Naphthalimide compound as well as preparation method and application thereof

Abstract

The invention provides a naphthalimide compound as well as a preparation method and application thereof, and belongs to the technical field of organic compounds. N-(4-tert-butylphenyl) naphthalimide is used as an acceptor unit (a group A), 9, 9-dimethyl acridine, 9, 9-diphenyl acridine, phenoxazine, phenothiazine, 7H-benzo [c] carbazole or 9H-dibenzo [a, c] carbazole is used as an electron donor unit (a group D), and the donor unit and the acceptor unit are connected through ortho-positions or meta-positions of benzene bridges or derivatives thereof; the formation of the 3CT state depends on the CT effect between the D group and the A group, the specific D group and the benzene bridge unit are selected to control the distance and the dihedral angle between the D unit and the A unit so as to realize the regulation and control of the service life of the 3CT state, and meanwhile, the fine adjustment of the energy of the 3CT state is realized by virtue of the substituent group on the benzene bridge unit, so that the service life of the 3CT state is prolonged. Therefore, the naphthalimide compound has a long charge transfer triplet state lifetime in a single molecule state.

Description

Technical Field

[0001] The invention belongs to the technical field of organic compounds, and specifically relates to a naphthalene imide compound and a preparation method and application thereof. Background Art

[0002] Organic Room Temperature Phosphorescence (ORTP) compounds can achieve afterglow luminescence of a single organic compound. Since the phosphorescence emission process has a spin-forbidden nature, its triplet lifetime can reach milliseconds or even seconds, which can bring about afterglow emission. According to the transition properties between the molecular triplet state and the ground state, phosphorescence emission can generally be divided into three types: the local excited state and the triplet state. 3 LE) and triplet charge transfer state (Triplet Charge Transfer State, 3 CT) are two types. At present, the phosphorescence emission of most ORTP materials belongs to 3 LE transition properties. The LE state is actually a tightly bound electron-hole pair. Its highly localized nature means that there is a strong Coulomb interaction between its electrons and holes, and the exciton binding energy (0.5-1.0 eV) is high, making it difficult for the charge separation process to occur. The holes / electrons in the CT-type excited state are distributed on the D / A units respectively, which makes the CT state exciton binding energy (0.1-0.5 eV) lower, making it easier for electron transfer processes to occur than in the LE state. In addition, compared to the LE process, the CT process can participate in unique reactions. For example, the key step of photosynthesis in chloroplasts depends on the CT state between the cell membrane and the protein assembly to obtain the potential difference required for the electrochemical reaction; in organic photovoltaic devices, it is also necessary to form a CT state at the interface of the D and A materials, and then react to generate current. Therefore, it has a long life. 3 Room temperature phosphorescent materials with CT properties have advantages in improving the efficiency of photocatalytic reactions, promoting artificial simulation of photosynthesis, and improving the performance of photovoltaic materials. 3 CT-ORTP material life is much lower than 3 LE-ORTP materials. Therefore, it is necessary to improve 3 Increasing the life of CT-ORTP materials and expanding their applications have become technical challenges that need to be urgently addressed in this field. Summary of the invention

[0003] The object of the present invention is to provide a naphthalene imide compound and a preparation method and application thereof. The naphthalene imide compound provided by the present invention has a long 3CT life, can be used as an organic photoinitiator, and can emit room temperature phosphorescence, so the photocurable material formed by the initiated polymerization can emit fluorescence under dark field ultraviolet light conditions. After the ultraviolet light is turned off, there is a long afterglow, which can clearly, completely and quickly evaluate the fine graphics of the coating, so it can be used in photoresist, 3D printing and other fields, which is of great significance to expanding the application field of photocuring technology; it can also be used as an afterglow material in the anti-counterfeiting field.

[0004] In order to achieve the above-mentioned object of the invention, the present invention provides the following technical solutions:

[0005] The present invention provides a naphthalene imide compound having a chemical structure shown in Formula I:

[0006]

[0007] In the 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-chain alkyl or substituted C1-20 branched-chain alkyl;

[0009] The 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 naphthaleneimide compound has any one of the following structures:

[0013]

[0014]

[0015] The present invention also provides a method for preparing the naphthalene imide compound described in the above technical solution, comprising the following steps:

[0016] Compound 1, compound 2, a palladium catalyst, an acid-binding agent and a polar solvent are mixed to carry out a nucleophilic substitution reaction to obtain a naphthalene imide compound;

[0017] The compound 1 has a chemical structure shown in Formula II:

[0018]

[0019] The chemical structure of compound 2 is

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

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

[0022] (2) Compound 3 obtained in step (1), pinacol diboronate, an organic palladium catalyst, an acid binding agent and an organic solvent are mixed to carry out a second nucleophilic substitution reaction to obtain compound 1.

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

[0024] Compound 4, compound D, an organic palladium catalyst, an acid-binding agent and an organic solvent are mixed to carry out a nucleophilic substitution reaction, and then post-processed to obtain compound 2;

[0025] The structural formula of compound 4 is

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

[0027]

[0028] The present invention also provides the use of the naphthalene imide compound described in the above technical solution or the naphthalene imide compound prepared by the preparation method described in the above technical solution as an organic photoinitiator.

[0029] The present invention also provides the use of the naphthalene imide compound described in the above technical solution or the naphthalene imide compound prepared by the preparation method described in the above technical solution as an afterglow material.

[0030] 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 the naphthalene imide compound described in the above technical solution or the naphthalene imide compound prepared by the preparation method described in the above technical solution.

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

[0032] The present invention provides a naphthalene imide compound having a chemical structure shown in Formula I. The naphthalene imide compound provided by the present invention uses N-(4-tert-butylphenyl)naphthalene imide as an acceptor unit (A group), uses 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 and acceptor units are connected through the ortho or meta position of a benzene bridge or its derivatives; wherein, 3 The formation of CT state depends on the CT interaction between D group and A group, and the CT state can be adjusted by replacing D group or A group. 3 The energy of the CT state is achieved by selecting a specific D group and the benzene bridge unit to control the distance and dihedral angle between the D and A units. 3 The CT state lifetime is regulated by the substituents on the benzene bridge unit. 3 Fine-tuning of CT state energy enables the naphthaleneimide compounds to have a long charge transfer triplet lifetime in a single-molecule state; the naphthaleneimide compounds provided by the present invention can be used as a single-component photoinitiator for photopolymerization; the naphthaleneimide compounds provided by the present invention have fluorescent properties. As a photocuring agent, after the photoinitiation is completed, the molecular skeleton is not destroyed, and the formed solidified layer emits fluorescence under dark field ultraviolet irradiation conditions, which can clearly, completely and quickly evaluate the fine graphics of the coating; at the same time, it has room temperature phosphorescence properties, and the formed photocured layer can emit room temperature phosphorescence after being irradiated with dark field ultraviolet light for a certain period of time, and the afterglow time is long, which can clearly, completely and quickly evaluate the fine graphics of the coating; the naphthaleneimide compounds provided by the present invention can be used as raw materials for luminescent materials (fluorescence or phosphorescence), and can form a pure organic system without causing metal pollution, so that it can be used in fields such as photoresists that require strict control of metal ions. Experimental results show that, under a vacuum environment, the fluorescence lifetimes of the 1.5wt% concentration of the naphthalene imide compounds A1 and A3 provided by the present invention in the PMMA-doped film are only about 20ns (19.2ns and 27.6ns, respectively), and the lifetimes of the long-life excited species are 152ms and 217ms, respectively; the cured coating prepared with the naphthalene imide compound A3 is colorless and transparent under natural light, without any visual abnormalities, and can emit fluorescence under dark-field ultraviolet light, so that the pattern can be clearly observed; the ultraviolet light is turned off after 5s of irradiation, and the coating emits room temperature phosphorescence with an afterglow time of 4s. BRIEF DESCRIPTION OF THE DRAWINGS

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

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

[0035] Figure 3 The phosphorescence spectrum of the naphthalene imide compound A1 prepared in Example 1 in PS and PMMA;

[0036] Figure 4 The phosphorescence spectra of the naphthalene imide compound A3 prepared in Example 3 in PS and PMMA;

[0037] Figure 5 The pattern of the photocurable coating prepared from the naphthalene imide compound A3 prepared in Example 1 under sunlight;

[0038] Figure 6 The pattern of the photocurable coating prepared from the naphthalene imide compound A3 prepared in Example 1 under ultraviolet light;

[0039] Figure 7 This is the afterglow pattern of the photocurable coating prepared from the naphthalene imide compound A3 prepared in Example 1 after the ultraviolet lamp is turned off after irradiation for 5 seconds. DETAILED DESCRIPTION

[0040] The present invention provides a naphthalene imide compound having a chemical structure shown in Formula I:

[0041]

[0042] In the present invention, the R is

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

[0044]

[0045] In the present invention, 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; D has any one of the following structures:

[0046]

[0047] As an embodiment, R1, R2, R3 and R4 can independently be any one of hydrogen, fluorine, cyano, methoxy, methyl and isopropyl.

[0048] In the present invention, the naphthalene imide compound has any one of the following structures:

[0049]

[0050]

[0051] The naphthalene imide compound provided by the present invention uses N-(4-tert-butylphenyl)naphthalene imide as an acceptor unit (A group), uses 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 and acceptor units are connected through the ortho or meta position of a benzene bridge or its derivatives; wherein, 3 The formation of CT state depends on the CT interaction between D group and A group, and the CT state can be adjusted by replacing D group or A group. 3 The energy of the CT state is achieved by selecting a specific D group and the benzene bridge unit to control the distance and dihedral angle between the D and A units. 3 The CT state lifetime is regulated by the substituents on the benzene bridge unit. 3 Fine-tuning of CT state energy enables the naphthaleneimide compounds to have a long charge transfer triplet lifetime in a single-molecule state; the naphthaleneimide compounds provided by the present invention can be used as a single-component photoinitiator for photopolymerization; the naphthaleneimide compounds provided by the present invention have fluorescent properties. As a photocuring agent, after the photoinitiation is completed, the molecular skeleton is not destroyed, and the formed solidified layer emits fluorescence under dark field ultraviolet irradiation conditions, which can clearly, completely and quickly evaluate the fine graphics of the coating; at the same time, it has room temperature phosphorescence properties, and the formed photocured layer can emit room temperature phosphorescence after being irradiated with dark field ultraviolet light for a certain period of time, and the afterglow time is long, which can clearly, completely and quickly evaluate the fine graphics of the coating; the naphthaleneimide compounds provided by the present invention can be used as raw materials for luminescent materials (fluorescence or phosphorescence), and can form a pure organic system without causing metal pollution, so that it can be used in fields such as photoresists that require strict control of metal ions.

[0052] The naphthalene imide compounds provided by the present invention have a long charge transfer triplet lifetime, and their triplet excitons can be used to initiate photopolymerization, so the compounds can be used as a single-component photoinitiator and added to a common photocuring system. The added system can effectively initiate photocuring under an LED light source, and form a pure organic photocurable coating that emits light under ultraviolet light and has an afterglow property after the light is turned off. In addition, the naphthalene imide compounds can also be directly added to the coating to form an afterglow coating of a pure organic system. The compounds have a wide range of uses, including but not limited to photoresists, three-dimensional printing, anti-counterfeiting and other fields.

[0053] Among the naphthalene imide compounds provided by the present invention, A1, A3, A5, A7, A9, A11, A13, A15, A17, A19, A21 and A23 have a service life superior to that of other naphthalene imide compounds.

[0054] The present invention also provides a method for preparing the naphthalene imide compound described in the above technical solution, comprising the following steps:

[0055] Compound 1, compound 2, a palladium catalyst, an acid-binding agent and a polar solvent are mixed to carry out a nucleophilic substitution reaction to obtain a naphthalene imide compound.

[0056] The present invention has no particular limitation on the sources of the raw materials, and commercially available products known to those skilled in the art may be used.

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

[0058]

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

[0060] (1) mixing 4-bromo-1,8-naphthalene dicarboxylic anhydride, 4-tert-butylaniline and an organic solvent to carry out a first nucleophilic substitution reaction to obtain compound 3;

[0061] (2) Compound 3 obtained in step (1), pinacol diboronate, an organic palladium catalyst, an acid binding agent and an organic solvent are mixed to carry out a second nucleophilic substitution reaction to obtain compound 1.

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

[0063] In the present invention, the molar ratio of the 4-bromo-1,8-naphthalene dicarboxylic anhydride to 4-tert-butylaniline is preferably (1-2.25):(2-7).

[0064] As an embodiment, the molar ratio of the 4-bromo-1,8-naphthalene dicarboxylic anhydride to 4-tert-butylaniline may be (1.4-2.0):(2.5-3.5), or may be 1.45:2.88.

[0065] In the present invention, the organic solvent is preferably one or more of nitrogen methyl pyrrolidone, dimethylformamide, dimethylacetamide, dimethyl sulfoxide, hexamethylphosphoramide, cyclopentane, acetonitrile, ethanol and benzonitrile, more preferably ethanol. The present invention has no special requirements on the amount of the organic solvent, as long as the first nucleophilic substitution reaction is carried out smoothly.

[0066] The present invention has no special limitation on the operation of mixing the 4-bromo-1,8-naphthalene dicarboxylic anhydride, 4-tert-butylaniline and the organic solvent, and the technical scheme of preparing the mixed material by the operation well known to those skilled in the art can be used.

[0067] In the present invention, the temperature of the first nucleophilic substitution reaction is preferably 80 to 140°C, more preferably 80 to 120°C, and most preferably 80 to 100°C; the holding time of the first nucleophilic substitution reaction is preferably 12 to 24 hours, more preferably 16 to 24 hours, and more preferably 20 to 24 hours; the first nucleophilic substitution reaction is preferably carried out under the condition of magnetic stirring. The present invention has no special limitation on the operation of the magnetic stirring, and the operation well known to those skilled in the art can be used.

[0068] After the first nucleophilic substitution reaction is completed, the present invention preferably performs post-treatment on the product obtained by the first nucleophilic substitution reaction to obtain compound 3. The present invention can purify compound 3 by post-treatment.

[0069] In the present invention, the post-treatment preferably includes cooling, solid-liquid separation and washing performed in sequence.

[0070] The present invention has no particular limitation on the cooling operation, and cooling to room temperature is sufficient.

[0071] In the present invention, the solid-liquid separation is preferably pressure filtration. The present invention has no special limitation on the operation of the pressure filtration, and the operation well known to those skilled in the art can be adopted.

[0072] In the present invention, the washing agent used in the washing is preferably ethanol. The present invention has no special limitation on the washing operation, and the washing operation can be performed until the filtrate becomes colorless.

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

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

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

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

[0077] In the present invention, the organic solvent is preferably one or more of benzene, toluene, xylene, chlorobenzene, dichlorobenzene, tetrahydrofuran, 1,4-dioxane, nitrogen methyl pyrrolidone, dimethylformamide, dimethylacetamide, dimethyl sulfoxide, hexamethylphosphoramide, cyclopentane, acetonitrile and benzonitrile, more preferably 1,4-dioxane.

[0078] In the present invention, the molar ratio of the compound 3 to the diboric acid pinacol ester is preferably (4.24-10): (5.08-12); the molar ratio of the compound 3 to the organic palladium catalyst is preferably (4.24-10): (0.2-0.5); the molar ratio of the compound 3 to the acid binding agent is preferably (4.24-10): (12.7-30).

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

[0080] The present invention has no special requirement on the amount of the organic solvent, as long as the second nucleophilic substitution reaction is ensured to proceed smoothly.

[0081] The present invention has no special limitation on the operation of mixing the compound 3, pinacol diborate, the organopalladium catalyst, the acid-binding agent and the organic solvent, and the technical scheme of preparing the mixed material by the operation well known to those skilled in the art can be used.

[0082] In the present 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 6-12h, more preferably 6-10h, and most preferably 6-8h; 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. The present invention has no special limitation on the operation of the magnetic stirring, and the operation well known to those skilled in the art can be used.

[0083] After the second nucleophilic substitution reaction is completed, the present invention preferably performs post-treatment on the product obtained by the second nucleophilic substitution reaction to obtain compound 1. The present invention can purify compound 1 by post-treatment.

[0084] In the present invention, the post-treatment preferably includes cooling, solid-liquid separation, water washing, extraction, drying, vacuum rotary evaporation and column chromatography purification performed in sequence.

[0085] The present invention has no particular limitation on the cooling operation, and cooling to room temperature is sufficient.

[0086] In the present invention, the solid-liquid separation is preferably pressure filtration. The present invention has no special limitation on the operation of the pressure filtration, and the operation well known to those skilled in the art can be adopted.

[0087] The present invention has no particular limitation on the water washing operation, and any operation known to those skilled in the art can be used. The water washing of the present invention can fully remove the added salt.

[0088] In the present invention, the extraction agent used in the extraction is preferably dichloromethane; the number of extractions is preferably 3 times.

[0089] In the present invention, the reagent used for the drying is preferably anhydrous sodium sulfate. The present invention has no special limitation on the amount of the anhydrous sodium sulfate, which can be determined according to common sense.

[0090] The present invention has no special limitation on the operation of the vacuum rotary evaporation, and the operation well known to those skilled in the art can be adopted.

[0091] In the present invention, the eluent used in the 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] As an implementation mode, the volume ratio of PE to DCM may be (1-2):1.

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

[0094] In the present 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; D preferably has any one of the following structures:

[0095]

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

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

[0098]

[0099]

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

[0101] Compound 4, compound D, an organic palladium catalyst, an acid binding agent and an organic solvent are mixed to carry out a nucleophilic substitution reaction, and then post-processed to obtain compound 2.

[0102] In the present invention, the structural formula of the compound 4 is preferably The R1, R2, R3 and R4 are preferably 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.

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

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

[0105]

[0106] In the present invention, the organic palladium catalyst is preferably tetrakis(triphenylphosphine)palladium or [1,1'-bis(diphenylphosphino)ferrocene]palladium dichloride.

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

[0108] In the present invention, the organic solvent is preferably one or more of benzene, toluene, xylene, chlorobenzene, dichlorobenzene, tetrahydrofuran, 1,4-dioxane, nitrogen methyl pyrrolidone, dimethylformamide, dimethylacetamide, dimethyl sulfoxide, hexamethylphosphoramide, cyclopentane, acetonitrile and benzonitrile, more preferably toluene.

[0109] In the present invention, the molar ratio of compound D to compound 4 is preferably (5.15-10.98):(5.49-16.86).

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

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

[0112] As an embodiment, the molar ratio of the compound D to the organic palladium catalyst may be (10-10.98):(0.1-0.2), or may be 10:0.2.

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

[0114] As an embodiment, the molar ratio of the compound D to the acid-binding agent may be (5.15-6):(5.49-6.5), or may be 5.15:6.18.

[0115] The present invention has no special requirement on the amount of the organic solvent used, as long as the nucleophilic substitution reaction is ensured to proceed smoothly.

[0116] In the present invention, the temperature of the nucleophilic substitution reaction is preferably 80 to 110° C.; the time of the nucleophilic substitution reaction is preferably 6 to 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. The present invention has no special limitation on the operation of the magnetic stirring, and the operation well known to those skilled in the art can be used.

[0117] As an embodiment, the temperature of the nucleophilic substitution reaction may be 100 to 110° C.; the time of the nucleophilic substitution reaction may be 8 to 12 hours.

[0118] In the present invention, the post-treatment preferably includes cooling, washing, extraction, drying, vacuum rotary evaporation and column chromatography purification performed in sequence.

[0119] The present invention has no particular limitation on the cooling operation, and cooling to room temperature is sufficient.

[0120] The present invention has no particular limitation on the water washing operation, and any operation well known to those skilled in the art may be used.

[0121] In the present invention, the extraction agent used in the extraction is preferably dichloromethane; the number of extractions is preferably 3 times.

[0122] In the present invention, the reagent used for the drying is preferably anhydrous sodium sulfate. The present invention has no special limitation on the amount of the anhydrous sodium sulfate, which can be determined according to common sense.

[0123] The present invention has no special limitation on the operation of the vacuum rotary evaporation, and the operation well known to those skilled in the art can be adopted.

[0124] In the present invention, the eluent used in the column chromatography purification is preferably petroleum ether. The present invention has no special limitation on the amount of the eluent, which can be determined according to common sense.

[0125] In the present invention, the palladium catalyst is preferably tetrakis(triphenylphosphine)palladium.

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

[0127] In the present 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, nitrogen methyl pyrrolidone, dimethylformamide, dimethylacetamide, dimethyl sulfoxide, hexamethylphosphoramide, cyclopentane, acetonitrile and benzonitrile, more preferably toluene; the volume ratio of the first organic solvent to water is preferably 2:1.

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

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

[0130] The present invention has no special requirements on the amount of the polar solvent, as long as the nucleophilic substitution reaction is ensured to proceed smoothly.

[0131] In the present invention, the temperature of the nucleophilic substitution reaction is preferably 100-110°C; the time of the nucleophilic substitution reaction is preferably 12-36 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 stirring. The present invention has no special limitation on the stirring operation, and the operation well known to those skilled in the art can be used.

[0132] As an embodiment, the temperature of the nucleophilic substitution reaction may be 100 to 105° C.; the time of the nucleophilic substitution reaction may be 12 to 16 hours.

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

[0134] In the present invention, the post-treatment preferably includes cooling, washing, extraction, drying, vacuum rotary evaporation or column chromatography purification in sequence. The post-treatment of the present invention can improve the purity of the naphthalene imide compound.

[0135] The present invention has no particular limitation on the cooling operation, and cooling to room temperature is sufficient.

[0136] The present invention has no particular limitation on the water washing operation, and any operation well known to those skilled in the art may be used.

[0137] In the present invention, the extraction agent used in the extraction is preferably dichloromethane; the number of extractions is preferably 3 times.

[0138] In the present invention, the reagent used for the drying is preferably anhydrous sodium sulfate. The present invention has no special limitation on the amount of the anhydrous sodium sulfate, which can be determined according to common sense.

[0139] The present invention has no special limitation on the operation of the vacuum rotary evaporation, and the operation well known to those skilled in the art can be adopted.

[0140] In the present invention, the eluent used in the 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] As an implementation mode, the volume ratio of PE to DCM can be 2:1, or 3:1.

[0142] The preparation method provided by the invention has simple process.

[0143] The present invention also provides the use of the naphthalene imide compound described in the above technical solution or the naphthalene imide compound prepared by the preparation method described in the above technical solution as an organic photoinitiator.

[0144] The naphthalene imide compound provided by the invention has afterglow performance and can be used as an organic photoinitiator.

[0145] The present invention also provides the use of the naphthalene imide compound described in the above technical solution or the naphthalene imide compound prepared by the preparation method described in the above technical solution as an afterglow material.

[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 the naphthalene imide compound described in the above technical solution or the naphthalene imide compound prepared by the preparation method described in the above technical solution.

[0147] As an implementation manner, the photocurable material may be a photocurable coating.

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

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

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

[0151] In the present invention, when the organic photoinitiator is two kinds of naphthalene imide compounds, the mass ratio of any two naphthalene imide compounds is preferably 1:1.

[0152] In the present invention, the solvent is preferably an organic solvent; the organic solvent is preferably acetone or chloroform. The present invention has no special requirements on the amount of the organic solvent, and it only needs to dissolve the raw materials.

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

[0154] As an embodiment, the raw materials of the photocurable material can be 62-69.995% of pre-polymerized photosensitive resin, 30% of active monomer and 0.005-8% of organic photoinitiator in terms of mass percentage. It can also be calculated by mass percentage, and the raw materials of the photocurable material preferably include 65-69.99% of pre-polymerized photosensitive resin, 30% of active monomer and 0.01-5% of organic photoinitiator.

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

[0156] 1) mixing a prepolymerized photosensitive resin, an active monomer, an organic photoinitiator and a solvent to obtain a mixture;

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

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

[0159] In the present invention, the prepolymerized photosensitive resin, the active monomer, the organic photoinitiator and the solvent are preferably mixed to obtain a mixture.

[0160] The present invention has no special limitation on the operation of mixing the prepolymerized photosensitive resin, the active monomer, the organic photoinitiator and the solvent, and the technical scheme for preparing the mixed material well known to those skilled in the art can be adopted.

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

[0162] In the present invention, the coating thickness is preferably 200 μm; the drying temperature is preferably 90° C. The present invention has no special restrictions on the coating operation, and the operation well known to those skilled in the art can be adopted. The present invention has no special restrictions on the drying time, and the solvent can be completely removed.

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

[0164] In the present invention, the dry film is preferably attached to a mask during the photocuring; the exposure light source 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 to 240s; the solvent used for the 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°C, and the baking time is preferably 30min.

[0165] The technical solutions in the present invention will be described clearly and completely below in conjunction with the embodiments of the present invention. Obviously, the described embodiments are only a part of the embodiments of the present invention, not all of them. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0166] Example 1

[0167] The structural formula of the naphthalene imide compound A1 is:

[0168]

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

[0170] (1) 4-bromo-1,8-naphthalene dicarboxylic anhydride (2.0 g, 7.25 mmol), 4-tert-butylaniline (2.2 g / 3 mL, 14.40 mmol) and ethanol (100 mL) were added to a 250 mL three-necked flask, and the mixture was heated under reflux at 80° C. for 24 h to perform 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 solid crude product was then washed with ethanol for multiple times (25 mL×5) until the filtrate was colorless to obtain compound 3; wherein the chemical structure of compound 3 is

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

[0172] (3) Compound D1 (418 mg, 2.00 mmol), 1-bromo-2-iodobenzene (846 mg / 0.4 mL, 3.00 mmol), tetrakis(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. in an argon atmosphere for a nucleophilic substitution reaction for 6 h. 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 over anhydrous sodium sulfate and the organic solvent was removed under reduced pressure. Then, rapid column chromatography was performed using petroleum ether as the eluent to obtain compound 2.

[0173] (4) 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 a Tol-water mixed solvent (V Tol :V H2O=2:1, 15 mL in total), stirred in an argon atmosphere at 100 ° C for nucleophilic substitution reaction for 12 h, after the reaction system was cooled, washed with 20 mL of water and extracted with DCM (10 mL × 3), the extracted organic phase was dried over anhydrous sodium sulfate and evaporated to remove the solvent under reduced pressure, and then purified by flash column chromatography, PE and DCM (V PE :V DCM =2:1) ​​as the eluent to obtain the naphthalene imide 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 the naphthalene imide compound A2 is:

[0179]

[0180] The preparation method of the naphthylimide compound A2 is as follows: based on Example 1, the temperature of the nucleophilic substitution reaction in step (1) is modified to 100° C., the time is modified to 20 h, and the reaction temperature in step (3) is modified to 100° C., the reaction time is modified to 20 h, and the reaction temperature in step (4) is modified to 100° C., the reaction time is modified to 20 h, and the reaction time in step Modified to The other conditions remain unchanged to obtain naphthalene imide 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 the naphthalene imide compound A3 is:

[0184]

[0185] The preparation method of the naphthalene imide compound A3 is:

[0186] (1) The temperature of the nucleophilic substitution reaction in step (1) was changed to 120° C., and the time was changed to 16 h. Other conditions were the same as those in Example 1.

[0187] (2) Same as 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(diphenylphosphino)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, and the mixture was stirred at 110° C. in an argon atmosphere for 24 h to carry out a nucleophilic substitution reaction. 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 over anhydrous sodium sulfate and the organic solvent was removed under reduced pressure. The crude product was separated by rapid column chromatography using PE as an eluent to obtain compound 2;

[0189] (4) 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 a Tol-water mixed solvent (V Tol :V H2O =2:1, 6 mL in total), stirred in an argon atmosphere at 100 ° C for nucleophilic substitution reaction for 36 hours, after the reaction system was cooled, 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 under reduced pressure, and then purified by column chromatography. PE and DCM (V PE :V DCM =3:1) as the eluent to obtain the naphthalene imide 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 the naphthalene imide compound A4 is:

[0193]

[0194] The preparation method of the naphthylimide compound A4 is as follows: based on Example 3, the temperature of the nucleophilic substitution reaction in step (2) is modified to 90° C., the time is modified to 12 h, and the reaction temperature in step (3) is modified to 90° C., the reaction time is modified to 12 h, and the reaction temperature in step (4) is modified to 12 h. Modified to The other conditions remain unchanged to obtain naphthalene imide 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 the naphthalene imide compound A5 is:

[0198]

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

[0200] (1) Same as Example 1;

[0201] (2) The temperature of the nucleophilic substitution reaction in step (2) was changed to 110° C., and the time was changed to 10 h. The rest was 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(diphenylphosphino)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, and the mixture was stirred at 110° C. in an argon atmosphere for a nucleophilic substitution reaction for 8 h. After the reaction system was 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 vortexing. Then, rapid column chromatography was performed using PE as the eluent to obtain compound 2.

[0203] (4) 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 a Tol-water mixed solvent (V Tol :V H2O=2:1, 15 mL in total), stirred in an argon atmosphere at 100 ° C for nucleophilic substitution reaction for 12 hours, after the reaction system was cooled, 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 under reduced pressure, and then purified by column chromatography. PE and DCM (V PE :V DCM =2:1) ​​as the eluent to obtain the 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 the naphthalene imide compound A6 is:

[0207]

[0208] The preparation method of the naphthalene imide compound A6 is as follows: on the basis of Example 5, replace The other conditions remain unchanged to obtain naphthalene imide compound A6.

[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 the naphthalene imide compound A7 is:

[0212]

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

[0214] (1) to (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(diphenylphosphino)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, and the mixture was stirred at 110° C. in an argon atmosphere for a nucleophilic substitution reaction for 8 h. After the reaction system was 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 under reduced pressure. Then, rapid column chromatography was performed using PE as the eluent to obtain compound 2.

[0216] (4) 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 a Tol-water mixed solvent (V Tol :V H2O =2:1, 12 mL in total), stirred in an argon atmosphere at 100 ° C for nucleophilic substitution reaction for 12 h, after the reaction system was cooled, 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 under reduced pressure, and then purified by flash column chromatography. PE and DCM (V PE :V DCM =3:1) as the eluent to obtain the naphthalene imide 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 the naphthalene imide compound A8 is:

[0220]

[0221] The preparation method of the naphthalene imide compound A8 is as follows: on the basis of Example 7, replace The other conditions remain unchanged to obtain naphthalene imide compound A8.

[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 the naphthalene imide compound A9 is:

[0225]

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

[0227] (1) to (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), tetrakis(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, and the mixture was stirred at 110° C. in an argon atmosphere for a nucleophilic substitution reaction for 8 h. After the reaction system was 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 under reduced pressure. Then, rapid column chromatography was performed using PE as the eluent to obtain compound 2;

[0229] (4) 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 a Tol-water mixed solvent (V Tol :V H2O=2:1, 12 mL in total), stirred in an argon atmosphere at 100 ° C for nucleophilic substitution reaction for 12 h, after the reaction system was cooled, 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 under reduced pressure, and then purified by flash column chromatography. PE and DCM (V PE :V DCM =2:1) ​​as the eluent to obtain the naphthalene imide 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 the naphthalene imide compound A10 is:

[0233]

[0234] The preparation method of the naphthalene imide compound A10 is as follows: on the basis of Example 9, replace The other conditions remain unchanged to obtain the naphthalene imide compound A10.

[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] Embodiment 11

[0237] The structural formula of the naphthalene imide compound A11 is:

[0238]

[0239] The preparation method of the naphthalene imide compound A11 is:

[0240] (1) to (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(diphenylphosphino)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, and the mixture was stirred at 110° C. in an argon atmosphere for a nucleophilic substitution reaction for 8 h. After the reaction system was 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 under reduced pressure. Then, rapid column chromatography was performed using PE as the eluent to obtain compound 2;

[0242] (4) 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 a Tol-water mixed solvent (V Tol :V H2O=2:1, 12 mL in total), stirred in an argon atmosphere at 100 ° C for nucleophilic substitution reaction for 18 h, after the reaction system was cooled, 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 under reduced pressure, and then purified by flash column chromatography. PE and DCM (V PE :V DCM =3:1) as the eluent to obtain 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 the naphthalene imide compound A12 is:

[0246]

[0247] The preparation method of the naphthalene imide compound A12 is as follows: on the basis of Example 11, replace The other conditions remain unchanged to obtain the naphthalene imide 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] Embodiment 13

[0250] The structural formula of the naphthalene imide compound A13 is:

[0251]

[0252] The preparation method of the naphthalene imide compound A13 is:

[0253] (1) to (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(diphenylphosphino)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, and the mixture was stirred at 110° C. in an argon atmosphere for 18 h to carry out a nucleophilic substitution reaction. After the reaction system was 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 under reduced pressure. Then, rapid column chromatography was performed using PE as the eluent to obtain compound 2;

[0255] (4) 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 a Tol-water mixed solvent (V Tol :V H2O =2:1, 12 mL in total), stirred in an argon atmosphere at 100 ° C for nucleophilic substitution reaction for 28 hours, after the reaction system was cooled, 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 under reduced pressure, and then purified by column chromatography. PE and DCM (V PE :V DCM =3:1) as the eluent to obtain 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] Embodiment 14

[0258] The structural formula of the naphthalene imide compound A14 is:

[0259]

[0260] The preparation method of the naphthalene imide compound A14 is as follows: on the basis of Example 13, replace The other conditions remain unchanged to obtain naphthalene imide 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] Embodiment 15

[0263] The structural formula of the naphthalene imide compound A15 is:

[0264]

[0265] The preparation method of the naphthalene imide compound A15 is:

[0266] (1) to (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(diphenylphosphino)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, and the mixture was stirred at 110° C. in an argon atmosphere for 24 h to carry out a nucleophilic substitution reaction. After the reaction system was 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 under reduced pressure. Then, rapid column chromatography was performed using PE as the eluent to obtain compound 2.

[0268] (4) 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 a Tol-water mixed solvent (V Tol :V H2O =2:1, 12 mL in total), stirred at 100 ° C in an argon atmosphere for nucleophilic substitution reaction for 24 h, after the reaction system was cooled, 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 under reduced pressure, and then purified by column chromatography. PE and DCM (V PE :V DCM =3:1) as the eluent to obtain 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 the naphthalene imide compound A16 is:

[0272]

[0273] The preparation method of the naphthalene imide compound A16 is as follows: on the basis of Example 15, replace The other conditions remain unchanged to obtain naphthalene imide compound A16.

[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] Embodiment 17

[0276] The structural formula of the naphthalene imide compound A17 is:

[0277]

[0278] The preparation method of the naphthalene imide compound A17 is:

[0279] (1) to (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, and the mixture was stirred at 110° C. in an argon atmosphere for 18 h to carry out a nucleophilic substitution reaction. After the reaction system was 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 under reduced pressure. Subsequently, rapid column chromatography was performed using PE as the eluent to obtain compound 2;

[0281] (4) 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 a Tol-water mixed solvent (V Tol :V H2O=2:1, 12 mL in total), stirred in an argon atmosphere at 100 ° C for nucleophilic substitution reaction for 12 h, after the reaction system was cooled, 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 under reduced pressure, and then purified by column chromatography. PE and DCM (V PE :V DCM =3:1) as the eluent to obtain 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] Embodiment 18

[0284] The structural formula of the naphthalene imide compound A18 is:

[0285]

[0286] The preparation method of the naphthalene imide compound A18 is as follows: on the basis of Example 17, replace The other conditions remain unchanged to obtain naphthalene imide compound A18.

[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] Embodiment 19

[0289] The structural formula of the naphthalene imide compound A19 is:

[0290]

[0291] The preparation method of the naphthalene imide compound A19 is:

[0292] (1) to (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), tetrakis(triphenylphosphine)palladium (116 mg, 0.10 mmol), tri-tert-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, and the mixture was stirred at 110° C. in an argon atmosphere for a nucleophilic substitution reaction for 8 h. After the reaction system was 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 under reduced pressure. Subsequently, rapid column chromatography was performed using PE as the eluent to obtain compound 2;

[0294] (4) 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 a Tol-water mixed solvent (V Tol :V H2O =2:1, 12 mL in total), stirred in an argon atmosphere at 100 ° C for nucleophilic substitution reaction for 36 hours, after the reaction system was cooled, 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 under reduced pressure, and then purified by column chromatography. PE and DCM (V PE :V DCM =2:1) ​​as the eluent to obtain the naphthalene imide 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] Embodiment 20

[0297] The structural formula of the naphthalene imide compound A20 is:

[0298]

[0299] The preparation method of the naphthalene imide compound A20 is as follows: on the basis of Example 19, replace The other conditions remain unchanged to obtain the naphthalene imide compound A20.

[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] Embodiment 21

[0302] The structural formula of the naphthalene imide compound A21 is:

[0303]

[0304] The preparation method of the naphthalene imide compound A21 is:

[0305] (1) to (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(diphenylphosphino)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, and the mixture was stirred at 110° C. in an argon atmosphere for a nucleophilic substitution reaction for 8 h. After the reaction system was 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 under reduced pressure. Subsequently, rapid column chromatography was performed using PE as the eluent to obtain compound 2.

[0307] (4) 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 a Tol-water mixed solvent (V Tol :V H2O=2:1, 12 mL in total), stirred in an argon atmosphere at 100 ° C for nucleophilic substitution reaction for 30 hours, after the reaction system was cooled, 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 under reduced pressure, and then purified by column chromatography. PE and DCM (V PE :V DCM =2:1) ​​as the eluent to obtain the naphthalene imide 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] Embodiment 22

[0310] The structural formula of the naphthalene imide compound A22 is:

[0311]

[0312] The preparation method of the naphthalene imide compound A22 is as follows: on the basis of Example 21, replace Other conditions remain unchanged to obtain naphthalene imide 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] Embodiment 23

[0315] The structural formula of the naphthalene imide compound A23 is:

[0316]

[0317] The preparation method of the naphthalene imide compound A23 is:

[0318] (1) to (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(diphenylphosphino)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, and the mixture was stirred at 110° C. in an argon atmosphere for a nucleophilic substitution reaction for 6 h. 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 over anhydrous sodium sulfate and the organic solvent was removed under reduced pressure. Subsequently, rapid column chromatography was performed using petroleum ether as the eluent to obtain compound 2.

[0320] (4) 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 a Tol-water mixed solvent (V Tol :V H2O =2:1, 15 mL in total), stirred in an argon atmosphere at 100 ° C for nucleophilic substitution reaction for 12 h, after the reaction system was cooled, 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 under reduced pressure, and then purified by flash column chromatography. PE and DCM (V PE :V DCM =3:1) as the eluent to obtain the naphthalene imide 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] Embodiment 24

[0323] The structural formula of the naphthalene imide compound A24 is:

[0324]

[0325] The preparation method of the naphthalene imide compound A24 is as follows: on the basis of Example 23, replace The other conditions remain unchanged to obtain naphthalene imide 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 naphthalene imide 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 to 24 were studied (the solvent used was acetonitrile, and the test concentration was 1×10 -5 mol / L), and the results are shown in Table 1.

[0329] UV-visible absorption spectrum test: Use a pipette to transfer the solution to be tested into a cuvette with an optical path of 10 mm (with light passing through both sides), and then use a UV-visible spectrophotometer to test its UV-visible absorption spectrum. Equipment used for UV-visible absorption spectrum test: A560 double-beam UV-visible spectrophotometer from Aoyi Instruments (Shanghai).

[0330] Fluorescence emission spectrum test: Use a pipette to transfer the solution to be tested into a cuvette with a light path of 10 mm (with light passing through four sides), and then use a fluorimeter to test the fluorescence emission spectrum. Equipment used for fluorescence emission spectrum test: Horiba Fluoromax-M+ fluorimeter.

[0331] Table 1 Photophysical properties of naphthalene imide compounds A1 to A24

[0332]

[0333]

[0334] It can be seen from Table 1 that as shown in Table 1, the naphthalene imide 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 have high molar extinction coefficients in acetonitrile solution.

[0335] Film sample preparation method: Naphthalimide compounds A1, A3, A5, A7 and PMMA were dissolved in CF and prepared into a concentration of 10 mg / mL -1 A solution of 1.5 wt% naphthalene imide compound solution was added to the PMMA solution to obtain a mixed solution. The mixed solution was coated on the surface of the substrate using a pipette, and a coating machine was used to coat the mixed solution to obtain a film sample to be tested.

[0336] Spread glue machine model: KW-4A desktop spread glue machine produced by Microelectronics Research Center of Chinese Academy of Sciences.

[0337] Glue coating conditions: speed 300rmp min -1 , run for 10 seconds, then the speed increases to 1500 rpm min -1 , run for 60 seconds.

[0338] Life decay curve test method: The film sample to be tested is tested under vacuum conditions using the 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 the naphthalene imide compound A1 prepared in Example 1; Figure 2 This is the photoluminescence decay curve of the naphthalene imide compound A3 prepared in Example 3.

[0340] Figure 3 The phosphorescence spectrum of the naphthalene imide compound A1 prepared in Example 1 in PS and PMMA; Figure 4 The phosphorescence spectra of the naphthalene imide compound A3 prepared in Example 3 in PS and PMMA.

[0341] Table 2 Luminescence lifetime data of naphthalene imide compounds

[0342] Photoinitiator <![CDATA[τ F (ns)]]> <![CDATA[τ 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 naphthylimide compounds A1 and A3 as examples, under vacuum environment, the fluorescence lifetime in their 1.5wt% PMMA doped films is only about 20ns (19.2ns and 27.6ns, respectively), and the lifetime of long-lived excited species is 152ms and 217ms, respectively; the temperature-dependent PL decay curve ( Figure 1 and 2 ) showed that as the temperature decreased, the lifetime of the excited state gradually increased, while the relative content of the long-lived species did not decrease significantly, indicating that their long-lived luminescence originated from ORTP rather than delayed fluorescence; the solid-state medium effect test showed that when the doping matrix was replaced by PS with a smaller polarity from PMMA, the phosphorescence emission spectrum underwent a certain degree of blue shift ( Figure 3 and 4 ), indicating that it has 3 The above experimental results show that naphthalene imide compounds A1, A3, A5, A7, A9, A11, A13, A15, A17, A19, A21 and A23 are τ3 CT exceeds 100ms 3 CT-ORTP material, a long-life 3 CT phosphorescent materials, the remaining compounds can also achieve the same luminescence lifetime, and this long lifetime will be expected to be used as a highly efficient single-component photoinitiator.

[0344] Application Examples

[0345] Light-curing coating:

[0346] Component formulation (mass percentage):

[0347] Prepolymerized photosensitive resin;

[0348] Active monomer 30%;

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

[0350] The prepolymerized photosensitive resin is a copolymer of methacrylate / methacrylic acid / methyl methacrylate, the molar ratio of methacrylate, methacrylic acid and methyl methacrylate is 50:15:30, and the molecular weight (M w ) is 70000; the active monomers are as shown in Table 3, and 5 mL of acetone is added to dissolve, and 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 the 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 200 μm, dry it at 90°C for 5 minutes to remove the solvent, then cool the coated PET plate to room temperature, attach a mask, and expose it with an LED surface light source (365nm 100mW); then develop it at 25°C using a 1% NaOH aqueous solution, then wash it with ultrapure water, air dry it, and finally bake it at 220°C for 30 minutes to obtain a photocurable coating.

[0352] The graphics of the photocured coating prepared according to the corresponding example were evaluated, and the results were as follows Figures 5 to 7 And as shown in Table 3.

[0353] Figure 5 The pattern of the photocurable coating prepared from the naphthalene imide compound A3 prepared in Example 1 under sunlight; Figure 6 The pattern of the photocurable coating prepared from the naphthalene imide compound A3 prepared in Example 1 under ultraviolet light; Figure 7 This is the afterglow pattern of the photocurable coating prepared from the naphthalene imide compound A3 prepared in Example 1 after the ultraviolet lamp is turned off after irradiation for 5 seconds.

[0354] Table 3 Results of polymerization experiments of naphthalene imide compounds A1-A24 as photoinitiators

[0355]

[0356]

[0357] from Figures 5 to 7 As can be seen from Table 3, all the used temperature-raising naphthalene imide compounds 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 visual abnormalities. Figure 6) can emit fluorescence, so that the pattern can be clearly observed; the UV light is turned off after 5s of irradiation, and the coating emits room temperature phosphorescence with an afterglow time of 4s; the partial enlarged picture is shown in Figure 7 As shown, the afterglow times are 0, 1, and 3s, respectively. Taking the 1s pattern as an example, some of the solidified strips do not emit light, indicating that there are defects in the polymerization pattern here. The experimental results show that the afterglow luminescence clearly shows far richer details than the fluorescent pattern, which can provide detailed coating condition analysis for areas in need and can also be used for anti-counterfeiting.

[0358] The results of the compounds prepared in other examples were the same as that of the naphthalene imide compound A3.

[0359] From the above examples, it can be seen that the naphthalene imide compounds provided by the present invention have excellent 3 CT-ORTP has excellent performance and can be used as an organic photoinitiator. The photocurable material formed emits fluorescence under dark-field ultraviolet light irradiation conditions. After the ultraviolet light is turned off, there is an afterglow, which can clearly, completely and quickly evaluate the fine graphics of the coating, so it can be used in photoresist, 3D printing and other fields. It can also be used as an afterglow material in the anti-counterfeiting field.

[0360] The above is only a preferred embodiment of the present invention. It should be pointed out that for ordinary technicians in this technical field, several improvements and modifications can be made without departing from the principle of the present invention. These improvements and modifications should also be regarded as the scope of protection of the present invention.

Claims

1. A naphthalene imide compound having a chemical structure shown in Formula I: In the formula I, R is 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-chain alkyl or substituted C1-20 branched-chain alkyl; The D has any one of the following structures:

2. The naphthaleneimide compound according to claim 1, characterized in that: The R1, R2, R3 and R4 are independently any one of hydrogen, fluorine, cyano, methoxy, methyl and isopropyl.

3. The naphthalene imide compound according to claim 1, characterized in that: The naphthalene imide compound has any one of the following structures:

4. The method for preparing the naphthalimide compound according to any one of claims 1 to 3, comprising the following steps: Compound 1, compound 2, a palladium catalyst, an acid-binding agent and a polar solvent are mixed to carry out a nucleophilic substitution reaction to obtain a naphthalene imide compound; The compound 1 has a chemical structure shown in Formula II: The chemical structure of compound 2 is 5. The preparation method according to claim 4, characterized in that: The preparation method of compound 1 comprises the following steps: (1) Mixing 4-bromo-1,8-naphthalene dicarboxylic anhydride, 4-tert-butylaniline and an organic solvent, and performing a first nucleophilic substitution reaction to obtain a compound 3; the chemical structure of the compound 3 is (2) Compound 3 obtained in step (1), pinacol diboronate, an organic palladium catalyst, an acid binding agent and an organic solvent are mixed to carry out a second nucleophilic substitution reaction to obtain compound 1.

6. The preparation method according to claim 4, characterized in that: The preparation method of the compound 2 comprises the following steps: Compound 4, compound D, an organic palladium catalyst, an acid-binding agent and an organic solvent are mixed to carry out a nucleophilic substitution reaction, and then post-processed to obtain compound 2; The structural formula of compound 4 is The compound D is any one of compounds D1 to D6:

7. Use of the naphthalene imide compound according to any one of claims 1 to 3 or the naphthalene imide compound prepared by the preparation method according to any one of claims 4 to 6 as an organic photoinitiator.

8. Use of the naphthaleneimide compound according to any one of claims 1 to 3 or the naphthaleneimide compound prepared by the preparation method according to any one of claims 4 to 6 as an afterglow material.

9. 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 the naphthaleneimide compound described in any one of claims 1 to 3 or the naphthaleneimide compound prepared by the preparation method described in any one of claims 4 to 6.

10. The photocurable material according to claim 9, characterized in that: The prepolymerized photosensitive resin is a resin having a vinyl group; and the active monomer is a monomer having a vinyl group.

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