CN112048920B - Textile capable of quickly and automatically purifying chemical warfare agent simulants and preparation method thereof - Google Patents
Textile capable of quickly and automatically purifying chemical warfare agent simulants and preparation method thereof Download PDFInfo
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
- D06N3/12—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/223—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material containing metals, e.g. organo-metallic compounds, coordination complexes
- B01J20/226—Coordination polymers, e.g. metal-organic frameworks [MOF], zeolitic imidazolate frameworks [ZIF]
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/26—Synthetic macromolecular compounds
- B01J20/261—Synthetic macromolecular compounds obtained by reactions only involving carbon to carbon unsaturated bonds
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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
- 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
- D06M13/152—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 having a hydroxy group bound to a carbon atom of a six-membered aromatic ring
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- 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
- D06M13/50—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with organometallic compounds; with organic compounds containing boron, silicon, selenium or tellurium atoms
- D06M13/51—Compounds with at least one carbon-metal or carbon-boron, carbon-silicon, carbon-selenium, or carbon-tellurium bond
- D06M13/513—Compounds with at least one carbon-metal or carbon-boron, carbon-silicon, carbon-selenium, or carbon-tellurium bond with at least one carbon-silicon bond
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- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
- D06N3/0002—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the substrate
- D06N3/0011—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the substrate using non-woven fabrics
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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
- D06M2101/16—Synthetic fibres, other than mineral fibres
- D06M2101/18—Synthetic fibres consisting of macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D06M2101/20—Polyalkenes, polymers or copolymers of compounds with alkenyl groups bonded to aromatic groups
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- 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
- D06M2101/16—Synthetic fibres, other than mineral fibres
- D06M2101/18—Synthetic fibres consisting of macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D06M2101/22—Polymers or copolymers of halogenated mono-olefins
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
- Y02P70/62—Manufacturing or production processes characterised by the final manufactured product related technologies for production or treatment of textile or flexible materials or products thereof, including footwear
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Abstract
The invention discloses a textile for quickly and automatically purifying chemical warfare agent simulants and a preparation method thereof. The non-woven fabric modified by the polyphenol hybrid coating is obtained by immersing the non-woven fabric into a mixed solution containing a polyphenol compound and 3-aminopropyltriethoxysilane; drying the fabric, and then soaking the fabric into a solution containing zirconium tetrachloride and an organic ligand to carry out hydrothermal reaction, so that a zirconium-based metal organic framework compound generated by the reaction is loaded on the surface of the non-woven fabric modified by the polyphenol hybrid coating, and the textile of the rapid self-purification chemical warfare agent simulant is obtained. Through the mode, the prepared textile can keep the excellent adsorption capacity and catalytic property of the zirconium-based metal organic framework compound, has high degradation rate, short half-life period and high conversion rate on chemical warfare agent mimics, and can be recycled after self-purification; and the preparation process is simple, the reaction condition is mild, the used materials are all economical and easily obtained, and the method is suitable for industrial large-scale production and has wide application prospect.
Description
Technical Field
The invention relates to the technical field of textiles, in particular to a textile for quickly and automatically purifying chemical warfare agent mimics and a preparation method thereof.
Background
Chemical warfare agents are chemical substances used for warfare purposes, which are highly toxic and capable of poisoning or killing enemy animals and plants on a large scale, and which, whether accidentally or intentionally issued, pose a serious threat to humans and the environment. At present, defense against chemical warfare agents is mainly performed by utilizing adsorptivity of activated carbon-based filter media. However, these filter media often suffer from secondary emissions after saturation, low long-term activation capacity, and the like, and such filter media do not autonomously degrade chemical warfare agents and require additional means for their purification. Therefore, there is a need to develop a high performance biochemical protective textile capable of rapidly adsorbing and self-purifying chemical warfare agents under environmental conditions to protect human health and life safety.
In recent years, metal organic framework materials have been increasingly used in the degradation of chemical warfare agents. Among these, zirconium-based metal organic framework compounds have been shown to have excellent reactivity towards degradation of organophosphate chemical warfare agent mimics. However, the use of metal organic framework compound powder alone tends to deposit in the form of particles on the bottom of the reaction vessel, which limits its application in chemical warfare agent treatment to some extent. In order to expand the application of metal organic framework compounds in chemical warfare agent filtration, protective clothing and the like, particles of the metal organic framework compounds need to be attached to polymer fibers, but how to integrate the metal organic framework compounds into textiles and retain the functions of crystallinity, adsorbability, reactivity and the like is an important challenge faced by current researchers.
The patent with the publication number of CN111188196A provides preparation and application of a graphene composite fiber non-woven fabric for catalyzing and degrading a neurochemical warfare agent. According to the patent, graphene fibers are used as a carrier, and metal organic framework compound nanoparticles are grown on the surface of the graphene fibers with excellent photothermal conversion efficiency in situ through a solvothermal technology, so that the graphene composite fiber non-woven fabric with a rapid digestion effect is formed. However, the method needs graphene with high cost, and the graphene is prepared into partially reduced graphene oxide fiber non-woven fabric, so that the whole process is complex, the requirement on reaction conditions is high, the requirement on actual industrial production is difficult to meet, and the application of the graphene is limited.
In view of the above, there is still a need for a simpler and more versatile method for loading metal organic framework compounds on the fiber surface to prepare textiles capable of fast self-cleaning chemical warfare agent mimics, so as to solve the above problems.
Disclosure of Invention
In view of the above-mentioned drawbacks of the prior art, the present invention provides a textile for fast self-cleaning chemical warfare agent simulants and a method for preparing the same. The non-woven fabric modified by the polyphenol hybrid coating is prepared by soaking the non-woven fabric into a solution containing a polyphenol compound and 3-aminopropyltriethoxysilane, so that rich nucleation sites are provided for a zirconium-based metal organic framework compound; and then, a zirconium-based metal organic framework compound is grown in situ on the surface of the non-woven fabric modified by the polyphenol hybrid coating by utilizing a solvothermal technology, so that the prepared textile is loaded with the zirconium-based metal organic framework compound, and simultaneously retains the functions of crystallinity, adsorptivity, reactivity and the like, thereby achieving the effect of quickly and automatically purifying the chemical warfare agent simulant by a simple method.
In order to achieve the aim, the invention provides a textile for quickly and automatically purifying chemical warfare agent mimics, which comprises a textile substrate and zirconium-based metal organic framework compound particles loaded on the surface of the textile substrate; the textile base material is non-woven fabric modified by a polyphenol hybrid coating; the polyphenol hybrid coating is formed by reacting polyphenol compounds and 3-aminopropyltriethoxysilane in a solution.
Further, the polyphenol compound is one of tannic acid or gallic acid.
Further, the zirconium-based metal organic framework compound is UiO-66-NH 2 One of UiO-66 or UiO-67.
Further, the non-woven fabric is one of polypropylene non-woven fabric, polytetrafluoroethylene non-woven fabric or polyvinylidene fluoride non-woven fabric.
In order to realize the aim, the invention also provides a preparation method of the textile for the rapid self-purification chemical warfare agent simulant, which comprises the following steps:
s1, respectively preparing a polyphenol compound solution and a 3-aminopropyltriethoxysilane solution with preset concentrations, and then uniformly mixing the solutions to obtain a mixed solution;
s2, dipping the non-woven fabric into the mixed solution obtained in the step S1, taking out after oscillation reaction in constant-temperature water bath, washing and drying to obtain the non-woven fabric modified by the polyphenol hybrid coating;
s3, soaking the non-woven fabric modified by the polyphenol hybrid coating obtained in the step S2 into an acetone solution containing zirconium tetrachloride and organic ligands, ultrasonically dissolving, carrying out hydrothermal reaction, and taking out, so that the zirconium-based metal organic framework compound generated by the reaction is loaded on the surface of the non-woven fabric modified by the polyphenol hybrid coating; after washing and drying, the textile of the rapid self-purification chemical warfare agent simulant is obtained.
Further, in step S1, the polyphenol compound solution is formed by dissolving polyphenol compounds in a tris (hydroxymethyl) aminomethane-hydrochloric acid buffer solution with a pH of 8.0-9.5, and the concentration is 2-4 g/L; the 3-aminopropyltriethoxysilane solution is formed by dissolving 3-aminopropyltriethoxysilane in absolute ethyl alcohol, and the concentration is 8-12 g/L.
Further, in step S1, the mass ratio of the polyphenol compound to the 3-aminopropyltriethoxysilane in the mixed solution is (1-2): (0.8-1.2).
Further, in step S2, the temperature of the oscillating reaction process of the thermostatic waterbath is 30-37 ℃, the oscillating time is 10-12 h, and the oscillating speed is 300-500 r/min.
Further, in step S3, the ratio of the amounts of the zirconium tetrachloride to the organic ligand is 1 (1-2); the organic ligand is one of 2-amino terephthalic acid, terephthalic acid or biphenyl dicarboxylic acid.
Further, in step S3, the reaction temperature of the hydrothermal reaction is 80-90 ℃ and the reaction time is 20-28 h.
Compared with the prior art, the invention has the beneficial effects that:
1. according to the invention, the non-woven fabric is firstly soaked into a solution containing a polyphenol compound and 3-aminopropyltriethoxysilane, so that the non-woven fabric modified by a polyphenol hybrid coating is prepared, and abundant nucleation sites are provided for a zirconium-based metal organic framework compound; and then, a zirconium-based metal organic framework compound is grown in situ on the surface of the non-woven fabric modified by the polyphenol hybrid coating by utilizing a solvothermal technology, so that the prepared textile is loaded with the zirconium-based metal organic framework compound, and simultaneously retains the functions of crystallinity, adsorptivity, reactivity and the like, thereby achieving the effect of quickly and automatically purifying the chemical warfare agent simulant by a simple method.
2. According to the invention, by preparing a mixed solution containing a polyphenol compound and 3-aminopropyltriethoxysilane, and immersing the non-woven fabric into the mixed solution by adopting a water phase immersion method, a firm polyphenol hybrid coating can be formed on the surface of the non-woven fabric by utilizing the synergistic effect between the polyphenol compound and the 3-aminopropyltriethoxysilane. During the water phase impregnation process, the polyphenol compounds in the mixed solution can be quickly adhered to the surface of the non-woven fabric by utilizing the excellent adhesive property; the 3-aminopropyltriethoxysilane in the mixed solution generates hydrolysis reaction in the solution, and the hydrolysis product and the polyphenol oxidation product adhered to the non-woven fabric are subjected to covalent reaction through Michael addition and Schiff base to form a polyphenol hybrid coating with rough surface and strong adhesion, thereby providing a foundation for uniformly and stably adhering the zirconium-based metal organic framework compound. In addition, benzene rings and hydroxyl active groups in the polyphenol hybrid coating can improve the physical and chemical properties of the surface of the textile, so that the polyphenol hybrid coating has a wider application range and higher application value.
3. According to the invention, the non-woven fabric modified by the polyphenol hybrid coating is immersed in the solution containing zirconium tetrachloride and organic ligands, and subjected to hydrothermal reaction, so that the zirconium-based metal organic framework compound can be generated in situ on the surface of the non-woven fabric modified by the polyphenol hybrid coating by utilizing a solvothermal technology. The polyphenol hybrid coating modified on the surface of the non-woven fabric has strong adhesiveness to the surface of a material, has a chelating effect on metal ions, and also has rich polyhydroxy groups, so that rich nucleation sites can be provided for heterogeneous nucleation of a zirconium-based metal organic framework compound on the surface of a fiber, and the in-situ generated zirconium-based metal organic framework compound is promoted to be uniformly, stably and firmly attached to the surface of the fiber; meanwhile, the process does not influence the performance of the zirconium-based metal organic framework compound, and can keep the original crystallinity, adsorptivity and reactivity, so that the textile prepared by the method achieves the effect of self-purifying chemical warfare agent mimics by utilizing the degradation effect of the zirconium-based metal organic framework compound on the organophosphorus chemical warfare agent mimics.
4. The textile of the rapid self-purification chemical warfare agent simulant provided by the invention reserves the excellent adsorption capacity and catalytic property of the zirconium-based metal organic framework compound, can rapidly degrade the chemical warfare agent simulant, has short half-life period and high conversion rate, can be recycled after self-purification, and has higher application value. Meanwhile, the textile has the advantages of simple preparation process, mild reaction conditions, economy and easy obtainment of used materials, suitability for industrial large-scale production and wide application prospect.
Drawings
FIG. 1 is a scanning electron micrograph of a textile of a rapid self-cleaning chemical warfare agent simulant prepared according to example 1 of the present invention;
FIG. 2 is a XRD characterization of a textile of a rapid self-cleaning chemical warfare agent mimic made in accordance with example 1 of the present invention;
FIG. 3 is a graph showing the change in the degradation conversion rate of dimethyl 4-nitrophenyl phosphate in a textile for rapid self-cleaning chemical warfare agent mimics made in example 1 of the present invention.
Detailed Description
The following detailed description of the preferred embodiments of the present invention, taken in conjunction with the accompanying drawings, will make the advantages and features of the invention easier to understand by those skilled in the art, and thus will clearly and clearly define the scope of the invention. It is to be understood that the described embodiments are merely a few embodiments of the invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments of the present invention without any inventive step, are within the scope of the present invention.
The invention provides a textile for quickly and automatically purifying chemical warfare agent mimics, which comprises a textile substrate and zirconium-based metal organic framework compound particles loaded on the surface of the textile substrate; the textile base material is non-woven fabric modified by a polyphenol hybrid coating; the polyphenol hybrid coating is formed by reacting polyphenol compounds and 3-aminopropyltriethoxysilane in a solution.
The polyphenol compound is one of tannic acid or gallic acid.
The zirconium-based metal organic framework compound is UiO-66-NH 2 One of UiO-66 or UiO-67.
The non-woven fabric is one of polypropylene non-woven fabric, polytetrafluoroethylene non-woven fabric or polyvinylidene fluoride non-woven fabric.
The invention also provides a preparation method of the textile for the rapid self-purification chemical warfare agent simulant, which comprises the following steps:
s1, respectively preparing a polyphenol compound solution and a 3-aminopropyltriethoxysilane solution with predetermined concentrations, and then uniformly mixing the solutions to obtain a mixed solution;
s2, dipping the non-woven fabric into the mixed solution obtained in the step S1, taking out after oscillation reaction in constant-temperature water bath, washing and drying to obtain the non-woven fabric modified by the polyphenol hybrid coating;
s3, soaking the non-woven fabric modified by the polyphenol hybrid coating obtained in the step S2 into an acetone solution containing zirconium tetrachloride and organic ligands, ultrasonically dissolving, carrying out hydrothermal reaction, and taking out, so that the zirconium-based metal organic framework compound generated by the reaction is loaded on the surface of the non-woven fabric modified by the polyphenol hybrid coating; after washing and drying, the textile of the rapid self-purification chemical warfare agent simulant is obtained.
In step S1, the polyphenol compound solution is formed by dissolving polyphenol compounds in a trihydroxymethyl aminomethane-hydrochloric acid buffer solution with the pH value of 8.0-9.5, and the concentration is 2-4 g/L; the 3-aminopropyltriethoxysilane solution is formed by dissolving 3-aminopropyltriethoxysilane in absolute ethyl alcohol, and the concentration is 8-12 g/L.
In step S1, the mass ratio of the polyphenol compound to the 3-aminopropyltriethoxysilane in the mixed solution is (1-2): 0.8-1.2.
In step S2, the temperature of the constant temperature water bath oscillation reaction process is 30-37 ℃, the oscillation time is 10-12 h, and the oscillation speed is 300-500 r/min.
In step S3, the mass ratio of the zirconium tetrachloride to the organic ligand is 1 (1-2); the organic ligand is one of 2-amino terephthalic acid, terephthalic acid or biphenyl dicarboxylic acid.
In step S3, the reaction temperature of the hydrothermal reaction is 80-90 ℃, and the reaction time is 20-28 h.
The textile of the rapid self-cleaning chemical warfare agent simulant and the method for making the same provided by the present invention are illustrated by the following specific examples.
Example 1
The embodiment provides a preparation method of a textile for rapidly self-purifying a chemical warfare agent simulant, which comprises the following steps:
s1, dissolving 0.04g of Tannic Acid (TA) in 20mL of trihydroxymethyl aminomethane-hydrochloric acid buffer solution with the pH value of 8.5 to prepare 2g/L of tannic acid solution; then 0.04g of 3-Aminopropyltriethoxysilane (APTES) is dissolved in 4mL of absolute ethyl alcohol to prepare 10g/L of 3-aminopropyltriethoxysilane solution; uniformly mixing the two solutions to obtain a mixed solution; the mass ratio of tannic acid to 3-aminopropyltriethoxysilane in the mixed solution is 1: 1.
S2, soaking 0.2g of polypropylene (PP) non-woven fabric subjected to ethanol ultrasonic washing in the mixed solution obtained in the step S1 at a bath ratio of 1:100, and oscillating in a constant-temperature water bath at 30 ℃ and an oscillation speed of 300r/min for 12 hours; and taking out the non-woven fabric, washing the non-woven fabric for 3 times by using deionized water and absolute ethyl alcohol in sequence, and drying the non-woven fabric in an oven at the temperature of 60 ℃ for 10 hours to obtain the polypropylene non-woven fabric modified by the tannin hybrid coating (T-A).
S3, dipping the polypropylene non-woven fabric modified by the tannin hybrid coating (T-A) obtained in the step S2 in 20mL of acetone solution containing 0.34mmol of zirconium tetrachloride and 0.34mmol of 2-aminoterephthalic acid; after ultrasonic dissolution, the reaction mixed solution is put into a reaction kettle, and after hydrothermal reaction is carried out for 24 hours at 85 ℃, a zirconium-based metal organic framework compound UiO-66-NH is generated in situ on the surface of the polypropylene non-woven fabric 2 (ii) a Taking out the non-woven fabric, ultrasonically washing the non-woven fabric for 5 minutes by using acetone, and carrying out vacuum drying for 10 hours at the temperature of 40 ℃ to obtain the textile of the rapid self-purification chemical warfare agent simulant.
Scanning electron microscope tests were performed on the textiles of the rapid self-cleaning chemical warfare agent simulant prepared in this example, and the results are shown in fig. 1. As can be seen from FIG. 1, the textile fabric of the rapid self-cleaning chemical warfare agent simulant prepared in this example had its fiber surfaces covered with a rough tannin hybrid coating having also uniformly supported on its surface UiO-66-NH 2 Particles, indicating that the method provided in this example is capable of converting UiO-66-NH 2 Successfully loaded on the surface of the textile to achieve the effect of degrading chemical warfare agent mimics.
The XRD characterization results of the textile of the rapid self-decontaminating chemical warfare agent simulant prepared in this example are shown in fig. 2. In FIG. 2, PP @ T-A @ MOF is the t mutextile sample prepared in this mutexample, and it can be seen from its X-ray diffraction pattern that the sample has UiO-66-NH at the same time 2 Characteristic peaks of the Powder and Polypropylene (PP) indicating that this example successfully converts UiO-66-NH 2 Supported in a polypropylene non-woven fabric and retains UiO-66-NH 2 Original crystallinity and absorptionAttachment and reactivity to ensure that the textile article of the rapid self-decontamination chemical warfare agent mimic prepared in this example is capable of exhibiting rapid self-decontamination properties.
To examine the cleaning effect of the textile for fast self-cleaning chemical warfare agent simulant prepared in this example on the chemical warfare agent simulant, taking the commonly used chemical warfare agent simulant, namely, dimethyl 4-nitrophenyl phosphate (DMNP), the change of the degradation conversion rate of the textile prepared in this example on dimethyl 4-nitrophenyl phosphate with time was measured, and the result is shown in fig. 3. As can be seen from FIG. 3, the PP @ T-A @ MOF t mutextile prepared in this mutexample has the same degradation effect on dimethyl 4-nitrophenylphosphate as the same amount of UiO-66-NH 2 The degradation effect is basically consistent, which shows that the method provided by the embodiment can ensure UiO-66-NH 2 The original degradation performance is simultaneously carried on textiles, so that the application of the textile in the fields of protective clothing, wearable sensors and the like is expanded.
According to the first-order kinetic model, the half-life period of the textile of the rapid self-purification chemical warfare agent simulant prepared by the embodiment for degrading the 4-nitrobenzene dimethyl phosphate is calculated to be 8.5min, and the half-life period is short, so that the textile prepared by the embodiment realizes rapid self-purification of the 4-nitrobenzene dimethyl phosphate and can meet the requirements of practical application.
Examples 2 to 6
Embodiments 2 to 6 respectively provide a method for preparing a textile for rapid self-purification of a chemical warfare agent simulant, which is different from embodiment 1 in that part of raw materials and corresponding parameters in the preparation process are adjusted, and the rest steps are the same as those in embodiment 1, and are not described herein again. The raw materials and the relevant process parameters for each example are shown in table 1.
TABLE 1 raw materials and related Process parameters corresponding to examples 2-6
The degradation performance of the textiles of the rapid self-purification chemical warfare agent mimics prepared in examples 2-6 on dimethyl 4-nitrophenylphosphate was tested, and the results are shown in table 2.
TABLE 2 degradation of textiles prepared in examples 2-6 on dimethyl 4-nitrophenylphosphate
| Examples | Half-life period (min) |
| Example 2 | 8.6 |
| Example 3 | 7.8 |
| Example 4 | 8.9 |
| Example 5 | 7.5 |
| Example 6 | 8.1 |
As can be seen from Table 2, the textiles of the rapid self-cleaning chemical warfare agent mimics prepared in examples 2-6 all have a short half-life. The preparation method of the textile for quickly self-purifying the chemical warfare agent simulant provided by the invention has the advantages that relevant parameters can be adjusted within a certain range according to actual needs, the influence on the degradation effect of the prepared textile is small, the flexibility is high in actual application, and the application range is wider.
It should be noted that the above examples are only some of the examples. Those skilled in the art will appreciate that the step S2 is usedThe non-woven fabric can be one of polypropylene non-woven fabric, polytetrafluoroethylene non-woven fabric or polyvinylidene fluoride non-woven fabric; the organic ligand used in step S3 may be one of 2-aminoterephthalic acid, terephthalic acid or biphenyldicarboxylic acid, and the prepared zirconium-based metal-organic framework compound may be UiO-66-NH based on the kind of the organic ligand 2 One of UiO-66 or UiO-67; the reaction temperature of the hydrothermal reaction in the step S3 can be adjusted between 80 ℃ and 90 ℃, and the reaction time can be adjusted between 20 h and 28h, which all belong to the protection scope of the invention.
Comparative examples 1 to 3
Comparative examples 1 to 3 respectively provide a method for preparing a textile, and compared with example 1, the difference is that in comparative example 1, only 2g/L of tannic acid solution is prepared in step S1, and 3-aminopropyltriethoxysilane is not added; comparative example 2 in step S1, only 10g/L of 3-aminopropyltriethoxysilane solution was prepared without tannic acid; comparative example 3 no steps S1 to S2 were performed, and the corresponding textile was prepared by simply dipping the polypropylene nonwoven fabric in an acetone solution containing zirconium tetrachloride and 2-aminoterephthalic acid according to step S3 and performing a hydrothermal reaction.
The degradation performance of the textiles prepared in comparative examples 1 to 3 on dimethyl 4-nitrophenylphosphate is shown in table 3.
Table 3 half-life period for degrading dimethyl 4-nitrophenylphosphate by textiles prepared in comparative examples 1 to 3
| Comparative example | Half-life period (min) |
| Comparative example 1 | 57 |
| Comparative example 2 | 97 |
| Comparative example 3 | 143 |
As can be seen from Table 3, the half-life of the textile obtained in comparative example 3 without the treatment of the phenol hybrid coating is much longer than that of comparative example 1, the corresponding textile obtained in comparative examples 1-2 by treating the polypropylene non-woven fabric with only tannic acid or 3-aminopropyltriethoxysilane and then performing hydrothermal reaction, and the half-life of the textile obtained in example 1 for degrading the 4-nitrophenyl dimethyl phosphate is much longer than that of the textile obtained in example 1. The method has the advantages that the effect of promoting the zirconium-based metal organic framework compound to be loaded on the surface of the fiber is not obvious enough when the polyphenol compound or the 3-aminopropyltriethoxysilane is used alone, and the two are used simultaneously, so that the loading capacity of the zirconium-based metal organic framework compound can be greatly improved by utilizing the synergistic effect of the two, the degradation performance of the prepared textile is obviously improved, and the effect of quickly and automatically purifying the chemical warfare agent simulant is achieved.
In conclusion, the non-woven fabric modified by the polyphenol hybrid coating is obtained by immersing the non-woven fabric into a mixed solution containing a polyphenol compound and 3-aminopropyltriethoxysilane; drying the fabric, and then soaking the fabric into a solution containing zirconium tetrachloride and an organic ligand to carry out hydrothermal reaction, so that a zirconium-based metal organic framework compound generated by the reaction is loaded on the surface of the non-woven fabric modified by the polyphenol hybrid coating, and the textile of the rapid self-purification chemical warfare agent simulant is obtained. Through the mode, the prepared textile can keep the excellent adsorption capacity and catalytic property of the zirconium-based metal organic framework compound, has high degradation rate, short half-life period and high conversion rate on chemical warfare agent mimics, and can be recycled after self-purification; and the preparation process is simple, the reaction condition is mild, the used materials are all economical and easily obtained, and the method is suitable for industrial large-scale production and has wide application prospect.
The above description is only for the purpose of illustrating the technical solutions of the present invention and is not intended to limit the same; although the present invention has been described in detail with reference to the foregoing embodiments, it should be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; all the equivalent structures or equivalent processes performed by using the contents of the specification and the drawings of the invention, or directly or indirectly applied to other related technical fields, are included in the scope of the present invention.
Claims (9)
1. A preparation method of a textile for rapidly self-purifying chemical warfare agent simulants is characterized by comprising the following steps: the textile of the rapid self-cleaning chemical warfare agent simulant comprises a textile substrate and zirconium-based metal organic framework compound particles loaded on the surface of the textile substrate; the textile base material is non-woven fabric modified by a polyphenol hybrid coating; the polyphenol hybrid coating is formed by reacting polyphenol compounds and 3-aminopropyltriethoxysilane in a solution;
the preparation method comprises the following steps:
s1, respectively preparing a polyphenol compound solution and a 3-aminopropyltriethoxysilane solution with preset concentrations, and then uniformly mixing the solutions to obtain a mixed solution;
s2, dipping the non-woven fabric into the mixed solution obtained in the step S1, taking out after oscillation reaction in constant-temperature water bath, washing and drying to obtain the non-woven fabric modified by the polyphenol hybrid coating;
s3, soaking the non-woven fabric modified by the polyphenol hybrid coating obtained in the step S2 into an acetone solution containing zirconium tetrachloride and organic ligands, ultrasonically dissolving, carrying out hydrothermal reaction, and taking out, so that the zirconium-based metal organic framework compound generated by the reaction is loaded on the surface of the non-woven fabric modified by the polyphenol hybrid coating; after washing and drying, the textile of the rapid self-purification chemical warfare agent simulant is obtained.
2. The method of claim 1 for making a textile for rapid self-decontamination of chemical warfare agent mimics, the method comprising: the polyphenol compound is one of tannic acid or gallic acid.
3. The method of claim 1 for making a textile for rapid self-decontamination of chemical warfare agent mimics, the method comprising: the zirconium-based metal organic framework compound is UiO-66-NH 2 One of UiO-66 or UiO-67.
4. The method for preparing a textile for rapidly self-purifying chemical warfare agent mimics according to any one of claims 1-3, comprising the steps of: the non-woven fabric is one of polypropylene non-woven fabric, polytetrafluoroethylene non-woven fabric or polyvinylidene fluoride non-woven fabric.
5. The method of claim 1 for making a textile for rapid self-decontamination of chemical warfare agent mimics, the method comprising: in step S1, the polyphenol compound solution is formed by dissolving polyphenol compounds in a trihydroxymethyl aminomethane-hydrochloric acid buffer solution with the pH value of 8.0-9.5, and the concentration is 2-4 g/L; the 3-aminopropyltriethoxysilane solution is formed by dissolving 3-aminopropyltriethoxysilane in absolute ethyl alcohol, and the concentration is 8-12 g/L.
6. The method of claim 1 for making a textile for rapid self-decontamination of chemical warfare agent mimics, the method comprising: in step S1, the mass ratio of the polyphenol compound to the 3-aminopropyltriethoxysilane in the mixed solution is (1-2): 0.8-1.2.
7. The method of claim 1 for making a textile for rapid self-decontamination of chemical warfare agent mimics, the method comprising: in step S2, the temperature of the oscillating reaction process of the thermostatic waterbath is 30-37 ℃, the oscillating time is 10-12 h, and the oscillating speed is 300-500 r/min.
8. The method of claim 1 for making a textile for rapid self-decontamination of chemical warfare agent mimics, the method comprising: in step S3, the mass ratio of the zirconium tetrachloride to the organic ligand is 1 (1-2); the organic ligand is one of 2-amino terephthalic acid, terephthalic acid or biphenyl dicarboxylic acid.
9. The method of claim 1 for making a textile for rapid self-decontamination of chemical warfare agent mimics, the method comprising: in step S3, the reaction temperature of the hydrothermal reaction is 80-90 ℃ and the reaction time is 20-28 h.
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| US7141518B2 (en) * | 2003-10-16 | 2006-11-28 | Kimberly-Clark Worldwide, Inc. | Durable charged particle coatings and materials |
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| TW201038510A (en) * | 2009-03-16 | 2010-11-01 | Molycorp Minerals Llc | Porous and durable ceramic filter monolith coated with a rare earth for removing contaminates from water |
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