CN107881791B - Fabric capable of changing color by fluorescence in different solvents and preparation method thereof - Google Patents
Fabric capable of changing color by fluorescence in different solvents and preparation method thereof Download PDFInfo
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- 239000004744 fabric Substances 0.000 title claims abstract description 123
- 239000002904 solvent Substances 0.000 title claims abstract description 51
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000012621 metal-organic framework Substances 0.000 claims abstract description 69
- 239000000463 material Substances 0.000 claims abstract description 51
- 239000000243 solution Substances 0.000 claims abstract description 47
- 238000004528 spin coating Methods 0.000 claims abstract description 35
- 238000000034 method Methods 0.000 claims abstract description 21
- 239000013105 nano metal-organic framework Substances 0.000 claims abstract description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 19
- 238000003756 stirring Methods 0.000 claims abstract description 13
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000013289 nano-metal-organic framework Substances 0.000 claims abstract description 12
- 239000002253 acid Substances 0.000 claims abstract description 10
- 239000002981 blocking agent Substances 0.000 claims abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims abstract description 10
- 239000011259 mixed solution Substances 0.000 claims abstract description 6
- 238000002845 discoloration Methods 0.000 claims abstract description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 36
- 238000001816 cooling Methods 0.000 claims description 20
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 10
- 229910052751 metal Inorganic materials 0.000 claims description 9
- 238000002791 soaking Methods 0.000 claims description 9
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric Acid Chemical compound [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 8
- 230000008859 change Effects 0.000 claims description 8
- 239000002184 metal Substances 0.000 claims description 8
- 239000002245 particle Substances 0.000 claims description 7
- 150000003839 salts Chemical class 0.000 claims description 7
- 239000004280 Sodium formate Substances 0.000 claims description 5
- HLBBKKJFGFRGMU-UHFFFAOYSA-M sodium formate Chemical compound [Na+].[O-]C=O HLBBKKJFGFRGMU-UHFFFAOYSA-M 0.000 claims description 5
- 235000019254 sodium formate Nutrition 0.000 claims description 5
- ZNCPFRVNHGOPAG-UHFFFAOYSA-L sodium oxalate Chemical compound [Na+].[Na+].[O-]C(=O)C([O-])=O ZNCPFRVNHGOPAG-UHFFFAOYSA-L 0.000 claims description 5
- 229940039790 sodium oxalate Drugs 0.000 claims description 5
- 229910052802 copper Inorganic materials 0.000 claims description 4
- 229910052749 magnesium Inorganic materials 0.000 claims description 4
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- 230000008569 process Effects 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000004140 cleaning Methods 0.000 claims 1
- 238000001035 drying Methods 0.000 claims 1
- 238000005406 washing Methods 0.000 abstract description 11
- 229910052723 transition metal Inorganic materials 0.000 abstract description 3
- -1 transition metal salt Chemical class 0.000 abstract description 3
- 239000008367 deionised water Substances 0.000 description 16
- 229910021641 deionized water Inorganic materials 0.000 description 16
- OYFRNYNHAZOYNF-UHFFFAOYSA-N 2,5-dihydroxyterephthalic acid Chemical compound OC(=O)C1=CC(O)=C(C(O)=O)C=C1O OYFRNYNHAZOYNF-UHFFFAOYSA-N 0.000 description 14
- 239000003446 ligand Substances 0.000 description 10
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 8
- 238000001914 filtration Methods 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 6
- 238000011160 research Methods 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- 239000011365 complex material Substances 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 239000002178 crystalline material Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000005281 excited state Effects 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- XTLJJHGQACAZMS-UHFFFAOYSA-N 4-oxo-1h-pyridine-2,6-dicarboxylic acid Chemical compound OC(=O)C1=CC(=O)C=C(C(O)=O)N1 XTLJJHGQACAZMS-UHFFFAOYSA-N 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000005283 ground state Effects 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 230000005389 magnetism Effects 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 239000013212 metal-organic material Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000013110 organic ligand Substances 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- WXMKPNITSTVMEF-UHFFFAOYSA-M sodium benzoate Chemical compound [Na+].[O-]C(=O)C1=CC=CC=C1 WXMKPNITSTVMEF-UHFFFAOYSA-M 0.000 description 1
- 239000004299 sodium benzoate Substances 0.000 description 1
- 235000010234 sodium benzoate Nutrition 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
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- 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
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/687—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing atoms other than phosphorus, silicon, sulfur, nitrogen, oxygen or carbon in the main chain
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/008—Supramolecular polymers
-
- 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
- D06M11/38—Oxides or hydroxides of elements of Groups 1 or 11 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
- D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
- D06M2200/50—Modified hand or grip properties; Softening compositions
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Chemical Or Physical Treatment Of Fibers (AREA)
- Coloring (AREA)
Abstract
The invention discloses a fluorescent color-changing fabric in different solvents, which is characterized in that: preparing a metal organic framework material into a solution by using DMF (dimethyl formamide), spin-coating the solution on a treated fabric by using a spin-coating method to prepare the fabric coated with the micro-nano metal organic framework material on the surface, wherein the fabric can perform fluorescence discoloration in different solvents; the preparation method of the metal organic framework comprises the following steps: stirring transition metal salt, polycarboxylic acid and a blocking agent to obtain a mixed solution, placing the mixed solution in a reaction container, and reacting by taking water as a medium to obtain the micro-nano metal organic framework material. The size of the metal organic framework material is controllable, and the prepared fluorescent color-changing fabric is soft in hand feeling, good in washing resistance and sensitive to the indicating performance of a solution.
Description
Technical Field
The invention relates to a color-variable fabric, in particular to a fluorescent color-variable fabric in different solvents and a preparation method thereof.
Background
Metal organic framework Materials (MOFs) are typically organic-inorganic molecular crystalline materials, which are multidimensional crystalline materials formed by assembling under appropriate conditions using metal ions or metal clusters as centers and small molecular organic ligands as bridging bodies through coordination between the metals and the ligands. In the last decade, metal-organic framework compounds as new research fields show unique physical and chemical properties and potential huge application value in many aspects such as magnetism, fluorescence, nonlinear optics, adsorption, separation, catalysis and hydrogen storage.
Although the research on the metal-organic framework structure complex material is more, the reports of the application of the metal-organic framework structure complex material in the textile field are less, mainly because the particle size and the hardness of the prepared metal-organic framework structure material in the prior report are larger, the hand feeling of the fabric is seriously influenced when the metal-organic framework structure material is finished on the fabric, and the metal-organic framework material with larger particle size is difficult to be firmly fixed on the fabric due to the structure of the metal-organic framework structure material. If a binder or the like is used to bond the MOFs to the fabric, the doping of the binder will inevitably affect the functionality of the MOFs material.
In the prior art, most of the researches on ligands and metal centers are carried out in the research on MOFs materials, but the researches and reports on the MOFs materials containing ligands of chromophore and chromophoric group are relatively less, and the MOFs materials containing the ligands can emit different fluorescence in solvents with different polarities, so that the MOFs materials have a certain indicating function on different solvents.
The invention aims to prepare an MOFs material, wherein the MOFs material can perform fluorescent color change in different solvents, and the MOFs material is arranged on the surface of a fabric to prepare the fabric which performs fluorescent color change in different solvents.
Disclosure of Invention
The invention aims to provide a fluorescent color-changing fabric in different solvents and a preparation method thereof, wherein the fabric can generate fluorescence of different colors in different solvents, has an indication effect on the solvents, and is soft in hand feeling and good in washing fastness.
In order to realize the purpose of the invention, the invention prepares the metal organic framework material capable of fluorescent color change in different solvents, and the specific steps are as follows:
stirring different amounts of transition metal salt, polycarboxylic acid and blocking agent to obtain a mixed solution, placing the mixed solution in a reaction vessel, and reacting by taking water as a medium to obtain the micro-nano metal organic framework Materials (MOFs).
The transition metal salt is one or two of Cu and Mg salts.
The Cu and Mg salts are one of sulfate or nitrate thereof.
In the step, the stirring time is 1-5h, the reaction vessel is a hydrothermal kettle, the reaction time is 48-72 h, and the reaction temperature is 100-150 ℃.
After the hydrothermal reaction is finished, cooling is carried out, wherein the cooling rate is 1-3 ℃ per hour.
Because the MOFs in the prior art has larger size, in the preparation process of the MOFs, the blocking agent is added to prevent the irregular coordination reaction of metal and organic materials in the metal-organic framework material, so that the particle size of the MOFs material can be obviously reduced.
The blocking agent is one or more of sodium formate, sodium acetate, sodium oxalate or sodium benzoate.
The particle size of the prepared MOFs material is less than 10 μm, preferably less than 1 μm, preferably less than 0.5 μm, and more preferably less than 0.1 μm.
The MOFs can fluoresce and discolor in different solvents.
As the polycarboxylic acid, a carboxylic acid having a hydroxyl group, preferably a polyhydroxycarboxylic acid, is selected.
The polyhydroxycarboxylic acid is one or more of 2, 3-dihydroxysuccinic acid, 2, 5-dihydroxyterephthalic acid, citric acid, 2-dihydroxy-1, 1-dinaphthylmethane-3, 3-dicarboxylic acid or 4-hydroxypyridine-2, 6-dicarboxylic acid.
The ligand of the metal organic framework material is selected from carboxylic acid containing hydroxyl, the ligand has chromophoric groups, the chromophoric mechanism is mainly based on the excited state intramolecular proton transfer theory, and specifically, after the ligand is transited from a ground state to an excited state under the action of light, the proton hydrogen on one group in the ligand molecule is transferred to the adjacent heteroatom of the ligand molecule through intramolecular hydrogen bonds, and the optical change process of the tautomer is generated. The present invention specifically selects carboxylic acids containing hydroxyl groups, wherein the proton donor is the hydroxyl group in the ligand. In different solvents, due to the different polarities of the solvents, proton transitions in the metal organic material are changed, so that the effect of generating fluorescence of different colors in different solvents is macroscopically shown.
The molar ratio of the metal salt, the polycarboxylic acid and the blocking agent in the reaction is 1: 1: 1 to 3.
The particle size of the metal organic framework can be controlled to a certain extent by controlling the dosage of the metal salt, the polycarboxylic acid and the blocking agent, and the dosage ratio set by the invention can ensure that the metal organic framework material is in a smaller particle size range.
The invention prepares a fluorescent color-changing fabric in different solvents, and the surface of the fabric is attached with a metal organic framework material which can carry out fluorescent color-changing in different solvents.
The organic frame material with fluorescent color change in different solvents is processed on the fabric by a spin coating method.
The invention provides a preparation method of a fluorescent color-changing fabric in different solvents, which is characterized by comprising the following steps:
preparing MOFs into solutions with different concentrations by using DMF, spin-coating the solutions onto the treated fabric by using a spin-coating method, and airing the fabrics at room temperature to prepare the fluorescent color-changing fabric with the surface coated with the micro-nano MOFs in different solvents.
When the MOFs material is finished on the fabric, no adhesive is used, and the hydroxyl and carboxyl existing on the metal organic framework material are mainly utilized, and the groups can generate hydrogen bonds with the hydroxyl on the fabric so as to be attached to the fabric.
The fabric further comprises a pretreatment step of removing impurities on the fabric, wherein the pretreatment step is to soak the fabric in a solution containing NaOH for 10-30 min, take out, clean and dry the fabric for later use.
The concentration of the sodium hydroxide solution is 0.5-5%.
During spin coating treatment, the concentration of the MOFs spin coating solution is 1mLDMF containing 10-30 mgMOFs.
The spin-coating speed is 1000-2000 rpm, the spin-coating time is 60s per time, and the spin-coating times are 1-10.
The metal organic framework material prepared by the method has the performance of fluorescent discoloration in solutions with different polarities, and can indicate the solutions; by adding the blocking agent and controlling the consumption of the raw materials, the size of the metal organic framework material can be effectively controlled, the metal organic framework material is conveniently finished on the fabric, and the soft hand feeling of the fabric is kept; the fluorescent color-changing fabric prepared by the invention in different solvents has excellent washing resistance, good hand feeling and sensitivity to solution indication.
Drawings
FIG. 1 is a scanning electron micrograph of a fabric prepared in example 1
DETAILED DESCRIPTION OF EMBODIMENT (S) OF INVENTION
Example 1
A preparation method of a fluorescent color-changing fabric in different solvents comprises the following steps:
(1) firstly, soaking the fabric in a 1% NaOH solution for 20min, taking out the fabric, washing the fabric with deionized water for multiple times, and airing the fabric at room temperature for later use;
(2) stirring 1mol of copper nitrate, 1mol of 2, 3-dihydroxysuccinic acid and 1mol of sodium formate for 1h, placing the mixture in a hydrothermal kettle, adding deionized water, carrying out hydrothermal reaction at 120 ℃ for 48h, cooling to room temperature at a cooling rate of 3 ℃/h to obtain micro-nano metal organic framework Materials (MOFs), and filtering and taking out the MOFs for later use;
(3) preparing a solution of MOFs with DMF (dimethyl formamide) with the concentration of 10mg/ml, spin-coating the solution on the treated fabric by a spin-coating method, and airing the fabric at room temperature to prepare the fluorescent color-changing fabric coated with the micro-nano MOFs on the surface in different solvents.
The prepared fabric is soft in hand feeling, and still has good indicating performance in different solutions after being washed for 10 times.
Example 2
A preparation method of a fluorescent color-changing fabric in different solvents comprises the following steps:
(1) firstly, soaking the fabric in a 1% NaOH solution for 20min, taking out the fabric, washing the fabric with deionized water for multiple times, and airing the fabric at room temperature for later use;
(2) stirring 0.5mol of copper nitrate, 0.5mol of magnesium nitrate, 1mol of 2, 3-dihydroxysuccinic acid and 1mol of sodium formate for 1h, placing the mixture in a hydrothermal kettle, adding deionized water, carrying out hydrothermal reaction at 120 ℃ for 48h, cooling to room temperature at the cooling rate of 3 ℃/h to obtain micro-nano metal organic framework Materials (MOFs), and filtering and taking out the MOFs for later use;
(3) preparing a solution of MOFs with DMF (dimethyl formamide) with the concentration of 10mg/ml, spin-coating the solution on the treated fabric by a spin-coating method, and airing the fabric at room temperature to prepare the fluorescent color-changing fabric coated with the micro-nano MOFs on the surface in different solvents.
The prepared fabric is soft in hand feeling, and still has good indicating performance in different solutions after being washed for 10 times.
Example 3
A preparation method of a fluorescent color-changing fabric in different solvents comprises the following steps:
(1) firstly, soaking the fabric in a 1% NaOH solution for 20min, taking out the fabric, washing the fabric with deionized water for multiple times, and airing the fabric at room temperature for later use;
(2) stirring 1mol of copper nitrate, 1mol of 2, 5-dihydroxy terephthalic acid and 1mol of sodium formate for 1h, placing the mixture in a hydrothermal kettle, adding deionized water, carrying out hydrothermal reaction at 120 ℃ for 48h, cooling to room temperature at a cooling rate of 3 ℃/h to obtain micro-nano metal organic framework Materials (MOFs), and filtering and taking out the materials for later use;
(3) preparing a solution of MOFs with DMF (dimethyl formamide) with the concentration of 10mg/ml, spin-coating the solution on the treated fabric by a spin-coating method, and airing the fabric at room temperature to prepare the fluorescent color-changing fabric coated with the micro-nano MOFs on the surface in different solvents.
The prepared fabric is soft in hand feeling, and still has good indicating performance in different solutions after being washed for 10 times.
Example 4
A preparation method of a fluorescent color-changing fabric in different solvents comprises the following steps:
(1) firstly, soaking the fabric in a 1% NaOH solution for 20min, taking out the fabric, washing the fabric with deionized water for multiple times, and airing the fabric at room temperature for later use;
(2) stirring 1mol of copper nitrate, 1mol of 2, 5-dihydroxyterephthalic acid and 1mol of sodium oxalate for 1 hour, placing the mixture into a hydrothermal kettle, adding deionized water, carrying out hydrothermal reaction at 120 ℃ for 48 hours, cooling to room temperature at a cooling rate of 3 ℃/h to obtain micro-nano metal organic framework Materials (MOFs), and filtering and taking out the materials for later use;
(3) preparing a solution of MOFs with DMF (dimethyl formamide) with the concentration of 10mg/ml, spin-coating the solution on the treated fabric by a spin-coating method, and airing the fabric at room temperature to prepare the fluorescent color-changing fabric coated with the micro-nano MOFs on the surface in different solvents.
The prepared fabric is soft in hand feeling, and still has good indicating performance in different solutions after being washed for 10 times.
Example 5
A preparation method of a fluorescent color-changing fabric in different solvents comprises the following steps:
(1) firstly, soaking the fabric in a 1% NaOH solution for 20min, taking out the fabric, washing the fabric with deionized water for multiple times, and airing the fabric at room temperature for later use;
(2) stirring 1mol of copper nitrate, 1mol of 2, 5-dihydroxyterephthalic acid and 2mol of sodium oxalate for 1 hour, placing the mixture into a hydrothermal kettle, adding deionized water, carrying out hydrothermal reaction at 120 ℃ for 48 hours, cooling to room temperature at a cooling rate of 3 ℃/h to obtain micro-nano metal organic framework Materials (MOFs), and filtering and taking out the materials for later use;
(3) preparing a solution of MOFs with DMF (dimethyl formamide) with the concentration of 10mg/ml, spin-coating the solution on the treated fabric by a spin-coating method, and airing the fabric at room temperature to prepare the fluorescent color-changing fabric coated with the micro-nano MOFs on the surface in different solvents.
The prepared fabric is soft in hand feeling, and still has good indicating performance in different solutions after being washed for 10 times.
Comparative example 1
A preparation method of a fluorescent color-changing fabric in different solvents comprises the following steps:
(1) firstly, soaking the fabric in a 1% NaOH solution for 20min, taking out the fabric, washing the fabric with deionized water for multiple times, and airing the fabric at room temperature for later use;
(2) stirring 1mol of copper nitrate and 1mol of 2, 5-dihydroxy terephthalic acid for 1h, placing the mixture in a hydrothermal kettle, adding deionized water, carrying out hydrothermal reaction at 120 ℃ for 48h, cooling to room temperature at a cooling rate of 3 ℃/h to obtain metal organic framework Materials (MOFs), filtering and taking out the MOFs for later use;
(3) preparing a solution of MOFs with DMF (dimethyl formamide) with the concentration of 10mg/ml, spin-coating the solution on the treated fabric by a spin-coating method, and airing the fabric at room temperature to prepare the fluorescent color-changing fabric coated with the micro-nano MOFs on the surface in different solvents.
The fabric has poor hand feeling and rough surface, and has indicating performance in different solvents after being washed for 10 times, but the indicating performance is not obvious.
Comparative example 2
A preparation method of a fluorescent color-changing fabric in different solvents comprises the following steps:
(1) firstly, soaking the fabric in a 1% NaOH solution for 20min, taking out the fabric, washing the fabric with deionized water for multiple times, and airing the fabric at room temperature for later use;
(2) stirring 1mol of copper nitrate and 1mol of 2, 5-dihydroxy terephthalic acid for 1h, placing the mixture in a hydrothermal kettle, adding deionized water, carrying out hydrothermal reaction at 120 ℃ for 48h, cooling to room temperature at a cooling rate of 3 ℃/h to obtain metal organic framework Materials (MOFs), filtering and taking out the MOFs for later use;
(3) preparing MOFs into a solution with the concentration of 10mg/ml by using an adhesive, spin-coating the solution on the treated fabric by using a spin-coating method, and airing the treated fabric at room temperature to prepare the fluorescent color-changing fabric with the surface coated with the micro-nano MOFs in different solvents.
The fabric has poor hand feeling, stiffness and rough surface, has insensitive indicating performance and unobvious color change when not washed, and has indicating performance in different solvents after being washed for 10 times, but the indicating performance is unobvious.
Comparative example 3
A preparation method of a fluorescent color-changing fabric in different solvents comprises the following steps:
(1) firstly, soaking the fabric in a 1% NaOH solution for 20min, taking out the fabric, washing the fabric with deionized water for multiple times, and airing the fabric at room temperature for later use;
(2) stirring 1mol of copper nitrate, 1mol of 2, 5-dihydroxyterephthalic acid and 1mol of sodium oxalate for 1h, putting the mixture into a hydrothermal kettle, adding deionized water, carrying out hydrothermal reaction at 120 ℃ for 48h, cooling to room temperature at a cooling rate of 3 ℃/h to obtain micro-nano metal organic framework Materials (MOFs), and filtering and taking out the materials for later use;
(3) preparing MOFs into a solution with the concentration of 10mg/ml by using an adhesive, spin-coating the solution on the treated fabric by using a spin-coating method, and airing the treated fabric at room temperature to prepare the fluorescent color-changing fabric with the surface coated with the micro-nano MOFs in different solvents.
The fabric has poor hand feeling, stiffness and rough surface, has insensitive indicating performance and unobvious color change when not washed, and has indicating performance in different solvents after being washed for 10 times, but the indicating performance is unobvious.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, several changes, improvements and modifications can be made without departing from the spirit of the present invention, and these changes, improvements and modifications should also be construed as the protection scope of the present invention.
Claims (7)
1. A fabric capable of changing color by fluorescence in different solvents is characterized in that: preparing a metal organic framework material into solutions with different concentrations by using DMF (dimethyl formamide), spin-coating the solutions on a treated fabric by using a spin-coating method, and airing the fabric at room temperature to prepare the fabric coated with the micro-nano metal organic framework material on the surface, wherein the fabric can perform fluorescence discoloration in different solvents; the particle size of the metal organic framework material is less than 5 mu m; the preparation method of the metal organic framework comprises the following steps: stirring metal salt, polycarboxylic acid and a blocking agent to obtain a mixed solution, placing the mixed solution in a reaction container, and reacting by taking water as a medium to obtain a micro-nano metal organic framework material;
the metal salt is one or two of Cu and Mg, and the Cu and Mg are sulfate or nitrate;
the molar ratio of the metal salt, the polycarboxylic acid and the blocking agent in the reaction is 1: 1: 1-3;
the blocking agent is one or more of sodium formate and sodium oxalate;
the polycarboxylic acid is 2, 3-dihydroxysuccinic acid.
2. A fabric that fluoresces and changes color in different solvents according to claim 1, wherein: in the preparation method of the metal organic framework, the stirring time is 1-5h, the reaction vessel is a hydrothermal kettle, the reaction time is 48-72 h, and the reaction temperature is 100-150 ℃.
3. A fabric that fluoresces and changes color in different solvents according to any of claims 1-2, wherein: after the hydrothermal reaction is finished, cooling is carried out, wherein the cooling rate is 1-3 ℃ per hour.
4. A method for preparing a fabric with fluorescent color change in different solvents according to any one of claims 1 to 3, wherein the method comprises the following steps: preparing a solution of the metal organic framework material by DMF (dimethyl formamide), spin-coating the solution on the treated fabric by a spin coating method, and airing the fabric at room temperature to prepare the fluorescent color-changing fabric coated with the micro-nano metal organic framework material on the surface in different solvents.
5. A method of preparing a fabric that fluoresces and changes color in different solvents according to claim 4, wherein: the fabric comprises pretreatment, wherein the pretreatment comprises the steps of soaking the fabric in a solution containing sodium hydroxide, taking out, cleaning and drying.
6. A method of preparing a fabric that fluoresces and changes color in different solvents according to claim 5, wherein: the concentration of the sodium hydroxide solution is 0.5-5%, and the concentration of the spin coating solution of the metal organic framework material is 1mLDMF and contains 10-30 mg of the metal organic framework material.
7. A method of preparing a fabric that fluoresces and changes color in different solvents according to claim 4, wherein: the spin coating speed is 1000-2000 rpm, the spin coating time is 30-120s each time, and the spin coating times are 1-10 times in the spin coating process.
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