CN116253667A - Aggregation-induced emission material and preparation method thereof - Google Patents

Aggregation-induced emission material and preparation method thereof Download PDF

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CN116253667A
CN116253667A CN202211686434.2A CN202211686434A CN116253667A CN 116253667 A CN116253667 A CN 116253667A CN 202211686434 A CN202211686434 A CN 202211686434A CN 116253667 A CN116253667 A CN 116253667A
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reaction
aggregation
fluorescent
induced emission
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吴兵
齐庆杰
刘英杰
程会锋
柴佳美
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General Coal Research Institute Co Ltd
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Beijing Technology Research Branch Of Tiandi Technology Co ltd
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Abstract

The application provides an aggregation-induced emission material and a preparation method thereof, wherein the preparation method of the aggregation-induced emission material comprises the following steps: carrying out a first reaction on a fluorescent raw material, an organic solvent and chlorosulfonic acid in inert atmosphere under the action of a Lewis acid catalyst to obtain a reaction liquid; carrying out a second reaction on the reaction liquid and alkali to obtain the aggregation-induced emission material; the Lewis acid catalyst is trimethylchlorosilane. According to the preparation method of the aggregation-induced emission material, the chlorosulfonation reaction is promoted to be carried out efficiently by adopting the Lewis acid catalyst (trimethylchlorosilane), byproducts are avoided, the reaction steps are simple, the reaction is stable, the yield is high, the product has good water solubility, and the prepared fluorescent material can further expand application scenes, such as sensing and the like.

Description

Aggregation-induced emission material and preparation method thereof
Technical Field
The application belongs to the technical field of organic fluorescent material synthesis, and particularly relates to an aggregation-induced emission material and a preparation method thereof.
Background
The organic fluorescent material has the advantages of light weight, easy synthesis, easy molding, fine adjustment of performance and the like, has become one of research hot spots in the field of materials by virtue of the unique photophysical performance, has abundant application in the fields of chemical sensing, cell imaging, drug delivery, organic light-emitting diodes, disease diagnosis and treatment and the like, and plays an important role in scientific research and daily life. To date, many types of organic fluorescent compounds have been developed.
The concept of aggregation-induced emission (AIE) proposed by the university of hong Kong science and technology Tang Benzhong et al provides a new idea and method for solving the aggregation-induced fluorescence quenching problem. In the last twenty years, researchers develop a series of small molecules and polymers with AIE characteristics, and compared with the traditional fluorescent materials, the fluorescent materials are more suitable for application in solid-state scenes, and have wide theoretical and practical application values in the fields of chemical sensing, biological probes, photoelectric devices and the like. However, conventional AIE small molecules typically have rigid conjugated structures (e.g., benzene rings and other heterocycles), are poorly soluble in water, and are not suitable for detection in the aqueous phase.
In addition, polyelectrolytes fall into two broad categories, natural and synthetic, and many natural biological macromolecules, including proteins, nucleic acids and polysaccharides, are polyelectrolytes. The synthesized polyelectrolyte is mainly used in the food industry, sewage treatment, medical diagnosis and treatment, and the like. For example, a nitrogen-containing polyelectrolyte of high charge density has a strong electrostatic effect on negatively charged bacterial membranes, nucleic acids, etc., and can encapsulate bacteria to inhibit their growth, thereby killing the bacteria. Compared with uncharged molecules, the polyelectrolyte with a plurality of positive and negative charges has the advantages of good water solubility, biocompatibility, photostability, adjustable structure and function and the like. Currently, polyelectrolytes having AIE properties are less studied and focused on cationic, while negatively charged AIE conjugated polyelectrolytes are quite rarely studied.
By introducing a plurality of hydrophilic groups such as sodium sulfonate groups and the like, fluorescent micromolecules are synthesized or AIE conjugated polyelectrolyte with negative charges is constructed, so that the solubility of the AIE conjugated polyelectrolyte in water can be greatly improved, and the application range of the material is greatly expanded. Therefore, development of a fluorescent small molecule and polyelectrolyte for efficiently producing an AIE having a polysulfonate group and having good water solubility is an important issue at present. However, in the case of the above-mentioned fluorescent small molecules and negatively charged AIE conjugated polyelectrolytes, the existing methods tend to have complicated synthetic routes (multi-step synthesis, low yield, complicated separation and purification processes, etc.), or the reaction conditions are severe or efficient introduction of a plurality of sodium sulfonate groups cannot be achieved. For example TPE-2SO in paper Design of activatable red-emissive assay for cysteine detection in aqueous medium with aggregation induced emission characteristics by He Ning et al 3 The synthesis of Na, namely, removing methoxy groups by utilizing boron tribromide to obtain phenolic hydroxyl groups, and then reacting with 1, 3-propane sultone, wherein the synthesis route has more steps, low yield and poor water solubility due to the small number of sodium sulfonate groups. WS-TPE in the paper "Aggregation-reduced version (AIE) characteristic of water-soluble Tetraphenylethene (TPE) bearing four sulfonate salts" by Joji Ohshita et al is obtained by heating concentrated sulfuric acid to 115℃for reaction, and has high reaction temperature and low yield, and 1mol of water is generated every 1mol of sulfonation product is generated as a sulfonation reagent, thereby affecting the reaction rate. Zhao Jiangjiang et al, in the paper "synthesis of sulfonated tetraphenyl ethylene fluorescent dye and its luminescence property", TPE-1S, although chlorosulfonic acid sulfonation is adopted, only one sulfonic acid group can be introduced into the molecule, and the aqueous solution is poor. Currently, there is no precedent for AIE fluorescent polymers to build polyelectrolytes.
Disclosure of Invention
In view of this, an object of the present application is to provide a method for preparing an aggregation-induced emission material, which uses a lewis acid catalyst (trimethylchlorosilane) to promote chlorosulfonation reaction to proceed efficiently, without high temperature condition, and has the advantages of stable reaction, simple reaction steps, nearly hundred percent yield, far higher than reported values in literature, nearly no by-product, good water solubility of the product, and further expanding the application scenarios of the fluorescent material, such as sensing, etc.
It is another object of the present application to provide an aggregation-induced emission material.
To achieve the above object, an embodiment of a first aspect of the present application provides a method for preparing an aggregation-induced emission material, including:
carrying out a first reaction on a fluorescent raw material, an organic solvent and chlorosulfonic acid in inert atmosphere under the action of a Lewis acid catalyst to obtain a reaction liquid;
carrying out a second reaction on the reaction liquid and alkali to obtain the aggregation-induced emission material;
the Lewis acid catalyst is trimethylchlorosilane.
In some embodiments, the fluorescent material is one of a multi-benzene ring fluorescent small molecule or a multi-benzene ring fluorescent polymer.
In some embodiments, the organic solvent is one or more of ethyl acetate, methylene chloride, chloroform, carbon tetrachloride.
In some embodiments, the fluorescent materials include, but are not limited to, one of compounds 1-4 and polymers 5-8;
Figure BDA0004021219960000031
in some embodiments, the organic solvent is used in an amount of 5-30 milliliters of the organic solvent per gram of the fluorescent feedstock.
In some embodiments, the chlorosulfonic acid is used in an amount a times the number of moles of the multi-benzene ring fluorescent molecule or a times the number of moles of repeat units of the multi-benzene ring fluorescent polymer; and a is the molecular formula of the multi-benzene ring fluorescent molecule or the total number of exposed benzene rings in the repeating unit of the multi-benzene ring fluorescent polymer.
In some embodiments, the lewis acid catalyst is used in an amount of 0.001 to 0.08 times the mass of the fluorescent feedstock.
In some embodiments, the molar ratio of chlorosulfonic acid to the base is 1: (1.05-20).
In some embodiments, the first reaction temperature is (-5) -5 ℃, and the first reaction time is 1-5h.
In some embodiments, the second reaction temperature is room temperature, which may be 20-30 ℃, and the second reaction time is 0.1-1h.
In some embodiments, the method of preparing an aggregation-induced emission material further comprises: before the first reaction, the fluorescent raw material is dissolved in the organic solvent, then the Lewis acid catalyst is added, and the mixture of the fluorescent raw material, the organic solvent and the Lewis acid catalyst is obtained after cooling in ice water bath.
In some embodiments, the chlorosulfonic acid is added to the first reaction system by dropwise addition.
In some embodiments, the method of preparing an aggregation-induced emission material further comprises: and transferring the reaction solution to ice before the reaction solution and the alkali are subjected to a second reaction, and removing the organic solvent by rotary evaporation.
In some embodiments, the method of preparing an aggregation-induced emission material further comprises: and after the reaction liquid and the alkali are subjected to a second reaction, extracting by using an extractant to remove the Lewis acid catalyst, dialyzing to remove the alkali and sodium chloride, and drying to obtain the aggregation-induced emission material.
In some embodiments, the extractant is one or more of dichloromethane, ethyl acetate, chloroform.
In some embodiments, the base is sodium hydroxide.
In order to achieve the above object, a second aspect of the present application provides an aggregation-induced emission material, which is prepared by using the preparation method of the aggregation-induced emission material of the embodiment of the present application.
The preparation method of the aggregation-induced emission material has the following beneficial effects:
the method adopts a Lewis acid catalyst (trimethylchlorosilane) to promote the chlorosulfonation reaction to be carried out efficiently, does not need high-temperature conditions, has stable reaction, simple reaction steps, nearly hundred percent of yield, far higher than a literature report value, nearly no byproduct is produced, and the product has good water solubility, so that the prepared fluorescent material can further expand the application scene, such as sensing and the like.
Additional aspects and advantages of the application will be set forth in part in the description which follows and, in part, will be obvious from the description, or may be learned by practice of the application.
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The foregoing and/or additional aspects and advantages of the present application will become apparent and readily appreciated from the following description of the embodiments, taken in conjunction with the accompanying drawings, in which:
FIG. 1 is a nuclear magnetic resonance diagram of the product of example 1 of the present application.
FIG. 2 is a graph showing the decrease in fluorescence with increasing water content of the product of example 1 of the present application in a water-ethanol mixed solution.
Detailed Description
The following detailed description of embodiments of the present application is exemplary and intended to be used to explain the present application and should not be taken as limiting the present application.
In the application, the disclosure of numerical ranges includes disclosure of all values and further sub-ranges within the entire range, including endpoints and sub-ranges given for these ranges.
In the application, the related raw materials, equipment and the like are all raw materials and equipment which can be self-made by commercial paths or known methods unless specified otherwise; the methods involved, unless otherwise specified, are all conventional.
The preparation method of the aggregation-induced emission material comprises the following steps:
s101, performing a first reaction on a fluorescent raw material, an organic solvent and chlorosulfonic acid in an inert atmosphere under the action of a Lewis acid catalyst to obtain a reaction liquid; the Lewis acid catalyst is trimethylchlorosilane.
In other embodiments, to avoid the problem of reaction failure caused by insolubilization of the fluorescent material in the first reaction, the fluorescent material may be dissolved in an organic solvent prior to the first reaction, then a lewis acid catalyst may be added, and cooled in an ice water bath to obtain a mixture of the fluorescent material, the organic solvent, and the lewis acid catalyst. Wherein the cooling time includes, but is not limited to, 10-30 minutes. And then reacting the fluorescent raw material, the organic solvent and the Lewis acid catalyst mixture with chlorosulfonic acid. The chlorosulfonic acid may be added to the first reaction system by simple mixing or dripping. Preferably, in some embodiments, the chlorosulfonic acid is added dropwise to the first reaction system in order to ensure smoothness of the first reaction, since chlorosulfonic acid is exothermic in the first reaction. As a non-limiting example, the time for dropwise adding chlorosulfonic acid into the reaction system per milliliter is controlled to be between 5 and 30 minutes, for example, 10 minutes, and the dropwise adding time is less than 5 minutes, so that side reactions are easy to occur, the yield is low, the dropwise adding time is too long and uneconomical, and the time is wasted.
In some embodiments, the fluorescent material is one of a multi-benzene ring fluorescent small molecule or a multi-benzene ring fluorescent polymer. As non-limiting examples, fluorescent materials include, but are not limited to, one of compounds 1-4 and polymers 5-8;
Figure BDA0004021219960000051
wherein, the fluorescent raw materials 1-4 belong to the multi-benzene ring fluorescent micromolecules, and the fluorescent raw materials 5-8 belong to the multi-benzene ring fluorescent polymer. It should be noted that, in the present application, the number of sulfonic acid groups that can be introduced at most is determined according to the number of naked benzene rings in the fluorescent raw material, for example: the theoretical value of the dosage of chlorosulfonic acid in the compound 1 is 4 times of the 1 mole number of the fluorescent raw material compound when the compound contains 4 benzene rings capable of introducing sulfonic acid groups, and the reaction formula is shown as the formula (I); the theoretical value of the dosage of the compound 2-4 and chlorosulfonic acid is 2 times, 6 times and 2 times of the mole number of the fluorescent compound 2-4 respectively; each repeating unit (structure in brackets in the figure) of the polymer 5 contains 4 benzene rings capable of introducing sulfonic acid groups, so that the theoretical amount of chlorosulfonic acid is 4 times the mole number of the repeating unit of the fluorescent raw material 5 (the mole number of the repeating unit=mass/the amount of the repeating unit formula, and the following is the same), and the reaction formula is shown in a formula (II); the theoretical value of the dosage of the polymer 6-8 and chlorosulfonic acid is 2 times of the mole number x of the repeating units of the fluorescent raw material 6-8. To achieve a high degree of reaction of the polymer, the molecular weight of the polymers 5 to 8 does not exceed 6000g/mol as much as possible. That is, in the present application, when the fluorescent material adopts the multi-benzene ring fluorescent molecule, the amount of chlorosulfonic acid is a times the number of moles of the multi-benzene ring fluorescent molecule, and a is the total number of exposed benzene rings in the molecular formula of the multi-benzene ring fluorescent molecule; when the fluorescent material adopts the multi-benzene ring fluorescent polymer, the dosage of chlorosulfonic acid is a times of the mole number of the repeated units of the multi-benzene ring fluorescent polymer, and a is the total number of the exposed benzene rings in the repeated units of the multi-benzene ring fluorescent polymer.
Figure BDA0004021219960000061
In some embodiments, the first reaction may be performed in a corrosion resistant reaction vessel or flask, or the like.
It should be noted that, the fluorescent raw materials in the present application may be prepared by themselves, or may be obtained by a commercially available route; if the preparation is self-preparation, the preparation method is a known method and is not described in detail herein. Taking compound 1 (tetraphenyl ethylene (TPE)) as an example, it can be prepared by means of the makery reaction, i.e. the benzophenone is coupled in one step under the catalysis of zinc powder and titanium tetrachloride. Polymer 5 is described in Aggregation-Induced Emission and Photocyclization of Poly (hexaphenyl-1, 3-butadiene) s Synthesized from "1+2"Polycoupling of Internal Alkynes and Arylboronic Acids; polymers 6-8 are described in Luminogenic materials constructed from tetraphenylethene building blocks: synthesis, aggregation-induced emission, two-photon absorption, light reflection, and explosive detection.
In some embodiments, the ratio of the volume of organic solvent (mL) to the mass of fluorescent material (g) is 5-30, and further may be 7.5-22.5. As non-limiting examples, the ratio of the mass of the fluorescent raw material to the volume of the organic solvent includes, but is not limited to, 7.5, 10, 15, 17.5, 20, or 22.5, etc.
In some embodiments, the lewis acid catalyst is used in an amount of 0.001 to 0.08 times the mass of the fluorescent starting material, and further may be used in an amount of 0.005 to 0.05 times. As non-limiting examples, the amount of lewis acid catalyst used includes, but is not limited to, 0.005 times, 0.008 times, 0.01 times, 0.025 times, 0.04 times, 0.05 times, etc., the mass of the fluorescent feedstock. If the amount is less than 0.001, the effect of catalytic reaction cannot be achieved; if the ratio is more than 0.08, side reactions and other reasons may occur, which may result in reduced yield, wasted reagent and increased difficulty in purification and separation.
In some embodiments, the molar ratio of chlorosulfonic acid to base is 1: (1.05-20).
Preferably, the Lewis acid catalyst is trimethylchlorosilane, so that the reaction temperature is reduced to 0 ℃, side reactions can be avoided, the separation is easy, the purchase is easy, the whole scheme is convenient for commercialization, and the effect is that the yield is almost hundred percent, which cannot be realized by other catalysts.
In some embodiments, the first reaction temperature is (-5) -5 ℃ and the reaction time is 1-5h. As non-limiting examples, the reaction temperature includes, but is not limited to, 0, -5, or 5 ℃, and the first reaction time includes, but is not limited to, 1h, 2h, 3h, 4h, 5h, or the like. Preferably, the first reaction is carried out in an ice-water bath with a mass ratio of ice to fluorescent material in the range of 5 to 40. The first reaction temperature was only the temperature in the reaction flask regardless of the ambient room temperature.
In some embodiments, the organic solvent is one or more of ethyl acetate, methylene chloride, chloroform, carbon tetrachloride.
In some embodiments, the inert atmosphere includes, but is not limited to, one or more of argon, helium, nitrogen, or the like.
S102, carrying out a second reaction on the reaction liquid and alkali to obtain the aggregation-induced emission material.
In some embodiments, the second reaction temperature is room temperature, which may be 20-30 ℃, and the second reaction time is 0.1-1h.
In other embodiments, the organic solvent may be removed from the reaction solution prior to the second reaction of the reaction solution with the base to facilitate the reaction, and the method for removing the organic solvent from the reaction solution includes, but is not limited to: the organic solvent was removed by rotary evaporation.
In some embodiments, the base includes, but is not limited to, sodium hydroxide. For example, a sodium hydroxide solution prepared from 2.4g of sodium hydroxide and 5 to 15mL of water may be used.
In the present application, the base is preferably in excess, so that, on the one hand, it is ensured that all of the sulfonic acid groups produced by the first reaction are converted into salts, and, on the other hand, hydrogen chloride or the like produced by the first reaction can be removed.
In some embodiments, the method of preparing the aggregation-induced emission material further comprises a step of removing the lewis acid catalyst, the specific method including, but not limited to: after the reaction liquid and alkali are subjected to a second reaction, the Lewis acid catalyst is removed by extraction with an extractant, then alkali and sodium chloride are removed by dialysis, and the aggregation-induced emission material is obtained by drying. Wherein the extractant can be one or more of dichloromethane, ethyl acetate and chloroform. As a non-limiting example, the ratio of the volume of extractant (mL) to the mass of water in the system (g) is 1:0.1-10. The water mainly refers to the water brought into the system by alkali solution (sodium hydroxide solution) and ice melting.
In some embodiments, the method of dialysis to remove alkali and sodium chloride is: dialyzing in 100-500D dialysis bag in water for 8-15 hr, and changing water repeatedly until the residual alkali and sodium chloride in the dialysis bag are completely removed.
In some embodiments, the drying means may be reduced pressure rotary evaporation or freeze drying, wherein the temperature of freeze drying includes, but is not limited to, -90-0 ℃, and the temperature of reduced pressure rotary evaporation includes, but is not limited to, 30-90 ℃.
The preparation method of the aggregation-induced emission material has the following beneficial effects:
the method has the advantages that the chlorosulfonation reaction is promoted to be carried out efficiently by adopting a Lewis acid catalyst (trimethylchlorosilane), high-temperature conditions are not needed, the reaction is stable, the reaction steps are simple, the yield is nearly hundred percent, the method is far higher than a literature report value, almost no byproducts are produced, the product has good water solubility, and the prepared fluorescent material can further expand the application scene of the fluorescent material, such as sensing and the like.
The aggregation-induced emission material of the embodiment of the application is prepared by adopting the preparation method of the aggregation-induced emission material of the embodiment of the application.
The preparation method of the aggregation-induced emission material according to the embodiment of the present application is further described below with reference to specific examples.
Example 1
Compound 1 (0.003 mol) and dichloromethane (10 mL) were added sequentially to a round bottom flask, stirred until the solid was completely dissolved, and trimethylchlorosilane (8 mg) was added and cooled in an ice water bath for 15min. Chlorosulfonic acid (0.012 mol) was slowly added dropwise over 15min under argon protection and reacted at 0℃for 2h. The reaction solution was then carefully transferred to 20g of ice, the dichloromethane was removed by rotary evaporation, 10mL of sodium hydroxide solution (2.4 g of sodium hydroxide, 10mL of water) was added to react for 0.5h at 25 ℃, extraction was performed with dichloromethane (20 mL x 3 times), the lewis acid catalyst trimethylchlorosilane was removed, the aqueous phase was dialyzed in water with a 100-500D dialysis bag for 12h, during which time water was changed several times until all of the sodium hydroxide and sodium chloride remained in the dialysis bag were removed, and freeze-drying was performed to obtain a pale yellow solid product with a yield of 99%.
The pale yellow solid of this example was subjected to nuclear magnetic resonance, mass spectrometry, and infrared detection, and the result was: 1 H NMR(600MHz,D 2 o), δ (TMS, ppm) 7.53 (d, j=8.4 hz,8 h), 7.19 (d, j=8.4 hz,8 h) (as shown in fig. 1); 13 CNMR(150MHz,D 2 O),δ(TMS,ppm):127.78,134.36,143.57,143.71,148.12；HRMS(ESI):m/z(％):[M - 4H - ]calcd for C 26 H 16 O 12 S 4 ,161.9886；found 161.9882。FT-IR:1173,1128,1031,1014cm -1 . Indicating successful synthesis.
The graph of fluorescence decrease with increasing water content in the water-ethanol mixed solution (as shown in fig. 2) shows that the excitation wavelength is 350nm, which shows typical aggregation-induced emission characteristics, because the product (pale yellow solid) of this example has good solubility in the aqueous solution, no fluorescence, and has good fluorescence properties with decreasing water content due to limited intramolecular movement.
Example 2
Compound 2 (0.003 mol) and dichloromethane (12 mL) were added sequentially to a round bottom flask, stirred until the solid was completely dissolved, and trimethylchlorosilane (10 mg) was added and cooled in an ice water bath for 15min. Chlorosulfonic acid (0.012 mol) was slowly added dropwise over 15min under argon protection and reacted at 0℃for 2h. The reaction solution was then carefully transferred to 20g of ice, the dichloromethane was removed by rotary evaporation, 10mL of sodium hydroxide solution (2.4 g of sodium hydroxide, 10mL of water) was added to react for 0.5h at 25 ℃, extraction was performed with dichloromethane (20 mL x 3 times), the lewis acid catalyst trimethylchlorosilane was removed, the aqueous phase was dialyzed in water with a 100-500D dialysis bag for 12h, during which time water was changed several times until all of the sodium hydroxide and sodium chloride remained in the dialysis bag were removed, and freeze-drying was performed to obtain a pale yellow solid product with a yield of 99%.
Example 3
Compound 3 (0.003 mol) and dichloromethane (15 mL) were added sequentially to a round bottom flask, stirred until the solid was completely dissolved, and trimethylchlorosilane (13 mg) was added and cooled in an ice water bath for 15min. Chlorosulfonic acid (0.018 mol) was slowly added dropwise over 22min under argon and reacted at 0deg.C for 2h. The reaction solution was then carefully transferred to 20g of ice, the dichloromethane was removed by rotary evaporation, sodium hydroxide solution (3 g of sodium hydroxide, 10mL of water) was added and reacted at 25 ℃ for 0.5h, extraction was performed with dichloromethane (20 mL x 3 times), the lewis acid catalyst trimethylchlorosilane was removed, the aqueous phase was dialyzed in water with a 100-500D dialysis bag for 12h, during which time water was changed several times until all of the sodium hydroxide and sodium chloride remained in the dialysis bag were removed, and freeze-dried to obtain the product as a pale yellow solid with a yield of 99%.
Example 4
Compound 4 (0.003 mol) and chloroform (7.5 mL) were added sequentially to a round bottom flask, stirred until the solid was completely dissolved, and trimethylchlorosilane (6 mg) was further added and cooled in an ice water bath for 15min. Chlorosulfonic acid (0.006 mol) was slowly added dropwise over 8min under argon protection and reacted at 0℃for 2h. The reaction solution was then carefully transferred to 20g of ice, the chloroform was removed by rotary evaporation, sodium hydroxide solution (2.4 g of sodium hydroxide, 10mL of water) was added and reacted at 25 ℃ for 0.5h, extraction was performed with dichloromethane (20 mL x 3 times), the lewis acid catalyst trimethylchlorosilane was removed, the aqueous phase was dialyzed in water with a 100-500D dialysis bag for 12h, during which time water was changed several times until all of the sodium hydroxide and sodium chloride remained in the dialysis bag were removed, and freeze-dried to obtain a pale yellow solid product with a yield of 99%.
Example 5
Polymer 5 (1.3 g, M w To a round bottom flask was added 4500g/mol in sequence dichloromethane (25 mL), stirred until the solid was completely dissolved, then trimethylchlorosilane (11 mg) was added and cooled in an ice water bath for 20min. Chlorosulfonic acid (0.012 mol) was slowly added dropwise over 15min under argon protection and reacted at 0℃for 2h. The reaction solution was then carefully transferred to 20g of ice, the dichloromethane was removed by rotary evaporation, sodium hydroxide solution (2.4 g of sodium hydroxide, 10mL of water) was added and reacted at 25 ℃ for 0.5h, extraction was performed with dichloromethane (20 mL x 3 times), the lewis acid catalyst trimethylchlorosilane was removed, the aqueous phase was dialyzed in water with a 100-500D dialysis bag for 12h, during which time water was changed several times until all of the sodium hydroxide and sodium chloride remained in the dialysis bag were removed, and freeze-dried to obtain a yellow solid product with a yield of 99%.
Example 6
Polymer 6 (1.3 g, M w Sequentially added to a round bottom flask was dichloromethane (20 mL), stirred until the solid was completely dissolved, and trimethylchlorosilane (8 mg) was added and cooled in an ice water bath for 20min. Chlorosulfonic acid (0.006 mol) was slowly added dropwise over 8min under argon protection and reacted at 0℃for 2h. The reaction solution was then carefully transferred to 20g of ice, the dichloromethane was removed by rotary evaporation, sodium hydroxide solution (2.4 g sodium hydroxide, 10mL water) was added and reacted at 25 ℃ for 0.5h, extracted with dichloromethane (20 mL x 3 times), the lewis acid catalyst trimethylchlorosilane was removed, the aqueous phase was dialyzed in water with a 100-500D dialysis bag for 12h, and water was changed several times until the inside of the dialysis bag remainedSodium hydroxide and sodium chloride were all removed and freeze-dried to give the product as a yellow solid in 99% yield.
Example 7
This embodiment is substantially the same as embodiment 1 except that: the amount of trimethylchlorosilane used was 80mg and the yield was 99%.
Example 8
This embodiment is substantially the same as embodiment 1 except that: the first reaction (reaction of compound 1, chlorosulfonic acid and trimethylchlorosilane) was carried out for 5h in 99% yield.
Example 9
This embodiment is substantially the same as embodiment 1 except that: the organic solvent was ethyl acetate with a 99% yield.
Example 10
This embodiment is substantially the same as embodiment 1 except that: the organic solvent is chloroform and carbon tetrachloride according to the volume ratio of 1:1 in 99% yield.
Comparative example 1
This comparative example is substantially the same as example 1 except that: the catalyst adopts aluminum trichloride, and the yield is 15%.
Comparative example 2
This comparative example is substantially the same as example 1 except that: the catalyst was used in an amount of 0.1mg and the yield was 23%.
Comparative example 3
This comparative example is substantially the same as example 1 except that: the catalyst was used in an amount of 200mg and the yield was 31%.
Comparative example 4
This comparative example is substantially the same as example 1 except that: the amount of sodium hydroxide is 0.12g, and the purification cannot be performed.
Comparative example 5
This comparative example is substantially the same as example 1 except that: the first reaction (reaction of compound 1, chlorosulfonic acid and trimethylchlorosilane) was carried out for 0.5h in 18% yield.
Comparative example 6
This comparative example is substantially the same as example 1 except that: the first reaction (reaction of compound 1, chlorosulfonic acid and trimethylchlorosilane) was carried out for 10 hours in 100% yield.
It can be seen from example 1 and comparative example 6 that the first reaction time is not relevant, but beyond the first reaction time of the present application, the yield improvement is limited, the energy consumption is increased, and the improvement of the production efficiency is not good.
The terms "one embodiment," "some embodiments," "examples," "specific examples," or "some examples," etc., in this application, mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the present application. In this specification, schematic representations of the above terms are not necessarily directed to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, the different embodiments or examples described in this specification and the features of the different embodiments or examples may be combined and combined by those skilled in the art without contradiction.
Although embodiments of the present application have been shown and described above, it will be understood that the above embodiments are illustrative and not to be construed as limiting the application, and that variations, modifications, alternatives, and variations may be made to the above embodiments by one of ordinary skill in the art within the scope of the application.

Claims (10)

1. A method for preparing an aggregation-induced emission material, comprising:
carrying out a first reaction on a fluorescent raw material, an organic solvent and chlorosulfonic acid in inert atmosphere under the action of a Lewis acid catalyst to obtain a reaction liquid;
carrying out a second reaction on the reaction liquid and alkali to obtain the aggregation-induced emission material;
the Lewis acid catalyst is trimethylchlorosilane.
2. The preparation method according to claim 1, wherein the fluorescent raw material is one of a multi-benzene ring fluorescent molecule or a multi-benzene ring fluorescent polymer;
and/or the organic solvent is one or more of ethyl acetate, dichloromethane, chloroform and carbon tetrachloride.
3. The preparation method according to claim 2, wherein the fluorescent raw material is one of compounds 1 to 4 and polymers 5 to 8;
Figure FDA0004021219950000011
4. the method according to claim 2, wherein the amount of the organic solvent is 5 to 30 ml per g of the fluorescent raw material;
and/or the dosage of chlorosulfonic acid is a times of the mole number of the multi-benzene ring fluorescent molecules or a times of the mole number of the repeated units of the multi-benzene ring fluorescent polymer; the a is the molecular formula of the multi-benzene ring fluorescent molecule or the total number of exposed benzene rings in the repeating unit of the multi-benzene ring fluorescent polymer;
and/or the dosage of the Lewis acid catalyst is 0.001-0.08 times of the mass of the fluorescent raw material;
and/or the molar ratio of chlorosulfonic acid to base is 1: (1.05-20).
5. The method of claim 1, wherein the first reaction temperature is (-5) -5 ℃, and the first reaction time is 1-5h;
and/or the second reaction temperature is room temperature, and the second reaction time is 0.1-1h.
6. The method of producing according to claim 1, wherein the method of producing an aggregation-induced emission material further comprises: before the first reaction, the fluorescent raw material is dissolved in the organic solvent, then the Lewis acid catalyst is added, and the mixture of the fluorescent raw material, the organic solvent and the Lewis acid catalyst is obtained after cooling in ice water bath.
7. The method of claim 1, wherein the chlorosulfonic acid is added to the first reaction system by dropwise addition.
8. The method of producing according to claim 1, wherein the method of producing an aggregation-induced emission material further comprises: transferring the reaction solution to ice before the reaction solution and the alkali are subjected to a second reaction, and removing the organic solvent by rotary evaporation;
and/or, the preparation method of the aggregation-induced emission material further comprises the following steps: and after the reaction liquid and the alkali are subjected to a second reaction, extracting and removing the Lewis acid catalyst by using an extracting agent, removing the alkali by dialysis, and the like, and freeze-drying to obtain the aggregation-induced emission material.
9. The preparation method according to claim 8, wherein the extractant is one or more of dichloromethane, ethyl acetate and chloroform;
and/or, the alkali is sodium hydroxide.
10. An aggregation-induced emission material, characterized in that it is prepared by the preparation method according to any one of claims 1 to 9.
CN202211686434.2A 2022-12-27 2022-12-27 Aggregation-induced emission material and preparation method thereof Pending CN116253667A (en)

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