CN110591687B - Polyacid-based photochromic material and preparation method thereof - Google Patents
Polyacid-based photochromic material and preparation method thereof Download PDFInfo
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- CN110591687B CN110591687B CN201910765406.1A CN201910765406A CN110591687B CN 110591687 B CN110591687 B CN 110591687B CN 201910765406 A CN201910765406 A CN 201910765406A CN 110591687 B CN110591687 B CN 110591687B
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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
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/24—Homopolymers or copolymers of amides or imides
- C09D133/26—Homopolymers or copolymers of acrylamide or methacrylamide
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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
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
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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
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/63—Additives non-macromolecular organic
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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
- C09K9/00—Tenebrescent materials, i.e. materials for which the range of wavelengths for energy absorption is changed as a result of excitation by some form of energy
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
- C08K2003/309—Sulfur containing acids
Abstract
The invention discloses a polyacid-based photochromic material and a preparation method thereof, wherein the polyacid-based photochromic material comprises, by mass, 0.0-30% of tungstate, 0.0-30% of molybdate, 0.0-10% of inorganic metal salt, 0.0-10% of inorganic acid, 0.0-10% of polyol ligand, 0.0-30% of phase transfer agent, 0.0-10% of organic amine and 0.0-5% of surfactant. The beneficial effects are that: the method comprises the steps of firstly synthesizing a high-quality pure polyacid material as a good electron acceptor, then further compounding the polyacid material with an organic amine compound (electron donor) with an active group amino group, and adding a surfactant to optimize the morphology of the material so as to obtain a composite nano material with uniform and smaller size, so that the photochromic response speed is accelerated. Different polyacid compounds affect the color change, and different organic amines affect the stability and rate of color change. The problem of single color change is solved; the polymeric organic amine can be used as a film forming substance of the coating, can also provide abundant electron donors, meets the requirement of photochromism, and can effectively improve the color change stability.
Description
Technical Field
The invention belongs to a color-changing material and a preparation method thereof, and particularly relates to a polyacid-based photochromic material and a preparation method thereof.
Background
The invention patent CN101307148A discloses a method for preparing a composite color-changing film, which comprises the following steps: 1) Mixing a compound which can form hydrogel and contains amino or hydroxyl with water, and stirring; 2) Adding inorganic transition metal oxide, isopoly acid or heteropoly acid into the reaction system in the step 1), mixing with water, and stirring to obtain a mixed solution; 3) And coating the mixed aqueous solution on a substrate, and gelling and drying to obtain the composite color-changing film. The compound capable of forming hydrogel and containing amino is poly L-lysine, poly L-glutamic acid and the like, and the inorganic transition metal oxide, isopoly acid or heteropoly acid is … … sodium tungstate, and Preyssler type heteropoly acid … … europium sandwich type heteropoly acid … … sodium molybdate.
CN104818653A discloses an ultraviolet photochromic reusable paper, and particularly discloses an ultraviolet photochromic reusable paper which is prepared by compounding an ultraviolet photochromic reversible material and paper, wherein the ultraviolet photochromic reversible material is composed of polyacrylamide and polyacid compounds, the polyacrylamide and the polyacid compounds form a donor-acceptor charge transfer compound, and the ratio of the polyacid compounds to the polyacrylamide is 10-2:1; wherein the polyacid compound is at least one of Keggin structure phosphotungstic acid and Keggin structure phosphomolybdic acid. The ultraviolet photochromic reusable paper is irradiated by a light source with the wavelength of 300-405 nm for 5-200ms, the irradiated part is changed into blue black, black or pure blue, and the paper naturally stands in the air for 6-30 hours and then completely fades.
The prior art provides the technical inspiration for preparing the photochromic material by taking organic amine (such as polyacrylamide) which can form a film and can provide electrons and polyacid (such as sodium tungstate, sodium molybdate or phosphotungstic acid and the like) which is taken as an electron acceptor as raw materials, has fast color change (the color changes after illumination for 5-200 ms), and can generate color change effects of different colors according to the difference of the polyacid.
The main difference between the invention and the prior art is that 1, the variety of the selected polyacid is different, and the polyacid of the invention is a molecular polyoxometalate cluster with a specific structure and size prepared by tungstate, molybdate, inorganic metal salt and inorganic acid according to a specific process; 2. the raw material of the invention also comprises a polyatomic alcohol ligand stable polyacid structure and a surfactant for improving the shape and the size of the polyacid, so that the color change responsiveness and the stability of the polyacid are more excellent.
The key point of the technology lies in the high-purity preparation of the molecular state polyoxometalate cluster (polyacid) with a specific structure and size, and the purity of the polyacid can not only influence the color change performance, but also influence the structural stability of the polyacid. Therefore, a polyacid sample with single crystal purity needs to be cultured; moreover, the synthesis process of the specific polyacid is sensitive to objective factors such as temperature, pH and the like, and is not easy to regulate and control; in addition, in order to realize large-scale application, the discoloration rate and discoloration stability of the material are still to be improved. The above are the deficiencies and drawbacks of the prior art.
Disclosure of Invention
The invention aims to provide a polyacid-based photochromic material and a preparation method thereof, which can solve the problems of single color, slow color change rate and unstable color change in the use process of the traditional photochromic material.
The technical scheme of the invention is as follows: a polyacid-based photochromic material comprises, by mass, 0.0-30% of tungstate, 0.0-30% of molybdate, 0.0-10% of inorganic metal salt, 0.0-10% of inorganic acid, 0.0-10% of polyol ligand, 0.0-30% of phase transfer agent, 0.0-10% of organic amine and 0.0-5% of surfactant.
The tungstate refers to sodium tungstate and hydrate thereof, and ammonium paratungstate and hydrate thereof.
The molybdate refers to sodium molybdate and hydrate thereof, and ammonium heptamolybdate and hydrate thereof;
the inorganic metal salt includes: sulfate, nitrate, hydrochloride and the like, and the structural general formula is as follows: am (BOx) n.yH 2 O, (where A = Al, cr, mn, fe, co, ni, cu, zn; B = S, N, cl; m, N, x, y =0,1,2,3,4 …).
The polyols include: triol ligands such as tris (hydroxymethyl) aminomethane and tris (hydroxymethyl) ethane, pentaerythritol, and the like;
the phase transfer agent comprises: tetrabutylammonium bromide, tetramethylammonium bromide, potassium chloride, cesium chloride, barium chloride, and the like.
The organic amines include: alkylamine R-NH2 (R = an alkane such as an ethylamino group or a propylamine group and a derivative thereof), polyacrylamide, an amine resin, and aromatic amine Ar-NH2 (Ar = an aromatic group such as a phenyl group, a biphenyl group, a styryl group, or an anilino group).
The surfactant comprises: polyvinylpyrrolidone (PVP), cetyltrimethylammonium bromide (CTAB), polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer (PEO-PPO-PEO), alkyl sulfonate salts, and the like.
The inorganic acid includes nitric acid, sulfuric acid, hydrochloric acid, etc.
A method for preparing a polyacid-based photochromic material comprises the following steps:
(1) Firstly, mixing and dissolving tungstate or molybdate in deionized water, heating to boil, and continuously heating and stirring to completely dissolve the tungstate or molybdate;
(2) Dissolving inorganic metal salt in deionized water, adding the solution, adjusting the pH value by using inorganic acid, controlling the pH value to be between 1 and 7, continuously heating and stirring to obtain a polyacid crude product, mixing the polyacid crude product with a polyol ligand, heating and refluxing, filtering, changing cations, and recrystallizing for multiple times to obtain a high-purity polyacid product;
(3) And adding deionized water and a proper amount of inorganic acid into the polyacid, the organic amine and the surfactant, stirring and mixing uniformly, standing, collecting a target product, and drying to obtain the target product.
The invention has the beneficial effects that: the method comprises the steps of firstly synthesizing a high-quality pure polyacid material as a good electron acceptor, then further compounding the polyacid material with an organic amine compound (electron donor) with an active group amino group, and adding a surfactant to optimize the morphology of the material so as to obtain a composite nano material with uniform and smaller size, so that the photochromic response speed is accelerated. Different polyacid compounds affect the color change, and different organic amines affect the stability and rate of color change. According to different proportions, types and contents of transition metal ions, the composite material can be changed from pink into green after being irradiated by ultraviolet light; or changing from colorless to blue; yellow to blue; pink to orange; the green color turns into the yellow soil; blue to earth yellow; the problem of single color change is solved; the polymeric organic amine can be used as a film forming substance of the coating, can also provide abundant electron donors, meets the requirement of photochromism, and can effectively improve the color change stability.
Detailed Description
The present invention will be described in further detail with reference to specific examples.
A polyacid-based photochromic material comprises the following components in parts by weight:
| components | Mass part (%) |
| Tungstate | 0.0～30 |
| Molybdate salt | 0.0～30 |
| Inorganic metal salt | 0.0～10 |
| Inorganic acid | 0.0～10 |
| Polyol ligands | 0.0～10 |
| Phase transfer agent | 0.0-30 |
| Organic amines | 0.0～10 |
| Surface active agent | 0.0～5.0 |
The tungstate refers to sodium tungstate and hydrates thereof, and ammonium paratungstate and hydrates thereof;
said molybdic acidThe salt is sodium molybdate and hydrate thereof, and ammonium heptamolybdate and hydrate thereof; the inorganic metal salt includes: sulfate, nitrate, hydrochloride and the like, and the structural general formula is as follows: am (BOx) n.yH 2 O, (where A = Al, cr, mn, fe, co, ni, cu, zn; B = S, N, cl; m, N, x, y =0,1,2,3,4 …);
the polyols include: triol ligands such as tris (hydroxymethyl) aminomethane and tris (hydroxymethyl) ethane, pentaerythritol, and the like;
the phase transfer agent includes: tetrabutylammonium bromide, tetramethylammonium bromide, potassium chloride, cesium chloride, barium chloride, and the like;
the organic amines include: alkylamine R-NH2 (R = alkanes such as ethylamino and propylamine and derivative groups thereof), polyacrylamide, amine resin, and aromatic amine Ar-NH2 (Ar = aromatic groups such as phenyl, biphenyl, styryl, and anilino)
The surfactant includes: polyvinylpyrrolidone (PVP), cetyltrimethylammonium bromide (CTAB), polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer (PEO-PPO-PEO), alkylsulfonic acid salts, and the like.
The inorganic acid includes nitric acid, sulfuric acid, hydrochloric acid, etc.
The materials selected in the following preparation steps include, but are not limited to, one or more mixtures of the above various types of components.
A method for preparing a polyacid-based photochromic material comprises the following steps:
(1) Firstly, mixing and dissolving tungstate or molybdate in deionized water, heating to boil, and continuously heating and stirring to completely dissolve the tungstate or molybdate;
(2) Dissolving inorganic metal salt in deionized water, then adding the solution, adjusting the pH value by using a proper amount of inorganic acid, controlling the pH value to be between 1 and 7, continuously heating and stirring, obtaining a polyacid crude product after a period of time, mixing the polyacid crude product with a polyol ligand, heating and refluxing for a period of time, filtering, changing cations, and recrystallizing for multiple times to obtain a high-purity polyacid product (the purity is crucial to the performance of a subsequent photochromic material);
(3) Taking a proper amount of polyacid, organic amine and surfactant, adding deionized water and a proper amount of inorganic acid, stirring and mixing uniformly, standing for a period of time, collecting a target product (which can be powder or can be prepared into a film sample), and drying to obtain the target product.
Wherein the tungstate, molybdate, inorganic metal salt, inorganic acid, polyalcohol ligand, phase transfer agent, organic amine and surfactant are the same as those selected from the polyacid-based photochromic material.
The components involved in the steps are different, and the color-changing performance is different. If different inorganic metal salts are used, polyacid color-changing materials with different colors can be obtained. When chromium nitrate is used as the inorganic metal salt, a pink to green color-changing material can be obtained, and when cobalt sulfate is used, a green to yellowish brown color-changing material can be obtained.
Example 1:
the polyacid-based photochromic material will be exemplified as a film sample. The film sample was prepared according to the following composition ratios. The specific operation steps are as follows:
| components | Mass part (%) |
| (NH4)6Mo7O24·4H2O | 12 |
| Cr(NO3)3·9H2O | 6 |
| Sulfuric acid | 1 |
| Pentaerythritol | 2 |
| Tetrabutylammonium bromide | 10 |
| Polyacrylamide | 5 |
| Polyvinylpyrrolidone | 1 |
Firstly, ammonium heptamolybdate (NH 4) 6Mo7O 24.4H 2O (abbreviated as Mo 7) is dissolved in 80mL of deionized water, heated to boiling, and continuously heated and stirred to be completely dissolved. Dissolving Cr (NO 3) 3.9H 2O in 20mL of deionized water, adding into the solution, adjusting pH value by adding sulfuric acid, controlling pH to be about =3, continuing heating and stirring, and separating after a period of time to obtain a polyacid crude product. The crude polyacid product and pentaerythritol are heated and refluxed for 12 hours, filtered and recrystallized to obtain pink stable Anderson polyacid crystal product ((NH 4) 3{ [ OHC (CH 2O) 3] -CrMo6O18 (OH) 3}, which is named as CrMo6 compound 1 for short). Pink powder product (compound 1, about 8 g) was obtained by room temperature drying. Weighing polyacrylamide, polyvinylpyrrolidone, tetrabutylammonium bromide (TBAB) and the obtained compound 1, uniformly mixing, adding 100mL of deionized water, uniformly mixing and dispersing to form a uniform mixed solution, smearing the mixed solution on tinplate to form a film, and drying at room temperature.
1.1 the photochromic performance comparison experiment of the polyacid-based photochromic material and the materials prepared by other polyacid compounds can refer to the following design comparison experiment:
1.2 comparative examples of different inorganic metal salts:
for Cr centered Anderson type polyacid (compound 1), we call it CrMo6 for short, and for other transition metal heteroatoms (such as Fe, co, ni, cu, etc.) Anderson type polyacid we name FeMo6, coMo6, niMo6 and CuMo6. The comparative properties were as follows:
Claims (2)
1. a polyacid-based photochromic material, characterized by: the method for preparing the polyacid-based photochromic material comprises the following steps,
(1) Firstly, mixing and dissolving molybdate in deionized water, heating to boil, and continuously heating and stirring to completely dissolve the molybdate;
(2) Dissolving inorganic metal salt in deionized water, adding the solution, adjusting the pH value by using inorganic acid, controlling the pH value to be 1~7, continuously heating and stirring to obtain a crude polyacid product, mixing the crude polyacid product with a polyol ligand, heating and refluxing, filtering, changing cations, and recrystallizing for multiple times to obtain a high-purity polyacid product;
(3) Adding deionized water and a proper amount of inorganic acid into polyacid, organic amine and surfactant, stirring and mixing uniformly, standing, collecting a target product, and drying to obtain the polyacid-based photochromic material;
the polyacid-based photochromic material comprises the following components in percentage by mass: 0.0-30% of molybdate, 0.0-10% of inorganic metal salt, 0.0-10% of inorganic acid, 0.0-10% of polyalcohol ligand, 0.0-30% of phase transfer agent, 0.0-10% of organic amine and 0.0-5% of surfactant; the mass percentage of each component is not 0.0;
the molybdate is ammonium heptamolybdate and a hydrate thereof;
the inorganic metal salt is nitrate, and the metal of the inorganic metal salt is one of Cr, fe, co, ni and Cu;
the polyalcohol is pentaerythritol;
the phase transfer agent is tetrabutylammonium bromide;
the organic amine is polyacrylamide;
the surfactant is polyvinylpyrrolidone (PVP);
the inorganic acid is sulfuric acid.
2. A method for preparing the polyacid-based photochromic material of claim 1, comprising the steps of,
(1) Firstly, mixing and dissolving molybdate in deionized water, heating to boil, and continuously heating and stirring to completely dissolve the molybdate;
(2) Dissolving inorganic metal salt in deionized water, then adding the deionized water into the solution, adjusting the pH value by using inorganic acid, controlling the pH value to be between pH =1~7, continuously heating and stirring to obtain a polyacid crude product, mixing the polyacid crude product with a polyol ligand, heating and refluxing, filtering, changing cations, and recrystallizing for multiple times to obtain a high-purity polyacid product;
(3) And adding deionized water and a proper amount of inorganic acid into the polyacid, the organic amine and the surfactant, stirring and mixing uniformly, standing, collecting a target product, and drying to obtain the polyacid-based photochromic material.
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| CN115594855A (en) * | 2021-06-28 | 2023-01-13 | 中国石油化工股份有限公司（Cn） | Photochromic polyester, polyester fiber and preparation method |
| CN114350345B (en) * | 2021-12-16 | 2023-08-18 | 华南理工大学 | Inorganic-organic hybrid photoelectrochromic material and preparation method and application thereof |
| CN116004225B (en) * | 2022-11-04 | 2024-04-02 | 山东第一医科大学(山东省医学科学院) | Preparation method of single-side amino modified alpha-Anderson polyacid modified ZnAgInS quantum dot |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1566259A (en) * | 2003-07-09 | 2005-01-19 | 中国科学院化学研究所 | Method for producing photochromic composite film and the product thereby |
| CN102977879A (en) * | 2012-12-03 | 2013-03-20 | 北京化工大学 | Polyacid-based photochromic supermolecule self-assembled material constructed by covalent bonds |
| CN104818653A (en) * | 2015-04-09 | 2015-08-05 | 李冠纯 | Ultraviolet photochromic repeatedly usable paper |
| CN109422244A (en) * | 2017-08-21 | 2019-03-05 | 中国科学技术大学 | Can ultraviolet blocking-up photochromic nano material and its preparation method and application |
-
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1566259A (en) * | 2003-07-09 | 2005-01-19 | 中国科学院化学研究所 | Method for producing photochromic composite film and the product thereby |
| CN102977879A (en) * | 2012-12-03 | 2013-03-20 | 北京化工大学 | Polyacid-based photochromic supermolecule self-assembled material constructed by covalent bonds |
| CN104818653A (en) * | 2015-04-09 | 2015-08-05 | 李冠纯 | Ultraviolet photochromic repeatedly usable paper |
| CN109422244A (en) * | 2017-08-21 | 2019-03-05 | 中国科学技术大学 | Can ultraviolet blocking-up photochromic nano material and its preparation method and application |
Non-Patent Citations (1)
| Title |
|---|
| "A series of unprecedented triol-stabilized [H3MW6O24]n-: the missing piece between A- and B-type Anderson-Evans polyoxometalates";Qi Li et al.,;《Chem. Commun.》;20180102;第54卷;第1375-1378页&支持信息 * |
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