CN114481622B - Moisture-permeable chemical protection fabric and preparation method and application thereof - Google Patents

Moisture-permeable chemical protection fabric and preparation method and application thereof Download PDF

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CN114481622B
CN114481622B CN202210091060.3A CN202210091060A CN114481622B CN 114481622 B CN114481622 B CN 114481622B CN 202210091060 A CN202210091060 A CN 202210091060A CN 114481622 B CN114481622 B CN 114481622B
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layer
graphene oxide
fabric
moisture
polydopamine
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CN114481622A (en
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徐斌
邱伟
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Beijing University of Chemical Technology
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Beijing University of Chemical Technology
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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
    • A—HUMAN NECESSITIES
    • A41—WEARING APPAREL
    • A41D—OUTERWEAR; PROTECTIVE GARMENTS; ACCESSORIES
    • A41D13/00—Professional, industrial or sporting protective garments, e.g. surgeons' gowns or garments protecting against blows or punches
    • A—HUMAN NECESSITIES
    • A41—WEARING APPAREL
    • A41D—OUTERWEAR; PROTECTIVE GARMENTS; ACCESSORIES
    • A41D31/00—Materials specially adapted for outerwear
    • A41D31/04—Materials specially adapted for outerwear characterised by special function or use
    • A41D31/12—Hygroscopic; Water retaining
    • A41D31/125—Moisture handling or wicking function through layered materials
    • 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
    • D06M11/73—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 carbon or compounds thereof
    • D06M11/74—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 carbon or compounds thereof with carbon or graphite; with carbides; with graphitic acids or their salts
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • 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
    • D06M15/61—Polyamines polyimines
    • 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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  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Physical Education & Sports Medicine (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)

Abstract

The invention provides a moisture-permeable chemical protective fabric and a preparation method and application thereof, belonging to the technical field of protective fabrics. According to the invention, the poly-dopamine layer with super-strong adhesion is arranged between the substrate and the graphene oxide film, the surface of the poly-dopamine layer contains a large number of hydroxyl groups and amino active groups capable of providing secondary reaction, and the poly-dopamine layer and the polyethylene imine can form a polyethylene imine layer rich in amino functional groups, and the amino functional groups in the polyethylene imine can generate covalent crosslinking action with carboxyl groups and epoxy groups in the graphene oxide. In the invention, the base material provides a mechanical support effect for the fabric, the polydopamine layer and the polyethyleneimine layer are used as bridges for connecting the base material and the graphene oxide film, so that the interface bonding strength between the materials is improved, the hydrophilicity of the base can be increased, the moisture permeability of the base is improved, the perspiration is promoted, the graphene oxide film layer provides a chemical protection property for the fabric, and the perspiration is allowed to be discharged.

Description

Moisture-permeable chemical protection fabric and preparation method and application thereof
Technical Field
The invention relates to the technical field of protective fabrics, in particular to a moisture-permeable chemical protective fabric and a preparation method and application thereof.
Background
Chemical protective clothing is also called chemical protective clothing, can protect self from being damaged by dangerous chemical reagents, and is widely applied to laboratories, chemical plants and the like. The existing insulation type chemical protective clothing takes chlorinated butyl rubber as a main material. The chlorinated butyl rubber is a synthetic rubber, is synthesized from isobutene and isoprene, has good air tightness and water tightness, is heat-resistant, strong acid and strong alkali resistant, has good protective performance for an isolated chemical protective suit prepared from the chlorinated butyl rubber, and simultaneously isolates the discharge of water vapor, and the rubber chemical protective suit has large weight, increases the burden of workers, and is operated for a long time, so that a great deal of heat and water vapor generated by human metabolism are accumulated in the suit, the wearing comfort is extremely poor, the thermal stress reaction of people occurs, and the safety of the human body is harmed. Therefore, the demand of the chemical protection fabric with high chemical protection and moisture permeability functions is urgent.
Due to the unique two-dimensional interlayer channel of the graphene oxide film, water molecules can pass through the graphene oxide film quickly, and other substances are blocked by the graphene oxide film through the size sieving effect and the donnan effect, so that the graphene oxide film is an ideal chemical protection material. However, the independent graphene oxide film has poor mechanical properties, is easy to break, is difficult to directly apply to clothes, and needs to be compounded with other materials to make up for the defects of the graphene oxide film. For a hydrophobic fabric with a non-polar surface, the surface has no functional group which can have a chemical action with graphene oxide, the interface bonding strength after the combination is weak, and the graphene oxide film is damaged due to the falling phenomenon in the use process, so that the protection performance is lost.
In order to solve the problem of weak interface bonding strength, the conventional method is to modify the surface of a hydrophobic fabric, add a specific functional group to perform a chemical reaction with a surface group of graphene oxide, and improve the wettability of a graphene oxide dispersion liquid on the fabric, so as to improve the interface bonding strength of a graphene oxide film and the hydrophobic fabric. For example, chinese patent CN201911384752.1 relates to a process for preparing polyaniline-aramid composite conductive fibers applied to protective clothing, which is characterized in that plasma treatment is performed on aramid to form active sites on the surface of the aramid, and then graphene oxide is modified to improve the bonding strength between the aramid and the graphene oxide. However, in the method, the fibers of the protective fabric need to be subjected to plasma treatment, and graphene oxide needs to be modified, otherwise, the peel strength between the aramid fiber and the graphene oxide modified layer cannot be ensured.
Therefore, it is highly desirable to provide a chemical protective fabric with a high peel strength of the surface modification layer of the fabric and excellent protective performance and moisture permeability.
Disclosure of Invention
The invention aims to provide a moisture-permeable chemical protection fabric, and a preparation method and application thereof.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a moisture-permeable chemical protection fabric which comprises a substrate layer and a graphene oxide layer which are sequentially arranged;
the base layer comprises a base material consisting of fibers, a polydopamine layer coated on the surface of the fibers and a polyethylene imine layer coated on the surface of the polydopamine layer.
Preferably, the base material is a high-strength flame-retardant fabric or a hydrophobic fabric.
The invention also provides a preparation method of the moisture-permeable chemical protective fabric, which comprises the following steps:
(1) Dipping the substrate material in a dopamine hydrochloride solution to obtain a composite material with a surface coated with a polydopamine layer;
(2) Soaking the composite material with the surface coated with the polydopamine layer obtained in the step (1) in a polyethyleneimine solution for addition reaction to obtain a substrate layer;
(3) And (3) coating the graphene oxide dispersion liquid on one side of the substrate layer obtained in the step (2), and carrying out a crosslinking reaction to obtain the moisture-permeable chemical protective fabric.
Preferably, the concentration of the dopamine hydrochloride solution in the step (1) is 0.5-6.0 g/L.
Preferably, the concentration of the polyethyleneimine solution in the step (2) is 2.0 to 10.0g/L.
Preferably, the time for the immersion in the step (1) and the step (2) is independently 8 to 24 hours.
Preferably, the concentration of the graphene oxide dispersion liquid in the step (3) is 8.0 to 12.0g/L.
Preferably, the thickness of the graphene oxide dispersion liquid applied in the step (3) is 0.5 to 2.5mm.
The invention also provides application of the moisture-permeable chemical protection fabric in the technical scheme or the moisture-permeable chemical protection fabric prepared by the preparation method in the technical scheme in manufacturing chemical protection clothes.
The invention provides a moisture-permeable chemical protection fabric, which comprises a substrate layer and a graphene oxide layer which are sequentially arranged; the base layer comprises a base material consisting of fibers, a polydopamine layer coated on the surface of the fibers and a polydopamine layer coated on the polydopamine layerA surface layer of polyethylene. According to the invention, the poly-dopamine layer with super-strong adhesion is arranged between the substrate and the graphene oxide film, the surface of the poly-dopamine layer contains a large number of hydroxyl groups and amino active groups capable of providing secondary reaction, and the poly-dopamine layer and the polyethylene imine can form a polyethylene imine layer rich in amino functional groups, and the amino functional groups in the polyethylene imine can generate covalent crosslinking action with carboxyl groups and epoxy groups in the graphene oxide. In the invention, the base material provides a mechanical support effect for the fabric, the polydopamine layer and the polyethyleneimine layer are used as a bridge for connecting the base material and the graphene oxide film, so that the interface bonding strength between the materials is improved, the hydrophilicity of the base can be increased, the moisture permeability of the base is improved, the perspiration is promoted, the graphene oxide film layer provides a chemical protection property for the fabric, and the perspiration is allowed to be discharged. According to the chemical protective fabric, the chemical protective fabric is formed by the arrangement of a multilayer structure and the combined action of the four. The example results show that the peel strength between the modification layer and the substrate in the moisture-permeable chemical protective fabric provided by the invention is improved by 3 times compared with that of a comparative example; the moisture permeability reaches 4109.16 g/(m) 2 24 h); chemical protection time>48h。
Drawings
FIG. 1 is an XPS map of a composite material with a surface coated with a polydopamine layer prepared in step (2) of example 1 of the present invention;
FIG. 2 is an SEM image of a polyethylene nanofiber membrane used in example 1 of the present invention;
FIG. 3 is an SEM photograph of a composite material with a poly-dopamine layer coated on the surface, prepared in step (2) of example 1;
FIG. 4 is an infrared spectrum of the substrate layer prepared in step (2) and step (3) of example 1 of the present invention;
FIG. 5 is an XPS plot of a base layer prepared in step (3) of example 1 of the present invention;
FIG. 6 is an SEM photograph of the base layer prepared in step (3) of example 1 of the present invention;
fig. 7 is an XRD pattern of the moisture-permeable chemical protective fabric prepared in step (4) of example 1 of the present invention.
Detailed Description
The invention provides a moisture-permeable chemical protection fabric, which comprises a substrate layer and a graphene oxide layer which are sequentially arranged;
the base layer comprises a base material consisting of fibers, a polydopamine layer coated on the surface of the fibers and a polyethylene imine layer coated on the surface of the polydopamine layer.
The moisture-permeable chemical protective fabric provided by the invention comprises a substrate layer. In the invention, the substrate layer comprises a substrate material consisting of fibers, a polydopamine layer coated on the surface of the fibers, and a polyethylene imine layer coated on the surface of the polydopamine layer.
In the present invention, the substrate layer comprises a substrate material consisting of fibres. In the present invention, the base material is preferably a high strength flame retardant fabric or a hydrophobic fabric, more preferably a polyethylene nanofiber membrane. The source and the type of the high-strength flame-retardant fabric or the hydrophobic fabric are not particularly limited, and the high-strength flame-retardant fabric or the hydrophobic fabric which is well known by the technical personnel in the field can be adopted to prepare the fabric of the protective clothing. In the present invention, the base material is composed of fibers, and as a main body of the moisture-permeable chemical protective fabric, the fibers have voids therebetween and have excellent moisture permeability. The thickness of the base material is not particularly limited and can be selected according to the requirement.
In the present invention, the substrate layer includes a polydopamine layer coated on the surface of the fiber. In the invention, the polydopamine layer is coated on the fiber surface of the base material, so that the polydopamine layer with super-strong adhesiveness can be formed on the fiber surface, and on one hand, the polydopamine layer can have excellent bonding strength with the base layer; on the other hand, the surface of the modified substrate contains a large number of hydroxyl and amino active groups which can provide secondary reaction, and the hydroxyl and amino active groups react with a subsequent modified layer, so that the bonding strength between the modified layer and the substrate layer is improved. The thickness of the polydopamine layer is not particularly limited and can be selected according to the needs.
In the present invention, the substrate layer includes a polyethylene imine layer coated on the surface of the polydopamine layer. In the invention, the polyethyleneimine layer can generate Michael addition reaction with hydroxyl and amino active groups in the polydopamine layer, so that the polyethyleneimine layer and the polydopamine layer are connected by covalent bonds, and the bonding strength is high. The thickness of the polyethyleneimine layer is not particularly limited, and may be selected as needed.
The moisture-permeable chemical protective fabric provided by the invention comprises the graphene oxide layer arranged on the substrate layer. In the present invention, the graphene oxide layer is coated on one side of the substrate layer. In the present invention, carboxyl groups, epoxy groups, and the like in the graphene oxide film can covalently crosslink with amino groups in the polyethylene imine layer, so that the graphene oxide layer is covalently bonded to one side of the base layer, and the bonding strength is high. The graphene oxide layer has excellent moisture permeability, and can provide chemical protection performance for the fabric. The thickness of the graphene oxide layer is not particularly limited, and can be selected according to needs.
In the moisture-permeable chemical protection fabric provided by the invention, the substrate material provides a mechanical support effect for the fabric, the polydopamine layer and the polyethyleneimine layer are used as bridges for connecting the substrate material and the graphene oxide layer, so that the interface bonding strength between the materials is improved, the hydrophilicity of the substrate can be increased, the moisture permeability is improved, the perspiration is promoted, the graphene oxide layer provides the chemical protection performance for the fabric, and the perspiration is allowed to be discharged. According to the invention, through the arrangement of the multilayer structure, the four materials act together to form the fabric with excellent moisture permeability and chemical protection property.
The invention also provides a preparation method of the moisture-permeable chemical protection fabric, which comprises the following steps:
(1) Dipping the substrate material in a dopamine hydrochloride solution to obtain a composite material with a surface coated with a polydopamine layer;
(2) Soaking the composite material with the surface coated with the polydopamine layer obtained in the step (1) in a polyethyleneimine solution for addition reaction to obtain a substrate layer;
(3) And (3) coating the graphene oxide dispersion liquid on one side of the substrate layer obtained in the step (2), and carrying out a crosslinking reaction to obtain the moisture-permeable chemical protective fabric.
The base material is soaked in dopamine hydrochloride solution to obtain the composite material with the surface coated with the polydopamine layer.
In the present invention, the base material is preferably pretreated before use. In the invention, the pretreatment is preferably to soak the substrate material in ethanol solution for ultrasonic cleaning and air-dry for later use. In the present invention, the pretreatment can remove impurities from the surface of the base material.
The preparation method of the dopamine hydrochloride solution is not particularly limited, and the preparation method of the dopamine hydrochloride solution known to those skilled in the art can be adopted. In the present invention, the preparation method of the dopamine hydrochloride solution is preferably: tris is dissolved in water and then mixed with an aqueous solution of dopamine Tris hydrochloride. The concentration of the Tris aqueous solution is not particularly limited, and the concentration of the Tris aqueous solution can be adjusted according to the experimental requirements. In the invention, when the preparation method of the dopamine hydrochloride solution is of the type, tris can provide a buffering effect and maintain the stability of the pH value of a solution system.
In the invention, the concentration of the dopamine hydrochloride solution is preferably 0.5-6.0 g/L, and more preferably 2.0-4.0 g/L. In the invention, when the concentration of the dopamine hydrochloride solution is in the range, the dopamine hydrochloride solution can be favorably fully infiltrated to the surface of the substrate material, and the dopamine layer can be formed on the surface of the substrate material by the dopamine along with the infiltration.
In the invention, the method for immersing the substrate material in the dopamine hydrochloride solution is preferably that the substrate material is directly immersed in the dopamine hydrochloride solution; or, the substrate material is placed in a Tris aqueous solution, and then dopamine hydrochloride is added into the Tris aqueous solution for impregnation.
In the present invention, the temperature of the impregnation is preferably 20 to 60 ℃, more preferably 25 to 35 ℃; the time for the impregnation is preferably 8 to 24 hours, more preferably 12 to 24 hours. In the present invention, during the impregnation process, dopamine undergoes a polymerization reaction on the surface of the fibers of the base material to form polydopamine. In the invention, when the dipping temperature and time are in the above ranges, the dopamine hydrochloride solution can be favorably and fully soaked on the surface of the substrate material, and the polydopamine is uniformly coated on the surface of the substrate material after polymerization reaction.
In the present invention, the impregnation is preferably carried out under stirring. In the present invention, the stirring is advantageous for forming a uniform dopamine layer on the surface of the base material. The stirring speed is not particularly limited and can be adjusted according to experiments.
According to the invention, the system obtained after dipping is preferably washed and dried in sequence to obtain the composite material with the surface coated with the polydopamine layer. In the present invention, the washing reagent is preferably deionized water; the temperature of the drying is preferably 50 ℃. In the invention, the washing and drying can remove the unreacted dopamine hydrochloride solution in the composite material coated with the poly dopamine layer on the surface.
After the composite material with the surface coated with the polydopamine layer is obtained, the composite material with the surface coated with the polydopamine layer is soaked in a polyethyleneimine solution for addition reaction to obtain the substrate layer.
The method for preparing the polyethyleneimine solution is not particularly limited in the present invention, and a method for preparing a polyethyleneimine solution known to those skilled in the art may be used. In the present invention, the method for preparing the polyethyleneimine solution is preferably: dissolving Tris in water; dissolving polyethyleneimine in water; and then adding the polyethyleneimine aqueous solution into a Tris aqueous solution, and dropwise adding dilute hydrochloric acid until the pH of the solution is between 8 and 9 to obtain the polyethyleneimine solution. The concentration of the Tris aqueous solution and the concentration of the polyethyleneimine aqueous solution are not particularly limited, and can be adjusted according to experimental needs. In the invention, when the preparation method of the polyethyleneimine solution is the type, tris can provide a buffering effect and maintain the stability of the pH value of a solution system.
In the present invention, the concentration of the polyethyleneimine solution is preferably 2.0 to 10.0g/L, and more preferably 5.0 to 10.0g/L. In the present invention, when the concentration of the polyethyleneimine solution is within the above range, the polyethyleneimine solution is favorably distributed on the surface of the composite material having a surface coated with the polydopamine layer.
In the present invention, an addition reaction occurs during the impregnation. In the present invention, the temperature of the impregnation is preferably 20 to 60 ℃, more preferably 25 to 35 ℃; the time for the impregnation is preferably 8 to 24 hours, more preferably 12 to 24 hours. In the present invention, when the temperature and time for the immersion are within the above ranges, the addition reaction is preferably sufficiently performed, so that the polyethyleneimine layer is covalently bonded to the surface of the polydopamine layer.
In the present invention, the impregnation is preferably carried out under stirring. In the invention, the stirring is beneficial to the distribution of the polyethyleneimine solution on the surface of the composite material with the surface coated with the polydopamine layer. The stirring speed is not particularly limited and can be adjusted according to experiments.
In the present invention, it is preferable that the system obtained after the addition reaction is sequentially washed and dried to obtain the base layer. In the present invention, the washing and drying operations are the same as those in the preparation of the composite material with the surface coated with the poly dopamine layer, and are not described herein again. In the present invention, the washing and drying can remove unreacted polyethyleneimine in the base layer.
After the base layer is obtained, the graphene oxide dispersion liquid is coated on one side of the base layer, and crosslinking reaction is carried out, so that the moisture-permeable chemical protective fabric is obtained.
In the present invention, the concentration of the graphene oxide dispersion liquid is preferably 8.0 to 12.0g/L, and more preferably 10.0 to 12.0g/L. In the present invention, when the concentration of the graphene oxide dispersion liquid is in the above range, the graphene oxide dispersion liquid is favorably and uniformly distributed on the surface of the substrate layer.
The reagent used in the graphene oxide dispersion liquid is not particularly limited, and the graphene oxide dispersion liquid can form a stable and uniform dispersion liquid. In the present invention, the reagent used for the graphene oxide dispersion liquid is preferably ethanol.
In the present invention, when the concentration of the graphene oxide dispersion is 8.0 to 12.0g/L, the thickness of the graphene oxide dispersion applied is preferably 0.5 to 2.5mm, more preferably 1.0 to 2.0mm. In the present invention, when the thickness of the graphene oxide dispersion is within the above range, graphene oxide and polyethyleneimine in the polyethyleneimine layer-coated composite material can be covalently bonded to each other by sufficiently reacting them.
The thickness of the coating is not particularly limited in the present invention, and the graphene oxide dispersion having the above thickness may be formed on the surface of the composite material coated with the polyethyleneimine layer by a coating method known to those skilled in the art. In the present invention, the coating is preferably knife coating.
In the present invention, the temperature of the crosslinking reaction is preferably 25 to 60 ℃, more preferably 30 to 40 ℃; the time of the crosslinking reaction is not particularly limited, and the process of the crosslinking reaction can be completed when the graphene oxide dispersion liquid is dried. In the present invention, when the temperature and time of the crosslinking reaction are within the above ranges, the crosslinking reaction of the polyethyleneimine and the graphene oxide can be sufficiently performed.
According to the preparation method provided by the invention, the polydopamine layer and the polyethyleneimine layer are arranged between the base material and the graphene oxide film, firstly, the polydopamine layer with super-strong adhesion is formed on the surface of the base material through the oxidative autopolymerization reaction of dopamine hydrochloride, a large number of hydroxyl groups and amino active groups capable of providing secondary reaction are contained on the surface of the polydopamine layer, the polydopamine layer and the polyethyleneimine can perform Michael addition reaction to form the polyethyleneimine layer rich in amino functional groups, and the amino functional groups in the polyethyleneimine can react with carboxyl groups and epoxy groups in graphene oxide to generate covalent crosslinking action, so that the chemical protection fabric with excellent chemical protection performance and good moisture permeability is obtained under the synergistic action of a multilayer structure.
The invention also provides application of the moisture-permeable chemical protective fabric prepared by the technical scheme or the preparation method in the technical scheme in manufacturing chemical protective clothing.
The preparation method of the moisture-permeable chemical protective fabric in the invention is not particularly limited, and the method for preparing the chemical protective fabric by using the fabric known by the technical personnel in the field can be adopted.
In the invention, the moisture-permeable chemical protection fabric has excellent chemical protection performance and good moisture permeability; and the decorative layer and the substrate layer have high bonding strength, and can be used for manufacturing chemical protective clothing.
The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. It should be apparent that the described embodiments are only some embodiments of the present invention, and not all embodiments. All other embodiments, which can be obtained by a person skilled in the art without making any creative effort based on the embodiments in the present invention, belong to the protection scope of the present invention.
Example 1
The moisture permeable chemical protection fabric consists of a substrate layer and a graphene oxide layer which are sequentially arranged; the base layer is composed of a base material consisting of fibers, a polydopamine layer coated on the surface of the fibers and a polyethylene imine layer coated on the surface of the polydopamine layer.
The preparation method of the moisture permeable chemical protective fabric comprises the following steps:
(1) Soaking the substrate material in an ethanol solution for ultrasonic cleaning, and airing for later use;
(2) 1.21g Tris was weighed into 1000mL water. Soaking a polyethylene nanofiber membrane serving as a substrate into a Tris solution, adding 2g of dopamine hydrochloride, stirring for 24 hours at the stirring speed of 300rpm, taking out the fiber membrane, washing with deionized water until no black polydopamine falls off on the surface, and drying at 50 ℃ for 30min to obtain a composite material with a polydopamine layer coated on the surface;
(3) 0.36g Tris was dissolved in 250mL water. Dissolving 1.8g of polyethyleneimine in 50mL of water, adding 50mL of polyethyleneimine solution into the Tris solution, and dropwise adding dilute hydrochloric acid until the pH value of the solution is between 8 and 9 to obtain 6mg/mL of polyethyleneimine solution. Then immersing the composite material with the surface coated with the polydopamine layer into a polyethyleneimine solution, stirring by magnetons for 24 hours, then taking out, washing by deionized water, and drying for 30min at 50 ℃ to obtain a substrate layer;
(4) Taking a certain amount of graphene oxide aqueous dispersion, carrying out centrifugal separation, removing supernatant, dispersing lower layer slurry in absolute ethyl alcohol, repeatedly centrifuging three times to obtain graphene oxide ethanol dispersion, carrying out ultrasonic treatment for 30min, vacuumizing to remove bubbles in the dispersion, and adjusting the concentration of the dispersion to 9.57mg/mL. Wetting a substrate layer with ethanol, spreading the substrate layer on a glass plate, airing, setting the scale of a scraper to be 1.0mm, setting the propelling speed of the scraper to be 20mm/s, blade-coating a layer of 9.57mg/mL graphene oxide ethanol dispersion liquid on the surface of a fiber membrane, and airing to obtain the moisture-permeable chemical protective fabric.
Test example 1
The composite material with the surface coated with the polydopamine layer prepared in the step (2) of example 1 was tested by X-ray photoelectron spectroscopy, and XPS shown in fig. 1 was obtained. As can be seen from fig. 1, the content of N in the composite material with the surface coated with the poly-dopamine layer is 6.26%, which indicates that the poly-dopamine is coated on the polyethylene nanofiber membrane.
The polyethylene nanofiber film used in example 1 was observed by a scanning electron microscope, and an SEM image thereof is shown in fig. 2. Scanning electron microscopy is adopted to observe the composite material with the surface coated with the poly dopamine layer prepared in the step (2) of the example 1, and an SEM image is obtained and shown in FIG. 3. As can be seen from fig. 2 and 3, after the poly dopamine layer is coated, the surface of the polyethylene nanofiber membrane is roughened, and the stripe-shaped gully lines are eliminated, because the poly dopamine layer is coated on the PE surface by the self-polymerization of dopamine.
The surface-coated polydopamine layer prepared in the step (2) of example 1 was tested by an infrared spectrometer, and an infrared spectrogram thereof is shown in fig. 4. As can be seen from FIG. 4, the infrared spectrum is 3000cm -1 To 3600cm -1 The broad peaks in (A) correspond to-OH and-NH 2 Vibration by extension of 1650cm -1 Is corresponding to-NH 2 The bending vibration of (2) indicates that the poly-dopamine is coated on the polyethylene nanofiber membrane.
The substrate layer prepared in step (3) of example 1 was tested by X-ray photoelectron spectroscopy, and XPS chart 5 was obtained. As can be seen in fig. 5, the N content of the base layer was 14.9%, indicating that the composite was coated with polyethyleneimine.
Scanning electron microscopy was used to observe the substrate layer prepared in step (3) of example 1, and the SEM image is shown in FIG. 6. As can be seen from fig. 6, the surface roughness of the polyethylene nanofiber film further increased after coating with polyethyleneimine.
The substrate layer prepared in step (3) of example 1 was tested using an infrared spectrometer and the infrared spectrum is shown in fig. 4. As can be seen from FIG. 4, the infrared spectrum is 1560cm -1 A new peak corresponding to C = N stretching vibration is present, indicating that the poly-dopamine and polyethyleneimine have michael addition reactions.
An X-ray single crystal diffractometer is used to detect the moisture-permeable chemical protective fabric prepared in step (4) of example 1, and an XRD pattern is obtained as shown in fig. 7. Calculated from the XRD spectrum in fig. 7, the interlayer spacing of the GO film in the composite fabric was 0.82nm. The graphene oxide film has a good layered structure and can provide a fast channel for water molecules.
Comparative example 1
The chemical protection fabric consists of a substrate layer and a graphene oxide layer which are sequentially arranged; the base layer is composed of a base material composed of fibers and a polydopamine layer coated on the surfaces of the fibers.
The preparation method of the chemical protective fabric comprises the following steps:
(1) Soaking the base material in an ethanol solution, ultrasonically cleaning, and airing for later use;
(2) 1.21g of Tris was weighed out and dissolved in 1000mL of water, followed by stirring and dissolution. Soaking a polyethylene nanofiber membrane serving as a substrate into a Tris solution, adding 2g of dopamine hydrochloride, stirring for 24 hours at the stirring speed of 300rpm, taking out the fiber membrane, washing with deionized water until no black polydopamine falls off on the surface, and drying at 50 ℃ for 30min to obtain the polydopamine-layer-coated fiber membrane for later use.
(3) Taking a certain amount of graphene oxide aqueous dispersion, carrying out centrifugal separation, removing supernatant, dispersing lower layer slurry in absolute ethyl alcohol, repeatedly centrifuging three times to obtain graphene oxide ethanol dispersion, carrying out ultrasonic treatment for 30min, vacuumizing to remove bubbles in the dispersion, and adjusting the concentration of the dispersion to 9.57mg/mL. Wetting the fiber membrane coated with the polydopamine layer by using ethanol, flatly paving the fiber membrane on a glass plate, airing, setting the scale of a scraper to be 1.0mm, setting the propelling speed of the scraper to be 20mm/s, blade-coating a layer of 9.57mg/mL graphene oxide ethanol dispersion liquid on the surface of the fiber membrane, and airing to obtain the chemical protection fabric.
Comparative example 2
Taking a certain amount of graphene oxide aqueous dispersion, carrying out centrifugal separation, removing supernatant, dispersing lower layer slurry in absolute ethyl alcohol, repeatedly centrifuging three times to obtain graphene oxide ethanol dispersion, carrying out ultrasonic treatment for 30min, vacuumizing to remove bubbles in the dispersion, and adjusting the concentration of the dispersion to 9.57mg/mL. Wetting a polyethylene nanofiber membrane with ethanol, spreading the polyethylene nanofiber membrane on a glass plate, airing, setting the scale of a scraper to be 1.0mm, setting the propelling speed of the scraper to be 20mm/s, blade-coating a layer of 9.57mg/mL graphene oxide ethanol dispersion on the surface of the fiber membrane, and airing to obtain the chemical protection fabric. Wherein the mass ratio of the substrate layer to the graphene oxide film layer is 10.
Test example 2
The protective fabrics prepared in example 1, comparative example 1 and comparative example 2 were respectively subjected to the peel strength test under the following conditions: the sample width was 1.5cm; the length is 10cm; the stretching speed is 100mm/min; the stretching mode is T-shaped peeling. The test results are shown in table 1.
Table 1 peel strength of protective fabrics prepared in example 1 and comparative examples 1 to 2
Material Example 1 Comparative example 1 Comparative example 2
Peel strength (N/1.5 cm) 0.48±0.06 0.24±0.03 0.13±0.02
As can be seen from the table 1, after the modification of the polydopamine, the polyethyleneimine and the graphene oxide, the bonding strength between the modification layer and the substrate of the protective fabric is obviously enhanced, and the peel strength is improved from 0.13 +/-0.02N/1.5 cm to 0.48 +/-0.06N/1.5 cm by 3 times.
The fabrics prepared in the step (2) of example 1, the step (3) of example 1 and the step (4) of example 1 were respectively subjected to a moisture permeability test, and were tested by a water vapor transmission rate tester according to the first partial moisture absorption method of GB/T12704.1-2009, and the results are shown in table 2.
TABLE 2 example 1 moisture vapor transmission Properties of the face fabric prepared in steps (2) to (4)
Figure BDA0003489209300000111
As can be seen from Table 2, after the modification of dopamine, polyethyleneimine and graphene oxide, the moisture permeability of the protective fabric is 4000 g/(m) 2 24 h) above, completely meeting the requirements of the moisture permeable protective clothing.
The polyethylene nanofiber membrane used in example 1, the protective fabric prepared in example 1, and the rubber chemical protective clothing material were subjected to chemical protective performance tests, respectively, using a permeation cell according to GB/T23462-2009. The chemical protective performance of the protective fabric prepared in example 1 on the thiopentan and the comparison between the chemical protective fabric and the rubber chemical protective clothing material and the polyethylene nanofiber membrane are respectively shown in table 3:
table 3 chemical protective properties of protective fabrics prepared in example 1
Figure BDA0003489209300000121
As can be seen from table 3, after the modification of dopamine, polyethyleneimine and graphene oxide, the chemical protective performance of the protective fabric is significantly enhanced.
The data show that the binding force between the moisture-permeable chemical protection fabric modification layer prepared by the invention and the fabric substrate is strong, and the fabric has excellent moisture permeability and chemical protection.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and amendments can be made without departing from the principle of the present invention, and these modifications and amendments should also be considered as the protection scope of the present invention.

Claims (8)

1. A moisture permeable chemical protection fabric is composed of a substrate layer and a graphene oxide layer which are sequentially arranged;
the base layer is a base material consisting of fibers, a polydopamine layer coated on the surface of the fibers and a polyethylene imine layer coated on the surface of the polydopamine layer;
the substrate material is a high-strength flame-retardant fabric or a hydrophobic fabric;
the preparation method of the moisture permeable chemical protective fabric comprises the following steps:
(1) Dipping the substrate material in a dopamine hydrochloride solution to obtain a composite material with a surface coated with a polydopamine layer;
(2) Soaking the composite material with the surface coated with the polydopamine layer obtained in the step (1) in a polyethyleneimine solution for addition reaction to obtain a substrate layer;
(3) And (3) coating the graphene oxide dispersion liquid on one side of the substrate layer obtained in the step (2), and carrying out a crosslinking reaction to obtain the moisture-permeable chemical protective fabric.
2. The method for preparing the moisture permeable chemical protective fabric according to claim 1 comprises the following steps:
(1) Dipping the substrate material in a dopamine hydrochloride solution to obtain a composite material with a surface coated with a polydopamine layer;
(2) Soaking the composite material with the surface coated with the polydopamine layer obtained in the step (1) in a polyethyleneimine solution for addition reaction to obtain a substrate layer;
(3) And (3) coating the graphene oxide dispersion liquid on one side of the substrate layer obtained in the step (2), and carrying out a crosslinking reaction to obtain the moisture-permeable chemical protective fabric.
3. The preparation method according to claim 2, wherein the concentration of the dopamine hydrochloride solution in the step (1) is 0.5 to 6g/L.
4. The method according to claim 2, wherein the concentration of the polyethyleneimine solution in the step (2) is 2.0 to 10.0g/L.
5. The method according to claim 2, wherein the time for the impregnation in the step (1) and the step (2) is independently 8 to 24 hours.
6. The method according to claim 2, wherein the concentration of the graphene oxide dispersion liquid in the step (3) is 8.0 to 12.0g/L.
7. The method according to claim 6, wherein the graphene oxide dispersion liquid applied in the step (3) has a thickness of 0.5 to 2.5mm.
8. The application of the moisture-permeable chemical protective fabric of claim 1 or the moisture-permeable chemical protective fabric prepared by the preparation method of any one of claims 2 to 7 in the preparation of chemical protective clothing.
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