CN113061368B - Novel fluorescent ink and preparation method and application thereof - Google Patents

Novel fluorescent ink and preparation method and application thereof Download PDF

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CN113061368B
CN113061368B CN202110357258.7A CN202110357258A CN113061368B CN 113061368 B CN113061368 B CN 113061368B CN 202110357258 A CN202110357258 A CN 202110357258A CN 113061368 B CN113061368 B CN 113061368B
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fluorescent ink
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acetonitrile
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CN113061368A (en
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龙腊生
邓永恺
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Xiamen University
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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
    • 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
    • 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
    • C07F5/003—Compounds containing elements of Groups 3 or 13 of the Periodic Table without C-Metal linkages
    • 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
    • C09D11/30—Inkjet printing inks
    • 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
    • C09D11/30—Inkjet printing inks
    • C09D11/36—Inkjet printing inks based on non-aqueous solvents
    • 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
    • C09K11/02—Use of particular materials as binders, particle coatings or suspension media therefor
    • 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
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B2200/00—Indexing scheme relating to specific properties of organic compounds
    • C07B2200/13—Crystalline forms, e.g. polymorphs
    • 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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  • Engineering & Computer Science (AREA)
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  • Inks, Pencil-Leads, Or Crayons (AREA)
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Abstract

A novel fluorescent ink and a preparation method and application thereof relate to fluorescent ink. The fluorescent ink composite material is Eu2Ti4‑NH2@ PEG; wherein Eu2Ti4‑NH2Is Eu2Ti4(μ2‑O)2(μ3‑O)4(phen)2(tbza)9(paza)]·7H2And O, PEG is methoxy polyethylene glycol succinimide carbonate. The preparation method comprises the following steps: hydrothermal synthesis of Eu2Ti4‑NH2And then dissolving the compound material and PEG in toluene for compounding to obtain the fluorescent ink composite material. Eu (Eu)2Ti4‑NH2Cluster and Eu2Ti4‑NH2The @ PEG composite material is simple to synthesize, rapid in preparation method and easy to operate. Has better solid fluorescence, low toxicity and good solubility, and can be used as fluorescent ink with low toxicity. The printed pattern is colorless and transparent under visible light, has bright fluorescence under ultraviolet light, and has confidentiality and anti-counterfeiting effectiveness.

Description

Novel fluorescent ink and preparation method and application thereof
Technical Field
The invention relates to fluorescent ink, in particular to novel fluorescent ink capable of being dissolved in a low-toxicity solvent, and a preparation method and application thereof.
Background
In recent years, counterfeit products have a lot of negative effects on social economy and pose serious security threats to the whole country, so that the counterfeit products become a difficult problem to solve urgently. Inkjet printing using fluorescent inks is a viable option. Many materials have been used for fluorescent inks, such as organic dyes, nanomaterials, quantum dots, metal-organic frameworks, etc. Each of these materials has advantages, but it has adverse effects on human health due to its toxicity or the use of highly toxic solvents for enhancing solubility. Therefore, much attention has been paid to the field of low-toxicity inks.
Polyethylene glycols (PEGs) are a very common polymeric material, which are non-toxic and can be used in biological systems and pharmaceutical engineering. And has a very wide dissolution range, and thus can be dissolved in a low-toxicity solvent. The rare earth titanium-oxygen cluster compound has excellent fluorescence property, and the ligand type can be freely changed, so the rare earth titanium-oxygen cluster compound can be easily compounded with polyethylene glycol to obtain the cluster compound @ polyethylene glycol composite material. The composite material can be dissolved in a low-toxicity solvent to be used as fluorescent ink.
Disclosure of Invention
The invention aims to provide a novel fluorescent ink composite material capable of being dissolved in a low-toxicity solvent, and a preparation method and application thereof.
The fluorescent ink composite material is Eu2Ti4-NH2@ PEG; wherein Eu2Ti4-NH2Is Eu2Ti4(μ2-O)2(μ3-O)4(phen)2(tbza)9(paza)]·7H2And O, PEG is methoxy polyethylene glycol succinimide carbonate.
The fluorescent ink composite material is yellow powder; the molecular weight of the composite material is about 4400g/mol, wherein Eu2Ti4-NH2The content of (b) is about 227. mu. mol/g.
The preparation method of the fluorescent ink composite material comprises the following steps:
1) hydrothermal synthesis of Eu2Ti4-NH2Said Eu2Ti4-NH2Belongs to the monoclinic system, space group P21/c, and the molecular formula is [ Eu2Ti4(μ2-O)2(μ3-O)4(phen)2(tbza)9(paza)]·7H2O, unit cell parameters a-16.9806, b-19.6263, c-21.4267, β -107.6290, V-6805.45;
2) the Eu synthesized in the step 1)2Ti4-NH2Dissolving the obtained product and methoxypolyethylene glycol succinimide carbonate in toluene for compounding to obtain the fluorescent ink composite material which is named Eu2Ti4-NH2@PEG。
In step 1), the preparation of Eu2Ti4-NH2The method comprises the following specific steps: mixing europium acetate tetrahydrate, p-tert-butylbenzoic acid, p-aminobenzoic acid and o-phenanthroline monohydrateDissolving the quinoline and titanium tetraisopropoxide in acetonitrile, transferring the acetonitrile into a serum bottle, heating to a constant temperature, then cooling to room temperature, filtering and washing to obtain Eu2Ti4-NH2Is light yellow bulk crystal;
wherein the ratio of the europium acetate tetrahydrate, the p-tert-butyl benzoic acid, the p-aminobenzoic acid, the phenanthroline monohydrate, the titanium tetraisopropoxide and the acetonitrile is 0.02-0.2 mmol: 0.18-0.72 mmol: 0.02-0.08 mmol: 0.2-0.8 mmol: 0.02-0.2 mmol: 2-8 mL, wherein the ratio of the p-tert-butyl benzoic acid to the p-aminobenzoic acid is 9: 1, and the ratio of the europium acetate tetrahydrate, the p-tert-butyl benzoic acid, the p-aminobenzoic acid, the phenanthroline monohydrate, the titanium tetraisopropoxide and the acetonitrile is preferably 0.08 mmol: 0.36 mmol: 0.04 mmol: 0.1 mmol: 0.08 mmol: 3 mL; the temperature rise rate can be 5-40 ℃/h, the constant temperature can be 60-80 ℃, the constant temperature time can be 24-72 h, and the rate of temperature reduction to room temperature can be 5-40 ℃/h.
In step 2), the preparation of Eu2Ti4-NH2Specific methods of @ PEG composites may be: eu is mixed2Ti4-NH2Dissolving methoxypolyethylene glycol succinimide carbonate in toluene, refluxing and stirring, cooling to room temperature, filtering, and washing with water to obtain Eu2Ti4-NH2@ PEG, as a pale yellow powder;
the Eu being2Ti4-NH2The ratio of the methoxypolyethylene glycol succinimide carbonate to the toluene is 0.005-0.1 mmol: 0.02-0.2 mmol: 10-24 mL, the molecular weight of the methoxypolyethylene glycol succinimide carbonate can be 2000Da, the reflux temperature can be 70-100 ℃, and the reflux time can be 72-144 h.
Eu pairs using steady-state transient fluorescence Spectroscopy (FLS-980)2Ti4-NH2、Eu2Ti4-NH2And performing fluorescence analysis on the @ PEG to test excitation and emission spectrograms, quantum yield and fluorescence lifetime of the @ PEG. Showing that Eu2Ti4-NH2、Eu2Ti4-NH2The @ PEG has better fluorescenceAnd (5) effect. Eu in solid state2Ti4-NH2Quantum yield 50.97%, Eu2Ti4-NH2@ PEG quantum yield 30.69%.
The fluorescent ink composite material Eu2Ti4-NH2@ PEG may be used in ink jet printing; the application is to add Eu2Ti4-NH2The @ PEG composite was dissolved in ethanol/ethylene glycol ink for inkjet printing.
The ratio of ethanol to ethylene glycol in the ethanol/ethylene glycol can be 4: 1-3: 2, and the Eu is2Ti4-NH2The concentration of @ PEG can be 18-36 mg/mL; the ink-jet printing can be achieved by using a Microfab JETLAB 2 printer equipped with a piezo-driven ink-jet nozzle with a diameter of 30 μm and an electric stage with an accuracy of 5 μm, a glass plate can be used as a printing substrate, a printing pattern can be designed by a computer, and the printing pattern is colorless and transparent under visible light and has very bright red fluorescence under the irradiation of ultraviolet light at 312 nm.
The invention has the following remarkable advantages:
1、Eu2Ti4-NH2cluster and Eu2Ti4-NH2The @ PEG composite material is simple to synthesize, rapid in preparation method, easy to operate and wide in synthesis application prospect.
2、Eu2Ti4-NH2Cluster and Eu2Ti4-NH2The @ PEG composite material has good solid fluorescence.
3、Eu2Ti4-NH2The @ PEG composite material has low toxicity and good solubility, and can be used as low-toxicity fluorescent ink.
4. The pattern printed by the novel fluorescent ink is colorless and transparent under visible light and has bright fluorescence under ultraviolet light, so that the novel fluorescent ink has good confidentiality and anti-counterfeiting effectiveness.
Drawings
FIG. 1 shows Eu2Ti4-NH2Crystal structure diagram.
FIG. 2 shows Eu2Ti4-NH2And (4) a core structure schematic diagram.
FIG. 3 shows Eu2Ti4-NH2Fluorescence spectrum of the cluster compound.
FIG. 4 shows Eu2Ti4-NH2Fluorescence spectra of @ PEG composites.
Fig. 5 is a schematic view of a process of ink-jet printing.
FIG. 6 shows Eu2Ti4-NH2@ PEG is used as a computer design drawing (left) of an ink printed pattern, and a photo under visible light irradiation (middle) and 312nm ultraviolet light irradiation (right), wherein a bright part emits red light.
Detailed Description
The invention is further illustrated by the following examples in conjunction with the accompanying drawings.
Example 1
Eu2Ti4-NH2The preparation process of the cluster compound comprises the following steps: dissolving 0.08mmol of europium acetate tetrahydrate, 0.36mmol of p-tert-butylbenzoic acid, 0.04mmol of p-aminobenzoic acid, 0.1mmol of phenanthroline monohydrate and 0.08mmol of titanium tetraisopropoxide in 3mL of acetonitrile, transferring the solution into a serum bottle, performing ultrasonic treatment for 30min, heating to 60 ℃ at the speed of 35 ℃/h, keeping the temperature for 24h, then slowly cooling to room temperature at the speed of 10 ℃/h, filtering and washing to obtain light yellow blocky crystals.
Eu2Ti4-NH2The preparation process of the @ PEG composite material comprises the following steps: adding 0.01mmol Eu2Ti4-NH20.2mmol of methoxypolyethylene glycol succinimide carbonate with molecular weight of 2000Da is dissolved in 30mL of toluene, refluxed and stirred for 5 days at 70 ℃, then cooled to room temperature, filtered and washed by water to obtain Eu2Ti4-NH2@ PEG composite, light yellow powder.
Example 2
Eu2Ti4-NH2The preparation process of the cluster compound comprises the following steps: dissolving 0.04mmol of europium acetate tetrahydrate, 0.18mmol of p-tert-butylbenzoic acid, 0.02mmol of p-aminobenzoic acid, 0.4mmol of phenanthroline monohydrate, and 0.06mmol of titanium tetraisopropoxide in 2mL of acetonitrile, transferring to serumAnd (3) performing ultrasonic treatment in a bottle for 30min, heating to 70 ℃ at the speed of 35 ℃/h, keeping the temperature for 48h, then slowly cooling to room temperature at the speed of 20 ℃/h, filtering and washing to obtain light yellow blocky crystals.
Eu2Ti4-NH2The preparation process of the @ PEG composite material comprises the following steps: adding 0.005mmol Eu2Ti4-NH20.02mmol of methoxypolyethylene glycol succinimide carbonate with molecular weight of 2000Da is dissolved in 20mL of toluene, refluxed and stirred for 3 days at the temperature of 60 ℃, then cooled to room temperature, filtered and washed by water to obtain Eu2Ti4-NH2@ PEG composite, light yellow powder.
Example 3
Eu2Ti4-NH2The preparation process of the cluster compound comprises the following steps: dissolving 0.2mmol of europium acetate tetrahydrate, 0.72mmol of p-tert-butylbenzoic acid, 0.08mmol of p-aminobenzoic acid, 0.8mmol of phenanthroline monohydrate and 0.2mmol of titanium tetraisopropoxide in 8mL of acetonitrile, transferring the solution into a serum bottle, carrying out ultrasonic treatment for 30min, heating to 80 ℃ at the speed of 10 ℃/h, keeping the temperature for 48h, then slowly cooling to room temperature at the speed of 40 ℃/h, filtering and washing to obtain light yellow blocky crystals.
Eu2Ti4-NH2The preparation process of the @ PEG composite material comprises the following steps: adding 0.02mmol Eu2Ti4-NH20.2mmol of methoxypolyethylene glycol succinimide carbonate with molecular weight of 2000Da is dissolved in 40mL of toluene, refluxed and stirred for 6 days at 80 ℃, then cooled to room temperature, filtered and washed by water to obtain Eu2Ti4-NH2@ PEG composite, light yellow powder.
Example 4
Sample characterization:
1. single crystal testing:
Eu2Ti4-NH2the structure is collected by an Agilent Super Nova Diffractometer X-ray single crystal Diffractometer at 112K. FIG. 1 shows Eu2Ti4-NH2FIG. 2 is a crystal structure diagram of Eu2Ti4-NH2And (4) a core structure schematic diagram.
Eu2Ti4-NH2Belongs to the monoclinic system, space group P21/c, and the molecular formula is [ Eu2Ti4(μ2-O)2(μ3-O)4(phen)2(tbza)9(paza)]·7H2O, unit cell parameters a-16.9806, b-19.6263, c-21.4267, β -107.6290, and V-6805.45. Each cluster molecule comprises 2 europium atoms and 4 titanium atoms, wherein the 4 titanium atoms are in a parallelogram, and the 2 europium atoms are distributed on two sides of the Ti4 parallelogram. 6 metal ions form a deformed octahedral structure [ Eu ]2Ti4O6]10+Through 4 μ3-O atom constituting face and 2 μ2The oxygen atoms of-O form the edges. All titanium atoms are 6 coordinated and the coordinating atoms are oxygen. Of which 3 are derived from oxygen atoms and 3 from carboxylic acid ligands. 2 europium atoms are all 8 coordination atoms, and the coordination atoms comprise 2 mu3-O atom, 4 oxygen atoms from the carboxylic acid ligand, and 2 nitrogen atoms from phenanthroline. The periphery of the cluster compound is protected by 10 carboxylic acid ligands, wherein the ratio of p-tert-butyl benzoic acid to p-aminobenzoic acid is 9: 1.
2. Fluorescence test
Eu pairs Using Steady-State transient fluorescence Spectroscopy (FLS-980)2Ti4-NH2、Eu2Ti4-NH2@ PEG was subjected to fluorescence analysis, and the results of the analysis are shown in FIGS. 3 and 4. The fluorescence excitation of the two is in the range of 240nm-400nm, and the peak values are respectively at 294nm and 299 nm. Both the emissions are 5 emission peaks, corresponding to 5 characteristic emissions of Eu, respectively. Eu in solid state2Ti4-NH2The quantum yield is 50.97%, the fluorescence lifetime is 1643 mus, Eu2Ti4-NH2The quantum yield of @ PEG was 30.69%, and the fluorescence lifetime was 1370. mu.s.
Example 5
Ink configuration: mixing 36mg Eu2Ti4-NH2@ PEG was dissolved in 0.8mL of ethanol, followed by addition of 0.2mL of ethylene glycol, and sonicated until uniform for use.
Example 6
Ink configuration: 18mg Eu to2Ti4-NH2@ PEG solubilizationAdding 0.3mL of glycol into 0.7mL of ethanol, and carrying out ultrasonic treatment until the mixture is uniform for later use.
Example 7
Ink configuration: mixing 24mg Eu2Ti4-NH2@ PEG was dissolved in 0.6mL of ethanol, followed by addition of 0.4mL of ethylene glycol, and sonicated until uniform for use.
Example 8
Ink-jet printing:
1. the printing process comprises the following steps: after designing the specified pattern in a computer, the ink-jet printing of the ink was completed by using a piezo-driven ink-jet nozzle equipped with a piezo-driven ink-jet diameter of 30 μm diameter and a motorized stage Microfab JETLAB 2 printer with an accuracy of 5 μm, the printing substrate being a glass plate. The specific printing process is shown in fig. 5.
2. And (3) observing the pattern: fig. 6 is a photograph of a visual observation under visible light irradiation and ultraviolet light irradiation, respectively. Under the irradiation of visible light, the glass sheet is transparent and the trace cannot be directly seen. Thus having good concealment. Under the irradiation of ultraviolet light at 312nm, a clear red trace appears. Therefore, the anti-counterfeiting paper has anti-counterfeiting effectiveness.

Claims (7)

1. A fluorescent ink composite material is characterized in that the molecular formula is Eu2Ti4-NH2@ PEG; wherein Eu2Ti4-NH2Is Eu2Ti4(µ2-O)2(µ3-O)4(phen)2 (tbza)9(paza)]•7H2O, PEG is methoxy polyethylene glycol succinimide carbonate;
the fluorescent ink composite material is prepared by the following method:
1) hydrothermal synthesis of Eu2Ti4-NH2: dissolving europium acetate tetrahydrate, p-tert-butylbenzoic acid, p-aminobenzoic acid, phenanthroline monohydrate and titanium tetraisopropoxide in acetonitrile, transferring the acetonitrile into a serum bottle, heating and keeping the temperature constant, then cooling to room temperature, filtering and washing to obtain Eu2Ti4-NH2Is light yellow bulk crystal;
2) the Eu synthesized in the step 1)2Ti4-NH2Dissolving the Eu and methoxypolyethylene glycol succinimide carbonate in toluene, refluxing and stirring, cooling to room temperature, filtering, and washing with water to obtain the fluorescent ink composite material Eu2Ti4-NH2@ PEG, light yellow powder.
2. The method of claim 1, comprising the steps of:
1) hydrothermal synthesis of Eu2Ti4-NH2Said Eu2Ti4-NH2Belongs to the monoclinic system, space group P21/c, and the molecular formula is [ Eu2Ti4(µ2-O)2(µ3-O)4(phen)2(tbza)9(paza)]•7H2O, unit cell parameters a =16.9806, b =19.6263, c =21.4267, β =107.6290, V = 6805.45;
the method comprises the following specific steps: dissolving europium acetate tetrahydrate, p-tert-butylbenzoic acid, p-aminobenzoic acid, phenanthroline monohydrate and titanium tetraisopropoxide in acetonitrile, transferring the acetonitrile into a serum bottle, heating and keeping the temperature constant, then cooling to room temperature, filtering and washing to obtain Eu2Ti4-NH2Is light yellow bulk crystal;
the proportion of the europium acetate tetrahydrate, the p-tert-butylbenzoic acid, the p-aminobenzoic acid, the phenanthroline monohydrate, the titanium tetraisopropoxide and the acetonitrile is 0.02-0.2 mmol: 0.18-0.72 mmol: 0.02-0.08 mmol: 0.2-0.8 mmol: 0.02-0.2 mmol: 2-8 mL, wherein the proportion of the p-tert-butylbenzoic acid to the p-aminobenzoic acid is 9: 1;
2) the Eu synthesized in the step 1)2Ti4-NH2Dissolving the obtained product and methoxypolyethylene glycol succinimide carbonate in toluene for compounding to obtain the fluorescent ink composite material which is named Eu2Ti4-NH2@PEG；
The specific method for obtaining the fluorescent ink composite material by compounding comprises the following steps: eu is mixed2Ti4-NH2Methoxy polyethylene glycol succinic acidDissolving the phthalimide carbonate in toluene, refluxing and stirring, cooling to room temperature, filtering, and washing with water to obtain the fluorescent ink composite material Eu2Ti4-NH2@ PEG, light yellow powder.
3. The method of claim 2, wherein in step 1), the ratio of europium acetate tetrahydrate, p-tert-butylbenzoic acid, p-aminobenzoic acid, phenanthroline monohydrate, titanium tetraisopropoxide, and acetonitrile is 0.08 mmol: 0.36 mmol: 0.04 mmol: 0.2 mmol: 0.08 mmol: 3 mL.
4. The method for preparing the fluorescent ink composite material as claimed in claim 2, wherein in the step 1), the temperature rising rate is 5-40 ℃/h, the constant temperature is 60-80 ℃, the constant temperature time is 24-72 h, and the temperature lowering rate to room temperature is 5-40 ℃/h.
5. The method of claim 2, wherein in step 2), the Eu is selected2Ti4-NH2The ratio of the methoxypolyethylene glycol succinimide carbonate to the toluene is 0.005-0.1 mmol: 0.02-0.2 mmol: 10-24 mL, the molecular weight of the methoxypolyethylene glycol succinimide carbonate is 2000Da, the reflux temperature is 70-100 ℃, and the reflux time is 72-144 h.
6. The fluorescent ink composite Eu according to claim 12Ti4-NH2@ PEG is used in ink jet printing; the application is to add Eu2Ti4-NH2The @ PEG composite material is dissolved in ethanol and glycol to obtain ink for ink-jet printing.
7. The use of claim 6, wherein ethanol: ethylene glycol = 4: 1-3: 2, and Eu is2Ti4-NH2The concentration of @ PEG is 18-36 mg/mL.
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