Fluorescent / phosphorescent dual-emission carbonized polymer point with self-assembly characteristic and preparation method thereof
The self-assembly-oriented fluorescent/phosphorescent dual-emission carbonized polymer dots were prepared by reacting polycarboxylic acids and polyamines, which solved the problems of insufficient self-assembly properties and fluorescence/phosphorescence performance in the existing technology. This method enables the preparation of high-purity carbonized polymer dots, which are suitable for optoelectronic devices, bioimaging and data encryption.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- DALIAN INSTITUTE OF CHEMICAL PHYSICS CHINESE ACADEMY OF SCIENCES
- Filing Date
- 2024-10-22
- Publication Date
- 2026-04-24
AI Technical Summary
Existing carbonized polymer dots have shortcomings in self-assembly properties and dual fluorescence/phosphorescence emission performance, making it difficult to meet the application requirements of optoelectronic devices, biological imaging, and data encryption.
Fluorescent/phosphorescent dual-emission carbonized polymer dots with self-assembly properties were prepared by a mixed reaction of polycarboxylic acids and polyamines, combined with high-temperature drying and a dissolution-precipitation method. The properties were adjusted by controlling reaction parameters such as temperature, time, and molar ratio.
The preparation of high-purity, self-assembling carbonized polymer dots with dual fluorescence/phosphorescence emission characteristics has been achieved, making them suitable for fields such as optoelectronic devices, biological imaging, and data encryption.
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Figure CN121914397A_ABST
Abstract
Description
Technical Field
[0001] This application relates to a fluorescent / phosphorescent dual-emission carbonized polymer dot with self-assembly properties and its preparation method, belonging to the field of new energy nanomaterials. Background Technology
[0002] Carbonized polymer dots (CPDs) not only possess the excellent optical properties of traditional carbon dots (CDs) but also exhibit polymer characteristics, forming highly cross-linked and tightly bound polymer backbone structures. Therefore, they possess advantages such as strong photoluminescence, low toxicity, good biocompatibility, abundant functional groups, and unique physicochemical properties. Fluorescence refers to the light emitted when the ground state (S0) is absorbed by ultraviolet and visible light, transitions to the lowest singlet state (S1), and then re-radiates back to S0. Phosphorescence, on the other hand, refers to long-lived emitting materials that continue to emit light even after the excitation light is turned off. This occurs when the generated excitons first enter S1 from S0, then enter the lowest triplet state (T1) through an intersystematic crossover (ISC) process, and finally return to S0, generating light through a radiative transition. Therefore, carbonized polymer dots exhibiting both fluorescence and phosphorescence emission have attracted widespread attention from researchers.
[0003] Self-assembly refers to the spontaneous formation of unique structures through intermolecular forces, resulting in oriented and ordered structures from individual molecules. It can be achieved through photo-induced and chemically-induced methods, by chemically modifying carbonized polymer dots to impart different functions such as luminescence and adsorption. Therefore, self-assembled carbonized polymer dots have enormous application potential in optoelectronic devices, bioimaging, data encryption, and advanced dynamic anti-counterfeiting. Summary of the Invention
[0004] According to one aspect of this application, a fluorescent / phosphorescent dual-emission carbonized polymer dot with self-assembly properties is provided, the carbonized polymer dot being polymerized from a polycarboxylic acid and a polyamine; the polycarboxylic acid is selected from at least one of isophthalic acid, terephthalic acid, tetrafluorosuccinic acid, and succinic acid; the polyamine is selected from at least one of ethylenediamine, o-phenylenediamine, and m-phenylenediamine.
[0005] Optionally, the molecular weight of the carbonized polymer dots is 1000 to 8000 Da.
[0006] Optionally, the fluorescence emitted by the carbonized polymer dots is selected from at least one of blue fluorescence and cyan-blue fluorescence;
[0007] The phosphorescence emitted by the carbonized polymer dots is selected from at least one of green phosphorescence, blue-green phosphorescence, and cyan-green phosphorescence;
[0008] The phosphorescence emission time is 0.1 to 10 seconds.
[0009] According to a second aspect of this application, a method for preparing fluorescent / phosphorescent dual-emission carbonized polymer dots with self-assembly properties is provided, comprising at least the following steps:
[0010] Step I: Mix polycarboxylic acids and polyamines, react them, and obtain a solid product;
[0011] Step II: Dissolve the solid product obtained in Step I in a solvent, add a precipitant, and dry to obtain carbonized polymer dots.
[0012] Optionally, in step I, the polycarboxylic acid is selected from at least one of isophthalic acid, terephthalic acid, tetrafluorosuccinic acid, and succinic acid;
[0013] The polyamine is selected from at least one of ethylenediamine, o-phenylenediamine, and m-phenylenediamine.
[0014] Optionally, in step I, the molar ratio of the polycarboxylic acid to the polyamine is 1:0.1 to 2.5.
[0015] Optionally, in step I, the reaction conditions are as follows:
[0016] The reaction was carried out in high-purity air;
[0017] The reaction temperature is 150–300°C;
[0018] The reaction time is 1 to 12 hours.
[0019] Optionally, in step II, the solvent is selected from at least one of dimethyl sulfoxide, acetonitrile, and ethanol;
[0020] The precipitant is selected from at least one of methanol, chloroform, and toluene.
[0021] Optionally, in step II, the volume ratio of the solvent to the organic solvent is 8:90 to 1:16.
[0022] Optionally, the concentration of the solid product in the solution is 0.1 to 0.5 g / mL.
[0023] Optionally, the drying conditions are as follows:
[0024] The drying temperature is 50–70°C;
[0025] The drying time is 4 to 10 hours.
[0026] Optionally, the yield of the carbonized polymer dots is 60-85%.
[0027] The beneficial effects that this application can produce include:
[0028] 1) The airflow assistance provided in this application can suppress the generation of side reactions.
[0029] 2) The dissolution-precipitation method provided in this application can significantly improve purification efficiency and product yield.
[0030] 3) The product provided in this application has self-assembly properties.
[0031] 4) The product provided in this application has dual emission characteristics of fluorescence and phosphorescence.
[0032] 5) This application can control the fluorescence / phosphorescence behavior of the product by adjusting parameters such as reaction time and reaction temperature. Attached Figure Description
[0033] Figure 1 The mass spectrum of the fluorescent / phosphorescent dual-emission carbonized polymer dots with self-assembly properties prepared in Example 1 of this application;
[0034] Figure 2 The fluorescence emission pattern of the fluorescent / phosphorescent dual-emission carbonized polymer dots with self-assembly properties prepared in Example 1 of this application;
[0035] Figure 3 Phosphorescence emission pattern of the fluorescent / phosphorescent dual-emission carbonized polymer dots with self-assembly properties prepared in Example 1 of this application;
[0036] Figure 4 The ultraviolet absorption spectrum of the fluorescent / phosphorescent dual-emission carbonized polymer dots with self-assembly properties prepared in Example 1 of this application;
[0037] Figure 5 Infrared spectrum of the fluorescent / phosphorescent dual-emission carbonized polymer dots with self-assembly properties prepared in Example 1. Detailed Implementation
[0038] The present application is described in detail below with reference to the embodiments, but the present application is not limited to these embodiments.
[0039] Unless otherwise specified, the raw materials and reagents used in the embodiments of this application were all purchased commercially.
[0040] The analysis method in the embodiments of this application is as follows:
[0041] Mass spectrometry analysis of carbonized polymer spots was performed using an ultra-high performance liquid chromatography / quadrupole time-of-flight mass spectrometer.
[0042] Fluorescence of carbonized polymer spots was measured using an F-4600 steady-state fluorescence spectrometer.
[0043] Phosphorescence testing of carbonized polymer spots was performed using an F-4600 steady-state fluorescence spectrometer.
[0044] The ultraviolet absorption of carbonized polymer dots was measured using a TU-1901 dual-beam UV-Vis spectrophotometer.
[0045] Infrared testing of carbonized polymer spots was performed using an infrared spectrometer.
[0046] The carbonized polymer point yield calculations in the embodiments of this application are as follows:
[0047] In the embodiments of this application, the carbonized polymer point yield is calculated based on 0.1 moles:
[0048] The yield of carbonized polymer points = total mass after synthesis / total mass of precursors.
[0049] According to one specific embodiment of this application, a fluorescent / phosphorescent dual-emission carbonized polymer dot with self-assembly properties and its preparation method specifically include the following steps:
[0050] (1) Polycarboxylic acid and polyamine compound are ground and thoroughly mixed, and dehydration polymerization reaction is carried out by air-assisted high-temperature dry burning;
[0051] (2) By adjusting parameters such as the type or molar ratio of precursors, reaction temperature, and reaction time, a carbonized polymer skeleton with low molecular weight is generated.
[0052] (3) After the reaction is completed, the unreacted precursors or endogenous impurities in the product are removed by the dissolution-precipitation method. After filtration and drying, fluorescent / phosphorescent dual-emission carbonized polymer dots with self-assembly characteristics are obtained.
[0053] The polycarboxylic acid mentioned in step (1) includes at least one of isophthalic acid, terephthalic acid, tetrafluorosuccinic acid, and succinic acid;
[0054] The polyamine compound mentioned in step (1) is at least one of ethylenediamine, o-phenylenediamine, and m-phenylenediamine;
[0055] The molar ratio of the polycarboxylic acid to the polyamine compound in step (2) is 1:0.1 to 2.5;
[0056] The reaction temperature described in step (2) is 150–300 °C;
[0057] The reaction time described in step (2) is 1 to 12 hours;
[0058] The molecular weight of the product described in step (2) is 1000-8000 Da;
[0059] The solvent mentioned in step (3) includes one of the following: dimethyl sulfoxide-methanol, acetonitrile-chloroform, and ethanol-toluene combination;
[0060] The self-assembly characteristic fluorescent / phosphorescent dual-emission carbonized polymer dots described in step (3) have a purification yield of 60-85%.
[0061] The phosphorescence emission time of the fluorescent / phosphorescent dual-emission carbonized polymer dots with self-assembly characteristics described in step (3) is 0.1 to 10.0 s.
[0062] Example 1
[0063] (1) Weigh 1.0 mol of terephthalic acid and 1.0 mol of ethylenediamine and place them in a mortar. Mix them evenly and then transfer them to a quartz boat. First, purge with high-purity air for 15 min. Then, slowly heat the mixture in a high-temperature muffle furnace to 250°C. After reacting at a constant temperature for 3 h, cool it to room temperature and grind the solid product into powder.
[0064] (2) Next, 0.5g of solid powder was dissolved in 3.0mL of dimethyl sulfoxide solvent, and then 30.0mL of methanol was added for rapid precipitation. The precipitate was filtered and then dried in a vacuum drying oven at 60℃ for 6h to obtain a white solid powder of fluorescent / phosphorescent dual-emission carbonized polymer dots with self-assembly characteristics. The yield was 78% and the molecular weight was 5000Da.
[0065] (3) The purified carbonized polymer dots can emit blue fluorescence and green phosphorescence, and the phosphorescence duration is 7.5s.
[0066] The results showed that the fluorescent / phosphorescent dual-emission carbonized polymer dots with self-assembly properties did not exhibit obvious impurity peaks after purification (see [link]). Figure 1 A voltage of 400V was selected, and spectral measurements were performed at excitation and emission slits of 5nm and an excitation wavelength of 373nm. The fluorescence emission wavelength was 458nm (see [link to relevant documentation]). Figure 2 The phosphorescence emission wavelength is 530 nm (see...). Figure 3 ), and has a distinct absorption peak at 260 nm (see Figure 4 Infrared spectroscopy results indicate that the carbonized polymer dots contain abundant functional groups such as carboxyl and amino groups (see...). Figure 5 ).
[0067] Example 2
[0068] (1) Weigh 1.0 mol of isophthalic acid and 0.5 mol of ethylenediamine and place them in a mortar. Mix them evenly and then transfer them to a quartz boat. First, introduce high-purity air for 15 min, then slowly heat the mixture in a high-temperature muffle furnace to 200°C. After reacting at a constant temperature for 5 h, cool it to room temperature and grind the solid product into powder.
[0069] (2) Next, 0.3g of solid powder was dissolved in 5.0mL of acetonitrile solvent, and then 50.0mL of chloroform was added for rapid precipitation. The precipitate was filtered and then dried in a vacuum drying oven at 50℃ for 8h to obtain a brown solid powder of fluorescent / phosphorescent dual emission carbonized polymer dots with self-assembly characteristics. The yield was 65% and the molecular weight was 7500Da.
[0070] (3) The purified carbonized polymer dots can emit blue fluorescence and green phosphorescence, and the phosphorescence duration is 6.3s.
[0071] Example 3
[0072] (1) Weigh 1.0 mol of tetrafluorosuccinic acid and 2.0 mol of o-phenylenediamine and place them in a mortar. Mix them evenly and then transfer them to a quartz boat. First, introduce high-purity air for 15 min, then slowly heat the mixture in a high-temperature muffle furnace to 180°C. After reacting at a constant temperature for 10 h, cool it to room temperature and grind the solid product into powder.
[0073] (2) Next, 0.6 g of solid powder was dissolved in 8.0 mL of dimethyl sulfoxide solvent, and then 90.0 mL of methanol was added for rapid precipitation. The precipitate was filtered and then dried in a vacuum drying oven at 65 °C for 10 h to obtain a yellow solid powder of fluorescent / phosphorescent dual-emission carbonized polymer with self-assembly characteristics. The yield was 73% and the molecular weight was 6000 Da.
[0074] (3) The purified carbonized polymer dots can emit blue fluorescence and blue-green phosphorescence, and the phosphorescence duration is 5.6s.
[0075] Example 4
[0076] (1) Weigh 1.0 mol of succinic acid and 1.5 mol of m-phenylenediamine and place them in a mortar. Mix them evenly and then transfer them to a quartz boat. First, introduce high-purity air for 15 min, then slowly heat the mixture in a high-temperature muffle furnace to 280°C. After reacting at a constant temperature for 10 h, cool it to room temperature and grind the solid product into powder.
[0077] (2) Next, 0.5g of solid powder was dissolved in 5.0mL of ethanol solvent, and then 80.0mL of toluene was added for rapid precipitation. The precipitate was filtered and then dried in a vacuum drying oven at 70℃ for 7h to obtain a white solid powder of fluorescent / phosphorescent dual-emission carbonized polymer dots with self-assembly characteristics. The yield was 82% and the molecular weight was 6800Da.
[0078] (3) The purified carbonized polymer dots can emit blue fluorescence and cyan-green phosphorescence, and the phosphorescence duration is 5.7s.
[0079] Example 5
[0080] (1) Weigh 1.0 mol of terephthalic acid and 2.5 mol of p-phenylenediamine and place them in a mortar. Mix them evenly and then transfer them to a quartz boat. First, introduce high-purity air for 15 min, then slowly heat the mixture in a high-temperature muffle furnace to 180°C. After reacting at a constant temperature for 6 h, cool it to room temperature and grind the solid product into powder.
[0081] (2) Next, 0.4 g of solid powder was dissolved in 6.0 mL of dimethyl sulfoxide solvent, and then 90.0 mL of methanol was added for rapid precipitation. The precipitate was filtered and then dried in a vacuum drying oven at 65 °C for 4 h to obtain a grayish-white solid powder of fluorescent / phosphorescent dual-emission carbonized polymer dots with self-assembly characteristics. The yield was 82% and the molecular weight was 7600 Da.
[0082] (3) The purified carbonized polymer dots can emit blue fluorescence and green phosphorescence, and the phosphorescence duration is 8.3s.
[0083] The above description is merely a few embodiments of this application and is not intended to limit this application in any way. Although this application discloses preferred embodiments as described above, it is not intended to limit this application. Any changes or modifications made by those skilled in the art without departing from the scope of the technical solution of this application using the disclosed technical content are equivalent to equivalent implementation cases and fall within the scope of the technical solution.
Claims
1. A fluorescent / phosphorescent dual-emission carbonized polymer dot with self-assembly properties, characterized in that, The carbonized polymer dots are polymerized from polycarboxylic acids and polyamines; The polycarboxylic acid is selected from at least one of isophthalic acid, terephthalic acid, tetrafluorosuccinic acid, and succinic acid; The polyamine is selected from at least one of ethylenediamine, o-phenylenediamine, and m-phenylenediamine.
2. The carbonized polymer dot according to claim 1, characterized in that, The molecular weight of the carbonized polymer dots is 1000–8000 Da; Preferably, the fluorescence emitted by the carbonized polymer dots is selected from at least one of blue fluorescence and cyan-blue fluorescence; The phosphorescence emitted by the carbonized polymer dots is selected from at least one of green phosphorescence, blue-green phosphorescence, and cyan-green phosphorescence; The phosphorescence emission time is 0.1 to 10 seconds.
3. A method for preparing fluorescent / phosphorescent dual-emission carbonized polymer dots with self-assembly properties, characterized in that, At least the following steps are included: Step I: Mix polycarboxylic acids and polyamines, react them, and obtain a solid product; Step II: Dissolve the solid product obtained in Step I in a solvent to form a solution, add a precipitant, and dry to obtain carbonized polymer dots.
4. The preparation method according to claim 3, characterized in that, In step I, the polycarboxylic acid is selected from at least one of isophthalic acid, terephthalic acid, tetrafluorosuccinic acid, and succinic acid; The polyamine is selected from at least one of ethylenediamine, o-phenylenediamine, and m-phenylenediamine; The molar ratio of the polycarboxylic acid to the polyamine is 1:0.1 to 2.
5.
5. The preparation method according to claim 3, characterized in that, In step I, the reaction conditions are as follows: The reaction was carried out in high-purity air; The reaction temperature is 150–300°C; The reaction time is 1 to 12 hours.
6. The preparation method according to claim 3, characterized in that, In step II, the solvent is selected from at least one of dimethyl sulfoxide, acetonitrile, and ethanol; The precipitant is selected from at least one of methanol, chloroform, and toluene.
7. The preparation method according to claim 3, characterized in that, In step II, the volume ratio of the solvent to the precipitant is 8:90 to 1:
16.
8. The preparation method according to claim 3, characterized in that, In step II, the concentration of the solid product in the solution is 0.1–0.5 g / mL.
9. The preparation method according to claim 3, characterized in that, The drying conditions are as follows: The drying temperature is 50–70°C; The drying time is 4 to 10 hours.
10. The preparation method according to claim 3, characterized in that, The yield of the carbonized polymer dots is 60-85%.