CN114214832B - Nanofiber material for protecting chemical weapon and preparation method and application thereof - Google Patents

Nanofiber material for protecting chemical weapon and preparation method and application thereof Download PDF

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CN114214832B
CN114214832B CN202111391733.9A CN202111391733A CN114214832B CN 114214832 B CN114214832 B CN 114214832B CN 202111391733 A CN202111391733 A CN 202111391733A CN 114214832 B CN114214832 B CN 114214832B
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nanofiber
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metal hydroxide
nanofiber material
hydroxide
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CN114214832A (en
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丁彬
郭竑宇
斯阳
廖亚龙
印霞
俞建勇
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Donghua University
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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
    • 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
    • D06M11/58—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 nitrogen or compounds thereof, e.g. with nitrides
    • D06M11/59—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 nitrogen or compounds thereof, e.g. with nitrides with ammonia; with complexes of organic amines with inorganic substances
    • D06M11/60—Ammonia as a gas or in solution
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
    • D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
    • 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
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/10—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
    • D06M13/144—Alcohols; Metal alcoholates

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Spinning Methods And Devices For Manufacturing Artificial Fibers (AREA)
  • Nonwoven Fabrics (AREA)
  • Artificial Filaments (AREA)
  • Chemical Or Physical Treatment Of Fibers (AREA)

Abstract

The invention relates to a nanofiber material for protecting a chemical weapon, a preparation method and application thereof, wherein the material is a multistage sheath-core structure fiber material, a core layer is a flexible metal hydroxide nanofiber, a sheath layer is a metal hydroxide buckling thin layer which vertically and uniformly grows around the core layer, the mass concentration of metal hydroxide in the material is more than or equal to 98%, and the molar content of metal hydroxide is 40% -80%. Compared with the prior art, the material has large specific surface area and a large number of surface active sites, has a degradation half-life of less than or equal to 5min for chemical weapons, can be used as an in-situ degradation type chemical protective material, can effectively avoid secondary pollution in the processes of decontamination and wearing and taking-off, can be singly used as a whole, can be used in combination with a base material and is good in flexibility and strength, easy to recycle, and the use bottleneck of the existing dispersion type degradation material is broken through.

Description

Nanofiber material for protecting chemical weapon and preparation method and application thereof
Technical Field
The invention belongs to the technical field of materials for chemical protection, and relates to a flexible metal hydroxide nanofiber material for chemical weapon protection, and a preparation method and application thereof.
Background
The chemical warfare agent has large toxicity, quick action and multiple poisoning routes. Therefore, strengthening the protection of chemical weapons during combat is a key to the life safety of the military and civilians.
The existing chemical weapon protective materials are mainly of an isolation type and an adsorption type, wherein the isolation type is generally made of airtight materials such as butyl rubber or double-sided coated rubberized fabric, for example, a new composite material of polyvinyl chloride and nitrile rubber (CN 107857906A) and a multilayer composite rubberized fabric for preventing chemical permeation and a preparation method thereof (CN 104404782A), and the materials can isolate chemical toxic agents in various forms, but have the defects of heavy equipment and poor heat and moisture comfort, and have very limited application fields and scenes; the adsorption type material mainly adopts porous materials such as active carbon, aerogel and the like as a core adsorption layer so as to complete rapid absorption of toxic chemical warfare agents, for example, a multifunctional breathable anti-poison garment fabric and a preparation method thereof (CN 107584824A), the material has good heat and humidity comfort, but the poison adsorption is a physical process, and the analysis of the poison is likely to be caused by the change of environmental temperature and humidity, so that secondary pollution is generated.
Therefore, the development of chemoprotective materials with in situ degradation of toxic chemical warfare agents is one of the important directions to solve the above problems.
Disclosure of Invention
The invention aims to provide a flexible metal hydroxide nanofiber material for protecting chemical weapons, and a preparation method and application thereof. In the invention, the nanofiber is a multistage sheath-core structure fiber material composed of whole metal hydroxide, the core layer is the metal hydroxide nanofiber, and the sheath layer is a metal hydroxide buckling thin layer vertically growing on the surface of the fiber. The material has high molar content of metal hydroxyl groups and large length-diameter ratio, has specific surface area and catalytic active sites which are in the same order of magnitude as those of micron/nano particle materials, and can realize the efficient degradation of various chemical warfare agents; meanwhile, the whole material is soft film-shaped, has certain mechanical strength, can be used independently, can also be used in combination with base materials such as non-woven fabrics and the like, and greatly widens the application field of metal hydroxide materials.
The aim of the invention can be achieved by the following technical scheme:
a nanofiber material for protecting chemical weapons is a multistage sheath-core structure fiber material (diameter is 50-800 nm), a core layer is a flexible metal hydroxide nanofiber, a skin layer is a metal hydroxide buckling thin layer, the thin layer vertically and uniformly grows around the core layer, the mass concentration of the metal hydroxide in the material is more than or equal to 98%, and the molar content of metal hydroxide groups is 40-80%.
Further, in the material, the multi-stage sheath-core structure fiberThe diameter of dimension is 100-1000nm, the length-diameter ratio is more than 1000, the softness is 10-200mN, the elastic modulus of single fiber is 2-60GPa, and the specific surface area is 50-1000m 2 /g。
A method for preparing a nanofiber material for protecting a chemical weapon, which comprises the following steps:
1) Dissolving an inorganic precursor in a solvent (stirring for 10-30 min), then adding a coordination protective agent, and fully stirring to obtain ligand-protected low-branching degree linear inorganic sol;
2) Controlling the hydrolysis and polycondensation of the inorganic precursor to prepare linear inorganic spinning sol with high polymerization degree and low branching degree;
3) Under the condition that the relative humidity is 30% -32%, carrying out continuous spinning on the linear inorganic spinning sol to obtain gel nanofiber;
4) Performing alcoholysis reaction on the gel nanofiber, and then cleaning and drying to obtain a flexible metal hydroxide nanofiber material;
5) And carrying out ultrasonic auxiliary thermal alkali treatment on the flexible metal hydroxide nanofiber material to enable a buckling nanometer thin layer on the surface of the hydroxide fiber to grow in situ in a directional manner, so as to obtain the nanofiber material with the multistage sheath-core structure.
Further, in step 1), the inorganic precursor includes one or more of zirconium source, aluminum source, titanium source, tin source, antimony source, lanthanum source, neodymium source, manganese source, iron source, cerium source, praseodymium source, cobalt source, copper source, chromium source or zinc source, but may be added at intervals of 0.5-4h in consideration of the principle of material hydrolysis and the difference of the rate, or mixed after step 2); the solvent comprises one or more of methanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol, tert-butanol, n-amyl alcohol, ethylene glycol, butanediol, hexanediol or glycerol, and the hydrolysis and polycondensation reaction time is controlled by regulating the type and proportion of the solvent; the coordination protective agent comprises glacial acetic acid or acetylacetone, and the selection of the coordination protective agent can directly influence the time and the reaction difficulty of the alcoholysis reaction in the step 4); the molar ratio of the inorganic precursor, the solvent and the coordination protective agent is 1 (0.4-0.6) (0.8-2.5), the proper molar ratio is determined according to the number of teeth of the ligand, and the branching degree of the sol after linear polycondensation can be controlled by accurate feeding; the stirring time is 4-10h, the stirring speed is 50-500rpm, the stirring temperature is 20-35 ℃, the stirring time can be properly reduced according to the rising of the stirring temperature, and the preparation process time is shortened.
Preferably, the inorganic precursor comprises one or more of a titanium source, a zirconium source and an aluminum source; the titanium source is selected from one of titanium tetramethoxide, titanium tetraethoxide, titanium n-propoxide, titanium isopropoxide, titanium n-butoxide, titanium isobutanol, titanium tert-butoxide, titanium tetra-pentanol and titanium isooctanol; the zirconium source is selected from one of zirconium tetramethoxide, zirconium tetraethoxide, zirconium n-propoxide, zirconium isopropoxide, zirconium n-butoxide, zirconium isobutanol, zirconium tert-butoxide and zirconium tetra-pentanol; the aluminum source is selected from one of trimethoxy aluminum, triethanol aluminum, tri-n-propoxy aluminum, isopropyl aluminum, n-butyl aluminum, sec-butyl aluminum and tert-butyl aluminum.
Preferably, the flexible metal hydroxide nanofiber material comprises: zirconium hydroxide, aluminum hydroxide, titanium hydroxide, tin hydroxide, antimony hydroxide, lanthanum hydroxide, neodymium hydroxide, manganese hydroxide, iron hydroxide, cerium hydroxide, praseodymium hydroxide, cobalt hydroxide, copper hydroxide, chromium hydroxide, zinc hydroxide, and the like.
Further, in the step 2), in the hydrolysis and polycondensation process of the inorganic precursor, the negative pressure is 0.05-0.2MPa, the temperature is 40-70 ℃ and the time is 0.5-3h, and the program pressure control and the program temperature control can be set, so that the gradient negative pressure or the gradient temperature rise is beneficial to controlling the polycondensation reaction speed, reducing the polymerization degree of the linear sol and improving the polycondensation reaction efficiency; the polymerization degree of the linear inorganic spinning sol is more than 2000, the branching degree is less than or equal to 0.1, and the viscosity is 10-3000 mpa.s. The degree of hydrolysis and polycondensation can be characterized by a rotational viscometer.
Further, in step 3), the process parameters of continuous spinning are: the voltage is 10-100kV, the receiving distance is 5-45cm, the pouring rate is 0.08-10mL/h, the spinning temperature is 15-35 ℃, and the rotating speed of the roller is 20-80rpm. The continuous spinning can be selected from electrostatic spinning, dry spinning and other spinning methods to prepare fiber materials with different diameters.
Further, in the step 4), the alcoholysis reaction is carried out in an alkali solution, the concentration of the alkali solution is 0.01-0.3mol/L, the alkali is sodium hydroxide, potassium hydroxide, calcium hydroxide, ammonia water, potassium ethoxide or sodium ethoxide, the solvent is water, ethanol or methanol, and the reaction temperature is 30-60 ℃. The degree of substitution of hydroxyl in the alcoholysis process is more than or equal to 98 percent. The concentration gradient of the alkali solution preferably comprises 1-4 gradients, and the alkali concentration in each gradient is increased gradually so as to accelerate the reaction time and reduce the manufacturing cost. The alcoholysis reaction temperature can be adjusted in a gradient manner according to the alkali concentration. The alcoholysis reaction can be carried out by ultrasonic auxiliary alcoholysis, the ultrasonic frequency is 20-100kHz, and the ultrasonic is carried out while shaking or stirring to increase the reaction rate, improve the degree of substitution of hydroxyl in the alcoholysis process and ensure that the degree of substitution of hydroxyl is more than or equal to 98 percent.
Further, in step 4), the cleaning process is: neutralizing residual alkali by using an alcohol solution of weak acid, and then washing by alcohol; the drying temperature is 70-100 ℃ and the drying time is 2-16h. For example, the residual alkali is neutralized by alcohol solution of weak acid with the same concentration and then repeatedly washed by alcohol, wherein the weak acid is acetic acid, citric acid, oxalic acid and the like, the washing times are 2-4 times, and the washing can be accompanied by shaking or stirring to ensure that the alcoholysis reaction solvent and the products after the reaction are sufficiently removed. The drying temperature is selected according to the strength of different hydroxide nanofiber materials, and vacuum or non-vacuum environment can be used in the drying process to ensure the stability of the fiber membrane.
Further, in step 5), the process parameters of the ultrasonic-assisted thermal alkali treatment are as follows: the ultrasonic amplitude is 30-80Hz, the temperature of the hot alkali is 60-80 ℃, the concentration of the hot alkali is 0.05-3mol/L, and the treatment time is 0.5-6h. The thermobase is preferably aqueous ammonia. And the alkali steam fumigation can be selected to be used for the heat alkali treatment so as to control the growth rate and the growth direction of the buckling thin layer and obtain the metal hydroxide nano thin layer with controllable thickness and length.
Use of a nanofiber material for chemical weapon protection, said material being used for chemical weapon protection.
The metal hydroxide nano material has the characteristics of large specific surface area, many surface defects, many active sites and the like, and can effectively degrade various chemical warfare agents in a short time. At present, the metal hydroxide nano material is mainly discontinuous materials such as metal hydroxide nano particles, metal hydroxide nano rods and the like, and has larger specific surface area, but the metal hydroxide nano material is required to be compounded with other materials in the use process due to the form dispersion, is easy to fall off powder and is difficult to recycle; the hydroxide sheet has the problems of difficult bending, large brittleness and the like, and greatly limits the practical application of the metal hydroxide.
The metal hydroxide nanofiber material for protecting chemical weapons is a multistage sheath-core structure fiber material composed of metal hydroxide, wherein the mass concentration of the metal hydroxide in the material is more than or equal to 98%, and the molar content of the metal hydroxide is 40% -80%. Wherein the core layer is flexible metal hydroxide nanofiber with diameter of 50-800nm and length-diameter ratio of more than 1000, the skin layer is metal hydroxide buckling thin layer which vertically and uniformly grows around the nanofiber, and the specific surface area is 50-1000m 2 And/g, the number of the surface active sites is large, and the degradation half-life of the chemical weapon is less than or equal to 5min. The whole material can be used alone or in combination with a base material.
Compared with the prior art, the invention has the following characteristics:
1) The metal hydroxide nanofiber material for protecting the chemical weapon is a multistage sheath-core structure fiber material composed of metal hydroxide, and has the advantages of large specific surface area, large number of surface active sites and half-life of degradation to the chemical weapon of less than or equal to 5min. The material is used as an in-situ degradation type chemical protective material, can effectively avoid secondary pollution caused in the processes of decontamination and wearing and taking off, can be used singly as a whole or can be used in combination with a base material, has good flexibility and good strength, is easy to recycle, and breaks through the use bottleneck of the existing dispersion type degradation material.
2) According to the invention, firstly, inorganic sol with low branching degree is continuously spun to prepare gel nano fibers, then the gel nano fibers are treated by alkali solution to complete alcoholysis reaction with high hydroxyl substitution degree, and the obtained whole flexible metal hydroxide nano fiber material is subjected to ultrasonic-assisted heat alkali treatment to enable buckling nano thin layers on the surface of the hydroxide fiber to grow in situ and directionally, so that the metal hydroxide fiber material with the multi-stage skin-core structure with ultra-high specific surface area is obtained. The preparation method can be used for preparing zirconium hydroxide, titanium hydroxide, aluminum hydroxide, magnesium hydroxide and other materials, and the prepared materials have good flexibility, large specific surface area and many active sites, and can realize the high-efficiency and rapid degradation of chemical warfare agents (including simulators thereof).
Drawings
FIG. 1 is an SEM image of a zirconia sheath-core structured nanofiber material prepared in example 1;
FIG. 2 is an SEM image of the aluminum hydroxide sheath-core structured nanofiber material prepared in example 2;
fig. 3 is an SEM image of the magnesium hydroxide skin-core structured nanofiber material prepared in example 3.
Detailed Description
The invention will now be described in detail with reference to the drawings and specific examples. The present embodiment is implemented on the premise of the technical scheme of the present invention, and a detailed implementation manner and a specific operation process are given, but the protection scope of the present invention is not limited to the following examples.
The invention provides a nanofiber material for protecting chemical weapons, which is a multistage sheath-core structure fiber material, wherein a core layer is a flexible metal hydroxide nanofiber, a sheath layer is a metal hydroxide buckling thin layer, the thin layer vertically and uniformly grows around the core layer, the mass concentration of metal hydroxide in the material is more than or equal to 98%, the molar content of metal hydroxide is 40% -80%, the diameter of the multistage sheath-core structure fiber is 100-1000nm, the length-diameter ratio is more than 1000, the softness is 10-200mN, the elastic modulus of single fiber is 2-60GPa, and the specific surface area is 50-1000m 2 /g。
The invention also provides a preparation method of the nanofiber material for protecting the chemical weapon, which comprises the following steps:
1) Dissolving an inorganic precursor in a solvent, adding a coordination protective agent, and fully stirring to obtain ligand-protected low-branching degree linear inorganic sol;
2) Controlling the hydrolysis and polycondensation of the inorganic precursor to prepare linear inorganic spinning sol with high polymerization degree and low branching degree;
3) Under the condition that the relative humidity is 30% -32%, carrying out continuous spinning on the linear inorganic spinning sol to obtain gel nanofiber;
4) Performing alcoholysis reaction on the gel nanofiber, and then cleaning and drying to obtain a flexible metal hydroxide nanofiber material;
5) And carrying out ultrasonic auxiliary thermal alkali treatment on the flexible metal hydroxide nanofiber material to enable a buckling nanometer thin layer on the surface of the hydroxide fiber to grow in situ in a directional manner, so as to obtain the nanofiber material with the multistage sheath-core structure.
In step 1), the inorganic precursor comprises one or more of a zirconium source, an aluminum source, a titanium source, a tin source, an antimony source, a lanthanum source, a neodymium source, a manganese source, an iron source, a cerium source, a praseodymium source, a cobalt source, a copper source, a chromium source or a zinc source, the solvent comprises one or more of methanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol, tert-butanol, n-pentanol, ethylene glycol, butanediol, hexanediol or glycerol, and the coordination protecting agent comprises one of glacial acetic acid or acetylacetone; the mol ratio of the inorganic precursor, the solvent and the coordination protective agent is 1 (0.4-0.6): 0.8-2.5); the stirring time is 4-10h, the stirring speed is 50-500rpm, and the stirring temperature is 20-35 ℃.
In the step 2), in the hydrolysis and polycondensation process of the inorganic precursor, the negative pressure is 0.05-0.2MPa, the temperature is 40-70 ℃ and the time is 0.5-3h; the polymerization degree of the linear inorganic spinning sol is more than 2000, the branching degree is less than or equal to 0.1, and the viscosity is 10-3000 mpa.s.
In the step 3), the technological parameters of continuous spinning are as follows: the voltage is 10-100kV, the receiving distance is 5-45cm, the pouring rate is 0.08-10mL/h, the spinning temperature is 15-35 ℃, and the rotating speed of the roller is 20-80rpm.
In the step 4), the alcoholysis reaction is carried out in an alkali solution, the concentration of the alkali solution is 0.01-0.3mol/L, the alkali is sodium hydroxide, potassium hydroxide, calcium hydroxide, ammonia water, potassium ethoxide or sodium ethoxide, the solvent is water, ethanol or methanol, and the reaction temperature is 30-60 ℃. The cleaning process comprises the following steps: neutralizing residual alkali by using an alcohol solution of weak acid, and then washing by alcohol; the drying temperature is 70-100 ℃ and the drying time is 2-16h.
In the step 5), the technological parameters of ultrasonic assisted thermal alkali treatment are as follows: the ultrasonic amplitude is 30-80Hz, the temperature of the hot alkali is 60-80 ℃, the concentration of the hot alkali is 0.05-3mol/L, and the treatment time is 0.5-6h.
The invention also provides application of the nanofiber material for protecting the chemical weapon, and the material is used for protecting the chemical weapon.
Example 1:
dissolving 12wt% of zirconium n-propoxide into a mixed solvent of n-propanol and ethanol (the mass ratio of the solvent is 1:1), stirring at the speed of 500rpm and the stirring temperature of 26 ℃, adding 8wt% of a coordination protective agent acetylacetone after fully stirring, stirring at room temperature for 8 hours to obtain a homogeneous multi-tooth ligand protective inorganic sol, controlling the hydrolysis and polycondensation of an inorganic precursor by a low-branching degree inorganic polymer sol spinning solution batch preparation device, controlling the polycondensation negative pressure at 0.1MPa, controlling the reaction temperature at 60 ℃ and the polycondensation time at 3 hours, and finally obtaining the linear inorganic spinning sol with the polymerization degree of 6500, the branching degree of-0.05, the viscosity of 1800MPa & s and the surface tension of 78mN/m.
The prepared linear inorganic spinning sol with high polymerization degree and low branching degree is filled into an injector connected with a peristaltic pump, high-voltage power of 25kV is applied to the tip of the injector, the distance between the tip and a receiving roller is controlled to be 25cm, the filling speed is 3mL/h, the rotating speed of the roller is 50rpm, the spinning temperature is 25 ℃, the relative humidity of spinning is 30-32%, and the gel nanofiber membrane material with the thickness of 34 mu m can be obtained after 4 hours of continuous spinning.
The prepared membrane material is put into an alcoholysis/cleaning integrated device, alkali is sodium hydroxide and sodium ethoxide, a solvent is ethanol, the number of concentration gradients is controlled to be 3, the concentration gradient is 0.01-0.05mol/L, the concentration gradient is 2 to be 0.05-0.1mol/L, the concentration gradient is 3 to be 0.1-0.3mol/L, the reaction temperature is 40 ℃, the auxiliary ultrasonic frequency is applied to be 70kHz, and the reaction time is 2h per gradient. Finally, a fiber material with an alcoholysis degree of 98% is obtained. The reacted membrane material was then washed 3 times in ethanol solution and assisted in shaking for 3h. And finally, drying the cleaned membrane material in a vacuum environment at the drying temperature of 80 ℃ for 4 hours.
The flexible zirconium hydroxide nano fiber material prepared by the method is treated by ultrasonic assisted concentrated ammonia water, the concentration of the ammonia water is 3mol/L, the temperature is 70 ℃, the time is 6 hours, the buckling nano thin layer on the surface of the zirconium hydroxide fiber grows controllably in situ (as shown in figure 1), the thickness of a thin sheet is 2nm, the diameter of the fiber is 545nm, the mass purity of the zirconium hydroxide is 99%, the molar content of metal hydroxide is 67%, and the specific surface area is 98.2m 2 Per g, the softness of the material is 18mN, and the degradation half-life of the material on the chemical warfare agent simulator DMMP is 4.2min.
Example 2:
dissolving 13wt% of aluminum n-propoxide into n-propanol, stirring for 30min at the stirring speed of 500rpm and the stirring temperature of 26 ℃, adding 11wt% of coordination protective agent acetylacetone after full stirring, stirring at room temperature for 8h to obtain homogeneous multi-tooth ligand-protected inorganic sol, controlling the hydrolysis and polycondensation of inorganic precursors by a low-branching degree inorganic polymer sol spinning solution batch preparation device, controlling the polycondensation negative pressure at 0.1MPa, controlling the reaction temperature at 60 ℃ and the polycondensation time at 3h, and finally obtaining the linear inorganic spinning sol with the polymerization degree of 8200, the branching degree of less than 0.05, the viscosity of 2400 mpa.s and the surface tension of 86mN/m.
The prepared linear inorganic spinning sol with high polymerization degree and low branching degree is filled into an injector connected with a peristaltic pump, high-voltage power of 25kV is applied to the tip of the injector, the distance between the tip and a receiving roller is controlled to be 20cm, the filling speed is controlled to be 2.5mL/h, the rotating speed of the roller is controlled to be 50rpm, the spinning temperature is 25 ℃, the relative humidity of spinning is 30-32%, and the gel nanofiber membrane material with the thickness of 37 mu m can be obtained after 4 hours of continuous spinning.
The prepared membrane material is put into an alcoholysis/cleaning integrated device, alkali is sodium hydroxide and sodium ethoxide, a solvent is ethanol, the number of concentration gradients is controlled to be 3, the concentration gradient is 0.01-0.05mol/L, the concentration gradient is 2 to be 0.05-0.1mol/L, the concentration gradient is 3 to be 0.1-0.3mol/L, the reaction temperature is 40 ℃, the auxiliary ultrasonic frequency is applied to be 60kHz, and the reaction time is 2h per gradient. Finally, a fiber material with an alcoholysis degree of 98% is obtained. The reacted membrane material was then washed 3 times in ethanol solution and assisted in shaking for 3h. And finally, drying the cleaned membrane material in a vacuum environment at the drying temperature of 80 ℃ for 4 hours.
The flexible aluminum hydroxide nanofiber material prepared by the method is treated by ultrasonic assisted concentrated ammonia water, the concentration of the ammonia water is 3mol/L, the temperature is 70 ℃, the time is 6 hours, the buckling nanometer thin layer on the surface of the aluminum hydroxide fiber grows controllably in situ (as shown in figure 2), the thickness of the thin sheet is 2.1nm, the fiber diameter is 353nm, the mass purity of the aluminum hydroxide is 99%, the molar content of metal hydroxyl is 72%, the softness of the material is 18mN, and the specific surface area is 98.2m 2 The degradation half-life of DMMP to chemical warfare agent simulator was 3.9min.
Example 3:
17wt% of magnesium nitrate is dissolved into ethanol, the stirring speed is 500rpm, the stirring temperature is 26 ℃, 9wt% of coordination protective agent acetic acid is added after full stirring, then the homogeneous multi-tooth ligand protective inorganic sol is obtained after stirring for 8 hours at room temperature, the sol is subjected to hydrolysis and polycondensation of an inorganic precursor by a low-branching degree inorganic polymer sol spinning solution batch preparation device, the polycondensation negative pressure is controlled to be 0.1MPa, the reaction temperature is 60 ℃, the polycondensation time is 3 hours, and finally the linear inorganic spinning sol with the polymerization degree of 6200, the branching degree of less than 0.05, the viscosity of 2400 mpa.s and the surface tension of 76mN/m is obtained.
The prepared linear inorganic spinning sol with high polymerization degree and low branching degree is filled into an injector connected with a peristaltic pump, high-voltage power of 20kV is applied to the tip of the injector, the distance between the tip and a receiving roller is controlled to be 20cm, the filling speed is 3mL/h, the rotating speed of the roller is 50rpm, the spinning temperature is 25 ℃, the relative humidity of spinning is 30-32%, and the gel nanofiber membrane material with the thickness of 37 mu m can be obtained after 4 hours of continuous spinning.
The prepared membrane material is put into an alcoholysis/cleaning integrated device, alkali is sodium hydroxide and sodium ethoxide, a solvent is ethanol, the number of concentration gradients is controlled to be 3, the concentration gradient is 0.01-0.05mol/L, the concentration gradient is 2 to be 0.05-0.1mol/L, the concentration gradient is 3 to be 0.1-0.3mol/L, the reaction temperature is 40 ℃, the auxiliary ultrasonic frequency is applied to be 60kHz, and the reaction time is 2h per gradient. Finally, a fiber material with an alcoholysis degree of 98% is obtained. The reacted membrane material was then washed 3 times in ethanol solution and assisted in shaking for 3h. And finally, drying the cleaned membrane material in a vacuum environment at the drying temperature of 80 ℃ for 4 hours.
The flexible magnesium hydroxide nanofiber material prepared by the method is treated by ultrasonic assisted concentrated ammonia water, the concentration of the ammonia water is 3mol/L, the temperature is 70 ℃, the time is 6 hours, the buckling nanometer thin layer on the surface of the magnesium hydroxide fiber grows controllably in situ (as shown in figure 3), the thickness of the thin sheet is 2.1nm, the fiber diameter is 415nm, the mass purity of the magnesium hydroxide is 99%, the molar content of metal hydroxyl is 78%, and the specific surface area is 91.4m 2 Per g, the softness of the material is 15.2mN, and the degradation half-life of the material on the chemical warfare agent simulator DMMP is 4.9min.
The previous description of the embodiments is provided to facilitate a person of ordinary skill in the art in order to make and use the present invention. It will be apparent to those skilled in the art that various modifications can be readily made to these embodiments and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above-described embodiments, and those skilled in the art, based on the present disclosure, should make improvements and modifications without departing from the scope of the present invention.

Claims (10)

1. The nanofiber material for protecting the chemical weapon is characterized in that the material is a multistage sheath-core structure fiber material, a core layer is a flexible metal hydroxide nanofiber, a sheath layer is a metal hydroxide buckling thin layer, the thin layer vertically and uniformly grows around the core layer, the mass concentration of the metal hydroxide in the material is more than or equal to 98%, and the molar content of metal hydroxide is 40% -80%;
the nanofiber material is prepared by the following method:
1) Dissolving an inorganic precursor in a solvent, adding a coordination protective agent, and fully stirring to obtain ligand-protected low-branching degree linear inorganic sol;
2) Controlling the hydrolysis and polycondensation of the inorganic precursor to prepare linear inorganic spinning sol with high polymerization degree and low branching degree;
3) Under the condition that the relative humidity is 30% -32%, carrying out continuous spinning on the linear inorganic spinning sol to obtain gel nanofiber;
4) Performing alcoholysis reaction on the gel nanofiber, and then cleaning and drying to obtain a flexible metal hydroxide nanofiber material;
5) Carrying out ultrasonic auxiliary thermal alkali treatment on the flexible metal hydroxide nanofiber material to enable a buckling nanometer thin layer on the surface of the hydroxide fiber to grow in situ in a directional manner, so as to obtain the nanofiber material with a multistage sheath-core structure;
the inorganic precursor comprises one or more of a zirconium source, an aluminum source, a titanium source, a tin source, an antimony source, a lanthanum source, a neodymium source, a manganese source, an iron source, a cerium source, a praseodymium source, a cobalt source, a copper source, a chromium source or a zinc source;
the coordination protective agent comprises one of glacial acetic acid or acetylacetone.
2. The nanofiber material for protecting chemical warfare according to claim 1, wherein the diameter of the multistage sheath-core structure fiber is 100-1000nm, the length-diameter ratio is more than 1000, the softness is 10-200mN, the elastic modulus of single fiber is 2-60GPa, and the specific surface area is 50-1000m 2 /g。
3. A method of preparing a nanofiber material for protection against chemical weapons according to claim 1 or 2, characterized in that the method comprises the steps of:
1) Dissolving an inorganic precursor in a solvent, adding a coordination protective agent, and fully stirring to obtain ligand-protected low-branching degree linear inorganic sol;
2) Controlling the hydrolysis and polycondensation of the inorganic precursor to prepare linear inorganic spinning sol with high polymerization degree and low branching degree;
3) Under the condition that the relative humidity is 30% -32%, carrying out continuous spinning on the linear inorganic spinning sol to obtain gel nanofiber;
4) Performing alcoholysis reaction on the gel nanofiber, and then cleaning and drying to obtain a flexible metal hydroxide nanofiber material;
5) And carrying out ultrasonic auxiliary thermal alkali treatment on the flexible metal hydroxide nanofiber material to enable the buckling nanometer thin layer on the fiber surface to grow in situ and directionally, so as to obtain the nanofiber material with the multistage sheath-core structure.
4. A method of preparing a nanofiber material for chemical weapon protection according to claim 3, wherein in step 1), the solvent comprises one or more of methanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol, tert-butanol, n-pentanol, ethylene glycol, butylene glycol, hexylene glycol or glycerol; the mol ratio of the inorganic precursor, the solvent and the coordination protective agent is 1 (0.4-0.6): 0.8-2.5; the stirring time is 4-10h, the stirring speed is 50-500rpm, and the stirring temperature is 20-35 ℃.
5. The method for preparing a nanofiber material for chemical weapon protection according to claim 3, wherein in the step 2), the negative pressure is 0.05-0.2MPa, the temperature is 40-70 ℃ and the time is 0.5-3h in the hydrolysis and polycondensation process of the inorganic precursor; the polymerization degree of the linear inorganic spinning sol is more than 2000, the branching degree is less than or equal to 0.1, and the viscosity is 10-3000 mpa.s.
6. A method for preparing a nanofiber material for chemical weapon protection according to claim 3, wherein in step 3), the technological parameters of continuous spinning are as follows: the voltage is 10-100kV, the receiving distance is 5-45cm, the pouring rate is 0.08-10mL/h, the spinning temperature is 15-35 ℃, and the rotating speed of the roller is 20-80rpm.
7. The method for preparing a nanofiber material for chemical weapon protection according to claim 3, wherein in the step 4), the alcoholysis reaction is performed in an alkali solution, the concentration of the alkali solution is 0.01-0.3mol/L, the alkali is sodium hydroxide, potassium hydroxide, calcium hydroxide, ammonia water, potassium ethoxide or sodium ethoxide, the solvent is water, ethanol or methanol, and the reaction temperature is 30-60 ℃.
8. The method for preparing a nanofiber material for chemical weapon protection according to claim 7, wherein in step 4), the cleaning process is as follows: neutralizing residual alkali by using an alcohol solution of weak acid, and then washing by alcohol; the drying temperature is 70-100 ℃ and the drying time is 2-16h.
9. The method for preparing a nanofiber material for chemical weapon protection according to claim 3, wherein in step 5), the process parameters of the ultrasonic-assisted heat alkali treatment are as follows: the ultrasonic amplitude is 30-80Hz, the temperature of the hot alkali is 60-80 ℃, the concentration of the hot alkali is 0.05-3mol/L, and the treatment time is 0.5-6h.
10. Use of a nanofiber material for chemical weapon protection according to claim 1 or 2, wherein said material is used for chemical weapon protection.
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CN101058942A (en) * 2007-06-08 2007-10-24 武汉大学 Method of preparing magnetic nano composite fibre
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EP2086877A4 (en) * 2006-09-29 2011-01-05 Univ Akron Metal oxide fibers and nanofibers, method for making same, and uses thereof
US11072884B2 (en) * 2018-10-16 2021-07-27 Imam Abdulrahman Bin Faisal University Method of making an antimicrobial textile

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CN101058942A (en) * 2007-06-08 2007-10-24 武汉大学 Method of preparing magnetic nano composite fibre
CN108950864A (en) * 2018-07-27 2018-12-07 望江汇通纺织有限公司 A kind of medical sheath core fiber non-woven fabrics of hydrophilic and oleophilic

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