CN111270512B - Multi-tungsten-oxygen-cluster functionalized reversible color-changing cotton fabric and preparation method thereof - Google Patents
Multi-tungsten-oxygen-cluster functionalized reversible color-changing cotton fabric and preparation method thereof Download PDFInfo
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- 239000004744 fabric Substances 0.000 title claims abstract description 60
- 229920000742 Cotton Polymers 0.000 title claims abstract description 58
- 230000002441 reversible effect Effects 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 238000004519 manufacturing process Methods 0.000 title claims description 3
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 23
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 20
- 239000001301 oxygen Substances 0.000 claims abstract description 20
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 19
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 16
- 239000010937 tungsten Substances 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 9
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 33
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 30
- 239000000243 solution Substances 0.000 claims description 26
- 238000003756 stirring Methods 0.000 claims description 19
- 239000011259 mixed solution Substances 0.000 claims description 18
- -1 rare earth ion Chemical class 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- 239000002243 precursor Substances 0.000 claims description 13
- 238000002791 soaking Methods 0.000 claims description 13
- 238000005406 washing Methods 0.000 claims description 13
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 claims description 10
- 229910001379 sodium hypophosphite Inorganic materials 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 7
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- 238000001704 evaporation Methods 0.000 claims description 7
- 150000002500 ions Chemical class 0.000 claims description 7
- 238000005096 rolling process Methods 0.000 claims description 7
- 238000007605 air drying Methods 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 3
- 230000008020 evaporation Effects 0.000 claims description 3
- 238000004321 preservation Methods 0.000 claims description 3
- 239000011734 sodium Substances 0.000 claims description 3
- 239000000835 fiber Substances 0.000 abstract description 7
- 239000004753 textile Substances 0.000 abstract description 5
- 238000011161 development Methods 0.000 abstract description 3
- 238000011065 in-situ storage Methods 0.000 abstract description 3
- 230000008569 process Effects 0.000 abstract description 3
- 125000002843 carboxylic acid group Chemical group 0.000 abstract description 2
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 abstract description 2
- 229910001930 tungsten oxide Inorganic materials 0.000 abstract description 2
- 239000000463 material Substances 0.000 description 7
- 150000001450 anions Chemical class 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 150000001735 carboxylic acids Chemical class 0.000 description 3
- 229920002678 cellulose Polymers 0.000 description 3
- 239000001913 cellulose Substances 0.000 description 3
- 125000004430 oxygen atom Chemical group O* 0.000 description 3
- 150000002910 rare earth metals Chemical class 0.000 description 3
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 238000004134 energy conservation Methods 0.000 description 2
- 239000008103 glucose Substances 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 229920000447 polyanionic polymer Polymers 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 229910002370 SrTiO3 Inorganic materials 0.000 description 1
- 125000003172 aldehyde group Chemical group 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- DMLAVOWQYNRWNQ-UHFFFAOYSA-N azobenzene Chemical class C1=CC=CC=C1N=NC1=CC=CC=C1 DMLAVOWQYNRWNQ-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000010041 electrostatic spinning Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000002657 fibrous material Substances 0.000 description 1
- 125000002791 glucosyl group Chemical group C1([C@H](O)[C@@H](O)[C@H](O)[C@H](O1)CO)* 0.000 description 1
- 150000004676 glycans Chemical class 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 229920002521 macromolecule Polymers 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
- 239000013110 organic ligand Substances 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 150000005324 oxide salts Chemical class 0.000 description 1
- VVRQVWSVLMGPRN-UHFFFAOYSA-N oxotungsten Chemical compound [W]=O VVRQVWSVLMGPRN-UHFFFAOYSA-N 0.000 description 1
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical compound O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/10—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
- D06M13/144—Alcohols; Metal alcoholates
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/07—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with halogens; with halogen acids or salts thereof; with oxides or oxyacids of halogens or salts thereof
- D06M11/11—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with halogens; with halogen acids or salts thereof; with oxides or oxyacids of halogens or salts thereof with halogen acids or salts thereof
- D06M11/17—Halides of elements of Groups 3 or 13 of the Periodic Table
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/32—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond
- D06M11/36—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond with oxides, hydroxides or mixed oxides; with salts derived from anions with an amphoteric element-oxygen bond
- D06M11/48—Oxides or hydroxides of chromium, molybdenum or tungsten; Chromates; Dichromates; Molybdates; Tungstates
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/68—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with phosphorus or compounds thereof, e.g. with chlorophosphonic acid or salts thereof
- D06M11/70—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with phosphorus or compounds thereof, e.g. with chlorophosphonic acid or salts thereof with oxides of phosphorus; with hypophosphorous, phosphorous or phosphoric acids or their salts
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/10—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
- D06M13/184—Carboxylic acids; Anhydrides, halides or salts thereof
- D06M13/207—Substituted carboxylic acids, e.g. by hydroxy or keto groups; Anhydrides, halides or salts thereof
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/02—Natural fibres, other than mineral fibres
- D06M2101/04—Vegetal fibres
- D06M2101/06—Vegetal fibres cellulosic
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- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Chemical Or Physical Treatment Of Fibers (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
Abstract
The invention belongs to the technical field of textiles and discloses a multi-tungsten oxygen cluster functionalized reversible color-changing cotton fabric and a preparation method thereof. The poly tungstate is organically combined with carboxylic acid groups on the cotton cloth, so that the poly tungsten oxide cluster-rare earth carboxylic acid derivative directly grows in situ on the fibers during preparation, the process flow is simplified, the poly tungstate is directly synthesized on the fibers, the poly tungstate is more tightly combined with the fibers, and the prepared reversible color-changing cotton fabric has photochromic and thermochromic properties and can be applied to functional fabric development.
Description
Technical Field
The invention relates to the technical field of textiles, in particular to a multi-tungsten oxygen cluster functionalized reversible color-changing cotton fabric and a preparation method thereof.
Background
Cotton fabric is a natural fiber material which is widely applied in the field of textile materials, but with the increasing maturity of the traditional textile industry, the research of the textile industry is developed to multifunctional fabrics. Photo/thermochromic behaviour can be achieved, for example, by treating cotton fibres. At present, the fiber color-changing material is inorganic and organic, and the inorganic material is mainly SrTiO3However, the material is slower in color development and color dissipation. The organic materials include azobenzene derivatives, spiropyran derivatives and the like, but the materials are greatly influenced by the environment. And the method mainly adopts an electrostatic spinning technology, which is not beneficial to energy conservation and environmental protection.
The polyacid anion is a polyanion with a definite structure, and oxygen atoms on the surface of the polyacid anion have strong coordination and bonding capabilities, so that the polyacid anion is favorable for realizing the design and the assembly of molecules and becomes an important inorganic building unit for building molecules and materials with various structures and excellent performance. Carboxylic acids have flexible and variable coordination modes and are always regarded as an important organic ligand for synthesizing organic-inorganic hybrid compounds with novel structures. The polyacid anion can be condensed with carboxylic acid ligand to form hybrid material with double advantages of organic matter and inorganic matter.
Polytungstate heteropoly blue PredIs easy to regenerate and is a good precursor of reversible color-changing materials, based on the methodThe polyacid precursor and the carboxylic acid modified cotton fabric are combined through chemical bonds to prepare the reversible color-changing cotton fabric, and the method is simple, has low requirements on the environment, and meets the requirements of energy conservation and emission reduction in China at present.
Disclosure of Invention
The invention aims to provide a multi-tungsten-oxygen cluster functionalized reversible color-changing cotton fabric and a preparation method thereof.
In order to solve the technical problems, the invention provides a preparation method of a multi-tungsten oxygen cluster functionalized reversible color-changing cotton fabric, which comprises the following steps:
1) soaking cotton fabric in ethanol to remove surface attachments, washing with water, and air drying;
2) dissolving citric acid and sodium hypophosphite in deionized water to obtain a mixed solution;
3) placing the cotton fabric obtained by the treatment in the step 1) into the mixed solution, soaking twice and rolling twice, and then washing and airing;
4) putting the cotton fabric obtained by the treatment of the step 3) into a rare earth ion solution with the molar concentration of 0.004-0.06 mol/L, adding a poly tungstate precursor under the condition of vigorous stirring, adjusting the pH to 2-7 by using a sodium hydroxide solution, then carrying out heat preservation stirring for 1-3 h at the temperature of 50-70 ℃, taking out the cotton fabric, cooling to room temperature, and carrying out evaporation drying to obtain the multi-tungsten oxygen cluster functionalized reversible color-changing cotton fabric, wherein the molar ratio of the poly tungstate precursor to the rare earth ions is 1: 1-3;
the precursor of the poly tungstate is K7[PW11O39]·12H2O、Na8H[A-α-AsW9O34]·11H2O、K6[α-P2W18O62]·14H2O and K6[α-As2W18O62]·14H2And O is one of the compounds.
Preferably, in the mixed solution of step 2): the concentration of citric acid is 6-12 wt%, and the concentration of sodium hypophosphite is 2-10 wt%.
Preferably, the molar concentration of the rare earth ion solution in the step 4) is 0.015 mol/L.
Preferably, the rare earth ions in the rare earth ion solution in step 4) are selected from Eu3+Ions and Dy3+At least one of the ions.
Preferably, the concentration of the sodium hydroxide solution in the step 4) is 2-5 mol/L.
Preferably, the rotation speed of the vigorous stirring in the step 4) is the maximum stirring speed on the premise that the solution does not overflow.
The invention also provides the multi-tungsten oxygen cluster functionalized reversible color-changing cotton fabric prepared by the preparation method.
Compared with the prior art, the preparation method disclosed by the invention has the advantages that the poly tungstate is organically combined with the carboxylic acid groups on the cotton fabric, so that the poly tungsten oxide cluster-rare earth carboxylic acid derivative directly grows in situ on the fiber while being prepared, the process flow is simplified, the unnecessary resource waste is reduced, the poly tungstate is directly synthesized on the fiber, the poly tungstate is more tightly combined with the fiber, the prepared reversible color-changing cotton fabric has photochromic and thermochromic performances, and a foundation is laid for the development of a functional fabric in the future.
Detailed Description
For a further understanding of the invention, reference will now be made to the preferred embodiments of the present invention by way of example, and it is to be understood that the description is intended to further illustrate features and advantages of the present invention and is not intended to limit the scope of the claims which follow.
All of the starting materials of the present invention, without particular limitation as to their source, may be purchased commercially or prepared according to conventional methods well known to those skilled in the art.
The invention provides a preparation method of a multi-tungsten oxygen cluster functionalized reversible color-changing cotton fabric, which comprises the following steps:
1) soaking cotton fabric in ethanol to remove surface attachments, washing with water, and air drying;
2) dissolving citric acid and sodium hypophosphite in deionized water to obtain a mixed solution;
3) placing the cotton fabric obtained by the treatment in the step 1) into the mixed solution, soaking twice and rolling twice, and then washing and airing;
4) putting the cotton fabric obtained by the treatment of the step 3) into a rare earth ion solution with the molar concentration of 0.004-0.06 mol/L, adding a poly tungstate precursor under the condition of vigorous stirring, adjusting the pH to 2-7 by using a sodium hydroxide solution, then carrying out heat preservation stirring for 1-3 h at the temperature of 50-70 ℃, taking out the cotton fabric, cooling to room temperature, and carrying out evaporation drying to obtain the multi-tungsten oxygen cluster functionalized reversible color-changing cotton fabric, wherein the molar ratio of the poly tungstate precursor to the rare earth ions is 1: 1-3.
Specifically, the cotton fabric is soaked in ethanol to remove surface attachments, and then is washed and dried. And then dissolving citric acid and sodium hypophosphite in deionized water to obtain a mixed solution, putting the cotton fabric with the surface attachments removed into the mixed solution, soaking twice and rolling twice, and then washing and drying in the air. In the present invention, the concentration of citric acid in the mixed solution is preferably 6 to 12 wt%, more preferably 10 wt%, and the concentration of sodium hypophosphite is preferably 2 to 10 wt%, more preferably 5 wt%.
The main component of the cotton fabric is cellulose, the cellulose is macromolecular polysaccharide consisting of glucose, each glucose group has three relatively active hydroxyl groups, and through the oxidation reaction of an oxidant on the cellulose, three free hydroxyl groups at positions C2, C3 and C6 of a glucose residual ring and a potential aldehyde group at the tail end C1 of the macromolecule can be selectively oxidized into carboxyl. And the tungsten oxygen cluster polyanion in the polytungstic oxide salt can perform condensation reaction with oxygen atoms in carboxyl through the introduction of rare earth, thereby forming the stable polytungstic oxide cluster-rare earth carboxylic acid derivative. The method comprises the steps of putting the cotton fabric treated by the mixed solution containing citric acid and hypophosphorous acid into a rare earth ion solution with the molar concentration of 0.004-0.06 mol/L, more preferably into a rare earth ion solution with the molar concentration of 0.015mol/L, violently stirring, adding a poly tungstate precursor, adjusting the pH to 2-5 by using a sodium hydroxide solution, more preferably adjusting the pH to 3, heating to 50-70 ℃, keeping the temperature, stirring for 1-3 hours, and more preferably heating to 50-70 ℃, keeping the temperature, and stirring for 1-3 hoursAnd (3) heating to 60 ℃, keeping the temperature and stirring for 1h, finally taking out the cotton fabric, cooling to room temperature, evaporating and drying to obtain the multi-tungsten oxygen cluster functionalized reversible color-changing cotton fabric. In the process, the in-situ growth of the polyoxotungstate on the cotton fabric is realized, and the polyoxotungstate rare earth derivative is formed on the cotton fabric. In the invention, the molar ratio of the poly tungstate precursor to the rare earth ions is 1: 1-3, and the preferred rare earth ions in the rare earth ion solution are Eu3+Ions and Dy3+At least one of the ions, more preferably Eu3+Ions; the concentration of the adopted sodium hydroxide solution is preferably 2-5 mol/L, and more preferably 3 mol/L; the precursor of poly tungstate is selected from K7[PW11O39]·12H2O、Na8H[A-α-AsW9O34]·11H2O、K6[α-P2W18O62]·14H2O and K6[α-As2W18O62]·14H2One of O, preferably K7[PW11O39]·12H2O or K6[α-P2W18O62]·14H2And O. The rotation speed of vigorous stirring in the present invention is preferably the maximum stirring speed under the condition that the solution does not overflow.
The invention also provides the multi-tungsten oxygen cluster functionalized reversible color-changing cotton fabric prepared by the preparation method. When the multi-tungsten oxygen cluster rare earth derivative on the cotton fabric is stimulated by illumination or heating conditions, electrons on the multi-tungsten oxygen cluster are excited, and the electrons are transferred to adjacent W through oxygen atoms on the multi-tungsten oxygen cluster6+Let W be6+Reduction to W5+Therefore, the color change appears on the appearance of the cotton fabric, and when the cotton fabric is placed in the dark or cooled, the color can be reduced to the initial state, and the reversible photochromic and thermochromic performance is shown.
In order to further illustrate the invention, the following describes in detail a multi-tungsten oxygen cluster functionalized reversible color-changing cotton fabric and a preparation method thereof, which are provided by the invention, with reference to examples.
Example 1
(1) Soaking 5 x 5cm cotton fabric in ethanol, removing surface attachments, washing with water, and air drying.
(2) 10g of citric acid and 5g of sodium hypophosphite were dissolved in 85mL of deionized water to obtain a mixed solution.
(3) And (3) adding the cotton fabric obtained in the step (1) into the mixed solution obtained in the step (2), soaking twice and rolling twice, washing with water, and airing for later use.
(4) Placing the cotton fabric obtained in the step (3) into 40mL of EuCl with the molar concentration of 0.015mol/L3·6H2O solution, vigorously stirred and then added with 1.46g of K7[PW11O39]·12H2And O, adjusting the pH value to 3 by using a sodium hydroxide solution with the concentration of 3mol/L, stirring for 1h under the condition of keeping the temperature at 60 ℃, taking out, cooling to room temperature, and evaporating to dry to obtain the polytungstenic oxygen cluster functionalized reversible color-changing cotton fabric.
Example 2
(1) Soaking 5 x 5cm cotton fabric in ethanol, removing surface attachments, washing with water, and air drying.
(2) 10g of citric acid and 5g of sodium hypophosphite were dissolved in 85mL of deionized water to obtain a mixed solution.
(3) And (3) adding the cotton fabric obtained in the step (1) into the mixed solution obtained in the step (2), soaking twice and rolling twice, washing with water, and airing for later use.
(4) Placing the cotton fabric obtained in the step (3) into 40mL of EuCl with the molar concentration of 0.015mol/L3·6H2To the O solution, 2.23g of K are added vigorously6[α-P2W18O62]·14H2And O, adjusting the pH value to 3 by using a sodium hydroxide solution with the concentration of 3mol/L, stirring for 1h under the condition of keeping the temperature at 60 ℃, taking out, cooling to room temperature, and evaporating to dry to obtain the polytungstenic oxygen cluster functionalized reversible color-changing cotton fabric.
Example 3
(1) Soaking 5 x 5cm cotton fabric in ethanol, removing surface attachments, washing with water, and air drying.
(2) 10g of citric acid and 5g of sodium hypophosphite were dissolved in 85mL of deionized water to obtain a mixed solution.
(3) And (3) adding the cotton fabric obtained in the step (1) into the mixed solution obtained in the step (2), soaking twice and rolling twice, washing with water, and airing for later use.
(4) Mixing the cotton fabric obtained in the step (3) with 40mL of EuCl with the molar concentration of 0.015mol/L3·6H2The O solution is mixed, stirred vigorously and then 0.97g of K are added6[α-P2W18O62]·14H2And O, adjusting the pH value to 3 by using a sodium hydroxide solution with the concentration of 3mol/L, stirring for 1h under the condition of keeping the temperature at 60 ℃, taking out, cooling to room temperature, and evaporating to dry to obtain the polytungstenic oxygen cluster functionalized reversible color-changing cotton fabric.
While there have been shown and described what are at present considered the fundamental principles and essential features of the invention and its advantages, it will be apparent to those skilled in the art that the invention is not limited to the details of the foregoing exemplary embodiments, but is capable of other specific forms without departing from the spirit or essential characteristics thereof. The present embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein. Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (7)
1. A preparation method of a multi-tungsten oxygen cluster functionalized reversible color-changing cotton fabric is characterized by comprising the following steps:
1) soaking cotton fabric in ethanol to remove surface attachments, washing with water, and air drying;
2) dissolving citric acid and sodium hypophosphite in deionized water to obtain a mixed solution;
3) placing the cotton fabric obtained by the treatment in the step 1) into the mixed solution, soaking twice and rolling twice, and then washing and airing;
4) putting the cotton fabric obtained by the treatment of the step 3) into a rare earth ion solution with the molar concentration of 0.004-0.06 mol/L, adding a poly tungstate precursor under the condition of vigorous stirring, adjusting the pH to 2-7 by using a sodium hydroxide solution, then carrying out heat preservation stirring for 1-3 h at the temperature of 50-70 ℃, taking out the cotton fabric, cooling to room temperature, and carrying out evaporation drying to obtain the multi-tungsten oxygen cluster functionalized reversible color-changing cotton fabric, wherein the molar ratio of the poly tungstate precursor to the rare earth ions is 1: 1-3;
the precursor of the poly tungstate is K7[PW11O39]·12H2O、Na8H[A-α-AsW9O34]·11H2O、K6[α-P2W18O62]·14H2O and K6[α-As2W18O62]·14H2And O is one of the compounds.
2. The method according to claim 1, wherein, in the mixed solution of step 2): the concentration of citric acid is 6-12 wt%, and the concentration of sodium hypophosphite is 2-10 wt%.
3. The production method according to claim 1, wherein the molar concentration of the rare earth ion solution in step 4) is 0.015 mol/L.
4. The method according to claim 1, wherein the rare earth ions in the rare earth ion solution in step 4) are selected from Eu3+Ions and Dy3+At least one of the ions.
5. The preparation method according to claim 1, wherein the concentration of the sodium hydroxide solution in the step 4) is 2-5 mol/L.
6. The method according to claim 1, wherein the rotation speed of the vigorous stirring in the step 4) is a maximum stirring speed without overflowing the solution.
7. The multi-tungsten oxygen cluster functionalized reversible color-changing cotton fabric prepared by the preparation method according to any one of claims 1 to 6.
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