CN112250710A - Application of saving type rare earth europium complex/sodium acetate composite fluorescent powder in water-based ink - Google Patents
Application of saving type rare earth europium complex/sodium acetate composite fluorescent powder in water-based ink Download PDFInfo
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- CN112250710A CN112250710A CN201910661956.9A CN201910661956A CN112250710A CN 112250710 A CN112250710 A CN 112250710A CN 201910661956 A CN201910661956 A CN 201910661956A CN 112250710 A CN112250710 A CN 112250710A
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- sodium acetate
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- water
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- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 title claims abstract description 111
- 239000002131 composite material Substances 0.000 title claims abstract description 75
- 239000000843 powder Substances 0.000 title claims abstract description 68
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 49
- 235000017281 sodium acetate Nutrition 0.000 title claims abstract description 45
- 229910052693 Europium Inorganic materials 0.000 title claims abstract description 44
- 239000001632 sodium acetate Substances 0.000 title claims abstract description 43
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 title claims abstract description 39
- 229910052761 rare earth metal Inorganic materials 0.000 title claims description 27
- 150000002910 rare earth metals Chemical class 0.000 title description 14
- 238000002360 preparation method Methods 0.000 claims abstract description 8
- 229940040526 anhydrous sodium acetate Drugs 0.000 claims description 67
- 239000003446 ligand Substances 0.000 claims description 47
- 238000000034 method Methods 0.000 claims description 29
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 25
- FIQMHBFVRAXMOP-UHFFFAOYSA-N triphenylphosphane oxide Chemical compound C=1C=CC=CC=1P(C=1C=CC=CC=1)(=O)C1=CC=CC=C1 FIQMHBFVRAXMOP-UHFFFAOYSA-N 0.000 claims description 25
- -1 rare earth europium salt Chemical class 0.000 claims description 23
- TXBBUSUXYMIVOS-UHFFFAOYSA-N thenoyltrifluoroacetone Chemical compound FC(F)(F)C(=O)CC(=O)C1=CC=CS1 TXBBUSUXYMIVOS-UHFFFAOYSA-N 0.000 claims description 22
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 20
- 238000006243 chemical reaction Methods 0.000 claims description 17
- 239000000463 material Substances 0.000 claims description 17
- 239000002904 solvent Substances 0.000 claims description 16
- 238000003760 magnetic stirring Methods 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 8
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 6
- NNMXSTWQJRPBJZ-UHFFFAOYSA-K europium(iii) chloride Chemical compound Cl[Eu](Cl)Cl NNMXSTWQJRPBJZ-UHFFFAOYSA-K 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 5
- VVXLFFIFNVKFBD-UHFFFAOYSA-N 4,4,4-trifluoro-1-phenylbutane-1,3-dione Chemical compound FC(F)(F)C(=O)CC(=O)C1=CC=CC=C1 VVXLFFIFNVKFBD-UHFFFAOYSA-N 0.000 claims description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 4
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 claims description 4
- 150000000918 Europium Chemical class 0.000 claims description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 4
- 238000013329 compounding Methods 0.000 claims description 4
- NZZIMKJIVMHWJC-UHFFFAOYSA-N dibenzoylmethane Chemical compound C=1C=CC=CC=1C(=O)CC(=O)C1=CC=CC=C1 NZZIMKJIVMHWJC-UHFFFAOYSA-N 0.000 claims description 4
- AWDWVTKHJOZOBQ-UHFFFAOYSA-K europium(3+);trichloride;hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Cl-].[Eu+3] AWDWVTKHJOZOBQ-UHFFFAOYSA-K 0.000 claims description 4
- TZIHFWKZFHZASV-UHFFFAOYSA-N methyl formate Chemical compound COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 claims description 4
- 238000000967 suction filtration Methods 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 238000005303 weighing Methods 0.000 claims description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 2
- WVVLURYIQCXPIV-UHFFFAOYSA-N 4,4,4-trifluoro-1-naphthalen-2-ylbutane-1,3-dione Chemical compound C1=CC=CC2=CC(C(=O)CC(=O)C(F)(F)F)=CC=C21 WVVLURYIQCXPIV-UHFFFAOYSA-N 0.000 claims description 2
- XOBKSJJDNFUZPF-UHFFFAOYSA-N Methoxyethane Chemical compound CCOC XOBKSJJDNFUZPF-UHFFFAOYSA-N 0.000 claims description 2
- DGEZNRSVGBDHLK-UHFFFAOYSA-N [1,10]phenanthroline Chemical compound C1=CN=C2C3=NC=CC=C3C=CC2=C1 DGEZNRSVGBDHLK-UHFFFAOYSA-N 0.000 claims description 2
- 230000001476 alcoholic effect Effects 0.000 claims description 2
- 125000005233 alkylalcohol group Chemical group 0.000 claims description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 2
- 150000007942 carboxylates Chemical class 0.000 claims description 2
- 150000002576 ketones Chemical class 0.000 claims description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 2
- 239000013078 crystal Substances 0.000 claims 3
- 235000019441 ethanol Nutrition 0.000 claims 3
- 239000003125 aqueous solvent Substances 0.000 claims 1
- 239000006185 dispersion Substances 0.000 claims 1
- 239000003759 ester based solvent Substances 0.000 claims 1
- 150000002170 ethers Chemical class 0.000 claims 1
- 238000003672 processing method Methods 0.000 claims 1
- 239000002245 particle Substances 0.000 abstract description 17
- 238000009826 distribution Methods 0.000 abstract description 9
- 230000000694 effects Effects 0.000 abstract description 8
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 abstract description 2
- 239000000976 ink Substances 0.000 description 35
- 238000010521 absorption reaction Methods 0.000 description 17
- 230000005284 excitation Effects 0.000 description 6
- 230000007704 transition Effects 0.000 description 6
- 238000002189 fluorescence spectrum Methods 0.000 description 5
- 238000000862 absorption spectrum Methods 0.000 description 4
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 4
- 238000004020 luminiscence type Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000009210 therapy by ultrasound Methods 0.000 description 3
- 238000005979 thermal decomposition reaction Methods 0.000 description 3
- 238000002411 thermogravimetry Methods 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- BDKLKNJTMLIAFE-UHFFFAOYSA-N 2-(3-fluorophenyl)-1,3-oxazole-4-carbaldehyde Chemical compound FC1=CC=CC(C=2OC=C(C=O)N=2)=C1 BDKLKNJTMLIAFE-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000001506 fluorescence spectroscopy Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229940087562 sodium acetate trihydrate Drugs 0.000 description 2
- 229910016644 EuCl3 Inorganic materials 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical group C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 1
- 238000004847 absorption spectroscopy Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 229940051880 analgesics and antipyretics pyrazolones Drugs 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000021615 conjugation Effects 0.000 description 1
- 150000003983 crown ethers Chemical class 0.000 description 1
- 238000007405 data analysis Methods 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 1
- 230000005281 excited state Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000012844 infrared spectroscopy analysis Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000013110 organic ligand Substances 0.000 description 1
- MPQXHAGKBWFSNV-UHFFFAOYSA-N oxidophosphanium Chemical class [PH3]=O MPQXHAGKBWFSNV-UHFFFAOYSA-N 0.000 description 1
- 238000003921 particle size analysis Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- JEXVQSWXXUJEMA-UHFFFAOYSA-N pyrazol-3-one Chemical class O=C1C=CN=N1 JEXVQSWXXUJEMA-UHFFFAOYSA-N 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- VIGBIBDAVDHOTP-UHFFFAOYSA-M sodium;ethanol;acetate Chemical compound [Na+].CCO.CC([O-])=O VIGBIBDAVDHOTP-UHFFFAOYSA-M 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 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
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/50—Organo-phosphines
- C07F9/53—Organo-phosphine oxides; Organo-phosphine thioxides
- C07F9/5345—Complexes or chelates of phosphine-oxides or thioxides with metallic compounds or metals
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/50—Sympathetic, colour changing or similar inks
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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
-
- 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
- C09K2211/18—Metal complexes
- C09K2211/182—Metal complexes of the rare earth metals, i.e. Sc, Y or lanthanide
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Wood Science & Technology (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
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- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Inks, Pencil-Leads, Or Crayons (AREA)
Abstract
The invention provides a composite fluorescent powder, a preparation method thereof and application thereof in water-based anti-counterfeiting ink. The europium complex and sodium acetate composite fluorescent powder has excellent fluorescence performance, and the dispersibility and particle size distribution of the fluorescent powder are improved due to the addition of sodium ethoxide, so that the fluorescent powder has good thermal stability, and can exist in water-based ink uniformly and stably for a long time. So that the ink can emit fluorescence under the irradiation of the ultraviolet lamp, and the anti-counterfeiting effect can be stabilized for a long time.
Description
Technical Field
The invention relates to rare earth complex composite fluorescent powder and a preparation method thereof, and also relates to application of the rare earth complex composite fluorescent powder in water-based ink.
Background
The rare earth ion luminescence has the advantages of narrow band, long fluorescence lifetime and high luminescence intensity, and the appropriate organic ligand is selected to sensitize the luminescence of the rare earth ion, so that the rare earth organic complex luminescent material has wide applicability. The commonly used ligands mainly comprise carboxylic acids, beta-diketones, crown ethers, phosphine oxides, pyrazolones and other organic molecules, wherein the luminous efficiency of the beta-diketones ligand is the highest.
When the complex of europium element is excited by ultraviolet light source, the ligand will receive the energy of the excitation light source and transfer it to the central europium ion, and the excited europium ion will produce transition to produce fluorescence, wherein the emission peak of the ternary complex of europium comes mainly from the europium ion5D0-7F2The characteristic emission of the transition is not dependent on the addition of ligandAnd the fluorescence spectrum line of the complex has obvious europium characteristic peak, so that the characteristic red light of europium ions can be well characterized.
Chinese patent CN102558205A describes a preparation method of a rare earth complex, which is an application of a rare earth complex prepared by taking europium chloride, 2-thenoyltrifluoroacetone and sodium silicate as raw materials as well as a fluorescent sensor for detecting the content of ethanol in an organic solvent. However, when the rare earth complex disclosed in the invention is applied to ink, the fluorescence intensity does not meet the use requirement.
Chinese patent CN106243835A describes a preparation process of aqueous rare earth complex composite microsphere fluorescent aqueous ink. The ink has the characteristics of narrow light-emitting spectrum, high color purity, good photo-thermal stability and the like, but the process and the formula are relatively complex, and meanwhile, the fluorescence intensity and the anti-counterfeiting effect in the water-based ink need to be improved.
With the continuous development of society, people have more and more demands on materials such as ink and the like, the requirements on the quality of the ink are higher and higher, and the water-based ink is produced at the beginning, but the anti-counterfeiting work of the ink is always in the initial stage, so that the development of a fluorescent material with less rare earth consumption, low cost and good anti-counterfeiting performance is urgently needed.
Disclosure of Invention
Aiming at the technical problems in the prior art, the invention provides the composite fluorescent powder by compounding the rare earth europium complex and sodium acetate, and the water-based ink added with the composite fluorescent powder achieves excellent anti-counterfeiting effect, thereby completing the invention.
Therefore, one of the objectives of the present invention is to provide a composite phosphor, which is formed by compounding a rare earth europium complex and sodium acetate.
The invention also aims to provide a preparation method of the composite fluorescent powder, which comprises the following steps:
step 1, dispersing sodium acetate in a solvent to form a solution;
step 2, adding rare earth europium salt and optionally one or more ligands into the solution to react to form a composite fluorescent material;
and 3, carrying out post-treatment on the composite fluorescent material to form the composite fluorescent powder.
The invention also aims to provide the application of the composite fluorescent powder prepared by the method, in particular to the application of the composite fluorescent powder in water-based ink to realize an anti-counterfeiting function. Therefore, the composite fluorescent powder of the europium complex and the sodium acetate is added into the water-based ink and uniformly dispersed, so that the water-based ink containing the composite fluorescent powder is prepared.
The technical effects obtained by the invention comprise:
(1) the europium complex and sodium acetate composite fluorescent powder provided by the invention has excellent fluorescence property;
(2) sodium acetate as an alkaline substance can neutralize an acidic substance existing or generated during the formation of the europium complex, so that the coordination reaction is promoted to be smoothly and completely carried out;
(3) the addition of anhydrous sodium acetate improves the dispersibility and particle size distribution of the fluorescent powder, and has good thermal stability, so that the fluorescent powder can exist in the water-based ink uniformly and stably for a long time, and the comprehensive anti-counterfeiting performance of the water-based ink is greatly improved;
(4) on one hand, sodium acetate is cheap and easy to obtain, on the other hand, the using amount of europium in the whole compound is reduced, and the material cost and the preparation cost are greatly saved.
Drawings
FIG. 1 is a diagram showing the comparison of UV-visible absorption spectra of a composite phosphor prepared from anhydrous sodium acetate, europium complex and anhydrous sodium acetate with a phosphor prepared without anhydrous sodium acetate;
FIG. 2 is a graph showing a comparison of the IR spectra of a phosphor of the present invention prepared with anhydrous sodium acetate and a phosphor prepared without anhydrous sodium acetate;
FIG. 3 shows a thermogravimetric analysis comparison of a phosphor of the present invention with anhydrous sodium acetate and a phosphor without anhydrous sodium acetate;
FIG. 4 is a graph showing a comparison of fluorescence emission spectra of the phosphor of the present invention with anhydrous sodium acetate and the phosphor without anhydrous sodium acetate.
Detailed Description
The features and advantages of the present invention will become more apparent and more readily appreciated by reference to the following detailed description of the invention.
According to one aspect of the invention, a composite phosphor is provided, which is compounded from a europium complex and anhydrous sodium acetate.
According to another aspect of the present invention, there is provided a method for preparing the above composite phosphor, the method comprising the steps of:
step 1, dispersing sodium acetate in a solvent to form a solution;
step 2, adding rare earth europium salt and optionally one or more ligands into the solution to react to form a composite fluorescent material;
and 3, carrying out post-treatment on the composite fluorescent material to form the composite fluorescent powder.
The invention is described and illustrated in detail below.
Step 1, sodium acetate is dispersed in a solvent to form a solution.
The inventor finds that by adding sodium acetate into the rare earth fluorescent complex, on one hand, the use amount of rare earth is reduced, on the other hand, various performances of the fluorescent material can be improved, and particularly, when the fluorescent material is used in anti-counterfeiting ink, the anti-counterfeiting performance can be greatly improved.
To this end, according to the invention, sodium acetate is first dispersed in a solvent.
According to a preferred embodiment of the invention, the sodium acetate is anhydrous sodium acetate. In order to obtain anhydrous sodium acetate, one method is to make the sodium acetate strictly anhydrous, and the other method is to first make the sodium acetate with water of crystallization and then remove the water of crystallization.
This is because the rare earth element is an oxophilic element, and under the condition of the existence of water molecules, the water molecules can enter coordination as ligands, and the high-frequency vibration of O-H in water will cause energy loss, so the content of water molecules in the reaction process should be strictly limited, and preferably in an anhydrous environment.
In the present invention, the solvent may be any solvent containing no water, preferably an organic solvent, more preferably an alcohol such as a lower alkyl alcohol, e.g., methanol, ethanol, propanol, butanol, etc., particularly preferably anhydrous methanol, anhydrous ethanol, an ether such as dimethyl ether, methyl ethyl ether, tetrahydrofuran, dioxane, etc., a ketone such as acetone, or an ester solvent such as methyl formate, ethyl acetate.
In step 1 of the present invention, anhydrous sodium acetate is preferably dispersed in anhydrous ethanol.
According to the present invention, anhydrous sodium acetate may be pretreated by, for example:
putting anhydrous sodium acetate into a 105 ℃ oven to be dried to constant weight, wherein the drying time is 3 h;
another method for preparing anhydrous sodium acetate is to prepare sodium acetate trihydrate and then place the sodium acetate trihydrate in an oven at 125 ℃ for drying until the weight is constant;
the anhydrous sodium acetate is dissolved in anhydrous ethanol at normal temperature, the anhydrous ethanol is enough to dissolve the anhydrous sodium acetate and subsequent reactants, and the mass and volume ratio of the anhydrous sodium acetate to the ethanol is 1 (10-80) (g: mL), preferably 1 (15-60) (g: mL), and more preferably 2 (20-40) (g: mL);
promoting the anhydrous sodium acetate to be dissolved into the anhydrous ethanol by using a magnetic stirring and ultrasonic method, firstly carrying out magnetic stirring for 20-260 min, preferably 60-220 min, more preferably 90-180 min, and then further carrying out ultrasonic treatment for 10-80 min, preferably 20-70 min, more preferably 30-60 min.
Step 2, adding rare earth europium salt and optionally one or more ligands into the solution to react to form the composite fluorescent material.
In step 2 of the present invention, the rare earth europium salt may be europium chloride or europium chloride hexahydrate, preferably europium chloride hexahydrate;
the ligand can simultaneously use a first ligand and a second ligand, or only select the first ligand, the first ligand can select one of beta-diketone, carboxylic acid and carboxylate, aromatic carboxylic acid, heterocyclic carboxylic acid and long-chain carboxylic acid ligand, and the second ligand can select one of phenanthroline and derivative ligand thereof or triphenylphosphine oxide (TPPO);
the preferred embodiment uses the first ligand as a beta-diketone, which may be selected from one of dibenzoyl methane (DBM), 2-thenoyltrifluoroacetone (TTA), Benzoyltrifluoroacetone (BTA) or beta-naphthoyltrifluoroacetone (beta-NTA);
more preferably, 2-thenoyltrifluoroacetone (TTA) is used as a first ligand, and triphenylphosphine oxide (TPPO) is used as a second ligand;
a pi-pi conjugated system in the complex formed by TTA has a higher absorption coefficient, good molecular rigidity and good electron mobility, so that the rare earth ions have high luminous efficiency and better fluorescence.
TPPO as a second ligand enables Eu3+The fluorescence intensity of (2) is greatly enhanced. TPPO can replace coordinated water, so that energy loss caused by high-frequency vibration of O-H in water is reduced, and the fluorescence efficiency of the complex is increased; TPPO and the first ligand have similar characteristics, the conjugation degree of TPPO is good, the lowest excited triplet state of TPPO is matched with the excited state energy level of the rare earth ions, and the second ligand can also transfer the absorbed energy to the rare earth ions, or transfer the energy to the first ligand first and then to the rare earth ions through the first ligand, so that the fluorescence efficiency of the complex is increased.
TTA, TPPO and EuCl3·6H2The molar ratio of O is (1-8): 0.1-2), preferably (1.5-5): 0.5-1.5, more preferably (2-4): 1;
the reaction is carried out in an oil bath, the reaction temperature is 60-120 ℃, the preferable temperature is 70-110 ℃, and the constant temperature reaction can ensure that the coordination reaction can be effectively carried out at a constant speed; the reaction is carried out under magnetic stirring, and the stirring speed is 60-100 r/min, preferably 70-90 r/min; the reaction time is 90-150 min, preferably 110-130 min, and the TPPO, TTA and EuCl can be stirred3·6H2The O is better dispersed in the solution, and the reaction can be accelerated.
And 3, carrying out post-treatment on the composite fluorescent material to form the composite fluorescent powder.
In step 3 of the invention, after the reaction is finished, the sample is cooled to room temperature, and after suction filtration, the sample is put into a blast drying oven and dried at 85 ℃ for 2-7 h, preferably 3-5 h, and more preferably 3.5-4.5 h. The composite fluorescent powder is prepared through the steps.
The phosphor provided by the present invention is obtained by compounding a europium salt and a sodium salt, and for example, in the ultraviolet visible absorption spectrum of the composite phosphor, not only the characteristic absorption peak (around 339 nm) of europium element, but also the absorption peak around 290nm can be seen, which is derived from the transition of n → pi orbital electrons in sodium acetate molecules.
In addition, the infrared spectrogram of the composite fluorescent powder prepared by adding anhydrous sodium acetate and the fluorescent powder prepared without adding countless sodium acetate shows that the Eu-O stretching vibration absorption peak is 530cm-1And the P ═ O stretching vibration peak 1188cm of ligand TPPO-11656cm of asymmetric stretching vibration absorption peak of 2 carbonyl groups of ligand TTA-1And 1620cm-1All have small-amplitude red shift, which shows that the europium atom and the ligand molecule are coordinated to reduce the bond length, so that the red shift is generated;
the infrared absorption peak of the complex added with anhydrous sodium acetate is partially shifted, 1620cm-1COO containing sodium acetate on both sides-Characteristic peak of radical asymmetric absorption, 1410cm-1Left and right are COO of sodium acetate-The characteristic peak of group symmetrical absorption shows that sodium acetate, europium, TTA and TPPO form a better complex, the functional group structures of TTA and TPPO are not changed, and the reaction is more complete.
According to the invention, the thermal decomposition temperature of the composite fluorescent powder obtained after adding anhydrous sodium acetate is about 320 ℃, and the melting point boiling point is slightly improved compared with that of the composite fluorescent powder without adding anhydrous sodium acetate, which indicates that the thermal stability is improved.
The particle size of the composite fluorescent powder provided by the invention is mainly distributed in 700nm-4400nm, the average particle size is about 2200nm, compared with the fluorescent powder without anhydrous sodium acetate (the particle size distribution is about 8400nm-15000nm, and the average particle size is over 12000 nm), the particle size distribution is more uniform, and the anhydrous sodium acetate is considered to be taken as a core and a bridge after the anhydrous sodium acetate is added, so that the composite fluorescent powder is not easy to agglomerate.
According to a third aspect of the invention, the composite fluorescent powder or the composite fluorescent powder prepared by the method is applied to water-based ink and used as an anti-counterfeiting material.
According to the invention, the composite fluorescent powder of the europium complex and sodium acetate or the composite fluorescent powder prepared by the method is applied to water-based ink, and can realize an excellent anti-counterfeiting effect when being used as an anti-counterfeiting material.
In the invention, the anti-counterfeiting material, namely the water-based ink added with the composite fluorescent powder, can be prepared by the method comprising the following steps:
a, quantitatively weighing the europium complex and sodium acetate composite fluorescent powder, and adding the europium complex and sodium acetate composite fluorescent powder into water-based ink, wherein the mass ratio of the europium complex and sodium acetate composite fluorescent powder to the water-based ink is (0.05-10): 30g, preferably (0.1-6): 30g, and more preferably (0.2-2): 30 g;
b, performing ultrasonic dispersion on the mixture in the step a for 30-90 min; and then carrying out magnetic stirring for 20-40 min.
The anhydrous sodium acetate plays a role of a bridge and a core in the compound, so that the transmission of light between the ligand and the luminescence center is improved, the maximum emission fluorescence intensity of the europium complex is improved, the particle size and the thermal stability of the europium complex are well improved, the application space of the europium complex is improved, the content of europium is reduced, and the aim of saving cost is fulfilled.
In addition, the composite fluorescent powder of the europium complex and sodium acetate has excellent fluorescence performance, and the dispersibility and particle size distribution of the fluorescent powder are improved due to the addition of sodium ethoxide, so that the fluorescent powder has good thermal stability. Therefore, the water-based ink can keep a uniform and long-term stable state, and the excellent fluorescence property of the composite fluorescent powder enables the water-based ink to have good anti-counterfeiting property.
The addition of anhydrous sodium acetate greatly reduces the consumption of europium in the whole compound, and saves the preparation cost. After the composite fluorescent powder is added into the water-based ink, the maximum excitation wavelength of the composite fluorescent powder is unchanged with the maximum excitation wavelength of a pure anhydrous sodium acetate composite sample, which shows that the anti-counterfeiting effect of the water-based ink is still good, and the relative intensity of fluorescence can reach 266450a.u. to the maximum.
Examples
Example 1
Putting anhydrous sodium acetate into a 105 ℃ oven, placing for 3h, taking out, placing in a dryer, and cooling for later use. 10g of anhydrous sodium acetate is weighed and put into a three-necked bottle filled with a proper amount of anhydrous ethanol, and the mixture is stirred for 130min and then subjected to ultrasonic treatment for 30 min.
5.5662g of triphenyl phosphorus oxide (TPPO), 6.6304g of 2-thenoyltrifluoroacetone (TTA) and 3.6493g of europium chloride hexahydrate are weighed and put into the sodium acetate ethanol solution, and magnetons are added into a three-neck flask to be stirred for 2 hours under the condition of an oil bath at 80 ℃.
And after the reaction is finished, taking out the three-neck flask, placing the three-neck flask in the air, naturally cooling to room temperature, carrying out suction filtration to obtain composite fluorescent powder, marking filter residues after suction filtration, placing the filter residues in an oven at 85 ℃ for drying for about 4 hours, collecting the dried fluorescent powder, and placing the fluorescent powder in a dryer for storage.
Example 2
0.2g, 0.4g, 0.6g, 0.8g, 1.0g, 1.2g, 1.4g, 1.6g, 1.8g and 2g of the composite fluorescent powder obtained in the example 1 are respectively weighed and added into 30g of water-based ink, and ultrasonic treatment is firstly carried out for 60min at room temperature, and then magnetic stirring is carried out for 30 min.
And uniformly coating the water-based ink containing the composite fluorescent powder on a rectangular filter paper sheet, numbering, naturally drying, putting into a label bag, and placing in a dry environment to be tested.
Comparative example
Weighing triphenyl phosphorus oxide (TPPO), 2-Thenoyl Trifluoroacetone (TTA) and europium chloride according to a molar ratio of 3mol:2mol:1 mol.
And mixing and stirring the weighed TPPO, TTA and europium chloride, and dropwise adding triethylamine in the stirring process. And continuously measuring the pH value of the reaction system in the dripping process until the dripping is stopped when the pH value is 7.
And filtering and collecting the precipitate after reaction, and drying at 80 ℃ to collect the product.
Examples of the experiments
Experimental example 1
Ultraviolet-visible absorption spectroscopy of samples
FIG. 1 is a diagram of the ultraviolet-visible absorption spectra of a composite phosphor prepared from anhydrous sodium acetate, europium complex and anhydrous sodium acetate and a phosphor prepared without sodium acetate.
The ultraviolet visible absorption spectrum is generated by valence electron transition in molecules, according to the graph of figure 1, the composite fluorescent powder added with sodium acetate has a small peak about 290nm, the small peak is generated by n → pi x orbital electron transition in sodium acetate molecules, the peak of 341nm is the characteristic absorption of europium element, when anhydrous sodium acetate is added into the complex, the characteristic peak of europium slightly shifts, but the shift is not obvious, the shift can be ignored, and the sodium acetate can be considered to not change the valence electron transition of europium.
Experimental example 2
Infrared spectroscopic analysis of samples
FIG. 2 is an infrared spectrum of a composite phosphor prepared by adding anhydrous sodium acetate and a phosphor prepared without adding sodium acetate.
As can be seen from FIG. 2, 530cm-1The vicinity is a telescopic vibration absorption peak of Eu-O;
in the phosphor, the P ═ O stretching vibration of ligand TPPO is 1188cm-1The red shift to 1170cm-1Nearby;
ligand TTA has 2 carbonyl asymmetric stretching vibration absorption peaks, and a C ═ O stretching vibration absorption peak which is close to thiophene ring 1656cm-1C ═ O stretching vibration absorption peak 1620cm near trifluoromethyl group with strong electronegativity-1After the complex is formed, the red shift is respectively carried out to 1620cm-1And 1530cm-1；1300cm-1Is the absorption peak of TTA methyl;
at 3430cm-1A hydroxyl group nearby absorbs the adsorbed water possibly from the air and the alcoholic hydroxyl group in the reaction solvent, and the frequency of the carbonyl group shifts at low frequency, which shows that the coordination of europium element and the carbonyl group causes the bond length to decrease, so that red shift occurs;
the infrared absorption peak of the complex added with anhydrous sodium acetate is partially shifted, 1620cm-1COO containing sodium acetate on both sides-Characteristic peak of radical asymmetric absorption, 1410cm-1The left and right are sodium acetateCOO-Characteristic peaks of symmetric absorption of the groups;
the functional group structures of TTA and TPPO are not changed by adding anhydrous sodium acetate, which indicates that sodium acetate forms better complexes with europium and TTA and TPPO and the reaction is more complete.
Example 3
Particle size analysis of samples
According to the particle size distribution of anhydrous sodium acetate, the composite fluorescent powder added with anhydrous sodium acetate and the fluorescent powder not added with anhydrous sodium acetate:
the particle size distribution of the anhydrous sodium acetate is mainly 367.5nm to 665.1nm, and the average particle size is 459.7 nm;
the particle size distribution of the sample without the anhydrous sodium acetate is 8419nm-14227nm, and the average particle size is 13972 nm;
after anhydrous sodium acetate is added, the particle size is mainly distributed between 700nm and 4400nm, and the average particle size is 2208.2 nm;
from the data, the anhydrous sodium acetate is used as a core and a bridge, so that the sample is not easy to agglomerate, and the particle size distribution is more uniform.
Example 4
Thermogravimetric analysis of samples
FIG. 3 is a thermogravimetric analysis chart of the composite phosphor with anhydrous sodium acetate added at 0-1000 ℃ and the phosphor without sodium acetate added under nitrogen atmosphere.
As can be seen from the figure, the samples added with anhydrous sodium acetate and the samples not added with anhydrous sodium acetate have great mass loss in the temperature range of 250 ℃ and 360 ℃, the thermal decomposition temperature is about 300 ℃, the thermal decomposition temperature of the substance added with anhydrous sodium acetate is about 320 ℃, the melting point and the boiling point are both slightly improved, and the thermal stability is higher. In connection with data analysis, the application environment for both samples should not be higher than 200 ℃.
Example 5
Fluorescence emission spectroscopy of samples
FIG. 4 is a graph showing fluorescence emission spectra of a composite phosphor with anhydrous sodium acetate added and a phosphor without anhydrous sodium acetate added.
When the anhydrous sodium acetate composite fluorescent powder and the fluorescent powder without the anhydrous sodium acetate are measured, a tenfold dimmer is adopted, the excitation wavelength is 366nm, the emission wavelength of fluorescence is about 615nm, and the main substance for emitting fluorescence is europium ions in molecules. The fluorescent intensity of the composite fluorescent powder added with anhydrous sodium acetate is much higher than that of the non-nucleus fluorescent powder, the maximum fluorescent intensity of the non-nucleus fluorescent powder emitted light is 50 ten thousand cps under ten times of a dimmer, but the composite fluorescent powder taking the anhydrous sodium acetate as the nucleus can reach 70 ten thousand cps, and the fluorescent property is obviously improved. Therefore, the composite fluorescent powder with anhydrous sodium acetate as the core has better fluorescent effect and is more suitable for being used as anti-counterfeiting ink.
Example 6
Fluorescence emission spectrum analysis of anti-counterfeiting water-based ink sample
Table 1 shows fluorescence intensity data of fluorescence emission spectra of water-based inks obtained by adding different masses of europium complexes/sodium acetate fluorescent powder at a maximum generation wavelength of 615 nm. The detection was performed under the condition of a slit of 1nm corresponding to the maximum excitation wavelength.
When the europium composite fluorescent powder prepared by anhydrous sodium acetate is added into the water-based ink, the maximum emission wavelength is 615nm, and the maximum excitation wavelength is completely the same as that of a pure anhydrous sodium acetate composite sample, which shows that the water-based ink has good anti-counterfeiting effect, but the fluorescence intensity is reduced compared with that of the pure fluorescent powder sample. The fluorescence intensity of the water-based ink sample is firstly enhanced along with the increase of the using amount of the composite fluorescent powder, and then, the fluorescence intensity of the sample is reduced along with the increase of the adding amount of the anhydrous sodium acetate compound, which is mainly because the concentration quenching phenomenon occurs in the sample, and the fluorescence intensity of emitted light is reduced due to the mutual influence of the luminescence of solutes at high concentration.
TABLE 1 fluorescence data of composite fluorescent powder with different contents in water-based ink
The invention is described in detail in connection with the above detailed description and/or the exemplary embodiments and the accompanying drawings, which, however, should not be construed as limiting the invention. Those skilled in the art will appreciate that various equivalent substitutions, modifications or improvements may be made to the technical solution of the present invention and its embodiments without departing from the spirit and scope of the present invention, which fall within the scope of the present invention. The scope of the invention is defined by the appended claims.
Claims (10)
1. A composite fluorescent powder is prepared from europium complex and sodium acetate through compounding.
2. A method of preparing the composite phosphor of claim 1, comprising the steps of:
step 1, dispersing sodium acetate in a solvent to form a solution;
step 2, adding rare earth europium salt and optionally one or more ligands into the solution to react to form a composite fluorescent material;
and 3, carrying out post-treatment on the composite fluorescent material to form the composite fluorescent powder.
3. The method according to claim 2, wherein, in step 1,
the sodium acetate is anhydrous sodium acetate,
the solvent is a non-aqueous solvent, preferably an organic solvent, more preferably an alcoholic solvent, such as a lower alkyl alcohol, e.g. methanol, ethanol, propanol, butanol, etc.,
the molar volume ratio of the anhydrous sodium acetate to the solvent is 0.5 (5-30)/mmol: mL,
the anhydrous sodium acetate is dissolved in the solvent at normal temperature, the dissolving of the anhydrous sodium acetate in the solvent is preferably promoted by using a magnetic stirring method and an ultrasonic method,
the magnetic stirring time is 20-260 min,
the ultrasonic time is 10-80 min.
4. The method according to claim 3, wherein, in step 1,
the anhydrous sodium acetate can be prepared by two methods:
one method is to have strict absence of water during the preparation of sodium acetate,
the other method is to prepare sodium acetate with crystal water and then remove the crystal water, and the processing method comprises the following steps: putting the sodium acetate with the crystal water into a 125 ℃ oven for drying until the weight is constant,
the solvent is anhydrous methanol, anhydrous ethanol, ethers such as dimethyl ether, methyl ethyl ether, tetrahydrofuran, dioxane, etc., ketones such as acetone, or ester solvents such as methyl formate, ethyl acetate,
the molar and volume ratio of the anhydrous sodium acetate to the solvent is 1 (10-20)/mmol: mL,
the magnetic stirring time is 60-220 min,
the ultrasonic time is 20-70 min.
5. The method according to claim 3 or 4, wherein, in step 1,
the alcohol solvent is absolute ethyl alcohol,
the molar volume ratio of the anhydrous sodium acetate to the solvent is 2:15/mmol: mL,
the magnetic stirring time is 90-180 min,
the ultrasonic time is 30-60 min.
6. The method according to claim 2, wherein, in step 2,
the rare earth europium salt may be europium chloride, preferably europium chloride hexahydrate,
the ligand can simultaneously use a first ligand and a second ligand, or only select the first ligand, the first ligand can select one of beta-diketone, carboxylic acid and carboxylate, aromatic carboxylic acid, heterocyclic carboxylic acid and long-chain carboxylic acid ligand, the second ligand can select one of phenanthroline and derivative ligand thereof or triphenylphosphine oxide (TPPO),
the molar ratio of the first ligand, the second ligand and the europium salt is (1-8): 0.1-2,
the reaction is carried out in an oil bath at the temperature of 60-120 ℃,
the reaction is carried out under magnetic stirring, the stirring speed is 60-100 r/min,
the reaction time is 90-150 min.
7. The method according to claim 2 or 6, wherein, in step 2,
the first ligand is a beta-diketone, such as: dibenzoylmethane (DBM), 2-thenoyltrifluoroacetone (TTA), Benzoyl Trifluoroacetone (BTA) or beta-naphthoyltrifluoroacetone (beta-NTA),
the second ligand uses triphenylphosphine oxide (TPPO),
the molar ratio of the first ligand, the second ligand and the europium salt is (1.5-5): 0.5-1.5,
the reaction temperature is 70-110 ℃,
the stirring speed is 70 to 90r/min,
the reaction time is 110-130 min.
8. The method of claim 2, 6 or 7,
the first ligand beta-diketone is 2-Thenoyl Trifluoroacetone (TTA),
the molar ratio of the first ligand, the second ligand and the europium salt is (2-4): (2-4): 1.
9. The method according to claim 2, wherein, in step 3,
the post-treatment method of the product comprises suction filtration and drying, wherein the drying condition is drying for 2-6 h at 85 ℃, preferably 3.5-4.5 h, and more preferably 2-3 h.
10. Use of a composite phosphor according to claim 1 or a composite phosphor produced according to a method according to one of claims 2 to 9 for producing an anti-forgery aqueous ink,
preferably, the anti-counterfeiting water-based ink is prepared according to a method comprising the following steps:
step a, quantitatively weighing the europium complex and sodium acetate composite fluorescent powder, adding the europium complex and sodium acetate composite fluorescent powder into water-based ink to form anti-counterfeiting water-based ink, wherein the mass ratio of the europium complex and sodium acetate composite fluorescent powder to the water-based ink is (0.2-2): 30g,
and b, uniformly dispersing the anti-counterfeiting water-based ink, namely performing ultrasonic dispersion firstly, and then performing magnetic stirring dispersion, wherein the ultrasonic time is 30-90 min, and the magnetic stirring time is 20-40 min.
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