Perylene bisimide derivative-paraffin fluorescent composite material for anti-counterfeiting recognition as well as preparation method and application of perylene bisimide derivative-paraffin fluorescent composite material

Abstract

The invention belongs to the technical field of organic light-emitting materials, and particularly relates to a perylene bisimide derivative-paraffin fluorescent composite material for anti-counterfeiting recognition as well as a preparation method and application of the perylene bisimide derivative-paraffin fluorescent composite material. According to the technical scheme, the preparation method comprises the following steps: mixing a perylene bisimide compound and aliphatic amine or aromatic amine in a solvent under the protection of nitrogen, carrying out oil bath heating and reflux condensation, carrying out extraction, filtration, washing, liquid separation, secondary filtration and rotary evaporation, carrying out chromatographic separation, drying to obtain powder, heating and dissolving paraffin, adding a certain amount of powder, stirring, and carrying out ultrasonic mixing to obtain the perylene bisimide polymer. And fully and uniformly mixing the powder in the paraffin to obtain the perylene bisimide derivative-paraffin fluorescent composite material. The preparation method disclosed by the invention is simple and convenient in synthesis process, green and environment-friendly and low in production cost, and the prepared perylene bisimide derivative-paraffin fluorescent composite material is excellent in fluorescence luminescence property and high in fluorescence stability, has temperature responsiveness and can be applied to the fields of anti-counterfeiting identification, fluorescent temperature measurement test paper, phase change energy storage and the like.

Description

Technical Field

[0001] The invention belongs to the technical field of organic luminescent materials, and in particular relates to a perylene imide derivative-paraffin fluorescent composite material for anti-counterfeiting identification, and a preparation method and application thereof. Background Art

[0002] Phase change material-based fluorescent composite materials can present different colors and fluorescent properties according to changes in external temperature, and have temperature light responsiveness. This material can be used in fields such as smart curtains, smart clothing and temperature indicators to achieve temperature perception and intelligent control functions. The research on phase change material-based fluorescent color-changing materials not only has important scientific significance, but also has broad application prospects.

[0003] Paraffin is the most common organic solid-liquid phase change material in our daily life. It has the advantages of being cheap, non-toxic, and cost-effective. Paraffin is a mixture of various alkanes. Its melting point can be adjusted by controlling the content and proportion of various alkanes in the mixture. The melting point can be selected in a wide range, making it an ideal phase change material matrix.

[0004] Perylene imide derivatives have excellent fluorescence properties such as high fluorescence intensity and strong fluorescence stability, and are easy to modify, thus giving perylene imide compounds unique optical properties and functions. Due to the strong π-π stacking between perylene imide derivative molecules, the aggregation mode of perylene imide derivatives can be regulated to form a unique self-assembly structure, which is expected to make perylene imide compounds play a prominent role in the field of phase change material-based fluorescent composite materials. Summary of the invention

[0005] The present invention overcomes the shortcomings of the prior art and provides a method for preparing a perylene imide derivative-paraffin wax fluorescent composite material for anti-counterfeiting identification. A new type of fluorescent composite functional material with temperature responsiveness is prepared by a relatively simple method. The material has high luminous intensity and excellent luminous stability and can be used in the field of anti-counterfeiting identification.

[0006] The technical solution adopted by the present 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 comprises the following steps:

[0008] 1) Mix the perylene imide compound and the aliphatic amine / aromatic amine in a solvent and add the mixture into a round-bottom flask connected with a reflux condenser;

[0009] 2) Under a nitrogen atmosphere, the mixture in step 1) was heated in an oil bath and condensed under reflux;

[0010] 3) adding hydrochloric acid solution to the product obtained by the reaction in step 2);

[0011] 4) extracting the solution obtained in step 3) with dichloromethane, retaining the organic phase and filtering;

[0012] 5) washing the dichloromethane solution obtained by filtration in step 4) with a saturated sodium bicarbonate solution;

[0013] 6) drying the organic phase obtained after separation in step 5) over anhydrous sodium sulfate, and filtering again to collect the dichloromethane solution;

[0014] 7) The solution obtained in step 6) is subjected to rotary evaporation by a rotary evaporator to obtain a crude product;

[0015] 8) subjecting the crude product obtained in step 7) to chromatographic separation and vacuum drying to obtain a powder;

[0016] 9) adding the powder obtained in step 8) into the heated and dissolved paraffin, stirring and ultrasonicating, to obtain a perylene imide derivative-paraffin fluorescent composite material.

[0017] Furthermore, in the above preparation method, in 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-mentioned preparation method, in step 1), the aliphatic amine / aromatic amine is one of heptadecan-9-amine, n-dodecylamine, 4-aminoazobenzene, and 2,5-di-tert-butylaniline.

[0019] Furthermore, in the above-mentioned preparation method, in step 1), the molar ratio of the perylene imide compound to the aliphatic amine / aromatic amine is 1:2.5.

[0020] Furthermore, in the above preparation method, in step 1), the solvent is selected from a combination of one or more of imidazole, toluene and zinc acetate.

[0021] Furthermore, in the above preparation method, in step 2), the heating temperature is 100-120° C., and the condensation reflux time is 6-12 h.

[0022] Furthermore, in the above-mentioned preparation method, in step 8), the eluent in the chromatographic separation is a combination of one or more 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 the 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. and melted, poured into a mold, and cooled to form an anti-counterfeiting mark.

[0026] The beneficial effects of the present invention are as follows: the synthesis process of the present invention is easy to control, simple to operate, green and environmentally friendly, and has low production cost. It can quickly synthesize a perylene imide derivative-paraffin wax fluorescent composite material for anti-counterfeiting identification, and utilizes the unique optical properties and functions of perylene imide compounds such as excellent optical, thermal and chemical stability, and reacts aliphatic amines / aromatic amines with perylene tetracarboxylic dianhydride to carry out amine substitution, which can effectively weaken the π-π stacking between perylene imide molecules, and the solubility of the obtained perylene imide derivative in paraffin is significantly improved. The prepared perylene imide derivative-paraffin wax fluorescent composite material has high fluorescence intensity, strong fluorescence stability, and temperature responsiveness, and can be applied to anti-counterfeiting identification, fluorescent temperature measuring test paper, phase change energy storage and other fields. BRIEF DESCRIPTION OF THE DRAWINGS

[0027] Figure 1 The luminescence effect diagram of the composite material prepared in Example 1 before and after being irradiated with ultraviolet light with a wavelength of 365 nm at room temperature and after the phase transition point.

[0028] Figure 2 It is the differential scanning calorimetry test diagram of the composite material prepared in Example 1-3.

[0029] Figure 3 It is the fluorescence spectrum diagram of the composite material prepared in Example 1 at room temperature and after the phase transition point. DETAILED DESCRIPTION

[0030] In order to make the purpose, technical scheme and advantages of the present invention clearer, the present invention is further described in detail below in conjunction with embodiments. It should be understood that the specific embodiments described herein are only used to explain the present invention and are not intended to limit the present invention. For those of ordinary skill in the art, without departing from the concept of the present invention, some variations and improvements can also be made, which all belong to the protection scope of the present 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) 0.39 g of 3,4,9,10-perylenetetracarboxylic dianhydride and 0.64 g of heptadecan-9-amine were mixed with 5 g of imidazole and added into a round-bottom flask connected with a reflux condenser;

[0034] 2) Under a nitrogen atmosphere, the mixture in step 1) was heated to 120° C. in an oil bath and condensed under reflux for 6 h;

[0035] 3) 100 mL of 2 mol·L -1 Add the hydrochloric acid solution to the product obtained by the reaction in step 2);

[0036] 4) extracting the solution obtained in step 3) with dichloromethane, retaining the organic phase and filtering;

[0037] 5) washing the dichloromethane solution obtained by filtration in step 4) with a saturated sodium bicarbonate solution;

[0038] 6) drying the organic phase obtained after separation in step 5) over anhydrous sodium sulfate, and filtering again to collect the dichloromethane solution;

[0039] 7) The solution obtained in step 6) is subjected to rotary evaporation by a rotary evaporator to obtain a crude product;

[0040] 8) The crude product obtained in step 7) is subjected to chromatographic separation using dichloromethane as an eluent, and then vacuum dried to obtain a powder;

[0041] 9) 1.00 mg of the powder obtained in step 8) was added to 1 g of heated and dissolved paraffin, and the mixture was stirred and ultrasonicated to obtain a 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) 0.39 g of 3,4,9,10-perylenetetracarboxylic dianhydride and 0.46 g of n-dodecylamine were mixed with 1 g of zinc acetate and 10 g of imidazole, and added into a round-bottom flask connected with 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 h;

[0046] 3) 100mL of 2mol·L -1 Add the hydrochloric acid solution to the product obtained by the reaction in step 2);

[0047] 4) extracting the solution obtained in step 3) with dichloromethane, retaining the organic phase and filtering;

[0048] 5) washing the dichloromethane solution obtained by filtration in step 4) with a saturated sodium bicarbonate solution;

[0049] 6) The organic phase obtained after separation in step 5) is dried over anhydrous sodium sulfate, and filtered again to collect the dichloromethane solution.

[0050] 7) The solution obtained in step 6) is subjected to rotary evaporation by a rotary evaporator to obtain a crude product;

[0051] 8) The crude product obtained in step 7) is subjected to chromatographic separation using dichloromethane as an eluent, and then vacuum dried to obtain a powder;

[0052] 9) 1.00 mg of the powder obtained in step 8) was added to 1 g of heated and dissolved paraffin, and the mixture was stirred and ultrasonicated to obtain a perylene imide derivative-paraffin fluorescent composite material.

[0053] Example 3

[0054] 1) 0.87 g of 1,6,7,12-tetrachloro-3,4,9,10-perylenetetracarboxylic dianhydride and 0.46 g of n-dodecylamine were mixed in 100 mL of toluene and added into 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 condensed under reflux for 6 h;

[0056] 3) 100mL of 2mol·L -1 Add the hydrochloric acid solution to the product obtained by the reaction in step 2);

[0057] 4) extracting the solution obtained in step 3) with dichloromethane, retaining the organic phase and filtering;

[0058] 5) washing the dichloromethane solution obtained by filtration in step 4) with a saturated sodium bicarbonate solution;

[0059] 6) The organic phase obtained after separation in step 5) is dried over anhydrous sodium sulfate, and filtered again to collect the dichloromethane solution.

[0060] 7) The solution obtained in step 6) is subjected to rotary evaporation by a rotary evaporator to obtain a crude product;

[0061] 8) The crude product obtained in step 7) is subjected to chromatographic separation using dichloromethane and petroleum ether as eluents, and then vacuum dried to obtain a powder;

[0062] 9) 1.00 mg of the powder obtained in step 8) was added to 1 g of heated and dissolved paraffin, and the mixture was stirred and ultrasonicated to obtain a perylene imide derivative-paraffin fluorescent composite material.

[0063] Example 4

[0064] 1) 0.87 g of 1,6,7,12-tetrachloro-3,4,9,10-perylenetetracarboxylic dianhydride and 0.6 g of heptadecan-9-amine were mixed in 5 g of imidazole and 100 mL of toluene, and added into a round-bottom flask connected with a reflux condenser;

[0065] 2) Under a nitrogen atmosphere, the mixture in step 1) was heated in an oil bath to 100° C. and condensed under reflux for 12 h;

[0066] 3) 100 mL of 2 mol·L -1 Add the hydrochloric acid solution to the product obtained by the reaction in step 2);

[0067] 4) extracting the solution obtained in step 3) with dichloromethane, retaining the organic phase and filtering;

[0068] 5) washing the dichloromethane solution obtained by filtration in step 4) with a saturated sodium bicarbonate solution;

[0069] 6) The organic phase obtained after separation in step 5) is dried over anhydrous sodium sulfate, and filtered again to collect the dichloromethane solution.

[0070] 7) The solution obtained in step 6) is subjected to rotary evaporation by a rotary evaporator to obtain a crude product;

[0071] 8) The crude product obtained in step 7) is subjected to chromatographic separation using dichloromethane and petroleum ether as eluents, and then vacuum dried to obtain a powder;

[0072] 9) 3.00 mg of the powder obtained in step 8) was added to 1 g of heated and dissolved paraffin, and the mixture was stirred and ultrasonicated to obtain a 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 0.39 g of 3,4,9,10-perylenetetracarboxylic dianhydride and 0.49 g of 4-aminoazobenzene in 5 g of imidazole and add the mixture into 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 h;

[0077] 3) 100mL of 2mol·L -1 Add the hydrochloric acid solution to the product obtained by the reaction in step 2);

[0078] 4) extracting the solution obtained in step 3) with dichloromethane, retaining the organic phase and filtering;

[0079] 5) washing the dichloromethane solution obtained by filtration in step 4) with a saturated sodium bicarbonate solution;

[0080] 6) drying the organic phase obtained after separation in step 5) over anhydrous sodium sulfate, and filtering again to collect the dichloromethane solution;

[0081] 7) The solution obtained in step 6) is subjected to rotary evaporation by a rotary evaporator to obtain a crude product;

[0082] 8) The crude product obtained in step 7) is subjected to chromatographic separation using petroleum ether as an eluent, and then vacuum dried to obtain a powder;

[0083] 9) 0.50 mg of the powder obtained in step 8) was added to 1 g of heated and dissolved paraffin, and the mixture was stirred and ultrasonicated to obtain a 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 0.39 g of 3,4,9,10-perylenetetracarboxylic dianhydride and 0.51 g of 2,5-di-tert-butylaniline in 5 g of zinc acetate and add the mixture into a round-bottom flask connected to a reflux condenser;

[0087] 2) Under nitrogen atmosphere, the mixture in step 1) was heated to 120° C. in an oil bath and condensed under reflux for 10 h;

[0088] 3) 100mL of 2mol·L -1 Add the hydrochloric acid solution to the product obtained by the reaction in step 2);

[0089] 4) extracting the solution obtained in step 3) with dichloromethane, retaining the organic phase and filtering;

[0090] 5) washing the dichloromethane solution obtained by filtration in step 4) with a saturated sodium bicarbonate solution;

[0091] 6) drying the organic phase obtained after separation in step 5) over anhydrous sodium sulfate, and filtering again to collect the dichloromethane solution;

[0092] 7) The solution obtained in step 6) is subjected to rotary evaporation by a rotary evaporator to obtain a crude product;

[0093] 8) The crude product obtained in step 7) is subjected to chromatographic separation using dichloromethane as an eluent, and then vacuum dried to obtain a powder;

[0094] 9) 5.00 mg of the powder obtained in step 8) was added to 1 g of heated and dissolved paraffin, and the mixture was stirred and ultrasonicated to obtain a perylene imide derivative-paraffin fluorescent composite material.

[0095] Example 7

[0096] 1) Mix 0.87 g of 1,6,7,12-tetrachloro-3,4,9,10-perylenetetracarboxylic dianhydride and 0.49 g of 4-aminoazobenzene in 1 g of zinc acetate and 100 mL of toluene, and add the mixture into 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 h;

[0098] 3) 100mL of 2mol·L -1 Add the hydrochloric acid solution to the product obtained by the reaction in step 2);

[0099] 4) extracting the solution obtained in step 3) with dichloromethane, retaining the organic phase and filtering;

[0100] 5) washing the dichloromethane solution obtained by filtration in step 4) with a saturated sodium bicarbonate solution;

[0101] 6) The organic phase obtained after separation in step 5) is dried over anhydrous sodium sulfate, and filtered again to collect the dichloromethane solution.

[0102] 7) The solution obtained in step 6) is subjected to rotary evaporation by a rotary evaporator to obtain a crude product;

[0103] 8) The crude product obtained in step 7) is subjected to chromatographic separation using dichloromethane and petroleum ether as eluents, and then vacuum dried to obtain a powder;

[0104] 9) 0.07 mg of the powder obtained in step 8) was added to 1 g of heated and dissolved paraffin, and the mixture was stirred and ultrasonicated to obtain a perylene imide derivative-paraffin fluorescent composite material.

[0105] Example 8

[0106] 1) Mix 0.87 g of 1,6,7,12-tetrachloro-3,4,9,10-perylenetetracarboxylic dianhydride and 0.51 g of 2,5-di-tert-butylaniline in 100 mL of toluene and add the mixture into 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 h;

[0108] 3) 100mL of 2mol·L -1Add the hydrochloric acid solution to the product obtained by the reaction in step 2);

[0109] 4) extracting the solution obtained in step 3) with dichloromethane, retaining the organic phase and filtering;

[0110] 5) washing the dichloromethane solution obtained by filtration in step 4) with a saturated sodium bicarbonate solution;

[0111] 6) The organic phase obtained after separation in step 5) is dried over anhydrous sodium sulfate, and filtered again to collect the dichloromethane solution.

[0112] 7) The solution obtained in step 6) is subjected to rotary evaporation by a rotary evaporator to obtain a crude product;

[0113] 8) The crude product obtained in step 7) is subjected to chromatographic separation using petroleum ether as an eluent, and then vacuum dried to obtain a powder;

[0114] 9) 0.10 mg of the powder obtained in step 8) was added to 1 g of heated and dissolved paraffin, and the mixture was stirred and ultrasonicated to obtain a perylene imide derivative-paraffin fluorescent composite material.

[0115] Example 9

[0116] The prepared perylene imide derivative-paraffin fluorescent composite material is heated to 60°C and poured into a round mold to prepare a round anti-counterfeiting mark. The mark is irradiated with ultraviolet light at room temperature and 60°C to observe its fluorescent color change.

[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 an ultraviolet lamp having a wavelength of 365 nm. The results before and after irradiation at room temperature and under heating conditions were as follows: Figure 1 As shown in the results, under room temperature conditions, when the UV light is turned on, no fluorescent light can be seen. Figure 1 As shown in A, the content on the composite material is in an encrypted state. When the ultraviolet light is turned on, a circular fluorescence can be seen, and the fluorescence color is red. Figure 1 As shown in B; after heating the composite material to the phase transition point, turning on the ultraviolet light, circular fluorescence can still be seen, but the fluorescence color is yellow, as shown in FIG. Figure 1 As shown in C, therefore, the perylene imide derivative-paraffin fluorescent composite material has the function of anti-counterfeiting encryption of information.

[0119] Figure 2This is a differential scanning calorimetry test diagram of the composite material prepared in Example 1-3. As the temperature rises, two phase transition peaks appear. The first phase transition peak belongs to the phase transition peak of the paraffin crystal transformation, which belongs to the solid-solid phase transition. The real solid-liquid phase transition peak is the second phase transition peak. The paraffin composite material with the addition of perylene imide derivatives has a phase transition temperature of 60°C. The addition of fluorescent compounds does not significantly change the phase transition temperature of paraffin.

[0120] Figure 3 The fluorescence spectra of the composite material prepared in Example 1 at room temperature and after the phase transition point are significantly different. When the temperature reaches the phase transition point, two characteristic peaks of fluorescence emission belonging to the dispersed state appear at 530nm and 570nm, and the peak at 638nm turns into a shoulder peak again, which means that the phase transition of paraffin can cause the molecules to change from aggregation to dispersion.

Claims

1. A method for preparing a perylene imide derivative-paraffin fluorescent composite material for anti-counterfeiting identification, characterized in that: The steps include: 1) Mix the perylene imide compound and the aliphatic amine / aromatic amine in a solvent and add the mixture into a round-bottom flask connected with a reflux condenser; 2) Under a nitrogen atmosphere, the mixture in step 1) was heated in an oil bath and condensed under reflux; 3) adding hydrochloric acid solution to the product obtained by the reaction in step 2); 4) extracting the solution obtained in step 3) with dichloromethane, retaining the organic phase and filtering; 5) washing the dichloromethane solution obtained by filtration in step 4) with a saturated sodium bicarbonate solution; 6) drying the organic phase obtained after separation in step 5) over anhydrous sodium sulfate, and filtering again to collect the dichloromethane solution; 7) The solution obtained in step 6) is subjected to rotary evaporation by a rotary evaporator to obtain a crude product; 8) subjecting the crude product obtained in step 7) to chromatographic separation and vacuum drying to obtain a powder; 9) adding the powder obtained in step 8) into the heated and dissolved paraffin, stirring and ultrasonicating, to obtain a perylene imide derivative-paraffin fluorescent composite material.

2. The preparation method according to claim 1, characterized in that: In step 1), the perylene imide compound is one of 3,4,9,10-perylenetetracarboxylic dianhydride and 1,6,7,12-tetrachloro-3,4,9,10-perylenetetracarboxylic dianhydride.

3. The preparation method according to claim 1, characterized in that: In step 1), the aliphatic amine / aromatic amine is one of heptadecan-9-amine, n-dodecylamine, 4-aminoazobenzene, and 2,5-di-tert-butylaniline.

4. The preparation method according to claim 1, characterized in that: In step 1), the molar ratio of the perylene imide compound to the aliphatic amine / aromatic amine is 1:2.

5.

5. The preparation method according to claim 1, characterized in that: In step 1), the solvent is selected from one or more combinations of imidazole, toluene and zinc acetate.

6. The preparation method according to claim 1, characterized in that: In step 2), the heating temperature is 100-120° C., and the condensation reflux time is 6-12 h.

7. The preparation method according to claim 1, characterized in that: In step 8), the eluent in the chromatographic separation is a combination of one or more of dichloromethane and petroleum ether.

8. The preparation method according to claim 1, characterized in that: In step 9), the ratio of the powder to paraffin is 0.01-5 mg:1 g.

9. Use of the perylene imide derivative-paraffin fluorescent composite material prepared by the preparation method according to any one of claims 1 to 8 in the preparation of anti-counterfeiting marks.

10. The use according to claim 9, characterized in that: The perylene imide derivative-paraffin fluorescent composite material is heated to 60°C and melted, poured into a mold, and cooled to form an anti-counterfeiting mark.

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