CN109651416B - Three-color fluorescent anti-counterfeiting material based on excitation wavelength dependence, preparation method and application - Google Patents
Three-color fluorescent anti-counterfeiting material based on excitation wavelength dependence, preparation method and application Download PDFInfo
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- 230000005284 excitation Effects 0.000 title claims abstract description 47
- 239000000463 material Substances 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- QARVLSVVCXYDNA-UHFFFAOYSA-N bromobenzene Chemical compound BrC1=CC=CC=C1 QARVLSVVCXYDNA-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000000843 powder Substances 0.000 claims abstract description 20
- 235000011399 aloe vera Nutrition 0.000 claims abstract description 11
- 241001116389 Aloe Species 0.000 claims abstract description 9
- VDWRJEHDFHVBQN-UHFFFAOYSA-N boric acid triphenylene Chemical compound OB(O)O.c1ccc2c(c1)c1ccccc1c1ccccc21 VDWRJEHDFHVBQN-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000003086 colorant Substances 0.000 claims abstract description 9
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 42
- 238000006243 chemical reaction Methods 0.000 claims description 24
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 20
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 20
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 18
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 14
- 238000004809 thin layer chromatography Methods 0.000 claims description 13
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 10
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 10
- 238000004440 column chromatography Methods 0.000 claims description 9
- 229910052763 palladium Inorganic materials 0.000 claims description 9
- FJYFPBQHYWBQFL-UHFFFAOYSA-N triphenylen-1-ylboronic acid Chemical compound C1(=CC=CC=2C3=CC=CC=C3C3=CC=CC=C3C1=2)B(O)O FJYFPBQHYWBQFL-UHFFFAOYSA-N 0.000 claims description 8
- 239000003480 eluent Substances 0.000 claims description 7
- 230000008018 melting Effects 0.000 claims description 7
- 238000002844 melting Methods 0.000 claims description 7
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 7
- 239000003208 petroleum Substances 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 6
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- 238000000227 grinding Methods 0.000 claims description 5
- 239000004570 mortar (masonry) Substances 0.000 claims description 5
- 238000005303 weighing Methods 0.000 claims description 3
- 235000002961 Aloe barbadensis Nutrition 0.000 claims description 2
- 244000186892 Aloe vera Species 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims description 2
- 238000000605 extraction Methods 0.000 claims 1
- 238000006069 Suzuki reaction reaction Methods 0.000 abstract description 2
- 238000010438 heat treatment Methods 0.000 description 5
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- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 2
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- 239000000839 emulsion Substances 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 229910052747 lanthanoid Inorganic materials 0.000 description 1
- 150000002602 lanthanoids Chemical class 0.000 description 1
- 238000001840 matrix-assisted laser desorption--ionisation time-of-flight mass spectrometry Methods 0.000 description 1
- 239000002159 nanocrystal Substances 0.000 description 1
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
- C07F5/02—Boron compounds
- C07F5/025—Boronic and borinic acid compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M3/00—Printing processes to produce particular kinds of printed work, e.g. patterns
- B41M3/14—Security printing
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1003—Carbocyclic compounds
- C09K2211/1007—Non-condensed systems
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1096—Heterocyclic compounds characterised by ligands containing other heteroatoms
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Abstract
A preparation method of a three-color fluorescent anti-counterfeiting material based on excitation wavelength dependence comprises the following steps: triphenylene boric acid and 4-o-carborane bromobenzene are coupled to form carborane derivatives by Suzuki coupling reaction, the obtained carborane derivatives are melted and ground into powder, and the powder is doped into colorless aloe paste to prepare patterns. The pattern made of the carborane derivative has the characteristic of fluorescence in various colors, and the material presents three fluorescence colors under three excitation wavelengths and can be used as an anti-counterfeiting material.
Description
Technical Field
The invention belongs to the technical field of chemistry, and particularly relates to a three-color fluorescent anti-counterfeiting material based on excitation wavelength dependence, a preparation method and application.
Background
Currently, counterfeiting has become an increasingly serious worldwide problem, and thus, society needs more advanced anti-counterfeiting technologies to protect important information and things, such as luxury goods, paper money, certificates, and the like. Over the past several decades, various anti-counterfeiting technologies have been developed, including recent magnetic response technologies, plasma security tags, and luminescent printing, among others. Among them, since the luminescent printing has the characteristics of easy design, easy operation, and easy industrialization, it is most widely used in daily anti-counterfeiting, and the luminescent material conventionally used for anti-counterfeiting usually exhibits monochromatic, bicolor, dual-mode luminescence, etc. For example, professor "determine" to switch between luminescence in two modes, up-conversion and down-conversion, by doping inorganic nanocrystals of different lanthanides (nano scale.2011,3, 4804-; the method comprises the steps of (in Song Yanlin professor) (Patterning Fluorescent Quantum Dot Nanocomposites by Reactive Inkjet Printing, Small.2015,11, 1649-1654) Patterning the nanocomposite material containing the Fluorescent Quantum dots by Reactive Inkjet Printing, thereby realizing the anti-counterfeiting purpose; professor Linnaheng, Triple-Mode emulsions of Carbon Dots, applied for Advanced Anti-ti-couterfeiting, Angew. chem.2016,55, 7231-7235, implemented three-Mode Anti-Counterfeiting forms of photoluminescence, upconversion and room temperature phosphorescence using polymers formed from m-diphenylamine, polyvinyl alcohol and luminescent Carbon Dots. However, there is no three-color anti-counterfeiting material that can rely on excitation by using pure organic small molecules.
Disclosure of Invention
The invention aims to provide a three-color fluorescent anti-counterfeiting material based on excitation wavelength dependence, a preparation method and application.
The technical scheme adopted by the invention is as follows:
a preparation method of a three-color fluorescent anti-counterfeiting material based on excitation wavelength dependence comprises the following synthetic route:
weighing 4-o-carborane bromobenzene (I), triphenylene boric acid (II), palladium tetratriphenylphosphine and sodium carbonate, and dissolving in tetrahydrofuran; stirring and reacting at 80-100 ℃ for 10-15h under the protection of nitrogen atmosphere, simultaneously, determining that the raw materials completely react by combining Thin Layer Chromatography (TLC), extracting the reaction system with water and pure dichloromethane for several times, collecting an extract phase, drying by spinning, and purifying by column chromatography to obtain white powder, namely the target product carborane derivative (III); and melting the obtained carborane derivative, grinding the carborane derivative into powder in a mortar, and doping the powder into colorless aloe cream to obtain the anti-counterfeiting material.
Further, 4-carborane bromobenzene (I): triphenyleneboronic acid (II): palladium tetratriphenylphosphine: sodium carbonate 1mmol: 1.0-1.2 mmol:0.05-0.1 mmol: 0.5-1.0 mmol.
Further, 4-carborane bromobenzene (I): tetrahydrofuran was 1mmol: 30-40 ml.
Further, the eluent for column chromatography is composed of petroleum ether and dichloromethane in a volume ratio of 10: 1.
Further, the mass ratio of the carborane derivative to the aloe vera paste is 1-5%.
Furthermore, the pattern made of the doped aloe cream presents different colors under three excitation wavelengths, namely blue under 390nm, white under 365nm and yellow under 254nm, and is used as an anti-counterfeiting material.
The invention has the beneficial effects that:
the method comprises the following steps of coupling triphenylene boric acid and 4-carborane bromobenzene to form carborane derivatives by utilizing a Suzuki coupling reaction, and finding that the derivatives have three different fluorescence colors at different excitation wavelengths in an amorphous state through research. So far, the three-color anti-counterfeiting material which can be relied on by excitation through utilizing the pure organic small molecules has not been applied, so that the three-color anti-counterfeiting material can be used for anti-counterfeiting. Based on the assumption of anti-counterfeiting application, the obtained carborane derivative is melted, the solid is ground and then is doped into colorless aloe cream to prepare inkpad, then the stamp is used for printing a required pattern (in two embodiments of the invention, a puppy and a two-dimensional code pattern are adopted), and the obtained pattern is irradiated under three excitation wavelengths to show three fluorescence. The anti-counterfeiting application mode has the characteristics of convenience in inspection and irreplaceability.
Drawings
FIG. 1 is a single crystal spectrum of the molecular structure of carborane derivatives of the present invention;
FIG. 2 is a fluorescence spectrum of the three-color fluorescent anti-counterfeiting material in an amorphous state at different excitation wavelengths, according to the fluorescence spectrum, under 390nm excitation, the peak value is mainly 420nm, so that the fluorescence is blue, with the decrease of the excitation wavelength, the 560nm peak is gradually enhanced to become two double peaks of 420 and 560, under 365nm excitation, the fluorescence is white, the excitation wavelength is continuously decreased to become dominant with the 560nm peak, so that the 254nm excitation is yellow;
FIG. 3 is a photograph showing different colors of the three-color fluorescent anti-counterfeiting material (puppy pattern) under three excitation wavelengths, wherein the material is blue under excitation of 390nm, white under excitation of 365nm and yellow under excitation of 254 nm;
FIG. 4 is a photograph showing different colors of the three-color fluorescent anti-counterfeiting material (two-dimensional code pattern) under three excitation wavelengths, wherein the three-color fluorescent anti-counterfeiting material is blue under excitation of 390nm, white under excitation of 365nm and yellow under excitation of 254 nm.
Detailed Description
The present invention is further illustrated by the following examples.
The invention discloses a preparation method of a three-color fluorescent anti-counterfeiting material based on excitation wavelength dependence, which comprises the following steps:
the synthetic route is as follows:
weighing 4-o-carborane bromobenzene (I), triphenylene boric acid (II), palladium tetratriphenylphosphine and sodium carbonate, and dissolving in tetrahydrofuran; wherein, the 4-carborane bromobenzene (I): triphenyleneboronic acid (II): palladium tetratriphenylphosphine: sodium carbonate: 1mmol of tetrahydrofuran, 1-1.2mmol, 0.05-0.1 mmol: 0.5-1 mmol: 30-40 ml; heating and stirring at 80-100 ℃ for reaction for 10-15h under the protection of nitrogen atmosphere; determining the reaction process by Thin Layer Chromatography (TLC), extracting the reaction system for three times by using a water and dichloromethane system after the reaction is ended, collecting an extract phase, and purifying by using petroleum ether and dichloromethane 10:1 eluent for column chromatography to obtain white powder, namely a carborane derivative (III) as a target product, wherein the molecular weight of 4-carborane bromobenzene (I) is 299 g/mol; 272g/mol of triphenyleneboronic acid (II); carboborane derivative (III)446 g/mol.
Example 1
A preparation method of a three-color fluorescent anti-counterfeiting material based on excitation wavelength dependence comprises the following steps:
0.299g (1mmol) of 4-carborane bromobenzene (I), 0.272g (1mmol) of triphenylene boric acid (II), 0.057g (0.05mmol) of palladium tetrakistriphenylphosphine and 0.0525g (0.5mmol) of sodium carbonate are weighed and dissolved in 30ml of tetrahydrofuran; heating and stirring at 80 ℃ for reaction for 10h under the protection of nitrogen atmosphere; meanwhile, determining the reaction progress by combining Thin Layer Chromatography (TLC), extracting the reaction system for three times by using water and a dichloromethane system after the reaction is ended, and then performing column chromatography purification by using petroleum ether and dichloromethane eluent with the volume ratio of 10:1 to obtain 0.134g of white powder with the yield of 30 percent, namely the target product carborane derivative (III), wherein the characterization data is as follows:1H NMR(400MHz,CDCl3)δ8.81-8.80(d,J＝4Hz,1H),8.74-8.66(m,5H),7.86-7.83(dd,J＝8,4Hz,1H),7.77-7.74(m,2H),7.72-7.67(m,4H),7.65-7.62(m,2H),4.03(s,1H),2.92-2.17(m,10H),HRMS(MALDI-TOF)m/z:[M]+446.885；
the single crystal structure of the molecule is shown in figure 1, and the carborane derivative prepared by the invention is a brand new structure substance.
Example 2
A preparation method of a three-color fluorescent anti-counterfeiting material based on excitation wavelength dependence comprises the following steps:
0.299g (1mmol) of 4-carborane bromobenzene (I), 0.326g (1.2mmol) of triphenylene boric acid (II), 0.057g (0.05mmol) of palladium tetrakistriphenylphosphine and 0.0525g (0.5mmol) of sodium carbonate are weighed and dissolved in 30ml of tetrahydrofuran; heating and stirring at 80 ℃ for reaction for 12 hours under the protection of nitrogen atmosphere; meanwhile, determining the reaction progress by combining Thin Layer Chromatography (TLC), extracting the reaction system for three times by using water and a dichloromethane system after the reaction is ended, and purifying by using petroleum ether and dichloromethane 10:1 eluent for column chromatography to obtain 0.147g of white powder, wherein the yield is 33 percent, namely the target product carborane derivative (III);
example 3
A preparation method of a three-color fluorescent anti-counterfeiting material based on excitation wavelength dependence comprises the following steps:
0.299g (1mmol) of 4-carborane bromobenzene (I), 0.299g (1.1mmol) of triphenylene boric acid (II), 0.091g (0.8mmol) of tetrakistriphenylphosphine palladium and 0.0525g (0.5mmol) of sodium carbonate are weighed and dissolved in 40ml of tetrahydrofuran; heating and stirring at 100 ℃ for reaction for 15h under the protection of nitrogen atmosphere; meanwhile, determining the reaction process by combining Thin Layer Chromatography (TLC), extracting the reaction system for three times by using water and a dichloromethane system after the reaction is ended, and purifying by using petroleum ether and dichloromethane 10:1 eluent for column chromatography to obtain 0.156g of white powder with the yield of 35 percent, namely the target product carborane derivative (III);
example 4
A preparation method of a three-color fluorescent anti-counterfeiting material based on excitation wavelength dependence comprises the following steps:
0.299g (1mmol) of 4-carborane bromobenzene (I), 0.326g (1.2mmol) of triphenylene boric acid (II), 0.114g (0.1mmol) of palladium tetrakistriphenylphosphine and 0.0525g (0.5mmol) of sodium carbonate are weighed and dissolved in 40ml of tetrahydrofuran; heating and stirring at 90 ℃ for reaction for 15h under the protection of nitrogen atmosphere; meanwhile, determining the reaction process by combining Thin Layer Chromatography (TLC), extracting the reaction system for three times by using water and a dichloromethane system after the reaction is ended, and purifying by using petroleum ether and dichloromethane 10:1 eluent for column chromatography to obtain 0.142g of white powder with the yield of 32 percent, namely the target product carborane derivative (III); after the powder is subjected to melting treatment, the obtained solid is subjected to an emission spectrum test, the spectrum is mainly 420nm under 390nm excitation, and as the excitation wavelength is reduced, a peak appears at 560nm and is gradually enhanced to form a double peak, as shown in figure 2.
Melting the obtained carborane derivative, grinding into powder in a mortar, doping into colorless aloe paste with a mass ratio of 1-5%, patterning the doped aloe paste with a stamp, and making the prepared pattern appear blue under 390nm excitation, white under 365nm excitation and yellow under 254nm excitation.
Example 5
A three-color anti-counterfeiting format based on an excitation wavelength, comprising the steps of:
melting the white powder obtained in example 1 at 280 deg.C, grinding the solid into powder in a mortar, adding the powder into colorless aloe paste to obtain inkpad with a mass ratio of 5%, making into puppy pattern with a puppy stamp, wherein the obtained puppy pattern has different colors under three excitation wavelengths, blue under 390nm, white under 365nm, and yellow under 254nm, as shown in FIG. 3.
Example 6
A three-color anti-counterfeiting format based on an excitation wavelength, comprising the steps of:
melting the white powder obtained in example 1 at 280 ℃, grinding the solid after melting and solidification into powder in a mortar, doping the powder into colorless aloe cream to prepare inkpad with the mass ratio of 3%, and preparing a two-dimensional code pattern by using a two-dimensional code stamp, wherein the obtained two-dimensional code pattern presents different colors under three excitation wavelengths, blue under 390nm, white under 365nm and yellow under 254nm, as shown in fig. 4.
While the foregoing description shows and describes several preferred embodiments of the invention, it is to be understood, as noted above, that the invention is not limited to the forms disclosed herein, but is not to be construed as excluding other embodiments and is capable of use in various other combinations, modifications, and environments and is capable of changes within the scope of the inventive concept as expressed herein, commensurate with the above teachings, or the skill or knowledge of the relevant art. And that modifications and variations may be effected by those skilled in the art without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (7)
1. A preparation method of a three-color fluorescent anti-counterfeiting material based on excitation wavelength dependence is characterized by comprising the following preparation routes:
firstly, weighing 4-o-carborane bromobenzene (I), triphenylene boric acid (II), palladium tetratriphenylphosphine and sodium carbonate, and dissolving in tetrahydrofuran; stirring and reacting at 80-100 ℃ for 10-15h under the protection of nitrogen atmosphere, simultaneously, extracting a reaction system for several times by using water and dichloromethane after determining that the raw materials completely react by combining thin layer chromatography, collecting an extraction phase, and purifying by using column chromatography after spin-drying to obtain a white powdery carborane derivative (III); and finally, melting and solidifying the obtained carborane derivative, grinding the carborane derivative into powder in a mortar, and doping the powder into colorless aloe cream to obtain the anti-counterfeiting material.
2. The method for preparing the three-color fluorescent anti-counterfeiting material based on the excitation wavelength as claimed in claim 1, wherein the ratio of 4-o-carborane bromobenzene (I): triphenyleneboronic acid (II): palladium tetratriphenylphosphine: sodium carbonate 1mmol: 1.0-1.2 mmol:0.05-0.1 mmol: 0.5-1.0 mmol.
3. The preparation method of the three-color fluorescent anti-counterfeiting material based on the excitation wavelength dependence of claim 1, wherein the ratio of 4-o-carborane bromobenzene (I): tetrahydrofuran was 1mmol: 30-40 ml.
4. The method for preparing a trichromatic fluorescent anti-counterfeiting material based on excitation wavelength dependence as claimed in claim 1, wherein an eluent for column chromatography is composed of petroleum ether and dichloromethane in a volume ratio of 10: 1.
5. The method of claim 1, wherein the carborane derivative is 1-5% by mass of the aloe vera paste.
6. A three-color fluorescent anti-counterfeiting material based on excitation wavelength dependence, which is characterized by being prepared by the method of any one of claims 1 to 5.
7. An application of a three-color fluorescent anti-counterfeiting material based on excitation wavelength dependence is characterized in that the anti-counterfeiting material according to claim 6 is made into a seal pattern, and then different colors are presented under three excitation wavelengths, namely blue under 390nm, white under 365nm and yellow under 254 nm.
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| JP2001066651A (en) * | 1999-08-24 | 2001-03-16 | Univ Tohoku | Fullerene carborane rigid rod hybrid compound and its synthesis |
| CN104610812A (en) * | 2015-01-22 | 2015-05-13 | 苏州大学 | Application of fluorescent silica nanoparticles as anti-fake mark |
| CN106866716A (en) * | 2017-04-28 | 2017-06-20 | 南京大学 | A kind of carborane derivative as well as preparation method and application thereof |
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|---|---|---|---|---|
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