(dd,1H),7.59(dd,1H),7.54-7.50(m,2H),7.46(t,2H),7. 33(d,1H),7.18-7.15(m,3H),7.06(t,1H),6.94(t,1H),6.85(t,1H),6.74(t,1 H),6.44(t,1H),1.69(s,3H),1.36(s,9H),0.36(s,3H).HRMSfound: 613.2854.

[0177] Example 2

[0178] The structural formula of naphthalimide compound A2 is:

[0179]

[0180] The preparation method of the naphthalimide compound A2 is as follows: Based on Example 1, the temperature of the nucleophilic substitution reaction in step (1) is modified to 100℃, and the time is modified to 20h. The step (3) is modified as follows: Modified to With other conditions unchanged, we obtained naphthalimide compound A2.

[0181] The characterization data of the naphthalene imide compound A2 prepared in Example 2 are as follows: 1 H NMR(400MHz, CDCl3)δ8.48(dd,1H),8.36(dd,1H),8.31(d,1H),7.86(d,1H),7.77(t,1H),7.65(dd,1H),7.44(td, 1H),7.34-7.21(m,6H),7.17-7.11(m,1H),7.13-7.08(m,1H),7.11-7.05(m,1H),6.91(dd,2H),1.34(s,9H).HRMS Found: 630.2683.

[0182] Example 3

[0183] The structural formula of naphthalimide compound A3 is:

[0184]

[0185] The preparation method of the naphthalimide compound A3 is as follows:

[0186] (1) Modify the temperature of the nucleophilic substitution reaction in step (1) to 120°C and the time to 16h, while keeping the other conditions the same as in Example 1;

[0187] (2) Same as in Example 1;

[0188] (3) Compound D2 (666 mg, 2.00 mmol), 1-bromo-2-iodobenzene (846 mg / 0.4 mL, 3.00 mmol), [1,1'-bis(diphenylphosphine)ferrocene]palladium dichloride (29 mg, 0.04 mmol), potassium tert-butoxide (269 mg, 2.40 mmol) and anhydrous Tol (10 mL) were added to a 100 mL three-necked flask. The nucleophilic substitution reaction was carried out under an argon atmosphere and at 110 °C for 24 h with stirring. After the reaction system was cooled, it was washed with 20 mL of water and extracted with DCM (10 mL × 3). The organic phase was dried with anhydrous sodium sulfate and the organic solvent was removed by vacuum rotation. The crude product was separated by rapid column chromatography with PE as the eluent to obtain compound 2.

[0189] (4) Add compound 2 (150 mg, 0.34 mmol), compound 1 (222 mg, 0.51 mmol), tetrakis(triphenylphosphine)palladium (12 mg, 0.01 mmol), cesium carbonate (886 mg, 2.72 mmol), and Tol-water mixed solvent (V) to a 100 mL pressure-resistant branch tube. Tol V H2O = 2:1 (6 mL total), nucleophilic substitution reaction was carried out under argon atmosphere and stirred at 100 °C for 36 h. After the reaction system cooled, it was washed with 20 mL of water and extracted with DCM (10 mL × 3). The extracted organic phase was dried over anhydrous sodium sulfate and the organic solvent was removed by vacuum extraction. Then it was purified by column chromatography. PE and DCM (V PE V DCM Using a ratio of 3:1 as the eluent, we obtained a naphthalimide compound A3.

[0190] The characterization data of the naphthalene imide compound A3 prepared in Example 3 are as follows: 1 HNMR(400MHz, CDCl3)δ8.40(dd,1H),7.88(d,1H),7.84-7.80(m,2H),7.70- 7.65(m,2H),7.60(d,2H),7.48(dd,1H),7.36(td,1H),7.30-7.28(m,2H),7. 18-7.15(m,3H),7.12(d,1H),7.04(t,2H),6.90(t,2H),6.78-6.74(m,4H),6 .67-6.63(m,3H),6.56(dd,2H),6.48(d,1H),6.09(d,2H),1.40(s,9H).HRMS Found: 737.3169.

[0191] Example 4

[0192] The structural formula of naphthalimide compound A4 is:

[0193]

[0194] The preparation method of the naphthalimide compound A4 is as follows: Based on Example 3, the temperature of the nucleophilic substitution reaction in step (2) is modified to 90℃, and the time is modified to 12h. The step (3) is modified as follows: Modified to With other conditions unchanged, we obtained naphthalimide compound A4.

[0195] The characterization data of the naphthalene imide compound A4 prepared in Example 4 are as follows: 1HNMR(400MHz, CDCl3)δ8.48(dd,1H),8.37(dd,1H),8.31(d,1H),7.84(d,1H),7.75(t,1H),7.49(d,1H),7.34-7.20(m,9 H),7.10(dd,1H),7.08(dd,1H),7.08-7.02(m,1H),7.05-6.98(m,3H),7.01-6.95(m,3H),2.34(s,3H),1.34(s,9H).HRMS found: 750.3246.

[0196] Example 5

[0197] The structural formula of naphthalimide compound A5 is:

[0198]

[0199] The preparation method of the naphthalimide compound A5 is as follows:

[0200] (1) Same as Example 1;

[0201] (2) Modify the temperature of the nucleophilic substitution reaction in step (2) to 110°C and the time to 10h, and keep the rest the same as in Example 1;

[0202] (3) Compound D3 (1.0 g, 5.46 mmol), 1-bromo-2-iodobenzene (1.9 g / 1.0 mL, 6.55 mmol), [1,1'-bis(diphenylphosphine)ferrocene]palladium dichloride (80 mg, 0.11 mmol), potassium tert-butoxide (734 mg, 6.55 mmol), and anhydrous Tol (15 mL) were added to a 25 mL pressure-resistant branch tube. The nucleophilic substitution reaction was carried out under an argon atmosphere and at 110 °C for 8 h with stirring. After the reaction system was cooled, it was washed with 20 mL of water and extracted with DCM (10 mL × 3). The organic phase was dried with anhydrous sodium sulfate and the organic solvent was removed under reduced pressure. Then, rapid column chromatography was performed with PE as the eluent to obtain compound 2.

[0203] (4) Add compound 2 (660 mg, 1.96 mmol), compound 1 (1.3 g, 2.94 mmol), tetrakis(triphenylphosphine)palladium (92 mg, 0.08 mmol), potassium carbonate (2.2 g, 15.68 mmol), and Tol-water mixed solvent (V) to a 100 mL pressure-resistant branch tube. Tol V H2O= 2:1 (total 15 mL), nucleophilic substitution reaction was carried out under argon atmosphere and stirred at 100 °C for 12 h. After the reaction system cooled, it was washed with 20 mL of water and extracted with DCM (10 mL × 3). The extracted organic phase was dried over anhydrous sodium sulfate and the organic solvent was removed by vacuum extraction. Then it was purified by column chromatography. PE and DCM (V PE V DCM Using a ratio of 2:1 as the eluent, we obtained a naphthalene imide compound A5.

[0204] The characterization data of the naphthalene imide compound A5 prepared in Example 5 are as follows: 1 HNMR(400MHz, CDCl3)δ8.54(dd,1H),8.33(d,1H),8.01(dd,1H),7.78(td,1H),7.67(td,1H ),7.62(d,1H),7.56-7.50(m,4H),7.24-7.21(m,2H),6.51-6.03(m,8H),1.37(s,9H).HRMS found: 587.2329.

[0205] Example 6

[0206] The structural formula of naphthalimide compound A6 is:

[0207]

[0208] The preparation method of the naphthimide compound A6 is as follows: based on Example 5, using... replace With other conditions unchanged, naphthalimide compound A6 was obtained.

[0209] The characterization data of the naphthalene imide compound A6 prepared in Example 6 are as follows: 1 HNMR(400MHz, CDCl3)δ8.48(dd,1H),8.35-8.26(m,2H),7.86(d,1H),7.77(t,1H),7.34-7 .17(m,6H),7.20-7.11(m,4H),6.93(dd,1H),6.86(dd,2H),3.83(s,3H),1.34(s,9H).HRMS Found: 616.2362.

[0210] Example 7

[0211] The structural formula of naphthalimide compound A7 is:

[0212]

[0213] The preparation method of the naphthalimide compound A7 is as follows:

[0214] (1)~(2) are the same as in Example 1;

[0215] (3) Compound D4 (1.0 g, 5.00 mmol), 1-bromo-2-iodobenzene (1.7 g / 0.9 mL, 6.00 mmol), [1,1'-bis(diphenylphosphine)ferrocene]palladium dichloride (73 mg, 0.10 mmol), potassium tert-butoxide (672 mg, 6.00 mmol), and anhydrous Tol (15 mL) were added to a 25 mL pressure-resistant branch tube. The nucleophilic substitution reaction was carried out under an argon atmosphere and at 110 °C for 8 h with stirring. After the reaction system was cooled, it was washed with 20 mL of water and extracted with DCM (10 mL × 3). The organic phase was dried with anhydrous sodium sulfate and the organic solvent was removed under reduced pressure. Then, rapid column chromatography was performed with PE as the eluent to obtain compound 2.

[0216] (4) Add compound 2 (353 mg, 1.00 mmol), compound 1 (500 mg, 1.10 mmol), tetrakis(triphenylphosphine)palladium (17 mg, 0.02 mmol), potassium carbonate (806 mg, 5.84 mmol), and Tol-water mixed solvent (V) to a 100 mL pressure-resistant branch tube. Tol V H2O = 2:1 (total 12 mL), nucleophilic substitution reaction was carried out under argon atmosphere and stirred at 100 °C for 12 h. After the reaction system cooled, it was washed with 20 mL of water and extracted with DCM (10 mL × 3). The extracted organic phase was dried over anhydrous sodium sulfate and the organic solvent was removed by vacuum rotation. Then it was purified by rapid column chromatography. PE and DCM (V PE V DCM Using a ratio of 3:1 as the eluent, we obtained naphthalimide compound A7.

[0217] The characterization data of the naphthalene imide compound A7 prepared in Example 7 are as follows: 1 H NMR(400MHz, CDCl3)δ8.45(dd,1H),8.40(d,1H),7.82-7.73(m,2H),7.71-7.60(m,3H), 7.56-7.54(m,2H),7.29(d,1H),7.24-7.20(m,2H),6.85-6.68(m,8H),1.38(s,9H).HRMS found: 603.2101.

[0218] Example 8

[0219] The structural formula of naphthalimide compound A8 is:

[0220]

[0221] The preparation method of the naphthalimide compound A8 is as follows: based on Example 7, using... replace With other conditions unchanged, naphthalene imide compound A8 was obtained.

[0222] The characterization data of the naphthalene imide compound A8 prepared in Example 8 are as follows: 1 HNMR(400MHz, CDCl3)δ8.48(dd,8.43(dt,1H),8.37(d,1H),7.85-7.75(m,2H), 7.61(dd,1H),7.51(t,1H),7.40-7.23(m,8H),7.18(td,2H),1.34(s,8H).HRMS found: 627.1980.

[0223] Example 9

[0224] The structural formula of naphthalimide compound A9 is:

[0225]

[0226] The preparation method of the naphthalimide compound A9 is as follows:

[0227] (1)~(2) are the same as in Example 1;

[0228] (3) Compound D5 (1.1 g, 5.00 mmol), 1-bromo-2-iodobenzene (1.7 g / 0.9 mL, 6.00 mmol), tetra(triphenylphosphine)palladium (116 mg, 0.10 mmol), potassium acetate (589 mg, 6.00 mmol) and anhydrous Tol (15 mL) were added to a 25 mL pressure-resistant branch tube. The nucleophilic substitution reaction was carried out under an argon atmosphere and at 110 °C for 8 h with stirring. After the reaction system was cooled, it was washed with 20 mL of water and extracted with DCM (10 mL × 3). The organic phase was dried with anhydrous sodium sulfate and the organic solvent was removed under reduced pressure. Then, rapid column chromatography was performed with PE as the eluent to obtain compound 2.

[0229] (4) Add compound 2 (372 mg, 1.00 mmol), compound 1 (500 mg, 1.10 mmol), tetrakis(triphenylphosphine)palladium (17 mg, 0.02 mmol), potassium carbonate (806 mg, 5.84 mmol), and Tol-water mixed solvent (V) to a 100 mL pressure-resistant branch tube. Tol V H2O= 2:1 (total 12 mL), nucleophilic substitution reaction was carried out under argon atmosphere and stirred at 100 °C for 12 h. After the reaction system cooled, it was washed with 20 mL of water and extracted with DCM (10 mL × 3). The extracted organic phase was dried over anhydrous sodium sulfate and the organic solvent was removed by vacuum rotation. Then it was purified by rapid column chromatography. PE and DCM (V PE V DCM Using a ratio of 2:1 as the eluent, we obtained naphthalimide compound A9.

[0230] The characterization data of the naphthalene imide compound A9 prepared in Example 9 are as follows: 1 HNMR(400MHz, CDCl3)δ8.50-8.41(m,2H),8.34(dt,1H),8.29(d,1H),8.18-8.12(m,1H),8.06-7.99(m,1H),7.90-7.82(m,2H),7.79-7 .72(m,2H),7.71-7.66(m,1H),7.57-7.48(m,3H),7.42(dd,1H),7.36-7.28(m,3H),7.27(s,1H),7.28-7.23(m,1H),1.34(s,9H).HRMS Found: 620.2464.

[0231] Example 10

[0232] The structural formula of naphthalimide compound A10 is:

[0233]

[0234] The preparation method of the naphthalimide compound A10 is as follows: based on Example 9, using... replace With other conditions unchanged, naphthalimide compound A10 was obtained.

[0235] The characterization data of the naphthalene imide compound A10 prepared in Example 10 are as follows: 1HNMR(400MHz, CDCl3)δ8.50-8.41(m,2H),8.38-8.33(m,1H),8.30(d,1H), 8.18-8.13(m,1H),8.06-7.99(m,1H),7.87(dd,2H),7.79(dd,1H),7.75(t, 1H),7.71-7.62(m,2H),7.56-7.50(m,2H),7.36-7.23(m,4H),7.18-7.12( m,1H),3.05-2.94(m,1H),1.34(s,9H),1.28(d,6H).HRMSfound: 662.2933.

[0236] Example 11

[0237] The structural formula of naphthalimide compound A11 is:

[0238]

[0239] The preparation method of the naphthalimide compound A11 is as follows:

[0240] (1)~(2) are the same as in Example 1;

[0241] (3) Compound D6 (1.3 g, 5.00 mmol), 1-bromo-2-iodobenzene (1.7 g / 0.9 mL, 6.00 mmol), [1,1'-bis(diphenylphosphine)ferrocene]palladium dichloride (73 mg, 0.10 mmol), potassium tert-butoxide (672 mg, 6.00 mmol) and anhydrous Tol (15 mL) were added to a 25 mL pressure-resistant branch tube. The nucleophilic substitution reaction was carried out under an argon atmosphere and at 110 °C for 8 h with stirring. After the reaction system was cooled, it was washed with 20 mL of water and extracted with DCM (10 mL × 3). The organic phase was dried with anhydrous sodium sulfate and the organic solvent was removed by vacuum rotation. Then, rapid column chromatography was performed with PE as eluent to obtain compound 2.

[0242] (4) Add compound 2 (422 mg, 1.00 mmol), compound 1 (500 mg, 1.10 mmol), tetrakis(triphenylphosphine)palladium (17 mg, 0.02 mmol), potassium carbonate (806 mg, 5.84 mmol), and Tol-water mixed solvent (V) to a 100 mL pressure-resistant branch tube. Tol V H2O= 2:1 (total 12 mL), nucleophilic substitution reaction was carried out under argon atmosphere and stirred at 100 °C for 18 h. After the reaction system cooled, it was washed with 20 mL of water and extracted with DCM (10 mL × 3). The extracted organic phase was dried over anhydrous sodium sulfate and the organic solvent was removed by vacuum rotation. Then it was purified by rapid column chromatography. PE and DCM (V PE V DCM Using a ratio of 3:1 as the eluent, we obtained the naphthalene imide compound A11.

[0243] The characterization data of the naphthalene imide compound A11 prepared in Example 11 are as follows: 1 HNMR(400MHz, CDCl3)δ8.55(dd,1H),8.48(dd,1H),8.34(dt,1H),8.29(d,1H),8.22-8.07(m,3H),7.85 (d,1H),7.82-7.72(m,2H),7.66-7.53(m,3H),7.56-7.40(m,3H),7.36-7.24(m,6H),1.34(s,9H).HRMS found: 670.2620.

[0244] Example 12

[0245] The structural formula of naphthalimide compound A12 is:

[0246]

[0247] The preparation method of the naphthalimide compound A12 is as follows: based on Example 11, using... replace With other conditions unchanged, we obtained the naphthalimide compound A12.

[0248] The characterization data of the naphthalene imide compound A12 prepared in Example 12 are as follows: 1 HNMR(400MHz, CDCl3)δ8.55(dd,1H),8.48(dd,1H),8.38-8.33(m,1H),8.30(d,1H),8.22-8.08(m,3H),7.8 5(d,1H),7.75(t,1H),7.66-7.44(m,5H),7.36-7.21(m,5H),6.92(dd,1H),3.82(s,3H),1.34(s,9H).HRMS found: 700.2726.

[0249] Example 13

[0250] The structural formula of naphthalimide compound A13 is:

[0251]

[0252] The preparation method of the naphthalimide compound A13 is as follows:

[0253] (1)~(2) are the same as in Example 1;

[0254] (3) Compound D1 (1.3 g, 5.00 mmol), 1-bromo-3-iodobenzene (1.7 g / 0.9 mL, 6.00 mmol), [1,1'-bis(diphenylphosphine)ferrocene]palladium dichloride (73 mg, 0.10 mmol), potassium acetate (589 mg, 6.00 mmol), and anhydrous Tol (15 mL) were added to a 25 mL pressure-resistant branch tube. The nucleophilic substitution reaction was carried out under an argon atmosphere and at 110 °C for 18 h with stirring. After the reaction system was cooled, it was washed with 20 mL of water and extracted with DCM (10 mL × 3). The organic phase was dried with anhydrous sodium sulfate and the organic solvent was removed under reduced pressure. Then, rapid column chromatography was performed with PE as the eluent to obtain compound 2.

[0255] (4) Add compound 2 (364 mg, 1.00 mmol), compound 1 (500 mg, 1.10 mmol), tetrakis(triphenylphosphine)palladium (17 mg, 0.02 mmol), potassium carbonate (806 mg, 5.84 mmol), and Tol-water mixed solvent (V) to a 100 mL pressure-resistant branch tube. Tol V H2O = 2:1 (total 12 mL), nucleophilic substitution reaction was carried out under argon atmosphere and stirred at 100 °C for 28 h. After the reaction system cooled, it was washed with 20 mL of water and extracted with DCM (10 mL × 3). The extracted organic phase was dried over anhydrous sodium sulfate and the organic solvent was removed by vacuum extraction. Then it was purified by column chromatography. PE and DCM (V PE V DCM Using a ratio of 3:1 as the eluent, we obtained the naphthalene imide compound A13.

[0256] The characterization data of the naphthalene imide compound A13 prepared in Example 13 are as follows: 1H NMR(400MHz, CDCl3)δ8.47(dd,1H),8.38(dd,1H),8.31(d,1H),7.80-7.73(m,2H),7.48(t,1H),7.42(dd,1H),7.38-7.32(m,1 H),7.34-7.24(m,4H),7.22(dt,1H),7.17-7.11(m,1H),7.13-7.08(m,1H),7.11-7.05(m,1H),6.98(dd,1H),1.34(s,9H).HRMS found: 612.2777.

[0257] Example 14

[0258] The structural formula of naphthalimide compound A14 is:

[0259]

[0260] The preparation method of the naphthalimide compound A14 is as follows: based on Example 13, using... replace With other conditions unchanged, we obtained naphthalimide compound A14.

[0261] The characterization data of the naphthalene imide compound A14 prepared in Example 14 are as follows: 1 HNMR(400MHz, CDCl3)δ8.47(dd,1H),8.42(dt,1H),8.34(d,1H),7.86-7.73(m,3H),7.52(t,1H),7. 34-7.27(m,1H),7.30-7.24(m,3H),7.21(t,1H),7.17-7.05(m,3H),6.98(dd,1H),1.34(s,9H).HRMS found: 637.2729.

[0262] Example 15

[0263] The structural formula of naphthalimide compound A15 is:

[0264]

[0265] The preparation method of the naphthalimide compound A15 is as follows:

[0266] (1)~(2) are the same as in Example 1;

[0267] (3) Compound D2 (666 mg, 2.00 mmol), 1-bromo-3-iodobenzene (846 mg / 0.4 mL, 3.00 mmol), [1,1'-bis(diphenylphosphine)ferrocene]palladium dichloride (29 mg, 0.04 mmol), potassium tert-butoxide (269 mg, 2.40 mmol) and anhydrous Tol (10 mL) were added to a 100 mL three-necked flask. The nucleophilic substitution reaction was carried out under an argon atmosphere and at 110 °C for 24 h with stirring. After the reaction system was cooled, it was washed with 20 mL of water and extracted with DCM (10 mL × 3). The organic phase was dried with anhydrous sodium sulfate and the organic solvent was removed by vacuum rotation. Then, rapid column chromatography was performed with PE as eluent to obtain compound 2.

[0268] (4) Add compound 2 (488 mg, 1.00 mmol), compound 1 (500 mg, 1.10 mmol), tetrakis(triphenylphosphine)palladium (17 mg, 0.02 mmol), potassium carbonate (806 mg, 5.84 mmol), and Tol-water mixed solvent (V) to a 100 mL pressure-resistant branch tube. Tol V H2O = 2:1 (total 12 mL), nucleophilic substitution reaction was carried out under argon atmosphere and stirred at 100 °C for 24 h. After the reaction system cooled, it was washed with 20 mL of water and extracted with DCM (10 mL × 3). The extracted organic phase was dried over anhydrous sodium sulfate and the organic solvent was removed by vacuum extraction. Then it was purified by column chromatography. PE and DCM (V PE V DCM Using a ratio of 3:1 as the eluent, we obtained the naphthalene imide compound A15.

[0269] The characterization data of the naphthalene imide compound A15 prepared in Example 15 are as follows: 1 HNMR(400MHz, CDCl3)δ8.47(dd,1H),8.38(dd,1H),8.31(d,1H),7.80-7.73(m,2H),7.48(t, 1H),7.42(dd,1H),7.38-7.19(m,11H),7.09(dd,1.6Hz,2H),6.99(dd,5H),1.34(s,9H).HRMS found: 736.3090.

[0270] Example 16

[0271] The structural formula of naphthalimide compound A16 is:

[0272]

[0273] The preparation method of the naphthimide compound A16 is as follows: based on Example 15, using... replace With other conditions unchanged, naphthalene imide compound A16 was obtained.

[0274] The characterization data of the naphthalene imide compound A16 prepared in Example 16 are as follows: 1 HNMR(400MHz, CDCl3)δ8.47(dd,1H),8.39(dt,1H),8.32(d,1H),7.80-7.73(m,2H), 7.34-7.19(m,12H),7.09(dd,2H),7.02-6.95(m,5H),2.26(s,2H),1.34(s,9H).HRMS found: 750.3246.

[0275] Example 17

[0276] The structural formula of naphthalimide compound A17 is:

[0277]

[0278] The preparation method of the naphthalimide compound A17 is as follows:

[0279] (1)~(2) are the same as in Example 1;

[0280] (3) Compound D3 (0.92 g, 5.00 mmol), 1-bromo-3-iodobenzene (1.7 g / 0.9 mL, 6.00 mmol), tetrakis(triphenylphosphine)palladium (116 mg, 0.10 mmol), potassium tert-butoxide (672 mg, 6.00 mmol) and anhydrous Tol (15 mL) were added to a 25 mL pressure-resistant branch tube. The nucleophilic substitution reaction was carried out under an argon atmosphere and at 110 °C for 18 h with stirring. After the reaction system cooled, it was washed with 20 mL of water and extracted with DCM (10 mL × 3). The organic phase was dried with anhydrous sodium sulfate and the organic solvent was removed under reduced pressure. Then, rapid column chromatography was performed with PE as the eluent to obtain compound 2.

[0281] (4) Add compound 2 (338 mg, 1.00 mmol), compound 1 (500 mg, 1.10 mmol), tetrakis(triphenylphosphine)palladium (17 mg, 0.02 mmol), potassium carbonate (806 mg, 5.84 mmol), and Tol-water mixed solvent (V) to a 100 mL pressure-resistant branch tube. Tol V H2O= 2:1 (total 12 mL), nucleophilic substitution reaction was carried out under argon atmosphere and stirred at 100 °C for 12 h. After the reaction system cooled, it was washed with 20 mL of water and extracted with DCM (10 mL × 3). The extracted organic phase was dried over anhydrous sodium sulfate and the organic solvent was removed by vacuum extraction. Then it was purified by column chromatography. PE and DCM (V PE V DCM Using a ratio of 3:1 as the eluent, we obtained the naphthalene imide compound A17.

[0282] The characterization data of the naphthalene imide compound A17 prepared in Example 17 are as follows: 1 HNMR(400MHz, CDCl3)δ8.47(dd,1H),8.38(dd,1H),8.31(d,1H),7.80-7.73(m,2H),7. 48-7.39(m,2H),7.38-7.32(m,1H),7.34-7.11(m,9H),6.86(dd,2H),1.34(s,9H).HRMS found: 586.2256.

[0283] Example 18

[0284] The structural formula of naphthalimide compound A18 is:

[0285]

[0286] The preparation method of the naphthimide compound A18 is as follows: based on Example 17, using... replace With other conditions unchanged, naphthalene imide compound A18 was obtained.

[0287] The characterization data of the naphthalene imide compound A18 prepared in Example 18 are as follows: 1 HNMR(400MHz, CDCl3)δ8.48(dd,1H),8.37(dd,1H),8.31(d,1H),7.83(dd,1H), 7.78(t,1H),7.63(dd,1H),7.38-7.10(m,10H),6.86(dd,2H),1.34(s,9H).HRMS found: 604.2162.

[0288] Example 19

[0289] The structural formula of naphthalimide compound A19 is:

[0290]

[0291] The preparation method of the naphthimide compound A19 is as follows:

[0292] (1)~(2) are the same as in Example 1;

[0293] (3) Compound D4 (1.0 g, 5.00 mmol), 1-bromo-3-iodobenzene (1.7 g / 0.9 mL, 6.00 mmol), tetra(triphenylphosphine)palladium (116 mg, 0.10 mmol), tritert-butylphosphine tetrafluoroborate (87 mg, 0.30 mmol), potassium tert-butoxide (672 mg, 6.00 mmol) and anhydrous Tol (15 mL) were added to a 25 mL pressure-resistant branch tube. The nucleophilic substitution reaction was carried out under an argon atmosphere and at 110 °C for 8 h with stirring. After the reaction system was cooled, it was washed with 20 mL of water and extracted with DCM (10 mL × 3). The organic phase was dried with anhydrous sodium sulfate and the organic solvent was removed by vacuum rotation. Then, rapid column chromatography was performed with PE as eluent to obtain compound 2.

[0294] (4) Add compound 2 (353 mg, 1.00 mmol), compound 1 (500 mg, 1.10 mmol), tetrakis(triphenylphosphine)palladium (17 mg, 0.02 mmol), potassium carbonate (806 mg, 5.84 mmol), and Tol-water mixed solvent (V) to a 100 mL pressure-resistant branch tube. Tol V H2O = 2:1 (total 12 mL), nucleophilic substitution reaction was carried out under argon atmosphere and stirred at 100 °C for 36 h. After the reaction system cooled, it was washed with 20 mL of water and extracted with DCM (10 mL × 3). The extracted organic phase was dried over anhydrous sodium sulfate and the organic solvent was removed by vacuum extraction. Then it was purified by column chromatography. PE and DCM (V PE V DCM Using a ratio of 2:1 as the eluent, we obtained naphthalimide compound A19.

[0295] The characterization data of the naphthalene imide compound A19 prepared in Example 19 are as follows: 1 HNMR(400MHz, CDCl3)δ8.47(dd,1H),8.38(dd,1H),8.31(d,1H),7.80-7.73( m,2H),7.48(t,1H),7.45-7.23(m,8H),7.23-7.14(m,2H),1.34(s,9H).HRMS found: 602.2028.

[0296] Example 20

[0297] The structural formula of naphthalimide compound A20 is:

[0298]

[0299] The preparation method of the naphthalimide compound A20 is as follows: based on Example 19, using... replace With other conditions unchanged, naphthalimide compound A20 was obtained.

[0300] The characterization data of the naphthalene imide compound A20 prepared in Example 20 are as follows: 1 H NMR(400MHz, CDCl3)δ8.47(dd,1H),8.38(dt,1H),8.31(d,1H),7.81-7.73(m,2H),7.44(dt,1 H),7.40-7.34(m,2H),7.34-7.23(m,6H),7.22-7.14(m,2H),6.96(dt,1H),1.34(s,9H).HRMS found: 620.1934.

[0301] Example 21

[0302] The structural formula of naphthalimide compound A21 is:

[0303]

[0304] The preparation method of the naphthalimide compound A21 is as follows:

[0305] (1)~(2) are the same as in Example 1;

[0306] (3) Compound D5 (1.1 g, 5.06 mmol), 1-bromo-3-iodobenzene (1.7 g / 0.9 mL, 6.00 mmol), [1,1'-bis(diphenylphosphine)ferrocene]palladium dichloride (73 mg, 0.10 mmol), potassium tert-butoxide (672 mg, 6.00 mmol) and anhydrous Tol (15 mL) were added to a 25 mL pressure-resistant branch tube. The nucleophilic substitution reaction was carried out under an argon atmosphere and at 110 °C for 8 h with stirring. After the reaction system was cooled, it was washed with 20 mL of water and extracted with DCM (10 mL × 3). The organic phase was dried with anhydrous sodium sulfate and the organic solvent was removed under reduced pressure. Then, rapid column chromatography was performed with PE as the eluent to obtain compound 2.

[0307] (4) Add compound 2 (372 mg, 1.00 mmol), compound 1 (500 mg, 1.10 mmol), tetrakis(triphenylphosphine)palladium (17 mg, 0.02 mmol), potassium carbonate (806 mg, 5.84 mmol), and Tol-water mixed solvent (V) to a 100 mL pressure-resistant branch tube. Tol V H2O= 2:1 (total 12 mL), nucleophilic substitution reaction was carried out under argon atmosphere and stirred at 100 °C for 30 h. After the reaction system cooled, it was washed with 20 mL of water and extracted with DCM (10 mL × 3). The extracted organic phase was dried over anhydrous sodium sulfate and the organic solvent was removed by vacuum extraction. Then it was purified by column chromatography. PE and DCM (V PE V DCM Using a ratio of 2:1 as the eluent, we obtained naphthalimide compound A21.

[0308] The characterization data of the naphthalene imide compound A21 prepared in Example 21 are as follows: 1 HNMR(400MHz, CDCl3)δ8.50-8.41(m,2H),8.38(dd,1H),8.32(d,1H),8.17-8.11(m,1H),8.07-7.99(m,1H),8.02( HRMS Found: 620.2464.

[0309] Example 22

[0310] The structural formula of naphthalimide compound A22 is:

[0311]

[0312] The preparation method of the naphthalimide compound A22 is as follows: based on Example 21, using... replace With other conditions unchanged, we obtained naphthalimide compound A22.

[0313] The characterization data of the naphthalene imide compound A22 prepared in Example 22 are as follows: 1 HNMR(400MHz, CDCl3)δ8.50-8.41(m,2H),8.36(dt,1H),8.31(d,1H),8.17-8.11(m,1H),8.07-7.99(m,1H),7.93(d,1H), 7.87-7.73(m,3H),7.71-7.66(m,1H),7.60-7.48(m,2H),7.35-7.23(m,5H),7.08(d,1H),3.91(s,3H),1.34(s,9H).HRMS Found: 650.2569.

[0314] Example 23

[0315] The structural formula of naphthalimide compound A23 is:

[0316]

[0317] The preparation method of the naphthalimide compound A23 is as follows:

[0318] (1)~(2) are the same as in Example 1;

[0319] (3) Compound D6 (535 mg, 2.00 mmol), 1-bromo-3-iodobenzene (846 mg / 0.4 mL, 3.00 mmol), [1,1'-bis(diphenylphosphine)ferrocene]palladium dichloride (29 mg, 0.04 mmol), potassium tert-butoxide (269 mg, 2.40 mmol) and anhydrous Tol (10 mL) were added to a 100 mL three-necked flask. The nucleophilic substitution reaction was carried out under an argon atmosphere and at 110 °C for 6 h with stirring. After the reaction system was cooled, it was washed with 20 mL of water and extracted with DCM (10 mL × 3). The organic phase was dried with anhydrous sodium sulfate and the organic solvent was removed by vacuum rotation. Then, rapid column chromatography was performed with petroleum ether as eluent to obtain compound 2.

[0320] (4) Add compound 2 (524 mg, 1.24 mmol), compound 1 (846 mg, 1.86 mmol), tetrakis(triphenylphosphine)palladium (58 mg, 0.05 mmol), potassium carbonate (1.4 g, 9.92 mmol), and Tol-water mixed solvent (V) to a 100 mL pressure-resistant branch tube. Tol V H2O = 2:1 (total 15 mL), nucleophilic substitution reaction was carried out under argon atmosphere and stirred at 100 °C for 12 h. After the reaction system cooled, it was washed with 20 mL of water and extracted with DCM (10 mL × 3). The extracted organic phase was dried over anhydrous sodium sulfate and the organic solvent was removed by vacuum extraction. Then it was purified by rapid column chromatography. PE and DCM (V PE V DCM Using a ratio of 3:1 as the eluent, we obtained naphthalimide compound A23.

[0321] The characterization data of the naphthalene imide compound A23 prepared in Example 23 are as follows: 1H NMR (400MHz, CDCl3) δ8.55(dd,1H),8.47(dd,1H),8.38(dd,1H),8.32(d,1H),8.21-8.12(m,3H),8.12-8.06(m,1H),8. 00(t,1H),7.80-7.72(m,2H),7.69-7.64(m,1H),7.62-7.43(m,6H),7.40(dd,1H),7.36-7.23(m,6H),1.34(s,9H).HRMS found: 670.2620.

[0322] Example 24

[0323] The structural formula of naphthalimide compound A24 is:

[0324]

[0325] The preparation method of the naphthalimide compound A24 is as follows: based on Example 23, using... replace With other conditions unchanged, we obtained naphthalimide compound A24.

[0326] The characterization data of the naphthalene imide compound A24 prepared in Example 24 are as follows: 1 HNMR(400MHz, CDCl3)δ8.55(dd,1H),8.48(dd,1H),8.39(dt,1H),8.32(d,1H) ,8.21-8.12(m,2H),8.12-8.06(m,1H),8.00(d,1H),7.80-7.72(m,2H),7.69-7 .64(m,1H),7.57(td,2H),7.53(td,1H),7.47(dd,1H),7.37(dd,1H),7.35-7.2 9(m,3H),7.32-7.24(m,3H),3.64-3.53(m,1H),1.34(s,9H),1.29(d,5H).HRMS found: 712.3090.

[0327] Test Example 1

[0328] The photophysical properties of the naphthalimide compounds A1, A2, A3, A4, A5, A6, A7, A8, A9, A10, A11, A12, A13, A14, A15, A16, A17, A18, A19, A20, A21, A22, A23, and A24 obtained in Examples 1–24 were studied (acetonitrile was used as the solvent, and the test concentration was 1 × 10⁻⁶). -5 (mol / L), the results are shown in Table 1.

[0329] UV-Vis absorption spectroscopy test: The solution to be tested is transferred to a cuvette (bilaterally transparent) with an optical path of 10 mm using a pipette, and its UV-Vis absorption spectrum is then measured using a UV-Vis spectrophotometer. Equipment used for UV-Vis absorption spectroscopy test: Aoyi Instruments (Shanghai) A560 double-beam UV-Vis spectrophotometer.

[0330] Fluorescence emission spectroscopy test: The test solution is transferred to a cuvette (with four-sided light transmission) with an optical path of 10 mm using a pipette, and then the fluorescence emission spectrum is measured using a fluorometer. Equipment used for fluorescence emission spectroscopy test: Horiba Fluoromax-M+ fluorometer.

[0331] Table 1. Photophysical properties of naphthimide compounds A1–A24

[0332]

[0333]

[0334] As shown in Table 1, naphthalimide compounds A1, A2, A3, A4, A5, A6, A7, A8, A9, A10, A11, A12, A13, A14, A15, A16, A17, A18, A19, A20, A21, A22, A23, and A24 all exhibit high molar extinction coefficients in acetonitrile solution.

[0335] Thin film sample preparation method: Naphthalimide compounds A1, A3, A5, A7 and PMMA were dissolved in CF to prepare solutions with a concentration of 10 mg / mL. -1 The solution was prepared by first adding a solution of naphthalimide compounds to the PMMA solution at a mass fraction of 1.5 wt% to obtain a mixed solution. Using quartz as a substrate, the mixed solution was coated onto the substrate surface using a pipette, and then a spin coater was used to obtain the thin film sample to be tested.

[0336] Model of spin coater: KW-4A desktop spin coater from the Microelectronics Research Center of the Chinese Academy of Sciences.

[0337] Spin coating conditions: Spindle speed 300 rpm min -1 Run for 10 seconds, then increase the speed to 1500 rpm. -1 Run for 60 seconds.

[0338] Lifetime degradation curve test method: The thin film sample to be tested was tested under vacuum using a Horiba Fluorolog-3 fluorescent spectrophotometer. The results are as follows: Figure 1and 2 And as shown in Table 2.

[0339] Figure 1 The photoluminescence decay curve of naphthalimide compound A1 prepared in Example 1; Figure 2 The photoluminescence decay curve of the naphthalimide compound A3 prepared in Example 3 is shown.

[0340] Figure 3 The phosphorescence spectra of the naphthalimide compound A1 prepared in Example 1 in PS and PMMA; Figure 4 The phosphorescence spectra of the naphthalimide compound A3 prepared in Example 3 in PS and PMMA are shown.

[0341] Table 2. Luminescence lifetime data of naphthalimide compounds

[0342] Photoinitiator F (ns)]]> ​ Ph (ms)]]> ​ A1 19.2 152 A3 27.6 217 A5 18.9 165 A7 16.1 199 A9 15.7 168 A11 18.2 155 A13 17.6 176 A15 20.1 192 A17 16.6 138 A19 22.1 198 A21 18.5 170 A23 15.1 147

[0343] Taking naphthalimide compounds A1 and A3 as examples, under vacuum conditions, their fluorescence lifetimes in 1.5 wt% PMMA-doped films were only about 20 ns (19.2 ns and 27.6 ns, respectively), while the lifetimes of long-lived excited species were 152 ms and 217 ms, respectively; their temperature-dependent PL decay curves ( Figure 1 and 2 The results showed that as the temperature decreased, the excited-state lifetimes gradually increased, while the relative abundance of long-lived species did not decrease significantly, indicating that their long-lived luminescence originated from ORTP rather than delayed fluorescence. Solid-state dielectric effect tests showed that when the doping matrix was changed from PMMA to PS with lower polarity, the phosphorescence emission spectrum underwent a certain degree of blue shift. Figure 3 and 4 This indicates that it has 3 CT-ORTP emission properties. The above experimental results prove that naphthalimide compounds A1, A3, A5, A7, A9, A11, A13, A15, A17, A19, A21, and A23 are all... τ3 CT exceeding 100ms 3 CT-ORTP material is characterized by its long lifespan. 3 CT phosphorescent materials, along with other compounds, can achieve the same luminescence lifetime. This long lifetime promises to be used as a highly efficient single-component photoinitiator.

[0344] Application examples

[0345] UV-cured coating:

[0346] Component composition (percentage by mass):

[0347] Prepolymerized photosensitive resin;

[0348] 30% active monomer;

[0349] Photoinitiator (content shown in Table 3);

[0350] The prepolymerized photosensitive resin is a copolymer of methacrylate / methacrylic acid / methyl methacrylate, with a molar ratio of methacrylate, methacrylic acid, and methyl methacrylate of 50:15:30. The molecular weight (M) of the prepolymerized photosensitive resin is... w The value is 70,000; the active monomers are shown in Table 3, and 5 mL of acetone is added for dissolution. The photoinitiator is one or more of the compounds prepared in Examples 1 to 24 above (when multiple compounds are used as photoinitiators, the mass ratio of photoinitiators is 1:1).

[0351] The preparation method of the photocurable material is as follows: Take the prepared photocurable component, coat it on a PET template with a wire rod, the film thickness is about 200μm, dry it at 90℃ for 5min to remove the solvent, then cool the coated PET board to room temperature, attach a mask, and expose it with an LED surface light source (365nm 100mW); then develop it at 25℃ using a 1% NaOH aqueous solution, wash it with ultrapure water, air dry it, and finally bake it at 220℃ for 30min to obtain the photocurable coating.

[0352] The patterns of the photocurable coatings prepared for the corresponding use cases were evaluated, and the results are as follows: Figures 5 to 7 And as shown in Table 3.

[0353] Figure 5 The pattern of the photocurable coating prepared from the naphthalimide compound A3 obtained in Example 1 under sunlight; Figure 6 The pattern of the photocurable coating prepared from the naphthalimide compound A3 obtained in Example 1 under ultraviolet light irradiation; Figure 7 The afterglow pattern of the photocurable coating prepared from the naphthalimide compound A3 obtained in Example 1 after 5 seconds of UV irradiation followed by the lamp being turned off.

[0354] Table 3. Polymerization results of naphthalimide compounds A1–A24 as photoinitiators

[0355]

[0356]

[0357] from Figures 5 to 7 As shown in Table 3, all the naphthaleneimide compounds used in the heating process can effectively initiate photocuring; taking the coating obtained by compound A3 as an example, Figure 5 The cured coating is colorless and transparent under natural light, with no visible abnormalities. Under dark ultraviolet light (…), it appears colorless and transparent. Figure 6It emits fluorescence, allowing for clear observation of the pattern; after irradiation with ultraviolet light for 5 seconds and then turning it off, the coating emits room-temperature phosphorescence with an afterglow time of up to 4 seconds; a magnified view is shown below. Figure 7 As shown, the afterglow times are 0, 1, and 3 seconds. Taking the 1-second pattern as an example, some of the cured strips did not emit light, indicating that there is a defect in the polymer pattern here. The experimental results prove that the afterglow emission clearly shows much richer details than the fluorescent pattern, which can provide fine coating condition analysis for the required fields and can also be used for anti-counterfeiting.

[0358] The results for the compounds prepared in other examples were the same as those for naphthalimide compound A3.

[0359] As can be seen from the above embodiments, the naphthalene imide compounds provided by the present invention have excellent properties. 3 CT-ORTP exhibits excellent performance, acting as an organic photoinitiator. The resulting photocurable material fluoresces under dark-field ultraviolet light irradiation and retains afterglow after the ultraviolet light is turned off. This allows for clear, complete, and rapid evaluation of the fine patterns in the coating, making it suitable for applications such as photoresists and 3D printing. It can also be used as an afterglow material in the field of anti-counterfeiting.

[0360] The above description is only a preferred embodiment of the present invention. It should be noted that for those skilled in the art, several improvements and modifications can be made without departing from the principle of the present invention, and these improvements and modifications should also be considered within the scope of protection of the present invention.

Claims

1. A naphthalimide compound having the chemical structure shown in Formula I: Formula I; In equation I, R is or ; R1, R2, R3 and R4 are independently hydrogen, halogen, cyano, methoxy or C1~20 straight-chain or branched alkyl groups; The D has any one of the following structures: 、 、 、 、 、 。 2. The naphthalimide compound according to claim 1, characterized in that, R1, R2, R3 and R4 are independently any one of hydrogen, fluorine, cyano, methoxy, methyl and isopropyl.

3. The naphthaleneimide compound according to claim 1, characterized in that, The naphthalimide compounds have any one of the following structures: 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 。 4. A method for preparing the naphthalimide compound according to any one of claims 1 to 3, comprising the following steps: Compound 1, compound 2, palladium catalyst, acid-binding agent and polar solvent were mixed and subjected to nucleophilic substitution reaction to obtain naphthalimide compounds; Compound 1 has the chemical structure shown in Formula II: Formula II; The chemical structure of compound 2 is as follows: or .

5. The preparation method according to claim 4, characterized in that, The preparation method of compound 1 includes the following steps: (1) 4-Bromo-1,8-naphthalenedicarboxylic anhydride, 4-tert-butylaniline, and an organic solvent were mixed and subjected to a first nucleophilic substitution reaction to obtain compound 3; the chemical structure of compound 3 is as follows: ; (2) The compound 3 obtained in step (1), pinacol diboronic acid ester, organic palladium catalyst, acid-binding agent and organic solvent are mixed and subjected to a second nucleophilic substitution reaction to obtain compound 1.

6. The preparation method according to claim 4, characterized in that, The preparation method of compound 2 includes the following steps: Compound 4, compound D, organopalladium catalyst, acid-binding agent and organic solvent were mixed and subjected to nucleophilic substitution reaction, followed by post-treatment to obtain compound 2; The structural formula of compound 4 is as follows: or ; The compound D is any one of compounds D1 to D6: 、 、 、 、 、 。 7. The application of the naphthalimide compound according to any one of claims 1 to 3 or the naphthalimide compound prepared by the preparation method according to any one of claims 4 to 6 as an organic photoinitiator.

8. The application of the naphthalimide compound according to any one of claims 1 to 3 or the naphthalimide compound prepared by the preparation method according to any one of claims 4 to 6 as a afterglow material.

9. A photocurable material, comprising a prepolymerized photosensitive resin, an active monomer, an organic photoinitiator, and a solvent, wherein the organic photoinitiator is a naphthalimide compound as described in any one of claims 1 to 3 or a naphthalimide compound prepared by the preparation method described in any one of claims 4 to 6; The prepolymerized photosensitive resin is a copolymer of methacrylate / methacrylic acid / methyl methacrylate; The active monomer is one or more of tripropylene glycol diacrylate, 1,6-hexanediol diacrylate, and trimethylolpropane triacrylate.

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