CN113089329B - Preparation method and application of intelligent fabric for information storage and hydrogen fluoride visual detection - Google Patents
Preparation method and application of intelligent fabric for information storage and hydrogen fluoride visual detection Download PDFInfo
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- CN113089329B CN113089329B CN202110368066.6A CN202110368066A CN113089329B CN 113089329 B CN113089329 B CN 113089329B CN 202110368066 A CN202110368066 A CN 202110368066A CN 113089329 B CN113089329 B CN 113089329B
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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
- D06M15/59—Polyamides; Polyimides
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/0007—Electro-spinning
- D01D5/0015—Electro-spinning characterised by the initial state of the material
- D01D5/003—Electro-spinning characterised by the initial state of the material the material being a polymer solution or dispersion
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/75—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated
- G01N21/77—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator
- G01N21/78—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator producing a change of colour
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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
- 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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Abstract
The invention discloses a preparation method and application of an intelligent fabric for information storage and hydrogen fluoride visual detection. The preparation method comprises the following steps: pretreating the fabric, preparing the azo-phenyl maleimide polymer into a polymer solution, spinning a layer of polymer on the surface of the pretreated fabric by utilizing electrostatic spinning, and taking down the fabric to obtain the orange intelligent fabric. The application of the intelligent fabric in information storage is as follows: the intelligent fabric is placed in an acid environment, and the intelligent fabric is changed from orange to orange-red; and placing the intelligent fabric after the color change in an alkaline environment, wherein the intelligent fabric is changed from orange red to orange. The fabric prepared by the method disclosed by the invention is developed under acid stimulation and recovered reversibly under alkali stimulation, so that reversible circulation of patterning is realized; the method can also be used for the visual detection of the hydrogen fluoride gas, and has important basic significance for the development of fluorine chemical industry.
Description
Technical Field
The invention relates to the technical field of reversible response materials, in particular to a preparation method and application of an intelligent fabric for information storage and hydrogen fluoride visual detection.
Background
In recent years, Reversible Response Materials (RRMs) have played an important role in the fields of rewritable media, encryption, sensors, security printing, etc., which can reveal the effect of external stimuli on vision. Especially rewritable media in the information field, offer new possibilities for reducing the burden of paper consumption, given the dangerous environmental and sustainable problems of billions of tons of paper consumption per year. However, due to the complexity of preparation and high cost, the development is limited in practical production.
Recently, textile products have been widely used in the fields of oil-water separation, biomedicine, electronic equipment, sensors, artificial intelligence, and the like, by virtue of the characteristics of lightness, porosity, flexibility and low cost. In particular, smart fabric surfaces modified with functional materials have successfully made wearable electronics, response coatings, and wearable strain sensors.
It is well known that hydrogen fluoride is a considerable profit for fluorochemicals, however, hydrogen fluoride gas leakage can lead to severe skin and bone damage and even death. Therefore, timely detection of the HF container is of great significance to guarantee life safety and normal production. Therefore, there is a need for an intelligent fabric coating that not only achieves reversible information storage properties, but also provides rapid detection of hydrogen fluoride gas.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides the intelligent fabric for information storage and hydrogen fluoride visual detection and the preparation method thereof, and has great significance and prospect for developing information storage materials and hydrogen fluoride visual sensing fields.
The invention is realized by the following technical scheme:
in a first aspect of the present invention, a method for preparing an intelligent fabric for information storage and hydrogen fluoride visual detection is provided, which comprises the following steps:
pretreating the fabric, preparing the azo-phenyl maleimide polymer into a polymer solution, spinning a layer of polymer on the surface of the pretreated fabric by utilizing electrostatic spinning, and taking down the fabric to obtain the orange intelligent fabric.
Preferably, the pretreatment is ultrasonic washing of the fabric with deionized water for 10-20min, ultrasonic washing of the fabric with countless ethanol for 10-20min, ultrasonic washing of the fabric with acetone for 10-20min, taking out of the fabric and drying in an oven at 60-100 ℃ for 1-6 h.
Preferably, the copolymer solution is prepared by mixing an azophenylmaleimide polymer and a solvent; the solvent is chloroform, N-dimethylformamide, N-dimethylacetamide, dimethyl sulfoxide or 1, 4-dioxane; the mass ratio of the azophenyl maleimide polymer to the solvent is 1: (10-100).
Preferably, the distance between the electrostatic spinning machine and the pretreated fabric is 10-40 cm; the relative humidity of air is 20-40%.
Preferably, the spinning time is 3-10 h, the spinning voltage is 15-20kV, and the flow rate of the spinning solution is 0.01-0.21 mL/h.
In a second aspect of the invention, the intelligent fabric prepared by the preparation method is provided.
The third aspect of the invention provides an application of the intelligent fabric in information storage, wherein the intelligent fabric is placed in an acid environment, and the intelligent fabric is changed from orange to orange-red; and placing the intelligent fabric after color change in an alkaline environment, wherein the intelligent fabric is changed from orange red to orange.
The application of the intelligent fabric prepared by the invention in HF visual detection is also within the protection scope of the invention.
In some fluorine chemical enterprises, a plurality of hydrogen fluoride storage tanks are separately stored, and like a timing bomb, serious damage can be caused once leakage occurs, so that the timely detection of the storage tanks is of great significance.
Preferably, the acidic environment is an environment containing acidic vapor or acidic liquid, both selected from trifluoroacetic acid, hydrogen fluoride or acetic acid; the alkaline environment is an environment containing alkaline steam or alkaline liquid, and the alkaline steam or the alkaline liquid is selected from triethylamine, ammonia water or ethylenediamine.
Preferably, the contact distance between the acidic liquid or the acidic steam and the intelligent fabric is 0-20cm, and the contact time is 5-20 s; the contact distance between the alkaline steam or the alkaline liquid and the intelligent fabric is 0-30cm, and the contact time is 10-30 s.
Preferably, the intelligent fabric realizes reversible color circulation through alternate acid-base stimulation, and the circulation frequency is 5-50 times.
The invention has the beneficial effects that:
according to the invention, the azo-phenyl maleimide polymer with acid-base responsiveness is successfully spun on the surface of the fabric through an electrostatic spinning technology, the reversible coating which develops color under acid stimulation and recovers under alkali stimulation is obtained under acid-base stimulation, a patterned reversible cycle test is realized, and multiple cycle tests prove that the intelligent coating has excellent cycle stability. In addition, the hydrogen fluoride gas stimulates the fabric, so that the rapid color reaction is realized, the method can be used for the visual detection of the hydrogen fluoride gas, and has important basic significance for the development of fluorine chemical industry.
Drawings
FIG. 1 is a SEM analysis of the surface of the coated fabric of example 1 before it is spun;
FIG. 2 is a SEM analysis of the surface of the coated fabric of example 1 after spinning;
FIG. 3 is a SEM analysis of the surface of the coating of the fabric in the comparative example;
FIG. 4 is an infrared analysis of the fabric of example 1 before and after spinning;
FIG. 5 is a pattern analysis of the fabric after spinning of example 2 under TFA stimulation;
FIG. 6 is a photograph of a large-scale smart fabric;
FIG. 7 is a photograph of the fabric after spinning in example 3 for rapid detection of hydrogen fluoride.
Detailed Description
It should be noted that the following detailed description is exemplary and is intended to provide further explanation of the disclosure. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs.
In order to make the technical solutions of the present application more clearly understood by those skilled in the art, the technical solutions of the present application will be described in detail below with reference to specific embodiments. If the experimental conditions not specified in the examples are specified, the conditions are generally conventional or recommended by the reagent company; reagents, consumables, and the like used in the following examples are commercially available unless otherwise specified.
Example 1
The white cotton cloth was treated as follows: ultrasonically washing with deionized water for 15min, ultrasonically washing with ethanol for 15min, ultrasonically washing with acetone for 5min, taking out, and oven drying at 80 deg.C for 3.5 h.
Azophenylmaleimide was reacted with a solvent at a molar ratio of 1 g: 55g of the polymer solution is prepared, and the solvent is dimethyl sulfoxide.
The single-shaft electrostatic spinning equipment is adopted for spinning, and the electrostatic spinning device consists of a high-voltage power supply, an extrusion injection device and a receiving device. The spinning solution was filled into a syringe having a volume of 2.5mL and an inner diameter of the syringe needle of 0.24 mm. The positive pole of the high-voltage power supply is connected with the needle head, and the receiving plate is connected with the ground wire. The spinning voltage was 16kV, the flow rate of the spinning solution was 0.11mL/h, the acceptance distance was 15cm, and the indoor relative humidity was 30%. And (3) drying the prepared intelligent fabric in an oven at 100 ℃ to completely volatilize the solvent.
The smart fabric prepared in example 1 was subjected to SEM scanning and infrared examination, and as shown in fig. 1, the fabric consisted of 10-20 μm fibers before spinning, and had a number of depressed structures on the fiber surface. As shown in fig. 2, the original recessed structure of the surface of the obtained electrospun fabric was filled with the polymer, resulting in a smooth fabric coating. As shown in FIG. 4, the fabric before electrospinning had a large number of hydroxyl groups, and the peak position was particularly 3260cm-1When coated with the azophenylmaleimide polymer, hydroxyl groups on the fabric surface are covered, and thus the peak strength of hydroxyl groups on the surface of the resulting smart fabric is weakened, thus showing that the polymer is successfully spun on the fabric surface by electrospinning.
Example 2
The white cotton cloth was treated as follows: ultrasonically washing with deionized water for 20min, ultrasonically washing with countless ethanol for 10min, ultrasonically washing with acetone for 20min, taking out, and oven drying at 60 deg.C for 6 h.
Azophenylmaleimide was reacted with a solvent at a molar ratio of 1 g: 100g of the polymer solution was prepared, and the solvent was chloroform.
The spinning solution was filled into a syringe having a volume of 2.5mL and an inner diameter of the syringe needle of 0.24 mm. The positive pole of the high-voltage power supply is connected with the needle head, and the receiving plate is connected with the ground wire. The spinning voltage was 18kV, the dope flow rate was 0.1mL/h, the acceptance distance was 18cm, and the indoor relative humidity was 28%. And (3) drying the prepared intelligent fabric in an oven at 80 ℃ to completely volatilize the solvent.
Example 3
The white cotton cloth was treated as follows: ultrasonically washing with deionized water for 10min, ultrasonically washing with countless ethanol for 20min, ultrasonically washing with acetone for 10min, taking out, and oven drying at 100 deg.C for 6 h.
Azophenylmaleimide was reacted with a solvent at a molar ratio of 1 g: 10g of the polymer solution is prepared, and the solvent is N, N-dimethylformamide.
The spinning solution was filled into a syringe having a volume of 2.5mL and an inner diameter of the syringe needle of 0.24 mm. The positive pole of the high-voltage power supply is connected with the needle head, and the receiving plate is connected with the ground wire. The spinning voltage was 17kV, the dope flow rate was 0.12mL/h, the acceptance distance was 15cm, and the indoor relative humidity was 38%. The prepared intelligent fabric is placed in an oven at 110 ℃ for drying, so that the solvent is completely volatilized.
Comparative example
The white cotton cloth was treated as follows: ultrasonically washing with deionized water for 15min, ultrasonically washing with ethanol for 15min, ultrasonically washing with acetone for 5min, taking out, and oven drying at 80 deg.C for 3.5 h.
Azophenylmaleimide was reacted with a solvent at a molar ratio of 1 g: 55g of the polymer solution was prepared, and the solvent was tetrahydrofuran.
And (3) dip-dyeing the treated fabric in a polymer solution, starting ultrasound for 40min in the dip-dyeing process to enable the polymer to be uniformly adhered to the surface of the fabric, obtaining an orange fabric after the ultrasound is finished, and drying the orange fabric in a drying oven for later use, wherein the drying temperature is 75 ℃ and the drying time is 6 h.
As shown in fig. 3, which is SEM analysis of the fabric after padding, it can be seen that the fabric obtained by padding is rough and uneven, and blocks the space around the fibers, which may block the steam passage upon TFA stimulation, resulting in liquefied accumulation of steam in the fabric, affecting patterning.
Application example 1
Preparation of patterning (information storage): the intelligent fabric prepared in example 2 was bonded to a hollow material using a hollow material with tiger, trifluoroacetic acid vapor was protonated on the surface of the hollow fabric, resulting in rapid color change, and a fabric having the pattern shown in fig. 5 was obtained, which was rapidly recovered upon stimulation with organic alkali vapor.
As shown in fig. 5, under TFA stimulation, the orange intelligent fabric is contacted with acid vapor by using the pattern provided by the hollow material, so that proton conversion occurs rapidly, and the intelligent fabric prepared in example 2 has a clear tiger pattern with orange-red color.
Application example 2
Visual detection of hydrogen fluoride: under the stimulation of hydrogen fluoride (the stimulation reaction time of the hydrogen fluoride is 3-10s), the intelligent fabric coating prepared in example 3 can be rapidly changed into orange red, the rapid detection of the hydrogen fluoride is realized, the intelligent fabric coating can be rapidly changed from the orange red into the orange under the stimulation of organic alkali, and the intelligent fabric coating has excellent reversible cyclicity.
The hydrogen fluoride gas visual sensing coating is constructed as shown in fig. 7, orange fabric can be rapidly changed into orange red under the stimulation of hydrogen fluoride, the rapid detection of the hydrogen fluoride is realized, the orange fabric can be rapidly changed into orange from orange red under the stimulation of organic alkali, the reversible cyclicity is excellent, and the cycle frequency is 5-50 times through verification.
The above description is only a preferred embodiment of the present application and is not intended to limit the present application, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, improvement and the like made within the spirit and principle of the present application shall be included in the protection scope of the present application.
Claims (8)
1. A preparation method of intelligent fabric for information storage and hydrogen fluoride visual detection is characterized by comprising the following steps:
pretreating the fabric, preparing an azophenyl maleimide polymer into a polymer solution, and spinning the polymer solution on the surface of the pretreated fabric by utilizing electrostatic spinning to obtain an orange intelligent fabric;
the pretreatment comprises the steps of ultrasonically washing the fabric for 10-20min by using deionized water, ultrasonically washing the fabric for 10-20min by using countless ethanol, ultrasonically washing the fabric for 10-20min by using acetone, taking out the fabric, and drying the fabric in an oven at the drying temperature of 60-100 ℃ for 1-6 h;
the polymer solution is prepared by mixing an azophenyl maleimide polymer and a solvent; the solvent is chloroform, N-dimethylformamide, N-dimethylacetamide, dimethyl sulfoxide or 1, 4-dioxane; the mass ratio of the azophenyl maleimide polymer to the solvent is 1: (10-100).
2. The method according to claim 1, wherein the distance between the electrospinning spinning machine and the pretreated fabric is 10-40 cm; the relative humidity of air is 20-40%.
3. The preparation method of claim 1, wherein the spinning time is 3-10 h, the spinning voltage is 15-20kV, and the flow rate of the spinning solution is 0.01-0.21 mL/h.
4. The intelligent fabric prepared by the preparation method of any one of claims 1 to 3.
5. The use of the smart fabric of claim 4 in information storage, wherein the smart fabric is exposed to an acidic environment, and the smart fabric changes from orange to red-orange; and placing the intelligent fabric after color change in an alkaline environment, wherein the intelligent fabric is changed from orange red to orange.
6. Use according to claim 5, wherein the acidic environment is an environment containing an acidic vapour or an acidic liquid, each selected from trifluoroacetic acid, hydrogen fluoride or acetic acid; the alkaline environment is an environment containing alkaline steam or alkaline liquid, and the alkaline steam or the alkaline liquid is selected from triethylamine, ammonia water or ethylenediamine.
7. Use according to claim 6, wherein the contact distance of the acidic liquid or acidic vapour with the smart fabric is 0-20cm and the contact time is 5-20 s; the contact distance between the alkaline steam or the alkaline liquid and the intelligent fabric is 0-30cm, and the contact time is 10-30 s.
8. The use of claim 5, wherein the intelligent fabric is subjected to color reversible cycling through alternate acid-base stimulation, wherein the number of cycling is 5-50.
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| CN110054731B (en) * | 2019-05-10 | 2021-01-05 | 济南大学 | Preparation method of reversible acid-base discoloration maleimide copolymer |
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