Reactive aggregation luminescent flame-retardant organic functional material and preparation method thereof

Abstract

The invention belongs to the field of organic functional molecules and organic polymer functional materials, and particularly relates to a reactive aggregation luminescent flame-retardant organic functional material and a preparation method thereof. A flame-retardant group DOPO is introduced into molecules containing an aggregation-induced emission TPE group, the flame-retardant group DOPO which simultaneously contains the TPE group with aggregation-induced emission performance and a flame-retardant function in the structure is designed and synthesized, and the flame-retardant group DOPO has good flame-retardant performance while the aggregation-induced emission function is guaranteed.

Description

Technical Field

[0001] This invention belongs to the field of organic functional molecules and organic polymer functional materials, specifically relating to a reactive aggregation luminescent flame-retardant organic functional material and its preparation method. Background Technology

[0002] Academician Tang Benzhong's team first proposed the concept of aggregation-induced emission (AIE), explaining the phenomenon that certain molecules or fragments exhibit enhanced luminescence in an aggregated state due to restricted intramolecular rotation, vibration, or motion. Common organic molecules with AIE function include imides, triphenylamines, phenothiazines, carbazoles, and tetraphenylethylenes. Based on these modules, many solid-state luminescent materials have been synthesized, as shown in the following structural formula: .

[0003] For example, patent [CN114163379] reports that carbazole derivatives containing fluorine and biphenyl groups have the function of emitting blue light; patent [CN120554345] reports that phenothiazine derivatives containing aromatic rings and other groups have the function of electroluminescence; patent [CN120904080] reports that organic light-emitting materials are prepared by chemically bonding two modules, tetraphenylethylene and triarylamine, into the same molecule; patent [CN120574162] reports that isoindoline imide compounds can be applied to OLED materials; and patent [WO2024202086] reports that triarylamine modified into naphthol derivatives has the function of photochromism, etc.

[0004] Tetraphenylethylene (TPE) is an organic light-emitting molecule with a simple molecular structure, which is already industrially produced and exhibits excellent aggregation-induced emission. Using TPE as a basic building block, TPE-based organic light-emitting materials containing different groups or functional groups have been developed, showing broad application prospects. For example, patent WO2025184691 reports an organic probe containing cyano-containing tetraphenylethylene, patent CN120398922 reports a tetraphenylethylene aggregation-emitting material containing a benzodithiophene derivative, patent CN118994189 reports a tetraphenylethylene luminescent material containing a crown ether, patent CN120887872 reports a tetraphenylethylene photosensitizer containing piperazine, and patent CN120904080 reports a tetraphenylethylene luminescent material containing a phenylacetonitrile group.

[0005] To expand the application range of TPE, derivatives containing chemically reactive functional groups are often obtained through chemical modification. For example, patent CN116903504 reports the introduction of carboxyl groups (TPE-COOH) into TPE to enhance water solubility; patent US20250170265 reports the introduction of amino groups (TPE-NH2) into TPE as active sites for further modification; patent WO2010027108 reports the introduction of grafted polyethylene glycol (TPE-PEG) into TPE to reduce biotoxicity; and patent US12391800 reports that the introduction of aldehyde groups (TPE-CHO) into TPE can prepare conjugated polymeric luminescent materials. The structural formulas are shown below: .

[0006] Based on TPE, many TPE-based organic light-emitting molecules have been developed, and their development is moving towards high performance, low cost, and multifunctionality. However, to date, there is no organic aggregated light-emitting molecule that combines aggregated light emission, flame retardancy, and multiple reactive functional groups. Summary of the Invention

[0007] The purpose of this invention is to solve the problem of simultaneously achieving aggregation-induced emission, flame retardancy, and reactivity. This invention selects specific raw materials and introduces a flame-retardant group, DOPO (an abbreviation for 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide), into a molecule containing an aggregation-induced emission TPE group. Specifically, it utilizes tetra(4-aminophenyl)ethylene (ATPE) containing TPE as the aggregation-induced emission molecule, designing and synthesizing a structure that simultaneously contains an aggregation-induced emission TPE group and a flame-retardant group, DOPO, thus ensuring good flame retardancy while maintaining aggregation-induced emission functionality. To ensure a wider range of applications, reactive functional groups such as alcohol hydroxyl, phenolic hydroxyl, secondary amine, and epoxy groups are designed into the reactive aggregation-induced emission flame-retardant organic functional molecule.

[0008] Therefore, this invention first synthesizes DOPO-HQ monoester (Ⅳ) by esterification reaction of DOPO-HQ [abbreviation of 10-(2,5-dihydroxyphenyl)-10-hydro-9-oxa-10-phosphaphenanthrene-10-oxide], a flame retardant containing DOPO groups, and 4-formylbenzoyl chloride raw material. Then, the aldehyde group in DOPO-HQ monoester (Ⅳ) reacts with part of the amino group in tetrakis(4-aminophenyl)ethylene (Ⅴ) to synthesize the intermediate imine (Ⅵ). Finally, hydroxyl and epoxy groups are introduced into the molecular structure to expand its reactivity and broaden its application.

[0009] Specifically, the present invention first provides a reactive aggregated luminescent flame-retardant organic functional material, the structural formula of which is shown in Formula I:

[0010] Formula I Wherein, G is selected from any of the following structural formulas:

[0011] Ⅰ-1 Ⅰ-2 Ⅰ-3 Ⅰ-4 Ⅰ-5 In G, each of the O atoms forms an ether bond with the carbon atom connected in formula I.

[0012] This invention also provides a method for preparing the above-mentioned reactive aggregated luminescent flame-retardant organic functional material. The preparation method includes the following steps: Step (1): DOPO-HQ (Formula II) reacts with 4-formylbenzoyl chloride (Formula III) to synthesize DOPO-HQ monoester (Formula IV).

[0013] Formula II Formula III Formula IV Step (2): DOPO-HQ monoester (Formula IV) reacts with tetrakis(4-aminophenyl)ethylene (Formula V) to synthesize an imine compound (Formula VI);

[0014] Formula V

[0015] Formula VI Step (3): The imine compound (Formula VI) is reacted with bisphenol A diglycidyl ether (Formula VII) to synthesize a reactive aggregated luminescent flame-retardant organic functional material (Formula I):

[0016] Formula VII In Equation VII, G (which is the same as G in Equation I) is selected from any of the following structural formulas;

[0017] Ⅰ-1 Ⅰ-2 Ⅰ-3 Ⅰ-4 Ⅰ-5 In this case, the O in G forms an ether bond with the carbon atom connected to either (Formula VII) or (Formula I).

[0018] Specifically, in step (1) of the above preparation method, the equivalent ratio of DOPO-HQ (Formula II) to 4-formylbenzoyl chloride (Formula III) is 1.0~1.1:1.0.

[0019] Specifically, in step (1) of the above preparation method, the reaction is carried out in the presence of an alkali.

[0020] Furthermore, in step (1) of the above preparation method, the base is selected from one or more of triethylamine, diisopropylethylamine, 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU), pyridine, and 4-(dimethylamino)pyridine. Triethylamine is preferred.

[0021] Specifically, in step (1) of the above preparation method, the equivalent ratio of the alkali to 4-formylbenzoyl chloride (Formula III) is 1.0~1.2:1.0.

[0022] Specifically, in step (1) of the above preparation method, the reaction temperature is -20 ℃ to 30 ℃, preferably -10 ℃ to 5 ℃. The reaction time is 1 to 10 h.

[0023] Specifically, in step (1) of the above preparation method, the solvent used in the reaction is selected from one or more of dichloromethane, tetrahydrofuran, dioxane, toluene, acetonitrile, ethylene glycol dimethyl ether, 2-methylfuran, and DMF. Preferably, it is selected from one or two of dichloromethane and tetrahydrofuran.

[0024] Specifically, in step (1) of the above preparation method, the mass ratio of the solvent to DOPO-HQ (Formula II) used in the reaction is 5~20:1. Preferably, it is 6~10.

[0025] Specifically, in step (2) of the above preparation method, the equivalent ratio of DOPO-HQ monoester (Formula IV) and tetra(4-aminophenyl)ethylene (Formula V) is 2.0~2.2:1.

[0026] Specifically, in step (2) of the above preparation method, the reaction temperature is 60 ℃~160 ℃. Preferably, it is 100 ℃~140 ℃.

[0027] Specifically, in step (2) of the above preparation method, the solvent used in the reaction is selected from dioxane, toluene, xylene, ethylene glycol diethyl ether, etc. N , N -Dimethylformamide (DMF) N , N One or more of dimethylacetamide (DMAc). Preferably, it is selected from one or two of DMF and DMAc.

[0028] Specifically, in step (2) of the above preparation method, the mass ratio of the solvent to tetra(4-aminophenyl)ethylene (formula V) used in the reaction is 10~40:1. Preferably, it is 20~30:1.

[0029] Specifically, in step (3) of the above preparation method, the equivalent ratio of the imine compound (formula VI) to bisphenol A diglycidyl ether (formula VII) is 1:2.0~2.4. Preferably, it is 1:2.1~2.2.

[0030] Specifically, in step (3) of the above preparation method, the reaction temperature is 80 ℃~180 ℃. Preferably, it is 120 ℃~160 ℃.

[0031] Specifically, in step (3) of the above preparation method, the solvent used in the reaction is selected from one or more of dioxane, toluene, ethylene glycol diethyl ether, 2-methylfuran, diisopropyl ether, methyl tert-butyl ether, 1,2-dichloroethane, xylene, DMF, and DMAc. Preferably, it is selected from one or two of DMF and DMAc.

[0032] Specifically, in step (3) of the above preparation method, the mass ratio of the solvent to the imine compound (Formula VI) used in the reaction is 10~40. Preferably, it is 20~25.

[0033] Specifically, in the above preparation method, the reaction is carried out under an inert atmosphere. A nitrogen atmosphere is preferred.

[0034] The present invention also provides the reactive aggregation luminescent flame-retardant organic functional material prepared by the above-mentioned method.

[0035] This invention provides a reactive aggregation-induced light-emitting flame-retardant organic functional material. It retains the tetraphenylethylene (TPE) functional group and introduces the flame-retardant functional group DOPO into the molecular structure through an imine group, thus endowing the aggregation-induced light-emitting material with certain flame-retardant properties. Considering the broader application value of reactive aggregation-induced light-emitting flame-retardant organic functional materials, epoxy groups, alcohol hydroxyl groups, and phenolic hydroxyl groups are introduced into the molecular structure, making the material reactive. It can be prepared into polymeric materials with different functions through different chemical reactions, broadening its application range, improving safety, and showing great application potential. The raw materials for the reactive aggregation-induced light-emitting flame-retardant organic functional material provided by this invention are readily available, and the preparation process is simple and safe. Attached Figure Description

[0036] Figure 1 The 1H NMR spectrum of DOPO-HQ monoester (Ⅳ) obtained in Example 1; Figure 2 The phosphorus NMR spectrum of DOPO-HQ monoester (Ⅳ) obtained in Example 1; Figure 3 The infrared spectra of imine (VI) and its raw material (IV) and ATPE (V) in Example 1 are compared. Figure 4 Comparison of phosphorus spectra of DOPO-HQ (left) and reactive aggregated luminescent flame-retardant organic functional material I-A (right); Figure 5Comparison of raw material ATPE (left) and reactive aggregated luminescent flame-retardant organic functional material I-A (right) under solid natural light; Figure 6 Comparison of raw material ATPE (left) and reactive aggregated luminescent flame-retardant organic functional material I-A (right) under solid ultraviolet light; Figure 7 The relationship between fluorescence intensity and concentration of reactive aggregated luminescent flame-retardant organic functional materials (Ⅰ-A); Figure 8 The relationship between fluorescence intensity and temperature for reactive aggregated luminescent flame-retardant organic functional materials (Ⅰ-A); Figure 9 Flame-retardant composite materials prepared by reactive aggregated luminescent flame-retardant organic functional materials (Ⅰ-A) and EP-51 general-purpose epoxy resin, showing their colors under natural light (left) and ultraviolet light (right); Figure 10 The transparency of flame-retardant composite materials prepared by reactive aggregated luminescent flame-retardant organic functional materials (Ⅰ-A) and EP-51 general-purpose epoxy resin. Detailed Implementation

[0037] The reactive, aggregated, luminescent, flame-retardant organic functional material represented by general formula I of this invention:

[0038] Formula I Wherein, G is selected from any of the following structural formulas:

[0039] Ⅰ-1 Ⅰ-2 Ⅰ-3 Ⅰ-4 Ⅰ-5 In G, each of the O atoms forms an ether bond with the carbon atom connected in formula I.

[0040] The preparation method of the reactive aggregated luminescent flame-retardant organic functional material represented by general formula I of the present invention includes the following three reaction steps: Step (1): DOPO-HQ (Formula II) reacts with 4-formylbenzoyl chloride (Formula III) to synthesize DOPO-HQ monoester (Formula IV): Solvent I, DOPO-HQ as shown in Formula II, and base I are added sequentially to a reactor. 4-formylbenzoyl chloride as shown in Formula III is added under stirring at a certain temperature. After the addition is complete, the reaction continues for 1–10 h, and the reaction progress is monitored by TLC. After the reaction is completed, the reactants are filtered, the filtrate is concentrated, and the residue is added to an aqueous solution of solvent II and base II, and stirred. The organic phase is separated and washed sequentially with saturated sodium carbonate and saturated brine aqueous solution. The organic phase is dried with anhydrous sodium sulfate, the drying agent is filtered, and the filtrate is concentrated to obtain a white solid. The solid is then dried under vacuum at 60–80 °C to obtain DOPO-HQ monoester as shown in Formula IV.

[0041] Formula II Formula III Formula IV Step (2): DOPO-HQ monoester (Formula IV) reacts with tetra(4-aminophenyl)ethylene (Formula V) to synthesize the intermediate imine (Formula VI): Solvent III, DOPO-HQ monoester (Formula IV), and tetra(4-aminophenyl)ethylene (Formula V) are added sequentially to a reactor, and the mixture is heated to a certain temperature with stirring. The reaction progress is monitored by TLC. After the reaction is complete, the reactants are filtered, and the filter cake is washed with solvent II to obtain a yellow solid. The solid is then dried under vacuum at 60–80 °C to obtain the imine compound shown in Formula VI.

[0042] Formula V

[0043] Formula VI Step (3), reacting imine compound (Formula VI) with bisphenol A diglycidyl ether (Formula VII) to synthesize reactive aggregated luminescent flame-retardant organic functional material (Formula I): Solvent IV, imine compound (Formula VI) and bisphenol A diglycidyl ether (Formula VII) are added sequentially to a reactor. The mixture is heated to a certain temperature under stirring until the reactants are homogeneous. The mixture is then cooled to room temperature, filtered, and the filtrate is concentrated to obtain the residue. The residue is washed with solvent V to obtain a yellow solid. The solid is then dried under vacuum at 60–100 °C to obtain the reactive aggregated luminescent flame-retardant organic functional molecule as shown in Formula I.

[0044] Formula VII In equation VII, G is the same as G in equation I, and is selected from any of the following structural formulas:

[0045] Ⅰ-1 Ⅰ-2 Ⅰ-3 Ⅰ-4 Ⅰ-5 In G, each of the O atoms forms an ether bond with the carbon atom connected to either formula VII or formula I.

[0046] In step (1), the solvent is selected from dichloromethane, tetrahydrofuran, dioxane, toluene, acetonitrile, ethylene glycol dimethyl ether, 2-methylfuran, and DMF. The mass ratio of solvent to DOPO-HQ is 5~20:1.

[0047] In step (1), the equivalent ratio of DOPO-HQ (Formula II) to 4-formylbenzoyl chloride (Formula III) is 1.0~1.1:1.0.

[0048] In step (1), the base is selected from triethylamine, diisopropylethylamine, 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU), pyridine, and 4-(dimethylamino)pyridine. The equivalent ratio of the base to 4-formylbenzoyl chloride (Formula III) is 1.0~1.2:1.0.

[0049] In step (1), solvent two is selected from dichloromethane, ethyl acetate, diisopropyl ether, methyl tert-butyl ether, 1,2-dichloroethane, and toluene. Preferably, it is one or both of dichloromethane and ethyl acetate. The mass ratio of solvent two to the residue is 5~20:1.

[0050] In step (1), the certain temperature range is -20 ℃ to 30 ℃.

[0051] In step (1), the second alkali is selected from 5%~10% sodium carbonate solution, 5%~10% potassium carbonate solution, 5% sodium hydroxide solution, and 5% potassium hydroxide solution. Preferably, it is a 5%~10% sodium carbonate solution. The volume ratio of the second alkali solution to the second solvent is 1:1.

[0052] In step (1), the ratio of the amount of saturated sodium carbonate and saturated brine to the volume of the organic phase is approximately 1:1.

[0053] In step (2), the solvent is selected from dioxane, toluene, xylene, ethylene glycol diethyl ether, and... N , N -Dimethylformamide (DMF) N , N -Dimethylacetamide (DMAc). The mass ratio of the solvent tris(4-aminophenyl)ethylene (formula V) is 10~40:1.

[0054] In step (2), the equivalent ratio of DOPO-HQ monoester (Formula IV) to tetra(4-aminophenyl)ethylene (Formula V) is 2.0~2.2:1.

[0055] In step (2), the heating to a certain temperature range is 60 ℃~160 ℃.

[0056] In step (3), the equivalent ratio of the imine compound (formula VI) to bisphenol A diglyceride (formula VII) is 1:2.0~2.4.

[0057] In step (3), solvent four is selected from dioxane, toluene, ethylene glycol diethyl ether, 2-methylfuran, diisopropyl ether, methyl tert-butyl ether, 1,2-dichloroethane, xylene, DMF, and DMAc. The mass ratio of solvent four to the imine compound (formula VI) is 10 to 40.

[0058] In step (3), the heating to a certain temperature range is 80 ℃~180 ℃.

[0059] In step (3), the solvent is selected from cyclohexane, n-hexane, n-heptane, and petroleum ether.

[0060] In this invention, for example, when G in equation VII is the structure shown in equation I-1 When, the structural formula of equation VII (denoted as VII-1) is:

[0061] Formula VII-1 Using formula VII-1 as raw material, the structural formula of the resulting reactive aggregation luminescent flame-retardant organic functional material (denoted as IA) is as follows:

[0062] Formula IA In this invention, for example, when G in equation VII is the structure shown in equation I-2 When, the structural formula of equation VII (denoted as VII-2) is:

[0063] Formula VII-2 Using formula VII-2 as raw material, the structural formula of the resulting reactive aggregated luminescent flame-retardant organic functional material (denoted as IB) is as follows:

[0064] Formula I-B The compound represented by general formula I of this invention contains epoxy groups, alcohol hydroxyl groups and phenolic hydroxyl functional groups in its molecular structure. At the same time, the molecular structure contains aggregation-induced light-emitting groups and flame-retardant groups. The aggregation-induced light-emitting groups and flame-retardant groups can be bonded to various organic materials through corresponding chemical reactions to prepare aggregation-induced light-emitting materials with flame-retardant properties.

[0065] The present invention will be further illustrated below with specific examples of synthetic reactive aggregated luminescent flame-retardant organic functional materials (Ⅰ-A), but these examples do not limit the invention in any way. Unless otherwise specified in the examples, conventional conditions or conditions recommended by the manufacturer should be followed. Reagents or instruments whose manufacturers are not specified are all commercially available products.

[0066] Example 1 (1) Synthesis of DOPO-HQ monoester (Ⅳ) Under nitrogen protection, DOPO-HQ (35.54 g, 109.60 mmol, 1.1 eq) and DCM (220 mL) of Formula II were added sequentially to a dry reaction flask. The mixture was cooled to -10 °C, and p-formylbenzoyl chloride (16.85 g, 99.65 mmol, 1.0 eq) of Formula III was added in portions. The mixture was then slowly heated to 10 °C and the reaction was continued for 6 h. Saturated Na2CO3 solution was then added dropwise until the pH of the reaction solution reached 9-10. The organic phase was separated and washed sequentially with equal volumes of saturated sodium carbonate solution and saturated NaCl solution. The separated organic phase was dried with anhydrous Na2SO4, filtered, concentrated by rotary evaporation, and dried to obtain a white solid DOPO-HQ monoester (IV).

[0067] 1H and 1P NMR spectra of DOPO-HQ monoester (Ⅳ) (solvent DMSO- d 6) See separately Figure 1 and Figure 2 Infrared spectrum (potassium bromide tablets) see [link to infrared spectrum]. Figure 3 (Black line IV).

[0068] (2) DOPO-HQ monoester (Ⅳ) reacts with ATPE (Ⅴ) to synthesize the intermediate imine (Ⅵ). Under nitrogen protection, tetratetra(4-aminophenyl)ethylene (3.92 g, 10.00 mmol), DOPO-HQ monoester (10.04 g, 22.00 mmol), and DMAc (100 mL) were added sequentially to a dry reaction flask. The mixture was heated to 120 °C with stirring, and the reaction was monitored by TLC (PE:EA = 1:1). After the reaction was completed, the mixture was cooled to below room temperature, filtered, and the filter cake was washed twice with dichloromethane and dried to obtain a deep yellow imine (VI). The imine is sparingly soluble in organic solvents. The infrared spectrum of imine (VI) is shown below. Figure 3 (Blue line VI) To compare the infrared spectra of DOPO-HQ monoester (black line IV) and ATPE (red line V), they were plotted simultaneously. Figure 3 .

[0069] (3) Synthesis of reactive aggregated luminescent flame-retardant organic functional materials (Ⅰ-A) Under nitrogen protection, imine (VI) (6.00 g, 4.72 mmol), bisphenol A diglycidyl ether (3.53 g, 10.38 mmol), and DMAc (180 mL) were added sequentially to a dry reaction flask. The mixture was heated to 140 °C with stirring until the reaction solution became homogeneous. The reaction solution was then cooled to room temperature and further cooled with ice water. After filtration, the filter cake was washed with n-hexane and dried to obtain the reactive aggregation-luminescent flame-retardant organic functional molecule (Ⅰ-A). The phosphorus NMR spectrum of the reactive aggregation-luminescent flame-retardant organic functional molecule (Ⅰ-A) was obtained using DMSO- d 6) For example Figure 4As shown on the right, Figure 4 (Left) Phosphorus spectrum of raw material DOPO-HQ (solvent DMSO-) d 6).

[0070] Under natural light, ATPE is a brown solid, see Figure 5 As shown on the left, the reactive aggregated luminescent flame-retardant organic functional molecule I-A is a yellow solid. Figure 5 As shown on the right. Under ultraviolet light, ATPE appears cyan. Figure 6 As shown on the left, the reactive aggregated luminescent flame-retardant organic functional molecule I-A is green. Figure 6 As shown on the right, this indicates that the reactive aggregation-luminescent flame-retardant organic functional molecule I-A still possesses aggregation-luminescent properties, and the emission wavelength has a red shift (the green wavelength is greater than the cyan wavelength).

[0071] Example 2 (1) Synthesis of DOPO-HQ monoester (Ⅳ) Under nitrogen protection, DOPO-HQ (16.20 g, 49.95 mmol, 1.0 eq) and toluene (100 mL) of Formula II were added sequentially to a dry reaction flask. The mixture was cooled to 0 °C, and p-formylbenzoyl chloride (8.42 g, 49.94 mmol, 1.0 eq) of Formula III was added in portions. The mixture was then kept at 0 °C and the reaction continued for 8 h. Saturated Na2CO3 solution was then added dropwise until the pH of the reaction solution reached 9-10. The organic phase was separated and washed sequentially with equal volumes of saturated sodium carbonate solution and saturated NaCl solution. The separated organic phase was dried with anhydrous Na2SO4, filtered, concentrated by rotary evaporation, and dried to obtain a white solid DOPO-HQ monoester (IV).

[0072] (2) DOPO-HQ monoester (Ⅳ) reacts with ATPE (Ⅴ) to synthesize imine (Ⅵ). Under nitrogen protection, tetratetra(4-aminophenyl)ethylene (1.96 g, 5.0 mmol), DOPO-HQ monoester (5.02 g, 11.0 mmol), and DMAc (80 mL) were added sequentially to a dry reaction flask. The mixture was heated to 140 °C with stirring, and the reaction progress was monitored by TLC (PE:EA = 1:1). After the reaction was completed, the mixture was cooled to below room temperature, filtered, and the filter cake was washed twice with dichloromethane and dried to obtain a deep yellow imine (VI).

[0073] (3) Synthesis of reactive aggregated luminescent flame-retardant organic functional molecules (Ⅰ-A) Under nitrogen protection, imine (VI) (3.00 g, 2.36 mmol), bisphenol A diglycidyl ether (1.76 g, 5.19 mmol), and DMF (100 mL) were added sequentially to a dry reaction flask. The mixture was heated to 140 °C with stirring until the reaction solution was homogeneous. The reaction solution was then cooled to room temperature and then cooled with ice water. After filtration, the filter cake was washed with n-hexane and dried to obtain the reactive aggregated luminescent flame-retardant organic functional molecule (Ⅰ-A).

[0074] Analysis of Aggregation-Luminescence Performance of Reactive Aggregation-Luminescent Flame-Retardant Organic Functional Materials (Ⅰ-A)

[0075] Using DMF as the solvent for reactive aggregated luminescent flame-retardant organic functional materials (Ⅰ-A), it was prepared to a concentration of 10. -3 In a mol / L DMF solution, the 10 of I-A was measured. -3 The fluorescence emission wavelength at a concentration of mol / L was 485 nm (20 °C). It was then sequentially diluted to 10... -4 mol / L, 10 -5 mol / L, 10 -6 mol / L, 10 -7 mol / L, 10 -8 mol / L and 10 -9 The relative fluorescence emission intensity of reactive aggregate-luminescent flame-retardant organic functional material (Ⅰ-A) was measured in mol / L DMF solution as a function of concentration. The change in fluorescence intensity with concentration was investigated, and the results are as follows: Figure 7 As shown in the figure. Experimental results show that the fluorescence intensity of I-A decreases with decreasing concentration, indicating that I-A has a strong aggregation-induced emission function.

[0076] With a concentration of 10 -3 A mol / L DMF solution of I-A was used to measure the fluorescence intensity at 20 ℃, 30 ℃, 40 ℃, 50 ℃, and 60 ℃, respectively, to investigate the change in fluorescence intensity with temperature. The results are as follows: Figure 8 As shown in the figure. Experimental results show that the fluorescence intensity of I-A decreases with increasing temperature, decreasing by 55.4% when heated to 60 ℃. This function can be used for safety protection alerts.

[0077] Application Examples of Epoxy Groups in Reactive Aggregation-Luminescent Flame-Retardant Organic Functional Material I-A

[0078] Weigh 10.00 g of EP-51 glycidyl ether epoxy resin preheated to 80-90 °C and place it in a beaker. Add 10.00 g of the reactive aggregated luminescent flame-retardant organic functional material I-A prepared in the example. After stirring until homogeneous, add 2.00 g of the curing agent m-phenylenediamine and continue stirring until the mixture is milky white. Pour the mixture into a mold preheated to 90-100 °C while stirring, and then place it in a constant temperature oven at 120 °C for curing reaction for 12 h.

[0079] Experimental results show that when reactive, aggregation-luminescent, flame-retardant organic functional material I-A is mixed with EP-51 general-purpose glycidyl ether epoxy resin, the resulting composite material, obtained under the action of a curing agent, still possesses aggregation-luminescent properties. It appears yellow under natural light and pale green under ultraviolet light. Figure 9 As shown.

[0080] Experimental results also show that reactive aggregated luminescent flame-retardant organic functional material I-A can maintain the transparency of EP-51 type general-purpose glycidyl ether epoxy resin composite material, such as... Figure 10 As shown.

[0081] Because reactive, aggregated, luminescent, flame-retardant organic functional material I-A contains halogen-free flame-retardant element phosphorus, it can impart certain flame-retardant properties to EP-51 general-purpose glycidyl ether epoxy resin composite materials, requiring three consecutive ignition attempts to ignite. The first attempt is difficult to ignite within 10''; the second attempt requires approximately 8'' to ignite, after which it self-extinguishes; the third attempt results in a slow flame spread, lasting approximately 1'20'' before self-extinguishing.

Claims

1. The reactive, aggregated, luminescent, flame-retardant organic functional material represented by general formula (I): ； Formula I in, G is selected from any of the following structural formulas: ； Ⅰ-1 Ⅰ-2 Ⅰ-3 Ⅰ-4 Ⅰ-5 In G, each of the O atoms forms an ether bond with the carbon atom connected in formula I.

2. The preparation method of the reactive aggregation luminescent flame-retardant organic functional material according to claim 1, characterized in that: Includes the following steps: Step (1): DOPO-HQ (Formula II) reacts with 4-formylbenzoyl chloride (Formula III) to synthesize DOPO-HQ monoester (Formula IV). ； Formula II Formula III Formula IV Step (2): DOPO-HQ monoester (Formula IV) reacts with tetrakis(4-aminophenyl)ethylene (Formula V) to synthesize an imine compound (Formula VI); ； Formula V ； Formula VI Step (3): The imine compound (Formula VI) is reacted with bisphenol A diglycidyl ether (Formula VII) to synthesize a reactive aggregated luminescent flame-retardant organic functional material (Formula I): ； Formula VII G is selected from any of the following structural formulas: ； Ⅰ-1 Ⅰ-2 Ⅰ-3 Ⅰ-4 Ⅰ-5 In G, each of the O atoms forms an ether bond with the carbon atom connected to the carbon atom in formula VII.

3. The preparation method of the reactive aggregated luminescent flame-retardant organic functional material according to claim 2, characterized in that: In step (1), the equivalent ratio of DOPO-HQ (Formula II) to 4-formylbenzoyl chloride (Formula III) is 1.0~1.1:1.

0.

4. The preparation method of the reactive aggregated luminescent flame-retardant organic functional material according to claim 2, characterized in that: In step (1), the reaction is carried out in the presence of a base; the base is selected from one or more of triethylamine, diisopropylethylamine, 1,8-diazabicyclo[5.4.0]undec-7-ene, pyridine, and 4-(dimethylamino)pyridine.

5. The preparation method of the reactive aggregated luminescent flame-retardant organic functional material according to claim 2, characterized in that: In step (1), the reaction temperature is -20 ℃ to 30 ℃.

6. The method for preparing the reactive aggregated luminescent flame-retardant organic functional material according to claim 2, characterized in that: In step (2), the equivalent ratio of DOPO-HQ monoester (Formula IV) to tetra(4-aminophenyl)ethylene (Formula V) is 2.0~2.2:

1.

7. The preparation method of the reactive aggregated luminescent flame-retardant organic functional material according to claim 2, characterized in that: In step (2), the reaction temperature is 60 ℃~160 ℃.

8. The method for preparing the reactive aggregated luminescent flame-retardant organic functional material according to claim 2, characterized in that: In step (3), the equivalent ratio of the imine compound (formula VI) to bisphenol A diglycidyl ether (formula VII) is 1:2.0~2.

4.

9. The preparation method of the reactive aggregated luminescent flame-retardant organic functional material according to claim 2, characterized in that: In step (3), the reaction temperature is 80 ℃~180 ℃.

10. The method for preparing reactive aggregated luminescent flame-retardant organic functional materials according to any one of claims 2-9, characterized in that: Meet at least one of the following conditions: In step (1), the solvent used in the reaction is selected from one or more of dichloromethane, tetrahydrofuran, dioxane, toluene, acetonitrile, ethylene glycol dimethyl ether, 2-methylfuran, and DMF; In step (2), the solvent used in the reaction is selected from dioxane, toluene, xylene, ethylene glycol diethyl ether, etc. N , N -Dimethylformamide, N , N One or more of dimethylacetamide; In step (3), the solvent used in the reaction is selected from one or more of dioxane, toluene, ethylene glycol diethyl ether, 2-methylfuran, diisopropyl ether, methyl tert-butyl ether, 1,2-dichloroethane, xylene, DMF, and DMAc.

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