Method for preparing multicolor fluorescent polymer based on Friedel-Crafts polymerization reaction and chemiluminescence application of multicolor fluorescent polymer
The multi-color fluorescent polymer prepared by Fuker polymerization solves the problem of fluorescence intensity quenching of existing fluorescent materials at high concentrations or solid states, and achieves efficient and adjustable chemiluminescence performance, which is suitable for large-scale production.
Patent Information
- Application Number
- CN202411651530.2
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-11-19
- Publication Date
- 2025-02-18
AI Technical Summary
Existing fluorescent materials are quenched at high concentrations or solid states, making it difficult to meet the needs of chemiluminescence applications.
Through the Fuker polymerization reaction, different phenyl compounds and chlorine-containing compounds were reacted in the presence of the Fuker reaction catalyst to prepare a multicolor fluorescent polymer with aggregation-induced luminescence effect.
It has achieved efficient synthesis of multi-color fluorescent polymers under normal temperature and air conditions, with high luminous efficiency, adjustable luminous color and good environmental stability, and is suitable for large-scale production.
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Figure CN119463125A_ABST
Abstract
Description
Technical Field
[0001] The invention relates to the field of synthesis of fluorescent polymers, and in particular to a polymerization method based on Friedel-Crafts reaction, preparation of synthesized fluorescent polymer materials and chemiluminescent applications thereof. Background Art
[0002] Friedel-Crafts reaction is a classic organic chemistry reaction used to introduce alkyl groups into aromatic rings. The reaction usually uses Lewis acid (such as aluminum chloride) as a catalyst to generate alkyl cations from alkyl halides, which then undergo electrophilic aromatic substitution reactions with aromatic rings. Friedel-Crafts alkylation is widely used in pharmaceuticals, materials science, and fragrance synthesis, and is valued for its high efficiency and diversity.
[0003] Aggregation-induced emission (AIE) refers to the phenomenon that certain molecules exhibit enhanced fluorescence in an aggregated state. This concept was first proposed by Professor Tang Benzhong in 2001 to solve the problem of fluorescence quenching of traditional fluorescent materials at high concentrations or in the solid state. AIE materials usually exhibit weak fluorescence in solution, while the fluorescence intensity is significantly enhanced when aggregated or in the solid state. This is because the intramolecular rotation and vibration are restricted in the aggregated state, reducing non-radiative energy loss. AIE materials are widely used in fields such as bioimaging, chemical sensing and optoelectronic devices due to their excellent optical properties, high sensitivity and good environmental stability.
[0004] Chemiluminescence is a phenomenon that produces light directly through chemical reactions, without the need for an external light source or power source. The basic principle is that chemical reactions release energy, causing molecules to enter an excited state, and then release photons when they return to the ground state. Chemiluminescence is widely used in entertainment, emergency lighting, and signage because it does not require electricity, is simple to operate, and can provide a variety of colors. Summary of the invention
[0005] The purpose of the present invention is to provide a new method for preparing a multicolor fluorescent polymer by Friedel-Crafts polymerization to form a multicolor fluorescent polymer material with excellent fluorescent properties. The synthesis method of the multicolor fluorescent polymer of the present invention can be carried out under normal temperature and air conditions, is simple and efficient, has low synthesis cost, and is suitable for large-scale production. The obtained polymer exhibits excellent performance in chemiluminescence applications, including high luminescence efficiency, adjustable luminescence color, and good environmental stability.
[0006] The fluorescent polymer has aggregation induced emission effect (AIE).
[0007] The object of the present invention is achieved by providing a method for synthesizing a multicolor fluorescent polymer based on Friedel-Crafts polymerization, characterized in that: a pure solvent or a mixed solvent of different phenyl compounds and chlorine-containing compounds is used to carry out Friedel-Crafts polymerization in the presence of a Friedel-Crafts reaction catalyst to obtain a multicolor fluorescent polymer, the pure solvent or the mixed solvent is dichloromethane, chloroform, or carbon tetrachloride, the Friedel-Crafts reaction catalyst is anhydrous aluminum trichloride, anhydrous tin tetrachloride, or anhydrous titanium tetrachloride, and the polymerization method can be carried out under normal temperature and air conditions.
[0008] Furthermore, the multicolor fluorescent polymer is a multicolor fluorescent polymer with aggregation-induced emission (AIE) properties with fluorescence red shift. The multicolor fluorescent polymer has conventional fluorescence in solution, and the fluorescence is enhanced and exhibits fluorescence red shift in the aggregated state, that is, the fluorescence emission wavelength moves to a longer wavelength.
[0009] Furthermore, the obtained multicolor fluorescent polymer is obtained by selecting pure solvents or mixed solvents of different phenyl compounds and chlorine-containing compounds to carry out Friedel-Crafts polymerization in the presence of a Friedel-Crafts reaction catalyst, thereby realizing diversified regulation of the fluorescence color. The fluorescence color is blue, cyan, yellow, orange or red fluorescence. The pure solvent or mixed solvent is dichloromethane, chloroform, carbon tetrachloride, and the Friedel-Crafts reaction catalyst is anhydrous aluminum trichloride, anhydrous tin tetrachloride or anhydrous titanium tetrachloride. The polymerization method can be carried out under normal temperature and air conditions.
[0010] Furthermore, the method for synthesizing a multicolor fluorescent polymer prepared based on Friedel-Crafts polymerization is characterized in that it specifically comprises the following steps: a phenyl compound is put into a Schlenk tube equipped with a Friedel-Crafts reaction catalyst, and dissolved in a pure solvent or a mixed solvent containing a chlorine compound to obtain a mixed solution; the pure solvent or the mixed solvent is dichloromethane, chloroform, or carbon tetrachloride, and the Friedel-Crafts reaction catalyst is anhydrous aluminum trichloride, anhydrous tin tetrachloride, or anhydrous titanium tetrachloride; the mixed solution is placed in the air at room temperature and slowly stirred for 12 hours, after 12 hours, the reaction is quenched with dilute sulfuric acid, extracted with dichloromethane and water, dried with anhydrous magnesium sulfate, and then the mixed solution is concentrated under reduced pressure, the product is precipitated in an excess of petroleum ether, filtered and vacuum dried to obtain a solid powder, and thus a multicolor fluorescent polymer is obtained.
[0011] The multicolor fluorescent polymer prepared by the above-mentioned synthesis method of the present invention is used in chemiluminescence, and is characterized in that: the multicolor fluorescent polymer, when used in chemiluminescence, has good luminous efficiency and long duration.
[0012] The above application of the present invention is characterized in that: a multicolor fluorescent polymer is mixed with bis(2,4,5-trichlorosalicylic acid n-pentyl ester) oxalate (CPPO) in THF, and hydrogen peroxide is added, and the solution emits strong fluorescence for a long time.
[0013] Specifically, the present invention provides a method for preparing the fluorescent polymer compound (taking 1,2-diphenylethane as an example), including the following specific production process:
[0014] In a Schlenk tube filled with anhydrous aluminum chloride, 1,2-diphenylethane was added and dissolved in dichloromethane. The mixed solution was placed in the air at room temperature and slowly stirred for 12 hours. After 12 hours, the reaction was quenched with dilute sulfuric acid and washed with dichloromethane and water. After drying with anhydrous magnesium sulfate, the mixed solution was concentrated under reduced pressure. The product was precipitated in excess petroleum ether, filtered and vacuum dried to obtain a solid powder, i.e., a multicolor fluorescent polymer.
[0015] Among them, the addition of different phenyl compounds can achieve the regulation of multi-color fluorescence, including but not limited to blue, cyan, yellow, orange and red fluorescence.
[0016] The invention discloses a method for preparing a multicolor fluorescent polymer applicable to chemiluminescence. The multicolor fluorescent polymer prepared by the method is mixed with bis(2,4,5-trichlorosalicylic acid n-pentyl ester) oxalate (CPPO) in THF, and hydrogen peroxide is added, and the solution emits strong fluorescence, which can last up to 30 minutes.
[0017] Compared with the prior art, the present invention has the following advantages and effects:
[0018] 1. Polymer multicolor fluorescence control capability: By simply adjusting the type of phenyl compounds (such compounds are widely commercially available), a wide range of color control can be achieved to meet different application requirements.
[0019] 2. Highly efficient aggregation-induced emission (AIE) properties: In the aggregated state, the polymer exhibits enhanced fluorescence intensity and red shift, overcoming the concentration quenching problem of traditional materials.
[0020] 3. The synthesis method is simple and efficient: The synthesis method of the polymer can be carried out under normal temperature and air conditions. It is simple and efficient, with low synthesis cost and is suitable for large-scale production.
[0021] 4. Applicable to the field of chemiluminescence: To improve its safety, fluorescent polymers usually have higher chemical stability and lower toxicity. By adjusting the chemical structure of the polymer, a wider range of color choices and more precise color control can be achieved. Fluorescent polymers usually have better light resistance and heat resistance. BRIEF DESCRIPTION OF THE DRAWINGS
[0022] Figure 1 This is the hydrogen nuclear magnetic resonance spectrum of the product obtained in specific example 1 of the present invention.
[0023] Figure 2This is the fluorescence spectrum curve of the product obtained in Example 1 of the present invention.
[0024] Figure 3 These are digital photos and fluorescence spectrum curves of the aggregation-induced emission effect of the product prepared in Example 1 of the present invention in THF / water mixed solutions at different volume ratios.
[0025] Figure 4 These are digital photos of the multicolor fluorescent polymer controlled by different phenyl compounds under sunlight and UV in Example 1 of the present invention.
[0026] Figure 5 This is a chemiluminescent digital photograph of specific embodiment 3 of the present invention. DETAILED DESCRIPTION
[0027] The following provides drawings and specific embodiments to describe the present invention in detail. The following specific implementation methods are only used to explain the present invention, and the protection scope is not limited by the following embodiments.
[0028] Unless otherwise specified, the experimental methods used in the following examples are all conventional methods; the reagents, materials, etc. used in the following examples, unless otherwise specified, can be obtained from commercial channels.
[0029] The experimental data in the examples were measured using the following instruments and measurement methods:
[0030] (1) Method for determining the chemical structure of the generated polymer: using nuclear magnetic resonance spectroscopy;
[0031] (2) Method for determining the fluorescence properties of the generated polymer: using a fluorescence spectrometer.
[0032] Example 1
[0033] Synthesis of multicolor fluorescent polymers (taking 1,2-diphenylethane as an example).
[0034] The chemical reaction formula of the Friedel-Crafts reaction between 1,2-diphenylethane and the catalyst anhydrous aluminum chloride used in this embodiment is as follows:
[0035]
[0036] This embodiment includes the following steps:
[0037] Step 1: Place anhydrous aluminum chloride (0.15 g, 1 eq) into a Schlenk tube, add 1,2-diphenylethane (0.2 g, 1 eq), and then use a dropper to drop dichloromethane (1.1 mL, 15 eq) to obtain a mixed solution.
[0038] Step 2: Place the mixed solution in air at room temperature and stir slowly for 12 hours.
[0039] Step 3: After 12 hours, the reaction was quenched with 0.5 mL of dilute sulfuric acid, and extracted with dichloromethane and water for three times. After drying with anhydrous magnesium sulfate, the mixed solution was concentrated to 2 mL under reduced pressure. The product was precipitated in excess petroleum ether, filtered and vacuum dried to obtain an orange solid powder, i.e., a fluorescent polymer, with a yield of 65%. The product exhibited orange fluorescence and had aggregation-induced emission (AIE) effect.
[0040] Example 2
[0041] Fluorescence spectra of the fluorescent polymer prepared in Example 1 in mixed solutions with different water contents were measured.
[0042] The fluorescent polymer prepared in Example 1 exhibited aggregation-induced emission in THF / water mixed solutions with different volume ratios. Figure 3 .Depend on Figure 3 It can be seen that in the mixed solutions of different THF / water volume ratios, as the content of the poor solvent (water) increases, the fluorescent polymer gradually precipitates to form nanoaggregates. As the degree of aggregation increases, the fluorescence shows a gradual red shift, showing an obvious aggregation-induced emission effect.
[0043] 5 mg of the fluorescent polymer prepared in Example 1 was dissolved in 1 mL of THF, and the solution was dotted on the TCL plate using a capillary. As the solvent on the plate gradually evaporated, the fluorescent polymer gradually aggregated, the fluorescence intensity on the TCL plate increased, and a red-shift phenomenon of fluorescence occurred, as shown in FIG. Figure 3 shown.
[0044] Example 3
[0045] The fluorescent polymer prepared in Example 1 replaces the traditional dye to participate in chemiluminescence.
[0046] Preparation of Solution A: Weigh 0.1 g of bis(2,4,5-trichlorosalicylic acid n-pentyl) oxalate (CPPO) and 0.005 g of the fluorescent polymer prepared in Example 1, and dissolve them in 1 mL of THF to obtain Solution A.
[0047] Preparation of Solution B: Use a pipette to mix 0.4 mL of 30 wt% H2O2 and 0.6 mL of THF to obtain Solution B.
[0048] Use a dropper to add liquid B into liquid A. In the dark, the mixed solution is observed to emit a strong orange fluorescence that lasts for a long time. Figure 5 shown.
Claims
1. A method for synthesizing a multicolor fluorescent polymer based on Friedel-Crafts polymerization, characterized in that: A multicolor fluorescent polymer is obtained by carrying out a Friedel-Crafts polymerization reaction using pure solvents or mixed solvents of different phenyl compounds and chlorine-containing compounds in the presence of a Friedel-Crafts reaction catalyst. The pure solvent or mixed solvent is dichloromethane, chloroform, or carbon tetrachloride. The Friedel-Crafts reaction catalyst is anhydrous aluminum trichloride, anhydrous tin tetrachloride, or anhydrous titanium tetrachloride. The polymerization method can be carried out under normal temperature and air conditions.
2. The method for synthesizing a multicolor fluorescent polymer based on Friedel-Crafts polymerization according to claim 1, characterized in that: The multicolor fluorescent polymer is a multicolor fluorescent polymer with aggregation-induced emission (AIE) properties of fluorescence red shift. The multicolor fluorescent polymer has conventional fluorescence in a solution state, and the fluorescence is enhanced and exhibits fluorescence red shift in an aggregated state, that is, the fluorescence emission wavelength moves to a longer wavelength.
3. The method for synthesizing a multicolor fluorescent polymer based on Friedel-Crafts polymerization according to claim 1, characterized in that: The obtained multicolor fluorescent polymer is obtained by selecting pure solvents or mixed solvents of different phenyl compounds and chlorine-containing compounds to carry out Friedel-Crafts polymerization in the presence of a Friedel-Crafts reaction catalyst, thereby realizing diversified regulation of the fluorescence color. The fluorescence color is blue, cyan, yellow, orange or red fluorescence. The pure solvent or mixed solvent is dichloromethane, chloroform or carbon tetrachloride. The Friedel-Crafts reaction catalyst is anhydrous aluminum trichloride, anhydrous tin tetrachloride or anhydrous titanium tetrachloride. The polymerization method can be carried out under normal temperature and air conditions.
4. The method for synthesizing a multicolor fluorescent polymer based on Friedel-Crafts polymerization according to claim 1, characterized in that: Specifically, the method comprises the following steps: a phenyl compound is put into a Schlenk tube equipped with a Friedel-Crafts reaction catalyst, and the phenyl compound is dissolved in a pure solvent or a mixed solvent containing a chlorine compound to obtain a mixed solution; the pure solvent or the mixed solvent is dichloromethane, chloroform, or carbon tetrachloride, and the Friedel-Crafts reaction catalyst is anhydrous aluminum trichloride, anhydrous tin tetrachloride, or anhydrous titanium tetrachloride; the mixed solution is placed in the air at room temperature and slowly stirred for 12 hours, after 12 hours, the reaction is quenched with dilute sulfuric acid, the mixture is extracted with dichloromethane and water, and the mixture is dried with anhydrous magnesium sulfate, and then the mixture is concentrated under reduced pressure, the product is precipitated in an excess of petroleum ether, and the solid powder is obtained after filtering and vacuum drying, namely, a multicolor fluorescent polymer.
5. The multicolor fluorescent polymer prepared by the synthesis method according to any one of claims 1 to 4 is used in chemiluminescence, characterized in that: The multicolor fluorescent polymer is applied in chemiluminescence, and has good luminous efficiency and long duration.
6. The use according to claim 5, characterized in that: When the multicolor fluorescent polymer was mixed with bis(2,4,5-trichlorosalicylic acid n-pentyl) oxalate (CPPO) in THF and hydrogen peroxide was added, the solution emitted strong fluorescence for a long time.