A perylene imide derivative-paraffin fluorescent composite material for anti-counterfeiting identification and a preparation method and application thereof
By preparing perylene imide derivative-paraffin fluorescent composite material, the problem of insufficient temperature responsiveness and fluorescence stability of phase change material-based fluorescent composite materials was solved, realizing anti-counterfeiting identification applications with high fluorescence intensity and temperature responsiveness.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- LIAONING UNIVERSITY
- Filing Date
- 2025-01-24
- Publication Date
- 2026-06-16
AI Technical Summary
In the existing technology, phase change material-based fluorescent composite materials are insufficient in terms of temperature responsiveness and fluorescence stability, making it difficult to meet the requirements of anti-counterfeiting identification.
By preparing perylene imide derivative-paraffin fluorescent composite materials, the reaction of perylene imide compounds with aliphatic/aromatic amines is utilized to weaken intermolecular π-π stacking, improve fluorescence intensity and stability, and combine with the phase transition properties of paraffin to form temperature-responsive materials.
The prepared material has high fluorescence intensity and excellent fluorescence stability, and can exhibit different fluorescence characteristics when the temperature changes, making it suitable for fields such as anti-counterfeiting identification and fluorescence thermometry.
Smart Images
Figure CN119823586B_ABST
Abstract
Description
Technical Field
[0001] This invention belongs to the field of organic light-emitting materials technology, specifically relating to a perylene imide derivative-paraffin fluorescent composite material for anti-counterfeiting identification, its preparation method, and its application. Background Technology
[0002] Phase change material-based fluorescent composites can exhibit different colors and fluorescence properties in response to changes in external temperature, demonstrating temperature-photoresponsiveness. This material can be used in fields such as smart curtains, smart clothing, and temperature indicators to achieve temperature sensing and intelligent control functions. Research on phase change material-based fluorescent color-changing materials not only has significant scientific importance but also broad application prospects.
[0003] Paraffin wax, as one of the most common organic solid-liquid phase change materials in our daily lives, has advantages such as low cost, non-toxicity, and high cost-effectiveness. Paraffin wax is a mixture of various alkanes, and its melting point can be adjusted by controlling the content and proportion of various alkanes in the mixture. It has a wide range of selectable melting points, making it an ideal matrix for phase change materials.
[0004] Perylene imide derivatives possess excellent fluorescence properties, including high fluorescence intensity and strong fluorescence stability, and are easily modified, thus endowing perylene imide compounds with unique optical properties and functions. Due to the strong π-π stacking among perylene imide derivative molecules, regulating the aggregation mode of perylene imide derivatives to form unique self-assembled structures holds promise for enabling perylene imide compounds to play a prominent role in the field of phase change material-based fluorescent composite materials. Summary of the Invention
[0005] To overcome the shortcomings of the prior art, this invention provides a method for preparing a perylene imide derivative-paraffin fluorescent composite material for anti-counterfeiting identification. This method produces a novel fluorescent composite functional material with temperature responsiveness, high luminescence intensity, and excellent luminescence stability, which can be used in the field of anti-counterfeiting identification.
[0006] The technical solution adopted in this invention is: a method for preparing a perylene imide derivative-paraffin fluorescent composite material for anti-counterfeiting identification, comprising the following steps:
[0007] A method for preparing a perylene imide derivative-paraffin fluorescent composite material for anti-counterfeiting identification includes the following steps:
[0008] 1) Mix perylene imide compounds and aliphatic / aromatic amines in a solvent and add the mixture to a round-bottom flask connected to a reflux condenser;
[0009] 2) Under a nitrogen atmosphere, the mixture in step 1) is heated in an oil bath and refluxed.
[0010] 3) Add hydrochloric acid solution to the product obtained from the reaction in step 2);
[0011] 4) Extract the solution obtained in step 3) with dichloromethane, retain the organic phase, and filter;
[0012] 5) Wash the dichloromethane solution obtained from filtering in step 4) with a saturated sodium bicarbonate solution;
[0013] 6) Dry the organic phase obtained after separation in step 5) with anhydrous sodium sulfate, and filter again to collect the dichloromethane solution;
[0014] 7) The solution obtained in step 6) is subjected to rotary evaporation to obtain the crude product;
[0015] 8) The crude product obtained in step 7) is subjected to chromatographic separation and vacuum drying to obtain powder;
[0016] 9) Add the powder obtained in step 8) to the heated and melted paraffin, stir and sonicate to obtain perylene imide derivative-paraffin fluorescent composite material.
[0017] Furthermore, in the above preparation method, step 1), the perylene imide compound is 3,4,9,10-perylenetetracarboxylic dianhydride, 1,6,7,12-tetrachloro-3,4,9,10-perylenetetracarboxylic dianhydride, etc.
[0018] Furthermore, in the above preparation method, in step 1), the aliphatic amine / aromatic amine is one of heptadecano-9-amine, n-dodecylamine, 4-aminoazobenzene, and 2,5-di-tert-butylaniline.
[0019] Furthermore, in the above preparation method, in step 1), the molar ratio of the perylene imide compound and the fatty amine / aromatic amine is 1:2.5.
[0020] Furthermore, in the above preparation method, in step 1), the solvent is selected from one or more combinations of imidazole, toluene, and zinc acetate.
[0021] Furthermore, in the above preparation method, step 2), the heating temperature is 100-120℃, and the condensation reflux time is 6-12h.
[0022] Furthermore, in the above preparation method, step 8), the eluent used in the chromatographic separation is one or a combination of dichloromethane and petroleum ether.
[0023] Furthermore, in the above preparation method, in step 9), the ratio of the powder to paraffin is 0.01–5 mg: 1 g.
[0024] Application of perylene imide derivative-paraffin fluorescent composite material prepared according to the above preparation method in the preparation of anti-counterfeiting marks.
[0025] Furthermore, in the above application, the perylene imide derivative-paraffin fluorescent composite material is heated to 60°C until it melts, poured into a mold, and cooled to produce an anti-counterfeiting mark.
[0026] The beneficial effects of this invention are: the synthesis process is easy to control, simple to operate, environmentally friendly, and has low production costs. It can rapidly synthesize perylene imide derivative-paraffin fluorescent composite materials for anti-counterfeiting identification. Utilizing the excellent optical, thermal, and chemical stability of perylene imide compounds, amine substitution is achieved through the reaction of aliphatic / aromatic amines with perylene tetracarboxylic dianhydrides. This effectively reduces the π-π stacking between perylene imide molecules, significantly improving the solubility of the resulting perylene imide derivative in paraffin. The prepared perylene imide derivative-paraffin fluorescent composite material exhibits high fluorescence intensity, strong fluorescence stability, and temperature responsiveness, making it applicable to anti-counterfeiting identification, fluorescent thermometric test strips, phase change energy storage, and other fields. Attached Figure Description
[0027] Figure 1 The images show the luminescence effect of the composite material prepared in Example 1 before and after irradiation with ultraviolet light at a wavelength of 365 nm at room temperature and after the phase transition point.
[0028] Figure 2 These are differential scanning calorimetry (DSC) graphs of the composite materials prepared in Examples 1-3.
[0029] Figure 3 The image shows the fluorescence spectra of the composite material prepared in Example 1 at room temperature and after the phase transition point. Detailed Implementation
[0030] To make the objectives, technical solutions, and advantages of this invention clearer, the invention will be further described in detail below with reference to embodiments. It should be understood that the specific embodiments described herein are merely illustrative and not intended to limit the invention. For those skilled in the art, various modifications and improvements can be made without departing from the concept of this invention, and these modifications and improvements all fall within the scope of protection of this invention.
[0031] Example 1
[0032] A method for preparing a perylene imide derivative-paraffin fluorescent composite material for anti-counterfeiting identification is as follows:
[0033] 1) Mix 0.39g of 3,4,9,10-perylenetetracarboxylic acid dianhydride and 0.64g of heptadecano-9-amine in 5g of imidazole and add the mixture to a round-bottom flask connected to a reflux condenser;
[0034] 2) Under a nitrogen atmosphere, the mixture in step 1) was heated to 120°C in an oil bath and refluxed for 6 hours;
[0035] 3) Add 100 mL of 2 mol·L⁻¹ solution to the solution. -1 The hydrochloric acid solution was added to the product obtained from the reaction in step 2);
[0036] 4) Extract the solution obtained in step 3) with dichloromethane, retain the organic phase, and filter;
[0037] 5) Wash the dichloromethane solution obtained from filtering in step 4) with a saturated sodium bicarbonate solution;
[0038] 6) Dry the organic phase obtained after separation in step 5) with anhydrous sodium sulfate, and filter again to collect the dichloromethane solution;
[0039] 7) The solution obtained in step 6) is subjected to rotary evaporation to obtain the crude product;
[0040] 8) The crude product obtained in step 7) was separated by chromatography using dichloromethane as the eluent, and then dried under vacuum to obtain a powder;
[0041] 9) Take 1.00 mg of the powder obtained in step 8) and add it to 1 g of heated and dissolved paraffin. Stir and sonicate to obtain perylene imide derivative-paraffin fluorescent composite material.
[0042] Example 2
[0043] A method for preparing a perylene imide derivative-paraffin fluorescent composite material for anti-counterfeiting identification is as follows:
[0044] 1) Mix 0.39g of 3,4,9,10-perylenetetracarboxylic acid dianhydride and 0.46g of n-dodecylamine in 1g of zinc acetate and 10g of imidazole, and add the mixture to a round-bottom flask connected to a reflux condenser;
[0045] 2) Under a nitrogen atmosphere, the mixture in step 1) was heated to 120°C in an oil bath and refluxed for 12 hours;
[0046] 3) Add 100 mL of 2 mol·L⁻¹ solution to the solution. -1 The hydrochloric acid solution was added to the product obtained from the reaction in step 2);
[0047] 4) Extract the solution obtained in step 3) with dichloromethane, retain the organic phase, and filter;
[0048] 5) Wash the dichloromethane solution obtained from filtering in step 4) with a saturated sodium bicarbonate solution;
[0049] 6) Dry the organic phase obtained after separation in step 5) with anhydrous sodium sulfate, and filter again to collect the dichloromethane solution.
[0050] 7) The solution obtained in step 6) is subjected to rotary evaporation to obtain the crude product;
[0051] 8) The crude product obtained in step 7) was separated by chromatography using dichloromethane as the eluent, and then dried under vacuum to obtain a powder;
[0052] 9) Take 1.00 mg of the powder obtained in step 8) and add it to 1 g of heated and dissolved paraffin. Stir and sonicate to obtain perylene imide derivative-paraffin fluorescent composite material.
[0053] Example 3
[0054] 1) Mix 0.87 g of 1,6,7,12-tetrachloro-3,4,9,10-perylenetetracarboxylic acid dianhydride and 0.46 g of n-dodecylamine in 100 mL of toluene and add the mixture to a round-bottom flask connected to a reflux condenser;
[0055] 2) Under a nitrogen atmosphere, the mixture in step 1) was heated to 100°C in an oil bath and refluxed for 6 hours;
[0056] 3) Add 100 mL of 2 mol·L⁻¹ solution to the solution. -1 The hydrochloric acid solution was added to the product obtained from the reaction in step 2);
[0057] 4) Extract the solution obtained in step 3) with dichloromethane, retain the organic phase, and filter;
[0058] 5) Wash the dichloromethane solution obtained from filtering in step 4) with a saturated sodium bicarbonate solution;
[0059] 6) Dry the organic phase obtained after separation in step 5) with anhydrous sodium sulfate, and filter again to collect the dichloromethane solution.
[0060] 7) The solution obtained in step 6) is subjected to rotary evaporation to obtain the crude product;
[0061] 8) The crude product obtained in step 7) was separated by chromatography using dichloromethane and petroleum ether as eluents, and then dried under vacuum to obtain a powder.
[0062] 9) Take 1.00 mg of the powder obtained in step 8) and add it to 1 g of heated and dissolved paraffin. Stir and sonicate to obtain perylene imide derivative-paraffin fluorescent composite material.
[0063] Example 4
[0064] 1) Mix 0.87g of 1,6,7,12-tetrachloro-3,4,9,10-perylenetetracarboxylic acid dianhydride and 0.6g of heptadecano-9-amine in 5g of imidazole and 100mL of toluene, and add the mixture to a round-bottom flask connected to a reflux condenser.
[0065] 2) Under a nitrogen atmosphere, the mixture in step 1) was heated to 100°C in an oil bath and refluxed for 12 hours;
[0066] 3) Add 100 mL of 2 mol·L⁻¹ solution to the solution. -1 The hydrochloric acid solution was added to the product obtained from the reaction in step 2);
[0067] 4) Extract the solution obtained in step 3) with dichloromethane, retain the organic phase, and filter;
[0068] 5) Wash the dichloromethane solution obtained from filtering in step 4) with a saturated sodium bicarbonate solution;
[0069] 6) Dry the organic phase obtained after separation in step 5) with anhydrous sodium sulfate, and filter again to collect the dichloromethane solution.
[0070] 7) The solution obtained in step 6) is subjected to rotary evaporation to obtain the crude product;
[0071] 8) The crude product obtained in step 7) was separated by chromatography using dichloromethane and petroleum ether as eluents, and then dried under vacuum to obtain a powder.
[0072] 9) Take 3.00 mg of the powder obtained in step 8) and add it to 1 g of heated and dissolved paraffin. Stir and sonicate to obtain perylene imide derivative-paraffin fluorescent composite material.
[0073] Example 5
[0074] A method for preparing a perylene imide derivative-paraffin fluorescent composite material for anti-counterfeiting identification is as follows:
[0075] 1) Mix 0.39g of 3,4,9,10-perylenetetracarboxylic acid dianhydride and 0.49g of 4-aminoazobenzene in 5g of imidazole and add it to a round-bottom flask connected to a reflux condenser;
[0076] 2) Under a nitrogen atmosphere, the mixture in step 1) was heated to 110°C in an oil bath and refluxed for 12 hours;
[0077] 3) Add 100 mL of 2 mol·L⁻¹ solution to the solution. -1 The hydrochloric acid solution was added to the product obtained from the reaction in step 2);
[0078] 4) Extract the solution obtained in step 3) with dichloromethane, retain the organic phase, and filter;
[0079] 5) Wash the dichloromethane solution obtained from filtering in step 4) with a saturated sodium bicarbonate solution;
[0080] 6) Dry the organic phase obtained after separation in step 5) with anhydrous sodium sulfate, and filter again to collect the dichloromethane solution;
[0081] 7) The solution obtained in step 6) is subjected to rotary evaporation to obtain the crude product;
[0082] 8) The crude product obtained in step 7) was separated by chromatography using petroleum ether as the eluent, and then dried under vacuum to obtain a powder;
[0083] 9) Take 0.50 mg of the powder obtained in step 8) and add it to 1 g of heated and dissolved paraffin. Stir and sonicate to obtain perylene imide derivative-paraffin fluorescent composite material.
[0084] Example 6
[0085] A method for preparing a perylene imide derivative-paraffin fluorescent composite material for anti-counterfeiting identification is as follows:
[0086] 1) Mix 0.39g of 3,4,9,10-perylenetetracarboxylic acid dianhydride and 0.51g of 2,5-di-tert-butylaniline in 5g of zinc acetate and add the mixture to a round-bottom flask connected to a reflux condenser.
[0087] 2) Under a nitrogen atmosphere, the mixture from step 1) was heated in an oil bath to 120°C and refluxed for 10 hours;
[0088] 3) Add 100 mL of 2 mol·L⁻¹ solution to the solution. -1 The hydrochloric acid solution was added to the product obtained from the reaction in step 2);
[0089] 4) Extract the solution obtained in step 3) with dichloromethane, retain the organic phase, and filter;
[0090] 5) Wash the dichloromethane solution obtained from filtering in step 4) with a saturated sodium bicarbonate solution;
[0091] 6) Dry the organic phase obtained after separation in step 5) with anhydrous sodium sulfate, and filter again to collect the dichloromethane solution;
[0092] 7) The solution obtained in step 6) is subjected to rotary evaporation to obtain the crude product;
[0093] 8) The crude product obtained in step 7) was separated by chromatography using dichloromethane as the eluent, and then dried under vacuum to obtain a powder;
[0094] 9) Take 5.00 mg of the powder obtained in step 8) and add it to 1 g of heated and dissolved paraffin. Stir and sonicate to obtain perylene imide derivative-paraffin fluorescent composite material.
[0095] Example 7
[0096] 1) Mix 0.87g of 1,6,7,12-tetrachloro-3,4,9,10-perylenetetracarboxylic acid dianhydride and 0.49g of 4-aminoazobenzene in 1g of zinc acetate and 100mL of toluene, and add the mixture to a round-bottom flask connected to a reflux condenser.
[0097] 2) Under a nitrogen atmosphere, the mixture in step 1) was heated to 110°C in an oil bath and refluxed for 12 hours;
[0098] 3) Add 100 mL of 2 mol·L⁻¹ solution to the solution. -1 The hydrochloric acid solution was added to the product obtained from the reaction in step 2);
[0099] 4) Extract the solution obtained in step 3) with dichloromethane, retain the organic phase, and filter;
[0100] 5) Wash the dichloromethane solution obtained from filtering in step 4) with a saturated sodium bicarbonate solution;
[0101] 6) Dry the organic phase obtained after separation in step 5) with anhydrous sodium sulfate, and filter again to collect the dichloromethane solution.
[0102] 7) The solution obtained in step 6) is subjected to rotary evaporation to obtain the crude product;
[0103] 8) The crude product obtained in step 7) was separated by chromatography using dichloromethane and petroleum ether as eluents, and then dried under vacuum to obtain a powder.
[0104] 9) Take 0.07 mg of the powder obtained in step 8) and add it to 1 g of heated and dissolved paraffin. Stir and sonicate to obtain perylene imide derivative-paraffin fluorescent composite material.
[0105] Example 8
[0106] 1) Mix 0.87g of 1,6,7,12-tetrachloro-3,4,9,10-perylenetetracarboxylic acid dianhydride and 0.51g of 2,5-di-tert-butylaniline in 100mL of toluene and add it to a round-bottom flask connected to a reflux condenser;
[0107] 2) Under a nitrogen atmosphere, the mixture in step 1) was heated to 120°C in an oil bath and refluxed for 10 hours;
[0108] 3) Add 100 mL of 2 mol·L⁻¹ solution to the solution. -1The hydrochloric acid solution was added to the product obtained from the reaction in step 2);
[0109] 4) Extract the solution obtained in step 3) with dichloromethane, retain the organic phase, and filter;
[0110] 5) Wash the dichloromethane solution obtained from filtering in step 4) with a saturated sodium bicarbonate solution;
[0111] 6) Dry the organic phase obtained after separation in step 5) with anhydrous sodium sulfate, and filter again to collect the dichloromethane solution.
[0112] 7) The solution obtained in step 6) is subjected to rotary evaporation to obtain the crude product;
[0113] 8) The crude product obtained in step 7) was separated by chromatography using petroleum ether as the eluent, and then dried under vacuum to obtain a powder;
[0114] 9) Take 0.10 mg of the powder obtained in step 8) and add it to 1 g of heated and dissolved paraffin. Stir and sonicate to obtain perylene imide derivative-paraffin fluorescent composite material.
[0115] Example 9
[0116] The perylene imide derivative-paraffin fluorescent composite material prepared above was heated to 60°C until it melted, and then poured into a circular mold to prepare a circular anti-counterfeiting mark. The mark was then irradiated with ultraviolet light at room temperature and 60°C to observe the change in its fluorescent color.
[0117] Example 10: Anti-counterfeiting performance of perylene imide derivative-paraffin fluorescent composite material at room temperature and after phase transition point
[0118] The composite material prepared in Example 1 was irradiated with a 365nm ultraviolet lamp. The results before and after irradiation under room temperature and heating conditions are shown as follows. Figure 1 As shown, the results indicate that under room temperature conditions, no fluorescence light can be observed before the ultraviolet lamp is turned on. Figure 1 As shown in Figure A, the content on the composite material is currently encrypted; when the ultraviolet light is turned on, a circular fluorescence can be seen, and the fluorescence color is red, as shown in Figure A. Figure 1 As shown in Figure B; after heating the composite material to its phase transition point and turning on the ultraviolet lamp, circular fluorescence can still be observed, but the fluorescence color is yellow, as shown in Figure B. Figure 1 As shown in Figure C, the perylene imide derivative-paraffin fluorescent composite material has the function of anti-counterfeiting encryption of information.
[0119] Figure 2These are differential scanning calorimetry (DSC) results for the composite materials prepared in Examples 1-3. Two phase transition peaks appeared with increasing temperature. The first peak represents a crystal transformation of paraffin, a solid-solid phase transition; the true solid-liquid phase transition peak is the second peak. The paraffin composite materials with added perylene imide derivatives all exhibited a phase transition temperature of 60°C. The addition of the fluorescent compound did not significantly alter the phase transition temperature of the paraffin.
[0120] Figure 3 The fluorescence spectra of the composite material prepared in Example 1 are shown at room temperature and after the phase transition point. The fluorescence spectra of the composite material at room temperature and after the phase transition point show significant differences. After the temperature reaches the phase transition point, two characteristic fluorescence emission peaks belonging to the dispersed state appear at 530 nm and 570 nm, while the peak at 638 nm becomes a shoulder peak again. This means that the phase transition of paraffin can cause the molecules to change from aggregation to dispersion.
Claims
1. The application of a perylene imide derivative-paraffin fluorescent composite material for anti-counterfeiting identification in the preparation of anti-counterfeiting marks, characterized in that, The perylene imide derivative-paraffin fluorescent composite material for anti-counterfeiting identification comprises the following steps: 1) A perylene imide compound, aliphatic amine, or aromatic amine is mixed in a solvent at a molar ratio of 1:2.5 and added to a round-bottom flask connected to a reflux condenser; the perylene imide compound is one of 3,4,9,10-perylenetetracarboxylic dianhydride or 1,6,7,12-tetrachloro-3,4,9,10-perylenetetracarboxylic dianhydride; the aliphatic amine or aromatic amine is one of heptadecano-9-amine, n-dodecylamine, 4-aminoazobenzene, or 2,5-di-tert-butylaniline; the solvent is selected from one or a combination of two of imidazole and toluene. 2) Under a nitrogen atmosphere, the mixture in step 1) is heated in an oil bath and refluxed at 100-120℃ for 6-12 hours; 3) Add hydrochloric acid solution to the product obtained from the reaction in step 2); 4) Extract the solution obtained in step 3) with dichloromethane, retain the organic phase, and filter; 5) Wash the dichloromethane solution obtained from the filtration in step 4) with a saturated sodium bicarbonate solution; 6) Dry the organic phase obtained after separation in step 5) with anhydrous sodium sulfate, and filter again to collect the dichloromethane solution; 7) The solution obtained in step 6) is subjected to rotary evaporation to obtain the crude product; 8) The crude product obtained in step 7) is subjected to chromatographic separation and vacuum drying to obtain powder; 9) Add the powder obtained in step 8) to the heated and melted paraffin, stir and sonicate to obtain perylene imide derivative-paraffin fluorescent composite material.
2. The application according to claim 1, characterized in that, In step 8), the eluent used in the chromatographic separation is one or a combination of dichloromethane and petroleum ether.
3. The application according to claim 1, characterized in that, In step 9), the ratio of the powder to paraffin is 0.01~5 mg : 1 g.
4. The application according to claim 1, characterized in that, The perylene imide derivative-paraffin fluorescent composite material was heated to 60 ℃ and melted, then poured into a mold and cooled to produce an anti-counterfeiting mark.