CN114457451B - Preparation method of micron-sized bonding fluorescent anti-counterfeiting fiber - Google Patents
Preparation method of micron-sized bonding fluorescent anti-counterfeiting fiber Download PDFInfo
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- CN114457451B CN114457451B CN202210106544.0A CN202210106544A CN114457451B CN 114457451 B CN114457451 B CN 114457451B CN 202210106544 A CN202210106544 A CN 202210106544A CN 114457451 B CN114457451 B CN 114457451B
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- 239000000835 fiber Substances 0.000 title claims abstract description 84
- 238000002360 preparation method Methods 0.000 title claims abstract description 31
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 37
- 150000002910 rare earth metals Chemical class 0.000 claims abstract description 34
- 239000000463 material Substances 0.000 claims abstract description 28
- 238000000034 method Methods 0.000 claims abstract description 23
- 238000010041 electrostatic spinning Methods 0.000 claims abstract description 14
- 239000000243 solution Substances 0.000 claims description 67
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 55
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 45
- 238000006243 chemical reaction Methods 0.000 claims description 31
- 238000009987 spinning Methods 0.000 claims description 28
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 20
- 239000000047 product Substances 0.000 claims description 19
- 229920000642 polymer Polymers 0.000 claims description 17
- IFQUPKAISSPFTE-UHFFFAOYSA-N 4-benzoylbenzoic acid Chemical compound C1=CC(C(=O)O)=CC=C1C(=O)C1=CC=CC=C1 IFQUPKAISSPFTE-UHFFFAOYSA-N 0.000 claims description 16
- KFDVPJUYSDEJTH-UHFFFAOYSA-N 4-ethenylpyridine Chemical compound C=CC1=CC=NC=C1 KFDVPJUYSDEJTH-UHFFFAOYSA-N 0.000 claims description 16
- GFISHBQNVWAVFU-UHFFFAOYSA-K terbium(iii) chloride Chemical compound Cl[Tb](Cl)Cl GFISHBQNVWAVFU-UHFFFAOYSA-K 0.000 claims description 16
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 15
- 239000003814 drug Substances 0.000 claims description 15
- 229940079593 drug Drugs 0.000 claims description 15
- 239000011259 mixed solution Substances 0.000 claims description 15
- 239000002244 precipitate Substances 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 10
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 10
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 10
- 229910052782 aluminium Inorganic materials 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 10
- 239000011888 foil Substances 0.000 claims description 10
- 239000003999 initiator Substances 0.000 claims description 10
- 238000002347 injection Methods 0.000 claims description 10
- 239000007924 injection Substances 0.000 claims description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims description 10
- 238000012360 testing method Methods 0.000 claims description 10
- 238000004458 analytical method Methods 0.000 claims description 9
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical group COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 8
- 239000000178 monomer Substances 0.000 claims description 8
- KKFHAJHLJHVUDM-UHFFFAOYSA-N n-vinylcarbazole Chemical compound C1=CC=C2N(C=C)C3=CC=CC=C3C2=C1 KKFHAJHLJHVUDM-UHFFFAOYSA-N 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 230000005684 electric field Effects 0.000 claims description 5
- 238000003760 magnetic stirring Methods 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 239000000843 powder Substances 0.000 claims description 5
- 238000005096 rolling process Methods 0.000 claims description 5
- 238000007789 sealing Methods 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 238000001291 vacuum drying Methods 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 238000005303 weighing Methods 0.000 claims description 5
- 238000012512 characterization method Methods 0.000 claims description 3
- 238000001514 detection method Methods 0.000 claims description 3
- 230000005284 excitation Effects 0.000 abstract description 3
- 229920001410 Microfiber Polymers 0.000 abstract 1
- 239000003658 microfiber Substances 0.000 abstract 1
- 238000005516 engineering process Methods 0.000 description 6
- 229920002521 macromolecule Polymers 0.000 description 4
- 238000002329 infrared spectrum Methods 0.000 description 3
- -1 rare earth ions Chemical class 0.000 description 3
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000002189 fluorescence spectrum Methods 0.000 description 2
- 239000003446 ligand Substances 0.000 description 2
- KGIGUEBEKRSTEW-UHFFFAOYSA-N 2-vinylpyridine Chemical compound C=CC1=CC=CC=N1 KGIGUEBEKRSTEW-UHFFFAOYSA-N 0.000 description 1
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical group C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001523 electrospinning Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 230000005476 size effect Effects 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
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- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/44—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds
- D01F6/52—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds of polymers of unsaturated carboxylic acids or unsaturated esters
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F230/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal
- C08F230/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal
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- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
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Abstract
The invention relates to a preparation method of micron-sized bonding fluorescent anti-counterfeiting fiber, and relates to the technical field of fluorescent anti-counterfeiting fiber. The method comprises the following steps: 1) Preparation of rare earth Complex Tb (C) 14 H 10 O 3 ) 3 (C 7 H 7 N) 2 The method comprises the steps of carrying out a first treatment on the surface of the 2) Preparing a bonding type high molecular fluorescent material PMNTb; 3) And preparing the micron-sized bonding fluorescent anti-counterfeiting fiber by electrostatic spinning. The micron-sized bonding fluorescent anti-counterfeiting fibers prepared by the method are randomly arranged, the diameters of the fibers are uniformly distributed, the surfaces of the fibers are smooth, and the diameters of the fibers are about 0.6-1.169 mu m; the thermal stability temperature of the bonding type fluorescent fiber can reach 274 ℃; the best excitation wavelength of the bonded fluorescent microfiber containing the rare earth complex is 350 nm, and the best emission wavelength is 544 nm.
Description
Technical Field
The invention relates to the technical field of fluorescent anti-counterfeiting fibers, in particular to a preparation method of micron-sized bonding fluorescent anti-counterfeiting fibers.
Background
With the rapid development of economy and science, counterfeiting of counterfeit products is endless. In order to cope with the challenges of continuous update of counterfeit technologies, it is necessary to continuously break the new type of counterfeit technology or to safely upgrade the existing counterfeit technology. The fluorescent anti-counterfeiting fiber is widely applied to the fields of bank notes, securities, certificate anti-counterfeiting and the like due to the advantages of good concealment and easy identification. The polymer rare earth luminescent material has unique luminescent property of rare earth ions and excellent processing and forming properties of polymers, and has wide application prospect in the fields of luminescent display, anti-counterfeiting, solar energy conversion and the like. However, most of the rare earth polymer fluorescent anti-counterfeiting fibers prepared at present are doped fluorescent fibers, and the defects of uneven distribution, phase separation and the like of the luminous units exist, so that the fluorescent performance of the fluorescent anti-counterfeiting material is reduced or even quenched. The bonded high molecular rare earth fluorescent material is paid attention to because the rare earth ions in the material are uniformly distributed, and the concentration quenching effect and the high fluorescence efficiency still cannot occur when the content of the rare earth ions is high. The fluorescent anti-counterfeiting fiber is developed by utilizing the electrostatic spinning technology, and the characteristics of small size effect, surface effect and the like of the micron fiber are combined with the excellent luminous performance of the bonded rare earth polymer fluorescent material, so that the novel application field can be opened up, and the fluorescent anti-counterfeiting fiber has positive promotion effect on the safety upgrading of the fluorescent anti-counterfeiting fiber.
Disclosure of Invention
The invention aims at providing a preparation method of micron-sized bonding fluorescent anti-counterfeiting fiber aiming at the background art. The method is to prepare rare earth complex Tb (C) by terbium chloride, 4-benzoyl benzoic acid and 4-vinyl pyridine 14 H 10 O 3 ) 3 (C 7 H 7 N) 2 Then with rare earth complex Tb (C 14 H 10 O 3 ) 3 (C 7 H 7 N) 2 N-vinylcarbazole and methyl methacrylate are used as polymer monomers, a free radical polymerization method is adopted to prepare a bonding type high molecular fluorescent material PMNTb, and then static is utilizedThe electrospinning technology prepares the bonding type high polymer fluorescent material PMNTb to obtain the bonding type fluorescent anti-counterfeiting fiber, and improves the fluorescent property of the fluorescent anti-counterfeiting fiber.
The invention is realized by the following technical scheme:
a preparation method of micron-sized bonding fluorescent anti-counterfeiting fiber comprises the following steps:
1) Preparation of rare earth Complex Tb (C) 14 H 10 O 3 ) 3 (C 7 H 7 N) 2
(1) Weigh and dissolve the drug
Respectively weighing 0.528 g +/-0.001 g of terbium chloride, 1.369 g +/-0.001 g of 4-benzoyl benzoic acid, 0.421 g +/-0.001 g of 4-vinylpyridine and 0.040 g +/-0.001 g of sodium hydroxide, respectively placing the weighed medicines into a beaker, adding absolute ethyl alcohol to dissolve the medicines, and respectively obtaining terbium chloride absolute ethyl alcohol solution, 4-benzoyl benzoic acid absolute ethyl alcohol solution, 4-vinylpyridine absolute ethyl alcohol solution and sodium hydroxide absolute ethyl alcohol solution;
(2) rare earth complex Tb (C) 14 H 10 O 3 ) 3 (C 7 H 7 N) 2 Is synthesized by (a)
Firstly, adding a 4-benzoyl benzoic acid absolute ethyl alcohol solution into a three-necked flask, then, putting the three-necked flask into a constant-temperature water bath kettle at 55 ℃ for magnetic stirring for 10 min, respectively and dropwise adding a terbium chloride absolute ethyl alcohol solution and a 4-vinyl pyridine absolute ethyl alcohol solution, and then, adjusting the pH value of the mixed solution to between 6.5 and 7 by using a sodium hydroxide absolute ethyl alcohol solution; a small amount of white precipitate appears in the mixed solution, the mixed solution containing the white precipitate is continuously stirred for reaction 4 h, after the reaction is finished, the precipitate product is taken and washed by absolute ethyl alcohol and then is placed in a vacuum drying oven at 55 ℃ for drying 24 h, and finally white powder is obtained, namely the rare earth complex Tb (C) 14 H 10 O 3 ) 3 (C 7 H 7 N) 2 Also denoted as complex Tb (4-BBA) 3 (4-VP) 2 The synthetic route is as follows:
2) Preparation of bonded Polymer fluorescent Material PMNTb
Adding 0.278g + -0.001 g rare earth complex Tb (C) into a branched test tube 14 H 10 O 3 ) 3 (C 7 H 7 N) 2 0.0175 g+ -0.001 g of initiator azodiisobutyronitrile and 3.00 mL + -0.001 mL of dimethyl sulfoxide, and ultrasonic oscillating to make the rare earth complex Tb (C) 14 H 10 O 3 ) 3 (C 7 H 7 N) 2 And an initiator azodiisobutyronitrile are fully dissolved; adding 2.00 mL +/-0.001 mL of methyl methacrylate monomer and 0.1 g +/-0.001 g of N-vinyl carbazole monomer into a branched test tube after introducing nitrogen for 15 minutes, continuously introducing nitrogen for 35 minutes, sealing a reaction device, placing the reaction device into a constant-temperature water bath kettle for constant-temperature reaction at 75 ℃ for 48 h, alternately washing the obtained product with deionized water and absolute ethyl alcohol after the reaction is finished, and drying the product in a vacuum oven at 55 ℃ for 24 h to obtain the bonding type high polymer fluorescent material PMNTb, wherein the synthetic route is as follows:
3) Micron-sized bonding fluorescent anti-counterfeiting fiber prepared by electrostatic spinning
(1) Preparation of spinning solution
Adding 5.962 g+/-0.001 g of bonding type high molecular fluorescent material PMNTb and 20 mL of N, N-dimethylformamide into a beaker, stirring and uniformly mixing to obtain a clear solution, and standing for 24 h to obtain the spinning solution;
(2) preparation of micron-sized bonding fluorescent anti-counterfeiting fiber
Electrostatic spinning conditions: the spinning electric field voltage is 15 kV; the receiving distance is 15 cm; the injection speed of the injector is 0.5 mL/h; the outer diameter of the syringe needle is 0.82 mm;
firstly, sucking spinning solution into a syringe, fixing the syringe on a syringe pump, adjusting parameters of the syringe pump, wrapping an aluminum foil on a receiving roller, connecting the aluminum foil with a negative electrode, and connecting a needle part of the syringe with a positive electrode; starting the injection pump and the rolling device, starting a high-voltage power supply when the first drop of spinning solution appears on the needle head, slowly adjusting the voltage to the required voltage, and obtaining the micron-sized bonding fluorescent anti-counterfeiting fiber on the grounded receiving roller.
Further, in the step 3), after the spinning is finished, the obtained micron-sized bonding fluorescent anti-counterfeiting fiber is placed in an oven 24 h, and the temperature is set to 55 ℃.
Further, the method of the present invention further comprises the detection, analysis and characterization of step 4); the method comprises the following steps:
detecting, analyzing and characterizing the morphology, the components, the structure, the fluorescence performance and the thermal stability of the prepared micron-sized bonding fluorescent anti-counterfeiting fiber;
performing morphology analysis on the micron-sized bonding fluorescent anti-counterfeiting fiber by using a scanning electron microscope;
performing fluorescence performance analysis on the micron-sized bonding type fluorescent anti-counterfeiting fiber by using a fluorescence spectrometer;
analyzing the structure of the micron-sized bonding fluorescent anti-counterfeiting fiber by using a Fourier infrared spectrometer;
and analyzing the thermal stability of the micron-sized bonding fluorescent anti-counterfeiting fiber by using a thermogravimetric analyzer.
The invention prepares bonding type macromolecule fluorescent material PMNTb through each process step and parameter, and only the bonding type macromolecule fluorescent material PMNTb prepared by adopting the process steps and parameters can be prepared into micron-sized bonding type fluorescence anti-counterfeiting fiber by adopting an electrostatic spinning technology; the bonding type high polymer fluorescent material PMNTb can be processed into micron bonding type fluorescent anti-counterfeiting fiber only by adopting the electrostatic spinning conditions and steps.
The micron-sized bonding fluorescent anti-counterfeiting fibers prepared by the method are randomly arranged, the diameters of the fibers are uniformly distributed, the surfaces of the fibers are smooth, and the diameters of the fibers are about 0.6-1.169 mu m; the thermal stability temperature of the micron-sized bonding fluorescent anti-counterfeiting fiber can reach 274 ℃; the optimal excitation wavelength of the micron-scale bonding fluorescent anti-counterfeiting fiber containing the rare earth complex is 350 nm, and the optimal emission wavelength is 544 nm.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present application, the drawings that are needed in the embodiments of the present application will be briefly described below, it should be understood that the following drawings only illustrate some embodiments of the present application and should not be considered as limiting the scope, and other related drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 shows the bonding type polymer fluorescent material PMNTb and the complex Tb (4-BBA) in the method of example 1 3 (4-VP) 2 Is a comparison of the infrared spectra of (a).
FIG. 2 is a thermogravimetric curve of the micron-sized bonding type fluorescent anti-counterfeiting fiber prepared by the method of example 1.
Fig. 3 is a scan of the micron-sized bonded fluorescent anti-counterfeiting fiber prepared by the method of example 1.
FIG. 4 is a fluorescence spectrum of the micron-sized bonding type fluorescent anti-counterfeiting fiber prepared by the method of example 1.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and fully with reference to the accompanying drawings, in which it is evident that the embodiments described are only some, but not all embodiments of the invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to fall within the scope of the invention.
Example 1
A preparation method of micron-sized bonding fluorescent anti-counterfeiting fiber comprises the following steps:
1) Preparation of rare earth Complex Tb (C) 14 H 10 O 3 ) 3 (C 7 H 7 N) 2
(1) Weigh and dissolve the drug
Respectively weighing terbium chloride of 0.528 g, 4-benzoyl benzoic acid of 1.369 g, 4-vinylpyridine of 0.421 g and sodium hydroxide of 0.040 g, respectively placing the weighed medicines in a beaker, adding absolute ethyl alcohol to dissolve the medicines, and respectively obtaining terbium chloride absolute ethyl alcohol solution, 4-benzoyl benzoic acid absolute ethyl alcohol solution, 4-vinylpyridine absolute ethyl alcohol solution and sodium hydroxide absolute ethyl alcohol solution;
(2) rare earth complex Tb (C) 14 H 10 O 3 ) 3 (C 7 H 7 N) 2 Is synthesized by (a)
Firstly, adding a 4-benzoyl benzoic acid absolute ethyl alcohol solution into a three-necked flask, then, putting the three-necked flask into a constant-temperature water bath kettle at 55 ℃ for magnetic stirring for 10 min, respectively and dropwise adding a terbium chloride absolute ethyl alcohol solution and a 4-vinyl pyridine absolute ethyl alcohol solution, and then, adjusting the pH value of the mixed solution to between 6.5 and 7 by using a sodium hydroxide absolute ethyl alcohol solution; a small amount of white precipitate appears in the mixed solution, the mixed solution containing the white precipitate is continuously stirred for reaction 4 h, after the reaction is finished, the precipitate product is taken and washed by absolute ethyl alcohol and then is placed in a vacuum drying oven at 55 ℃ for drying 24 h, and finally white powder is obtained, namely the rare earth complex Tb (C) 14 H 10 O 3 ) 3 (C 7 H 7 N) 2 ；
2) Preparation of bonded Polymer fluorescent Material PMNTb
Adding 0.278g of rare earth complex Tb (C) into a branched test tube 14 H 10 O 3 ) 3 (C 7 H 7 N) 2 0.0175g of initiator azodiisobutyronitrile and 3.00 mL of dimethyl sulfoxide, and ultrasonic vibration to make the rare earth complex Tb (C) 14 H 10 O 3 ) 3 (C 7 H 7 N) 2 And an initiator azodiisobutyronitrile are fully dissolved; adding 2.00 mL methyl methacrylate monomer and 0.1 g N-vinyl carbazole monomer into a branched test tube after introducing nitrogen for 15 minutes, continuing introducing nitrogen for 35 minutes, sealing a reaction device, placing the reaction device into a constant-temperature water bath kettle for constant-temperature reaction at 75 ℃ for 48 h, alternately washing the obtained product with deionized water and absolute ethyl alcohol after the reaction is finished, and drying the product in a vacuum oven at 55 ℃ for 24 h to obtain the bonding type high molecular fluorescent material PMNTb;
3) Micron-sized bonding fluorescent anti-counterfeiting fiber prepared by electrostatic spinning
(1) Preparation of spinning solution
Adding 5.962g bonding type high molecular fluorescent material PMNTb and 20 mL N, N-dimethylformamide into a beaker, stirring and uniformly mixing to obtain a clear solution, and standing for 24 h to obtain the spinning solution;
(2) preparation of micron-sized bonding fluorescent anti-counterfeiting fiber
Electrostatic spinning conditions: the spinning electric field voltage is 15 kV; the receiving distance is 15 cm; the injection speed of the injector is 0.5 mL/h; the outer diameter of the syringe needle is 0.82 mm; the concentration of the spinning solution is 24wt%;
firstly, sucking spinning solution into a syringe, fixing the syringe on a syringe pump, adjusting parameters of the syringe pump, wrapping an aluminum foil on a receiving roller, connecting the aluminum foil with a negative electrode, and connecting a needle part of the syringe with a positive electrode; starting an injection pump and a rolling device, starting a high-voltage power supply when a first drop of spinning solution appears on a needle, slowly adjusting the voltage to a required voltage, and obtaining the micron-sized bonding fluorescent anti-counterfeiting fiber on a grounded receiving roller;
and placing the obtained micron-sized bonding fluorescent anti-counterfeiting fiber in an oven at 24 h, setting the temperature to 55 ℃, and finally obtaining a finished product.
4) Detection, analysis and characterization of prepared micron-sized bonding fluorescent anti-counterfeiting fiber
Detecting, analyzing and characterizing the morphology, the components, the structure, the fluorescence performance and the thermal stability of the prepared micron-sized bonding fluorescent anti-counterfeiting fiber;
performing morphology analysis on the micron-sized bonding fluorescent anti-counterfeiting fiber by using a scanning electron microscope;
performing fluorescence performance analysis on the micron-sized bonding type fluorescent anti-counterfeiting fiber by using a fluorescence spectrometer;
analyzing the structure of the micron-sized bonding fluorescent anti-counterfeiting fiber by using a Fourier infrared spectrometer;
and analyzing the thermal stability of the micron-sized bonding fluorescent anti-counterfeiting fiber by using a thermogravimetric analyzer.
FIG. 1 shows the bonding type polymer fluorescent material PMNTb and the complex Tb (4-BBA) in the method of example 1 3 (4-VP) 2 Is a comparison of the infrared spectra of (a). As can be seen from the figure, 1346 cm is in the PMNTb infrared spectrum -1 A stretching vibration peak ascribed to C-N in NVK; 1730 cm -1 Telescoping vibration attributed to MMA ester carbonyl 2991 and 2950 cm -1 methylene-CH of MMA 2 -antisymmetric and symmetrical telescopic vibration peaks; 1650 and cm in the Complex -1 -c=c, 1419, 1499, 1539, 1592, cm attributed to the ligand vinylpyridine -1 (1610-1370 cm -1 ) The stretching vibration peak of-c=n bond belonging to ligand pyridine ring coincides with benzene ring absorption peak after forming polymer; the above results illustrate the high molecular monomers NVK, MMA and the complex monomer Tb (4-BBA) 3 (4-VP) 2 And successfully polymerizing to obtain PMNTb.
FIG. 2 is a thermogravimetric curve of the micron-sized bonding type fluorescent anti-counterfeiting fiber prepared by the method of example 1. As can be seen, the thermal stabilization temperature of the bonding fluorescent fiber can reach 274 ℃.
Fig. 3 is a scan of the micron-sized bonded fluorescent anti-counterfeiting fiber prepared by the method of example 1. As shown in the figure, the micron-sized bonding fluorescent anti-counterfeiting fibers are randomly arranged, the diameters of the fibers are uniformly distributed, the surfaces of the fibers are smooth, and the diameters of the fibers are about 0.6-1.169 mu m.
FIG. 4 is a fluorescence spectrum of the micron-sized bonding type fluorescent anti-counterfeiting fiber prepared by the method of example 1. From the figure, the optimum excitation wavelength is 350 nm, the optimum emission wavelength is 544 nm, tb 3+ Is characterized by an emission peak.
Example 2
A preparation method of micron-sized bonding fluorescent anti-counterfeiting fiber comprises the following steps:
1) Preparation of rare earth Complex Tb (C) 14 H 10 O 3 ) 3 (C 7 H 7 N) 2
(1) Weigh and dissolve the drug
Respectively weighing terbium chloride, 4-benzoyl benzoic acid of 1.368 g, 4-vinylpyridine of 0.420 g and sodium hydroxide of 0.041 g, respectively placing the weighed medicines in a beaker, adding absolute ethyl alcohol to dissolve the medicines, and respectively obtaining terbium chloride absolute ethyl alcohol solution, 4-benzoyl benzoic acid absolute ethyl alcohol solution, 4-vinylpyridine absolute ethyl alcohol solution and sodium hydroxide absolute ethyl alcohol solution;
(2) rare earth complex Tb (C) 14 H 10 O 3 ) 3 (C 7 H 7 N) 2 Is synthesized by (a)
Firstly, adding a 4-benzoyl benzoic acid absolute ethyl alcohol solution into a three-necked flask, then, putting the three-necked flask into a constant-temperature water bath kettle at 55 ℃ for magnetic stirring for 10 min, respectively and dropwise adding a terbium chloride absolute ethyl alcohol solution and a 4-vinyl pyridine absolute ethyl alcohol solution, and then, adjusting the pH value of the mixed solution to between 6.5 and 7 by using a sodium hydroxide absolute ethyl alcohol solution; a small amount of white precipitate appears in the mixed solution, the mixed solution containing the white precipitate is continuously stirred for reaction 4 h, after the reaction is finished, the precipitate product is taken and washed by absolute ethyl alcohol and then is placed in a vacuum drying oven at 55 ℃ for drying 24 h, and finally white powder is obtained, namely the rare earth complex Tb (C) 14 H 10 O 3 ) 3 (C 7 H 7 N) 2 ；
2) Preparation of bonded Polymer fluorescent Material PMNTb
Adding 0.279g of rare earth complex Tb (C) into a branched test tube 14 H 10 O 3 ) 3 (C 7 H 7 N) 2 0.0185g of azodiisobutyronitrile as initiator and 3.001. 3.001 mL of dimethyl sulfoxide, ultrasonic vibration to obtain rare earth complex Tb (C) 14 H 10 O 3 ) 3 (C 7 H 7 N) 2 And an initiator azodiisobutyronitrile are fully dissolved; adding 1.999-mL methyl methacrylate monomer and 0.101-g N-vinyl carbazole monomer into a branched test tube after introducing nitrogen for 15 minutes, continuing introducing nitrogen for 35 minutes, sealing a reaction device, placing the reaction device into a constant-temperature water bath kettle for constant-temperature reaction at 75 ℃ for 48 h, alternately washing the obtained product with deionized water and absolute ethyl alcohol after the reaction is finished, and drying the product in a vacuum oven at 55 ℃ for 24 h to obtain the bonding type macromolecule fluorescent material PMNTb;
3) Micron-sized bonding fluorescent anti-counterfeiting fiber prepared by electrostatic spinning
(1) Preparation of spinning solution
Adding 5.963 g bonding type high molecular fluorescent material PMNTb and 20 mL N, N-dimethylformamide into a beaker, stirring and uniformly mixing to obtain a clear solution, and standing for 24 h to obtain the spinning solution;
(2) preparation of micron-sized bonding fluorescent anti-counterfeiting fiber
Electrostatic spinning conditions: the spinning electric field voltage is 15 kV; the receiving distance is 15 cm; the injection speed of the injector is 0.5 mL/h; the outer diameter of the syringe needle is 0.82 mm;
firstly, sucking spinning solution into a syringe, fixing the syringe on a syringe pump, adjusting parameters of the syringe pump, wrapping an aluminum foil on a receiving roller, connecting the aluminum foil with a negative electrode, and connecting a needle part of the syringe with a positive electrode; starting an injection pump and a rolling device, starting a high-voltage power supply when a first drop of spinning solution appears on a needle, slowly adjusting the voltage to a required voltage, and obtaining the micron-sized bonding fluorescent anti-counterfeiting fiber on a grounded receiving roller;
and placing the obtained micron-sized bonding fluorescent anti-counterfeiting fiber in an oven at 24 h, setting the temperature to 55 ℃, and finally obtaining a finished product.
Example 3
A preparation method of micron-sized bonding fluorescent anti-counterfeiting fiber comprises the following steps:
1) Preparation of rare earth Complex Tb (C) 14 H 10 O 3 ) 3 (C 7 H 7 N) 2
(1) Weigh and dissolve the drug
Respectively weighing terbium chloride of 0.527 g, 4-benzoyl benzoic acid of 1.370 g, 4-vinylpyridine of 0.422 g and sodium hydroxide of 0.039 g, respectively placing the weighed medicines in a beaker, adding absolute ethyl alcohol to dissolve the medicines, and respectively obtaining terbium chloride absolute ethyl alcohol solution, 4-benzoyl benzoic acid absolute ethyl alcohol solution, 4-vinylpyridine absolute ethyl alcohol solution and sodium hydroxide absolute ethyl alcohol solution;
(2) rare earth complex Tb (C) 14 H 10 O 3 ) 3 (C 7 H 7 N) 2 Is synthesized by (a)
Firstly, adding a 4-benzoyl benzoic acid absolute ethyl alcohol solution into a three-necked flask, then, putting the three-necked flask into a constant-temperature water bath kettle at 55 ℃ for magnetic stirring for 10 min, respectively and dropwise adding a terbium chloride absolute ethyl alcohol solution and a 4-vinyl pyridine absolute ethyl alcohol solution, and then, adjusting the pH value of the mixed solution to between 6.5 and 7 by using a sodium hydroxide absolute ethyl alcohol solution; a small amount of white precipitate appears in the mixed solution, the mixed solution containing the white precipitate is continuously stirred for reaction 4 h, after the reaction is finished, the precipitate product is taken and washed by absolute ethyl alcohol and then is placed in a vacuum drying oven at 55 ℃ for drying 24 h, and finally white powder is obtained, namely the rare earth complex Tb (C) 14 H 10 O 3 ) 3 (C 7 H 7 N) 2 ；
2) Preparation of bonded Polymer fluorescent Material PMNTb
Adding 0.277g of rare earth complex Tb (C) into a branched test tube 14 H 10 O 3 ) 3 (C 7 H 7 N) 2 0.0165g of initiator azodiisobutyronitrile and 2.999 mL dimethyl sulfoxide, and ultrasonic vibration to make the rare earth complex Tb (C) 14 H 10 O 3 ) 3 (C 7 H 7 N) 2 And an initiator azodiisobutyronitrile are fully dissolved; adding 2.001 mL methyl methacrylate monomer and 0.099 g N-vinyl carbazole monomer into a branched test tube after introducing nitrogen for 15 minutes, continuing introducing nitrogen for 35 minutes, sealing a reaction device, placing the reaction device into a constant-temperature water bath kettle for constant-temperature reaction at 75 ℃ for 48 h, alternately washing the obtained product with deionized water and absolute ethyl alcohol after the reaction is finished, and drying the product in a vacuum oven at 55 ℃ for 24 h to obtain the bonding type macromolecule fluorescent material PMNTb;
3) Micron-sized bonding fluorescent anti-counterfeiting fiber prepared by electrostatic spinning
(1) Preparation of spinning solution
Adding 5.961 g bonding type high molecular fluorescent material PMNTb and 20 mL N, N-dimethylformamide into a beaker, stirring and uniformly mixing to obtain a clear solution, and standing for 24 h to obtain the spinning solution;
(2) preparation of micron-sized bonding fluorescent anti-counterfeiting fiber
Electrostatic spinning conditions: the spinning electric field voltage is 15 kV; the receiving distance is 15 cm; the injection speed of the injector is 0.5 mL/h; the outer diameter of the syringe needle is 0.82 mm;
firstly, sucking spinning solution into a syringe, fixing the syringe on a syringe pump, adjusting parameters of the syringe pump, wrapping an aluminum foil on a receiving roller, connecting the aluminum foil with a negative electrode, and connecting a needle part of the syringe with a positive electrode; starting an injection pump and a rolling device, starting a high-voltage power supply when a first drop of spinning solution appears on a needle, slowly adjusting the voltage to a required voltage, and obtaining the micron-sized bonding fluorescent anti-counterfeiting fiber on a grounded receiving roller;
and placing the obtained micron-sized bonding fluorescent anti-counterfeiting fiber in an oven at 24 h, setting the temperature to 55 ℃, and finally obtaining a finished product.
The foregoing embodiments are provided to illustrate the problems and advantages of the present invention in further detail, and it is to be understood that the foregoing embodiments are merely illustrative of the present invention and are not to be construed as limiting the invention, as various equivalent changes and modifications may be made within the spirit and scope of the invention as defined in the appended claims.
Claims (3)
1. The preparation method of the micron-sized bonding fluorescent anti-counterfeiting fiber is characterized by comprising the following steps of:
1) Preparation of rare earth Complex Tb (C) 14 H 10 O 3 ) 3 (C 7 H 7 N) 2
(1) Weigh and dissolve the drug
Respectively weighing 0.528 g +/-0.001 g of terbium chloride, 1.369 g +/-0.001 g of 4-benzoyl benzoic acid, 0.421 g +/-0.001 g of 4-vinylpyridine and 0.040 g +/-0.001 g of sodium hydroxide, respectively placing the weighed medicines into a beaker, adding absolute ethyl alcohol to dissolve the medicines, and respectively obtaining terbium chloride absolute ethyl alcohol solution, 4-benzoyl benzoic acid absolute ethyl alcohol solution, 4-vinylpyridine absolute ethyl alcohol solution and sodium hydroxide absolute ethyl alcohol solution;
(2) rare earth complex Tb (C) 14 H 10 O 3 ) 3 (C 7 H 7 N) 2 Is synthesized by (a)
Firstly, adding a 4-benzoyl benzoic acid absolute ethyl alcohol solution into a three-necked flask, then, putting the three-necked flask into a constant-temperature water bath kettle at 55 ℃ for magnetic stirring for 10 min, respectively and dropwise adding a terbium chloride absolute ethyl alcohol solution and a 4-vinyl pyridine absolute ethyl alcohol solution, and then, adjusting the pH value of the mixed solution to between 6.5 and 7 by using a sodium hydroxide absolute ethyl alcohol solution; a small amount of white precipitate appears in the mixed solution, the mixed solution containing the white precipitate is continuously stirred for reaction 4 h, after the reaction is finished, the precipitate product is taken and washed by absolute ethyl alcohol and then is placed in a vacuum drying oven at 55 ℃ for drying 24 h, and finally white powder is obtained, namely the rare earth complex Tb (C) 14 H 10 O 3 ) 3 (C 7 H 7 N) 2 ；
2) Preparation of bonded Polymer fluorescent Material PMNTb
Adding 0.278g + -0.001 g rare earth complex Tb (C) into a branched test tube 14 H 10 O 3 ) 3 (C 7 H 7 N) 2 0.0175 g+ -0.001 g of initiator azodiisobutyronitrile and 3.00 mL + -0.001 mL of dimethyl sulfoxide, and ultrasonic oscillating to make the rare earth complex Tb (C) 14 H 10 O 3 ) 3 (C 7 H 7 N) 2 And an initiator azodiisobutyronitrile are fully dissolved; adding 2.00 mL +/-0.001 mL of methyl methacrylate monomer and 0.1 g +/-0.001 g of N-vinyl carbazole monomer into a branched test tube after introducing nitrogen for 15 minutes, continuously introducing nitrogen for 35 minutes, sealing a reaction device, placing the reaction device into a constant-temperature water bath kettle for constant-temperature reaction at 75 ℃ for 48 h, alternately washing the obtained product with deionized water and absolute ethyl alcohol after the reaction is finished, and drying the product in a vacuum oven at 55 ℃ for 24 h to obtain the bonding type high polymer fluorescent material PMNTb;
3) Micron-sized bonding fluorescent anti-counterfeiting fiber prepared by electrostatic spinning
(1) Preparation of spinning solution
Adding 5.962g +/-0.001 g bonding type high molecular fluorescent material PMNTb and 20 mL N, N-dimethylformamide into a beaker, stirring and uniformly mixing to obtain a clear solution, and standing for 24 h to obtain the spinning solution;
(2) preparation of micron-sized bonding fluorescent anti-counterfeiting fiber
Electrostatic spinning conditions: the spinning electric field voltage is 15 kV; the receiving distance is 15 cm; the injection speed of the injector is 0.5 mL/h; the outer diameter of the syringe needle is 0.82 mm;
firstly, sucking spinning solution into a syringe, fixing the syringe on a syringe pump, adjusting parameters of the syringe pump, wrapping an aluminum foil on a receiving roller, connecting the aluminum foil with a negative electrode, and connecting a needle part of the syringe with a positive electrode; starting the injection pump and the rolling device, starting a high-voltage power supply when the first drop of spinning solution appears on the needle head, slowly adjusting the voltage to the required voltage, and obtaining the micron-sized bonding fluorescent anti-counterfeiting fiber on the grounded receiving roller.
2. The method for preparing micron-sized bonding fluorescent anti-counterfeiting fiber according to claim 1, wherein the method comprises the following steps: in the step 3), after the spinning is finished, the obtained micron-sized bonding fluorescent anti-counterfeiting fiber is placed in an oven 24 h, and the temperature is set to 55 ℃.
3. The method for preparing micron-sized bonding fluorescent anti-counterfeiting fiber according to claim 1 or 2, which is characterized in that: the method also comprises the detection, analysis and characterization of the step 4); the method comprises the following steps:
detecting, analyzing and characterizing the morphology, the components, the structure, the fluorescence performance and the thermal stability of the prepared micron-sized bonding fluorescent anti-counterfeiting fiber;
performing morphology analysis on the micron-sized bonding fluorescent anti-counterfeiting fiber by using a scanning electron microscope;
performing fluorescence performance analysis on the micron-sized bonding type fluorescent anti-counterfeiting fiber by using a fluorescence spectrometer;
analyzing the structure of the micron-sized bonding fluorescent anti-counterfeiting fiber by using a Fourier infrared spectrometer;
and analyzing the thermal stability of the micron-sized bonding fluorescent anti-counterfeiting fiber by using a thermogravimetric analyzer.
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