CN116693701A - Water vapor response room temperature phosphorescent material and preparation method and application thereof - Google Patents

Water vapor response room temperature phosphorescent material and preparation method and application thereof Download PDF

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CN116693701A
CN116693701A CN202210190472.2A CN202210190472A CN116693701A CN 116693701 A CN116693701 A CN 116693701A CN 202210190472 A CN202210190472 A CN 202210190472A CN 116693701 A CN116693701 A CN 116693701A
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polysaccharide
phosphorescent material
ionic liquid
methylimidazole
water vapor
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张金明
张鑫
张军
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Institute of Chemistry CAS
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B3/00—Preparation of cellulose esters of organic acids
    • C08B3/22—Post-esterification treatments, including purification
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08B3/00—Preparation of cellulose esters of organic acids
    • C08B3/14—Preparation of cellulose esters of organic acids in which the organic acid residue contains substituents, e.g. NH2, Cl
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    • C08B31/00—Preparation of derivatives of starch
    • C08B31/02—Esters
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    • C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
    • C08B37/0006—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid
    • C08B37/0024—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid beta-D-Glucans; (beta-1,3)-D-Glucans, e.g. paramylon, coriolan, sclerotan, pachyman, callose, scleroglucan, schizophyllan, laminaran, lentinan or curdlan; (beta-1,6)-D-Glucans, e.g. pustulan; (beta-1,4)-D-Glucans; (beta-1,3)(beta-1,4)-D-Glucans, e.g. lichenan; Derivatives thereof
    • C08B37/0027—2-Acetamido-2-deoxy-beta-glucans; Derivatives thereof
    • C08B37/003—Chitin, i.e. 2-acetamido-2-deoxy-(beta-1,4)-D-glucan or N-acetyl-beta-1,4-D-glucosamine; Chitosan, i.e. deacetylated product of chitin or (beta-1,4)-D-glucosamine; Derivatives thereof
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
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    • 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
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    • 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
    • C09D11/10—Printing inks based on artificial resins
    • C09D11/106—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
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    • 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
    • C09D11/10—Printing inks based on artificial resins
    • C09D11/106—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C09D11/108—Hydrocarbon resins
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    • 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
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    • 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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    • 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
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    • C—CHEMISTRY; METALLURGY
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    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2301/00—Characterised by the use of cellulose, modified cellulose or cellulose derivatives
    • C08J2301/08—Cellulose derivatives
    • C08J2301/10—Esters of organic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2303/00—Characterised by the use of starch, amylose or amylopectin or of their derivatives or degradation products
    • C08J2303/04—Starch derivatives
    • C08J2303/06—Esters
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08J2305/00—Characterised by the use of polysaccharides or of their derivatives not provided for in groups C08J2301/00 or C08J2303/00
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Abstract

The invention discloses a water vapor response room temperature phosphorescence material, a preparation method and application thereof, wherein the material has a porous structure, does not have room temperature phosphorescence property at first, and shows room temperature phosphorescence property when being fumigated by water vapor and dried. And this phenomenon is not repeatable and can only be performed once. The irreversible water vapor response characteristic of the water vapor response room temperature phosphorescent material is different from that of the common reversible water response material, so that the irreversible water vapor response material is difficult to forge and has authenticity and uniqueness. The water vapor response room temperature phosphorescent material has important application in the fields of anti-counterfeiting, information encryption, molecular logic gate, environment monitoring and the like.

Description

Water vapor response room temperature phosphorescent material and preparation method and application thereof
Technical Field
The invention belongs to the field of analysis detection and anti-counterfeiting materials, and particularly relates to a water vapor response room temperature phosphorescent material, a preparation method and application thereof.
Background
The room temperature phosphorescent material has the advantages of no background fluorescence and scattered light interference, large Stockes displacement, high signal to noise ratio, long service life and the like, and is widely paid attention to. Along with the discovery of a plurality of organic room temperature phosphorescent materials based on new structures and new systems, the organic room temperature phosphorescent materials are applied in the fields of anti-counterfeiting, information encryption and the like. The phosphorescent material with responsiveness can provide richer optical property change and realize more complex anti-counterfeiting effect. However, few responsive phosphorescent materials are reported. Ologoshi et al and Cai et al found that polystyrene sulfonate had reversible water responsiveness, phosphorescence disappeared in the presence of water and phosphorescence recovered in the absence of water (Adv.Funct.Mater.2018, 28,1707369;Nature Communications,2019,10,4247). Kwon et al report that polyvinyl alcohol composites have reversible water responsiveness (angel. Chem. Int. Ed.2014,53, 11177-11181). Therefore, development of a new responsive phosphorescent material has important practical value.
Disclosure of Invention
In order to improve the technical problems, the invention provides a water vapor response room temperature phosphorescent material, and a preparation method and application thereof.
In order to achieve the aim of the invention, the invention adopts the following technical scheme:
a phosphorescent material, the material comprising: polysaccharide derivatives having irreversible moisture responsiveness and optionally a polymer.
According to an embodiment of the present invention, the polysaccharide derivative having irreversible water vapor responsiveness has no room temperature phosphorescence property, and when it is fumigated with water vapor and dried, the resulting material exhibits room temperature phosphorescence property. This phenomenon is not repeatable and can only be performed once.
Preferably, the means of steam fumigation may be conventional in the art, for example, water may be sprayed directly or in the form of a spray onto the polysaccharide derivative material having irreversible steam responsiveness.
Preferably, the temperature of the drying may be 40 to 80 ℃, and is exemplified by 40 ℃, 60 ℃,80 ℃; the drying time is 0.5-2 h, and is exemplified by 0.5h, 1h, and 2h.
According to an embodiment of the present invention, the polysaccharide derivative having irreversible moisture responsiveness is a porous material having a porosity of not less than 10%, for example not less than 15%, and exemplified by 15%, 19%, 25%, 30%, 40%.
According to an embodiment of the present invention, the polysaccharide derivative having irreversible water vapor responsiveness has a repeating structural unit represented by the following formula I:
wherein:
A 1 、A 2 、A 3 identical or different, independently of one another, from H, R 1 Or (b)Y is selected from O or NH;
cations (cationic)Is->At least one of (a) and (b);
anions (v-v)The method comprises the following steps: cl - 、Br - 、F - 、BF 4 - 、PF 6 - 、NO 3 - 、SO 4 2- 、H 2 PO 4 - 、PO 4 3- 、HPO 4 2- 、(CF 3 SO 2 ) 2 N - 、C(CN) 3 - 、N(CN) 2 - 、Ac - 、HCOO - 、CH 3 CH 2 COO - 、CF 3 COO - 、CF 3 SO 3 - 、NO 3 - 、NO 2 - 、HCO 3 - 、CO 3 2- 、SO 4 2- 、SO 3 2- And B 4 O 7 2- At least one of (a) and (b);
R 1 is thatAt least one of (a) and (b);
x is at least one of Cl, br and I;
in formula I, DP represents a degree of polymerization, the Degree of Polymerization (DP) being 100 to 4000, preferably 100 to 2000, and exemplified by 100, 220, 500, 600, 650, 810, 1000, 1500, 2000, 3000, 4000;
R 2 、R 3 、R 4 、R 5 identical or different, independently of one another, from the group consisting of-H, halogen, -CHO, -SH, -COOH, C 1-10 Alkyl, C 1-6 Alkenyl, -C 1-6 Alkylcyano, -COO-C 1-6 Alkyl, -C 1-6 Alkyl hydroxy, -C 1-6 Alkyl sulfonic group, -C 1-6 An alkyl carboxylic acid group;
preferably, R 2 、R 3 、R 4 、R 5 Identical or different, independently of one another, from the group consisting of-H, halogen, -CHO, -SH, -COOH, C 1-6 Alkyl, C 1-4 Alkenyl, -C 1-4 Alkylcyano, -COO-C 1-4 Alkyl, -C 1-4 Alkyl hydroxy, -C 1-4 Alkyl sulfonic group, -C 1-4 An alkyl carboxylic acid group;
n is selected from 1-10; preferably 2-8, exemplified by 1,2, 3, 5, 8, 10;
m is selected from 0 to 10; preferably 1-6, exemplified by 1,2, 3, 5, 6, 8;
z is selected from 0 to 10; preferably 2-8, and exemplified by 1,2, 3, 5, 8, 10.
According to an embodiment of the present invention, the polysaccharide in the polysaccharide derivative is at least one of cellulose, starch, chitosan and chitin.
According to an embodiment of the present invention, when the polysaccharide in the polysaccharide derivative is at least one of cellulose, starch, chitosan and chitin, the cationThe degree of substitution in the polysaccharide derivative is 0.1 to 1.0, preferably 0.2 to 0.8, and exemplified by 0.1, 0.2, 0.42, 0.5, 0.65, 0.8;
R 1 the degree of substitution in the polysaccharide derivative is 0 to 1.0, preferably 0.1 to 0.8, and exemplified by 0.1, 0.21, 0.25, 0.5, 0.61, 0.72.
According to an embodiment of the invention, the polymer is at least one of polystyrene, polyethylene, polypropylene, polyacrylate, cellulose acetate, nitrocellulose, polycarbonate, polybutylene phthalate, cellulose acetate butyrate.
According to an embodiment of the invention, the phosphorescent material is a moisture responsive room temperature phosphorescent material.
According to an embodiment of the present invention, the polysaccharide derivative having irreversible water vapor responsiveness is prepared by reacting raw materials including a polysaccharide polymer, an acylating agent and an imidazole agent, and precipitating the raw materials with a precipitating agent.
Preferably, the precipitant is at least one of chloroform, dichloromethane, ethyl acetate, methanol, ethanol, isopropanol, chlorobenzene, and acetone. Preferably at least one of chloroform, dichloromethane and acetone, more preferably two of chloroform, dichloromethane and acetone.
According to an exemplary embodiment of the present invention, when the precipitant is two of chloroform, dichloromethane, and acetone, the mass ratio of the two solvents may be, for example, 1 (0.5-2), and exemplary are 1:0.5, 1:1, and 1:2.
Preferably, the polysaccharide macromolecule is selected from at least one of cellulose, starch, chitosan, chitin and polyvinyl alcohol (PVA); the polymerization degree of the polysaccharide polymer is 100-4000, preferably 100-2000, and exemplified by 100, 220, 500, 600, 650, 810, 1000, 1500, 2000, 3000, 4000;
preferably, the acylating agent is selected from the group consisting of a compound containing R 1 Acyl chloride, acyl bromide or carboxylic acid of the group; more preferably, is selected from the group consisting of R 1 Acyl chloride or acyl bromide of the group;
wherein R is 1 Has the meaning as described above.
Preferably, the imidazole reagent is selected from
Wherein: r is R 1 、R 2 、R 3 、R 4 、R 5 Has the meaning as described above.
Illustratively, the acylating reagent is selected from at least one of 2-chloropropionyl chloride, bromoacetyl bromide, and chloroacetyl chloride;
illustratively, the imidazole reagent is selected from at least one of (1-imidazolyl) acetonitrile, 1-methylimidazole, 1-hydroxyethyl imidazole, and 1-methyl-2 mercaptoimidazole.
The invention also provides a preparation method of the phosphorescence material, which comprises the steps of reacting polysaccharide macromolecule, acylating agent and imidazole agent, and obtaining the polysaccharide derivative with irreversible water vapor responsiveness after precipitation by a precipitator;
optionally, when the phosphorescent material contains a polymer, the preparation method further comprises mixing the polysaccharide derivative having irreversible moisture responsiveness with a polymer to prepare the phosphorescent material.
According to an embodiment of the invention, the polysaccharide macromolecule, the acylating agent and the imidazole agent are used in a ratio of 1 (0.8-2): (0.8-2.5), preferably 1 (1-1.8): (1-2), exemplified by 1:0.8:0.8, 1:0.8:2.5, 1:1.15:1.35, 1:1.5:1.4, 1:1.6:1.475, 1:1.44:2.05, 1:2:2.5.
According to an embodiment of the invention, the polysaccharide macromolecule, the acylating agent, the imidazole agent and the precipitant have the meanings as described above.
According to an embodiment of the present invention, the method for preparing a phosphorescent material includes the steps of:
(1) Dissolving a polysaccharide macromolecule in a solvent 1, adding an acylating reagent into the obtained solution, and reacting to obtain polysaccharide ester;
(2) Dissolving polysaccharide ester in a solvent 2, and adding an imidazole reagent into the solvent to perform a reaction;
(3) Pouring the reaction solution into a precipitator, stirring with strong force to form precipitate, filtering, washing and drying to obtain the polysaccharide derivative with irreversible water vapor responsiveness;
optionally, when the phosphorescent material contains a polymer, the preparation method further comprises step (4): mixing the polysaccharide derivative with irreversible water vapor responsiveness prepared in the step (3) with a polymer to prepare the phosphorescent material.
Preferably, the solvent 1 is selected from ionic liquids, and optionally amide solvents, with or without inclusion;
for example, the ionic liquid includes, but is not limited to, one of the following: 1-ethyl-3-methylimidazole chloride ionic liquid, 1-ethyl-3-methylimidazole bromide ionic liquid, 1-allyl-3-methylimidazole chloride ionic liquid (amicl), 1-allyl-3-methylimidazole bromide ionic liquid, 1-butyl-3-methylimidazole chloride ionic liquid (BmimCl), 1-butyl-3-methylimidazole bromide ionic liquid, 1-ethyl-3-methylimidazole acetate ionic liquid (EmimAc), 1-butyl-3-methylimidazole acetate ionic liquid, 1-ethyl-3-methylimidazole diethyl phosphate ionic liquid, 3-methylimidazole formate ionic liquid, N-methylpyridine formate ionic liquid, 1-ethyl-3-methylimidazole formate ionic liquid, 1-butyl-3-methylimidazole formate ionic liquid;
for example, the amide-based solvent is selected from at least one of N, N-Dimethylformamide (DMF) and N, N-dimethylacetamide;
preferably, the solvent 1 is selected from a mixed solvent of an ionic liquid and an amide solvent. For example, the mass ratio of the two may be 4 (0-4), preferably 4 (0-2), and exemplary are 4:0, 4:0.5, 4:1, and 4:2.
For example, the solvent 2 is at least one selected from sulfone-based solvents and amide-based solvents, such as at least one selected from dimethyl sulfoxide, N-Dimethylformamide (DMF) and N, N-dimethylacetamide; preferably N, N-Dimethylformamide (DMF).
The invention also provides application of the phosphorescent material in the fields of anti-counterfeiting, information encryption, molecular logic gate, environment monitoring and the like. For example, phosphorescent inks, phosphorescent paints, and the like can be prepared.
The invention also provides ink, which contains the phosphorescent material or is prepared by taking the phosphorescent material as a raw material. Preferably, the ink is a moisture responsive phosphorescent ink.
The invention also provides a preparation method of the ink, which comprises the following steps: comprises dissolving the phosphorescent material in a solvent to obtain the ink.
According to an embodiment of the invention, the mass concentration of the phosphorescent material solution is 0.01-30%, preferably 0.5-25%, exemplary 0.01%, 0.5%, 1%, 2%, 2.5%, 5%, 8%, 10%, 15%, 20%, 27.5%, 30%.
According to an embodiment of the present invention, the solvent is selected from at least one of water, dimethyl sulfoxide (DMSO), N-Dimethylformamide (DMF), N-dimethylacetamide (DMAc), chloroform, dichloromethane, 1, 2-dichloroethane, acetone, tetrahydrofuran (THF), N-methylpyrrolidone, pyridine, ethanol, methanol, isopropanol, ethyl acetate, butyl acetate, toluene, methyl ethyl ketone; acetone is preferred.
The invention also provides a coating, which comprises the above phosphorescent material or is prepared by taking the above phosphorescent material as a raw material.
The invention also provides a preparation method of the paint, which comprises the following steps: comprising dissolving the phosphorescent material in a solvent to obtain the coating.
According to an embodiment of the invention, the mass concentration of phosphorescent material in the coating is 0.01-30%, preferably 0.5-25%, exemplary 0.01%, 0.5%, 1%, 2%, 2.5%, 5%, 8%, 10%, 15%, 20%, 27.5%, 30%.
According to an embodiment of the present invention, the solvent is selected from at least one of water, dimethyl sulfoxide (DMSO), N-Dimethylformamide (DMF), N-dimethylacetamide (DMAc), chloroform, dichloromethane, 1, 2-dichloroethane, acetone, tetrahydrofuran (THF), N-methylpyrrolidone, pyridine, ethanol, methanol, isopropanol, ethyl acetate, butyl acetate, toluene, methyl ethyl ketone.
The invention has the beneficial effects that:
the invention discloses a polysaccharide-based room temperature phosphorescent material with irreversible water vapor responsiveness. The material has a porous structure, does not have room temperature phosphorescence property at first, and shows room temperature phosphorescence property when being fumigated by water vapor and dried. This phenomenon is not repeatable and can only be performed once. The present invention may also optionally incorporate a polymer into the polysaccharide derivative to further enhance the molding processability of the polysaccharide derivative. The polysaccharide-based room temperature phosphorescent material with irreversible moisture responsiveness of the invention is different from common reversible moisture responsiveness materials, and the irreversible moisture responsiveness makes the material difficult to forge, and has authenticity and uniqueness. Therefore, the phosphorescence material can have wide application prospect in the fields of anti-counterfeiting, information encryption, molecular logic gate, environment monitoring and the like.
Drawings
FIG. 1 is a hydrogen nuclear magnetic resonance spectrum of cellulose hydroxyethylimidazole chloride in example 1. (test instrument: bruker AV400 Nuclear magnetic resonance spectrometer, solvent: deuterated dimethyl sulfoxide (DMSO-d) 6 )。)
FIG. 2 is a scanning electron micrograph of hydroxyethylimidazole chloride of the cellulose in example 1. ( Test instrument: JSM6700 scanning electron microscope, voltage: 5kV. )
FIG. 3 shows fluorescence and phosphorescence of the hydroxyethylimidazole chloride powder of example 1, and fluorescence and phosphorescence after steam fumigation and drying. (photographing camera: sony. Alpha.7, excitation wavelength: 365 nm.)
Fig. 4 is a scanning electron micrograph of the hydroxyethylimidazole chloride of example 1 after steam fumigation and drying. ( Test instrument: JSM6700 scanning electron microscope, voltage: 5kV. )
FIG. 5 is a photograph of fluorescence and phosphorescence of a vapor-responsive phosphorescence pattern prepared by screen printing in example 1, an ultraviolet lamp of 365nm on and off, and fluorescence and phosphorescence after steam fumigation and drying of the pattern.
FIG. 6 is a photograph of fluorescence and phosphorescence of a vapor-responsive phosphorescence pattern prepared by screen printing in example 1, an ultraviolet lamp of 365nm on and off, and fluorescence and phosphorescence after steam fumigation and drying of the pattern.
Fig. 7 is a scanning electron micrograph of the starch methylimidazole bromide of comparative example 1.
Detailed Description
The present invention will be described in further detail with reference to specific examples. It is to be understood that the following examples are illustrative only and are not to be construed as limiting the scope of the invention. All techniques implemented based on the above description of the invention are intended to be included within the scope of the invention.
The experimental methods used in the following examples are all conventional methods unless otherwise specified; the reagents, materials, etc. used in the examples described below are commercially available unless otherwise specified.
Term definition and description:
unless defined otherwise below, all terms herein have the same meaning as commonly understood by one of ordinary skill in the art to which the claimed subject matter pertains. If there are multiple definitions of terms herein, the following definitions shall apply.
The numerical ranges recited in the specification and claims are equivalent to at least each specific integer number recited therein unless otherwise stated. For example, the numerical range "1 to 20" corresponds to the numerical range in which each of the integer numbers 1 to 10, i.e., 1,2, 3, 4,5, 6, 7, 8, 9,10, and each of the integer numbers 11 to 20, i.e., 11, 12, 13, 14, 15, &..times., 19, 20 are described. It is to be understood that "more" in one, two or more as used herein in describing substituents shall mean an integer of ≡3, such as 3, 4,5, 6, 7, 8, 9 or 10. Furthermore, when certain numerical ranges are defined as "numbers," it is to be understood that both endpoints of the range, each integer within the range, and each fraction within the range are delineated. For example, a "number of 0 to 10" should be understood to describe not only each integer of 0,1, 2, 3, 4,5, 6, 7, 8, 9 and 10, but also at least the sum of each integer with 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, respectively.
Example 1
The preparation of the cellulose hydroxyethyl imidazole chloride comprises the following steps:
(1) Weighing 2.0g of cellulose(DP is 600) is dissolved in 48.0g of 1-allyl-3-methylimidazole chloride ionic liquid (AmimCl), 2.3g of 2-chloropropionyl chloride is added for reaction for 1.5 hours at 40 ℃, and after the reaction is finished, the mixture is poured into ethanol, and the mixture is precipitated, washed and dried to obtain cellulose 2-chloropropionate;
(2) Weighing 0.5g of cellulose 2-chloropropionate prepared in the step (1), dissolving in 15mL of DMF, adding 2.95g of 1-hydroxyethyl imidazole, reacting for 24 hours at 80 ℃, pouring into dichloromethane, stirring strongly to form a precipitate, filtering the precipitate, washing the precipitate with dichloromethane, and drying to obtain cellulose hydroxyethyl imidazole chloride with a porous structure, wherein the cellulose hydroxyethyl imidazole chloride has a repeating structural unit shown in the following formula:
wherein A is 1 、A 2 、A 3 H, & gt>One of them.
The hydrogen nuclear magnetic spectrum of the cellulose hydroxyethyl imidazole chloride prepared in the embodiment is shown in figure 1, and the 2-chloropropionyl in the cellulose hydroxyethyl imidazole chloride is calculated by the ratio of the integral area of 2-chloropropionyl and 1-hydroxyethyl imidazole to the integral area of cellulose in the figureHas a degree of substitution of 0.52, hydroxyethyl imidazole cation +.>The degree of substitution was 0.65.
The cellulose hydroxyethyl imidazole chloride prepared in the embodiment is a porous material, the porosity is 25%, and the microscopic morphology is shown in figure 2.
As shown in FIG. 3, the cellulose hydroxyethyl imidazole chloride prepared in the embodiment emits blue fluorescence under 365nm ultraviolet irradiation, and no phosphorescence is generated after the ultraviolet lamp is turned off. The material is fumigated by water vapor and then dried (the water vapor fumigating mode is that water is directly sprayed or acts on the material in a spray mode, the adopted drying mode is that the material is placed in a blast oven at 60 ℃ for heating for more than 1 hour to remove water), the obtained material is changed into a compact material (shown in figure 4), effective hydrogen bond interaction can be formed, meanwhile, the compact structure can also isolate oxygen, phosphorescence quenching caused by the oxygen is avoided, and therefore the material emits yellow-green phosphorescence, and the phosphorescence service life is 153ms, as shown in figure 3.
0.5g of cellulose hydroxyethyl imidazole chloride, 5.0g of polystyrene and 20mL of acetone were mixed and stirred at room temperature for 30min to obtain an ink, which was used to prepare a water vapor responsive phosphorescent pattern by printing and screen printing, as shown in FIGS. 5 and 6. As can be seen from the figures: the water vapor responsive phosphorescent pattern produced by the ink of this example emits blue fluorescence upon irradiation with 365nm ultraviolet light, and does not phosphorescence upon turning off the ultraviolet lamp. When fumigated with water vapor and then dried, the pattern can re-emit yellow-green phosphorescence.
Example 2
The preparation of the starch methylimidazole bromine comprises the following steps:
(1) Weigh 2.0g of starch(DP is 100) is dissolved in 30.0g of 1-ethyl-3-methylimidazole chloride ionic liquid (EmimCl)/DMF (mass ratio of 4:1), 2.6g of bromoacetyl bromide is added for reaction for 2 hours at 40 ℃, and after the reaction is finished, the solution is poured into ethanol, and the solution is precipitated, washed and dried to obtain starch bromoacetate;
(2) Weighing 1.0g of the starch bromoacetate prepared in the step (1), dissolving in 20mL of DMF, adding 3.20g of 1-methylimidazole, reacting for 24 hours at 80 ℃, pouring into a chloroform/acetone mixed solvent (chloroform/acetone mass ratio, 1:1) after the reaction is finished, stirring strongly to form a precipitate, filtering the precipitate, washing with acetone, and drying to obtain starch methylimidazole bromine with a porous structure, wherein the starch methylimidazole bromine has a repeated structural unit shown as the following formula:wherein A is 1 、A 2 、A 3 Is H,One of them.
Bromoacetyl in the starch methylimidazole bromide prepared in this exampleIs 0.10,1-methylimidazoleThe degree of substitution was 0.58 and the porosity was 30%.
The starch methylimidazole bromine prepared in the embodiment emits blue fluorescence under 365nm ultraviolet irradiation, and does not have phosphorescence after an ultraviolet lamp is turned off. The material obtained is fumigated by water vapor and then dried, and the material emits yellow-green phosphorescence.
Example 3
The preparation of the chitosan cyanoethylimidazole chloride comprises the following steps:
(1) Weighing 2g of chitosan(DP is 4000) is dissolved in 48g of 1-butyl-3-methylimidazole acetate ionic liquid (BmimAC), 4.0g of 2-chloropropionyl chloride is added for reaction for 2 hours at 40 ℃, and after the reaction is finished, the mixture is poured into ethanol, and the mixture is precipitated, washed and dried to obtain chitosan 2-chloropropionyl ester;
(2) Weighing 1.0g of chitosan 2-chloropropionyl ester prepared in the step (1), dissolving in 20mL of DMF, adding 6.0g of (1-imidazolyl) acetonitrile, reacting for 24 hours at 80 ℃, pouring into dichloromethane after the reaction is finished, stirring strongly to form a precipitate, filtering the precipitate, washing the precipitate with dichloromethane, and drying to obtain chitosan cyanoethylimidazole chloride, wherein the chitosan cyanoethylimidazole chloride has a repeated structural unit shown in the following formula:wherein A is 1 、A 2 、A 3 H, & gt>One of them.
2-Chloropropionyl group in the Chitosan cyanoethylimidazole chloride prepared in this exampleHas a degree of substitution of 0.10, cyanoethylimidazole +.>The degree of substitution was 0.51 and the porosity was 19%.
The chitosan cyanoethylimidazole chloride prepared in the embodiment emits blue fluorescence under 365nm ultraviolet irradiation, and does not have phosphorescence after an ultraviolet lamp is turned off. The resulting material emits green phosphorescence after vapor fumigation and then drying.
Comparative example 1
The preparation of the starch methylimidazole bromine comprises the following steps:
(1) Weigh 2.0g of starch(DP is 100) is dissolved in 30.0g of 1-ethyl-3-methylimidazole chloride ionic liquid (EmimCl)/DMF (mass ratio of 4:1), 2.6g of bromoacetyl bromide is added for reaction for 2 hours at 40 ℃, and after the reaction is finished, the solution is poured into ethanol, and the solution is precipitated, washed and dried to obtain starch bromoacetate;
(2) Weighing 1.0g of the starch bromoacetate prepared in the step (1), dissolving in 20mL of DMF, adding 3.20g of 1-methylimidazole, reacting for 24 hours at 80 ℃, pouring into acetone after the reaction is finished, stirring strongly to form a precipitate, filtering, washing the precipitate by the acetone, and drying to obtain starch methylimidazole bromine with a compact structure, wherein the starch methylimidazole bromine has a repeated structural unit shown as the following formula:wherein A is 1 、A 2 、A 3 H, & gt>One of them. (see FIG. 7).
Bromoacetyl in the starch methylimidazole bromine prepared in this comparative exampleIs 0.10,1-methylimidazoleThe degree of substitution was 0.58.
The starch methylimidazole bromine prepared in the comparative example emits blue fluorescence under 365nm ultraviolet irradiation, and green phosphorescence is generated after an ultraviolet lamp is turned off.
The embodiments of the present invention have been described above. However, the present invention is not limited to the above embodiment. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (10)

1. A phosphorescent material, the material comprising: polysaccharide derivatives having irreversible moisture responsiveness and optionally a polymer.
Preferably, the polysaccharide derivative having irreversible moisture responsiveness is a porous material having a porosity of not less than 10%.
2. The phosphorescent material according to claim 1, characterized in that the polysaccharide derivative having irreversible water vapor responsiveness has a repeating structural unit represented by the following formula I:
wherein:
A 1 、A 2 、A 3 identical or different, independently of one another, from H, R 1 Or (b)Y is selected from O or NH;
cations (cationic)Is->At least one of (a) and (b);
anions (v-v)The method comprises the following steps: cl - 、Br - 、F - 、BF 4 - 、PF 6 - 、NO 3 - 、SO 4 2- 、H 2 PO 4 - 、PO 4 3- 、HPO 4 2- 、(CF 3 SO 2 ) 2 N - 、C(CN) 3 - 、N(CN) 2 - 、Ac - 、HCOO - 、CH 3 CH 2 COO - 、CF 3 COO - 、CF 3 SO 3 - 、NO 3 - 、NO 2 - 、HCO 3 - 、CO 3 2- 、SO 4 2- 、SO 3 2- And B 4 O 7 2- At least one of (a) and (b);
R 1 is thatAt least one of (a) and (b);
x is at least one of Cl, br and I;
in formula I, DP represents the degree of polymerization, said Degree of Polymerization (DP) being from 100 to 4000, preferably from 100 to 2000;
R 2 、R 3 、R 4 、R 5 identical or different, independently of one another, from the group consisting of-H, halogen, -CHO, -SH, -COOH, C 1-10 Alkyl, C 1-6 Alkenyl, -C 1-6 Alkylcyano, -COO-C 1-6 Alkyl, -C 1-6 Alkyl hydroxy, -C 1-6 Alkyl sulfonic group, -C 1-6 An alkyl carboxylic acid group;
n is selected from 1-10; preferably 2 to 8;
m is selected from 0 to 10; preferably 1 to 6;
z is selected from 0 to 10; preferably 2-8.
3. The phosphorescent material according to claim 1 or 2, characterized in that the polysaccharide in the polysaccharide derivative is at least one of cellulose, starch, chitosan and chitin.
Preferably, when the polysaccharide in the polysaccharide derivative is at least one of cellulose, starch, chitosan and chitin, the cationThe degree of substitution in the polysaccharide derivative is 0.1 to 1.0, preferably 0.2 to 0.8;
R 1 in polysaccharide derivativesThe degree of substitution in the organism is 0 to 1.0, preferably 0.1 to 0.8.
4. A phosphorescent material according to any of claims 1-3, characterized in that the polymer is at least one of polystyrene, polyethylene, polypropylene, polyacrylate, cellulose acetate, cellulose nitrate, polycarbonate, polybutylene phthalate, cellulose acetate butyrate.
5. The phosphorescent material according to any one of claims 1 to 4, characterized in that the polysaccharide derivative having irreversible moisture responsiveness is prepared by reacting raw materials comprising a polysaccharide polymer, an acylating agent and an imidazole agent, and precipitating the raw materials with a precipitating agent.
Preferably, the precipitant is at least one of chloroform, dichloromethane, ethyl acetate, methanol, ethanol, isopropanol, chlorobenzene, and acetone. Preferably at least one of chloroform, dichloromethane and acetone, more preferably two of chloroform, dichloromethane and acetone.
Preferably, the polysaccharide macromolecule is selected from at least one of cellulose, starch, chitosan, chitin and polyvinyl alcohol (PVA); the polymerization degree of the polysaccharide macromolecule is 100-4000, preferably 100-2000;
preferably, the acylating agent is selected from the group consisting of a compound containing R 1 Acyl chloride, acyl bromide or carboxylic acid of the group; more preferably, is selected from the group consisting of R 1 Acyl chloride or acyl bromide of the group;
preferably, the imidazole reagent is selected from the group consisting of containing R 2 、R 3 、R 4 、R 5 Imidazole of a group;
wherein: r is R 1 、R 2 、R 3 、R 4 、R 5 Has the meaning as claimed in claim 2.
6. The method of producing a phosphorescent material according to any one of claims 1 to 5, characterized in that the method comprises reacting a polysaccharide polymer, an acylating agent and an imidazole agent, and precipitating with a precipitating agent to obtain the polysaccharide derivative having irreversible moisture responsiveness;
optionally, when the phosphorescent material contains a polymer, the preparation method further comprises mixing the polysaccharide derivative having irreversible moisture responsiveness with a polymer to prepare the phosphorescent material.
Preferably, the dosage ratio of the polysaccharide macromolecule, the acylating agent and the imidazole agent is 1 (0.8-2): 0.8-2.5.
7. The method of preparing the phosphorescent material according to claim 6, comprising the steps of:
(1) Dissolving a polysaccharide macromolecule in a solvent 1, adding an acylating reagent into the obtained solution, and reacting to obtain polysaccharide ester;
(2) Dissolving polysaccharide ester in a solvent 2, and adding an imidazole reagent into the solvent to perform a reaction;
(3) Pouring the reaction solution into a precipitator, stirring with strong force to form precipitate, filtering, washing and drying to obtain the polysaccharide derivative with irreversible water vapor responsiveness;
optionally, when the phosphorescent material contains a polymer, the preparation method further comprises step (4): mixing the polysaccharide derivative with irreversible water vapor responsiveness prepared in the step (3) with a polymer to prepare the phosphorescent material.
Preferably, the solvent 1 is selected from ionic liquids, and optionally amide solvents, with or without inclusion;
preferably, the ionic liquid includes, but is not limited to, one of the following: 1-ethyl-3-methylimidazole chloride ionic liquid, 1-ethyl-3-methylimidazole bromide ionic liquid, 1-allyl-3-methylimidazole chloride ionic liquid (amicl), 1-allyl-3-methylimidazole bromide ionic liquid, 1-butyl-3-methylimidazole chloride ionic liquid (BmimCl), 1-butyl-3-methylimidazole bromide ionic liquid, 1-ethyl-3-methylimidazole acetate ionic liquid (EmimAc), 1-butyl-3-methylimidazole acetate ionic liquid, 1-ethyl-3-methylimidazole diethyl phosphate ionic liquid, 3-methylimidazole formate ionic liquid, N-methylpyridine formate ionic liquid, 1-ethyl-3-methylimidazole formate ionic liquid, 1-butyl-3-methylimidazole formate ionic liquid;
preferably, the amide solvent is selected from at least one of N, N-Dimethylformamide (DMF) and N, N-dimethylacetamide;
preferably, the solvent 1 is selected from a mixed solvent of an ionic liquid and an amide solvent. For example, the mass ratio of the two may be 4 (0-4), preferably 4 (0-2).
Preferably, the solvent 2 is at least one selected from sulfone solvents and amide solvents.
8. Use of the phosphorescent material according to any of claims 1-5 in the fields of anti-counterfeiting, information encryption, molecular logic gates, environmental monitoring and the like. For example, phosphorescent inks, phosphorescent paints, and the like can be prepared.
9. An ink, characterized in that the ink contains the phosphorescent material of any one of claims 1 to 5 or is prepared by taking the phosphorescent material of any one of claims 1 to 5 as a raw material. Preferably, the ink is a moisture responsive phosphorescent ink.
10. A coating, wherein the ink contains the phosphorescent material of any one of claims 1 to 5 or is prepared by taking the phosphorescent material of any one of claims 1 to 5 as a raw material.
CN202210190472.2A 2022-02-28 2022-02-28 Water vapor response room temperature phosphorescent material and preparation method and application thereof Pending CN116693701A (en)

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