WO2021103181A1 - Electrically-conductive humidity-sensitive textile having a janus structure and humidity responsiveness - Google Patents

Electrically-conductive humidity-sensitive textile having a janus structure and humidity responsiveness Download PDF

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WO2021103181A1
WO2021103181A1 PCT/CN2019/125137 CN2019125137W WO2021103181A1 WO 2021103181 A1 WO2021103181 A1 WO 2021103181A1 CN 2019125137 W CN2019125137 W CN 2019125137W WO 2021103181 A1 WO2021103181 A1 WO 2021103181A1
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textile
humidity
hydrophobic
conductive
janus structure
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PCT/CN2019/125137
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French (fr)
Chinese (zh)
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刘海峰
王美淑
魏俊锋
孙一峰
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广东省测试分析研究所（中国广州分析测试中心）
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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
    • D06M11/73—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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/04—Acids; Metal salts or ammonium salts thereof
    • C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/34—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate
    • 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
    • D06M11/83—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 metals; with metal-generating compounds, e.g. metal carbonyls; Reduction of metal compounds on textiles
    • 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
    • D06M13/165—Ethers
    • 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
    • D06M13/244—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 sulfur or phosphorus
    • D06M13/248—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 sulfur or phosphorus with compounds containing sulfur
    • D06M13/252—Mercaptans, thiophenols, sulfides or polysulfides, e.g. mercapto acetic acid; Sulfonium compounds
    • 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
    • D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/263—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof
    • 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
    • D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/263—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof
    • D06M15/267—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof of unsaturated carboxylic esters having amino or quaternary ammonium groups
    • 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
    • D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/356—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of other unsaturated compounds containing nitrogen, sulfur, silicon or phosphorus atoms
    • D06M15/3568—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of other unsaturated compounds containing nitrogen, sulfur, silicon or phosphorus atoms containing silicon
    • 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
    • D06M15/643—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
    • D06M2200/10—Repellency against liquids
    • D06M2200/12—Hydrophobic properties

Definitions

  • the invention belongs to the technical field of polymer materials and the technical field of functional textiles, and specifically relates to a Janus structure conductive wet-sensing textile with humidity responsiveness.
  • textiles with conductive functions have become the basic facilities of wearable devices. Textiles are no longer simply a function of keeping warm and beautiful, but also a carrier of smart devices. Common conductive textiles simply have a conductive function, but do not have responsiveness such as temperature and humidity.
  • the purpose of the present invention is to overcome the shortcomings of the prior art and provide a Janus structure conductive wet-sensing textile with humidity responsiveness.
  • the present invention loads the textile on the textile through a specific route design with conductive materials and temperature and humidity responsive polymer materials.
  • the surface imparts functionality to textiles and has potential uses in the field of smart textiles.
  • the purpose of the present invention is to provide a Janus structure conductive wet textile with humidity responsiveness, which is prepared by the following steps:
  • the pre-treated textile into the hydrophobic layer solution for 10-60 seconds. After the textile is taken out, it will be pressed to control the scalping rate of the textile to 80-170%, and then the textile will be irradiated with ultraviolet light on one side for 10 ⁇ 100s, the one-sided hydrophobic textile is obtained after washing the textile;
  • conductive wet textiles Disperse 1-20 parts by mass of hydrophilic polymer materials and 0.1-5 parts by mass of conductive materials in water, mix them evenly, and prepare a water dispersion with a mass fraction of 1 to 5%.
  • the water dispersion is dipped or coated to treat the unilateral hydrophobic textile prepared in step (1), and the treated unilateral hydrophobic textile is dried to obtain a conductive wet textile.
  • the solvent is selected from one of ethyl acetate, toluene, butyl acetate and tetrahydrofuran.
  • the aqueous dispersion is dipped into the hydrophobic textile prepared in step (1), and the treated hydrophobic textile is dried to obtain a conductive wet textile.
  • the specific steps are: immerse the hydrophobic textile prepared in step (1) in the aqueous dispersion, Due to the hydrophobicity of the hydrophobic layer on the hydrophobic textile, only the unmodified side can infiltrate the water dispersion. After the textile is taken out, use water to wash a small amount of liquid adhered to the hydrophobic layer, and put it in an oven at 120 ⁇ 170°C to dry for 3 ⁇ 120min. Got.
  • the aqueous dispersion is applied to the hydrophobic layer textile prepared in step (1), and the treated hydrophobic textile is dried to obtain a conductive wet textile.
  • the specific steps are: coating the aqueous dispersion on the textile in a certain pattern. On the water side, due to the hydrophobicity of the hydrophobic layer on the hydrophobic textile, only the unmodified side can absorb the water dispersion to obtain the modified effect. Put it in an oven at 120 ⁇ 170°C for 3 ⁇ 120min to obtain a moderate responsiveness of specific patterns or lines. Moisture-conducting textiles.
  • the pretreatment step of the pretreated textile is: washing the textile in water to remove dust and oil stains on the textile, and then drying to obtain the pretreated textile.
  • the wavelength of the ultraviolet light is 365 nm.
  • the hydrophilic polymer material is prepared by the following steps: 90-95 parts by mass of acrylic monomer and 5-10 parts by mass of ⁇ -methacryloxypropyltrimethoxysilane in a solvent The mixture is uniformly mixed, and 1 to 5 parts by mass of initiator are added, and a polymerization reaction occurs at 50 to 80° C. for 2 to 20 hours to prepare a hydrophilic polymer material.
  • the acrylic monomer is selected from the group consisting of dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, diethylaminoethyl acrylate, diethylaminoethyl methacrylate, methacrylic acid and methacrylic acid.
  • One of acyloxyethyl trimethylammonium chloride is selected from the group consisting of dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, diethylaminoethyl acrylate, diethylaminoethyl methacrylate, methacrylic acid and methacrylic acid.
  • acyloxyethyl trimethylammonium chloride One of acyloxyethyl trimethylammonium chloride.
  • the conductive material is selected from one of single-walled carbon nanotubes, multi-walled carbon nanotubes, graphene, expanded graphene, conductive graphite, and silver nanowires.
  • the solvent is selected from one of methanol, ethanol, dichloromethane, tetrahydrofuran and ethyl acetate.
  • the initiator is azobisisobutyronitrile or azobisisoheptonitrile.
  • the textile is a non-woven fabric or knitted fabric.
  • the specific step of drying the treated hydrophobic layer textile is: the treated hydrophobic layer textile is placed in an oven at 120-170° C. and dried for 3 to 120 minutes.
  • hydrophilic polymer (2) The introduction of ⁇ -methacryloxypropyltrimethoxysilane into the hydrophilic polymer can cross-link the polymer during curing and at the same time cure the conductive material to give the textile conductive properties.
  • the latter hydrophilic polymer will undergo volume changes (hydrogels) under different humidity conditions, which will cause changes in the electrical conductivity of the textiles, resulting in changes in electrical properties. It is used as an electrical switch to give moisture responsiveness.
  • Figure 1 is a diagram showing the humidity change of the conductive and wet-sensing wet non-woven fabric prepared in Example 1;
  • Example 2 is a graph showing the change in electrical conductivity of the conductive and moisture-sensitive wet non-woven fabric prepared in Example 1 with humidity.
  • the equipment and reagents used in the present invention are conventional commercially available products in the technical field.
  • a Janus structure conductive wet textile with humidity responsiveness is prepared by the following steps:
  • Figure 2 shows that when the water content increases, the gel system swells, resulting in less contact with the conductive material between the dopants, and thus the resistance increases.
  • hydrophilic polymer material is prepared by the following steps: dissolving 95g of dimethylaminoethyl methacrylate, 5g of ⁇ -methacryloxypropyltrimethoxysilane, and 2g of azobisisobutyronitrile in 500g of absolute ethanol In the reaction at 65°C for 10 hours, a hydrophilic polymer material was obtained.
  • Humidity detection The sample size is 90mm 2 , the brine is prepared according to AATCC-15, 16.6g of brine is dropped on the hydrophobic side of the textile within 20s, and the humidity is measured with a humidity meter.
  • Step (2) adds 6 g of hydrophilic polymer (calculated based on the solid content) to prepare a 1% water dispersion with a mass fraction.
  • the result showed no conductivity, and humidity could not be measured.
  • Step (2) adds 6 g of multi-walled carbon nanotubes, and prepares a 1% aqueous dispersion with a mass fraction. Can not form a film.
  • a Janus structure conductive wet textile with humidity responsiveness is prepared by the following steps:
  • hydrophilic polymer material is prepared by the following steps: 95g of dimethylaminoethyl acrylate, 5g of ⁇ -methacryloxypropyltrimethoxysilane, 5g of azobisisobutyronitrile are dissolved in 500g of tetrahydrofuran at 50°C React for 20h to obtain hydrophilic polymer material.
  • a Janus structure conductive wet textile with humidity responsiveness is prepared by the following steps:
  • hydrophilic polymer material is prepared by the following steps: dissolving 90 g of diethylaminoethyl acrylate, 10 g of ⁇ -methacryloxypropyl trimethoxysilane, and 5 g of azobisisoheptonitrile in 500 g of ethanol, React at 65°C for 10 hours to obtain a hydrophilic polymer material.
  • a Janus structure conductive wet textile with humidity responsiveness is prepared by the following steps:
  • the rate is controlled at 170%, and then placed in a UV box for single-side irradiation (365nm), taken out after 100s, and washed with ethyl acetate to prepare a single-side hydrophobic non-woven fabric.
  • hydrophilic polymer material is prepared by the following steps: 95g methacrylic acid, 5g ⁇ -methacryloxypropyltrimethoxysilane, 5g azobisisobutyronitrile are dissolved in 500g tetrahydrofuran and reacted at 50°C for 20h. Hydrophilic polymer material.
  • a Janus structure conductive wet textile with humidity responsiveness is prepared by the following steps:
  • the scouring rate is controlled at 100%, and then placed in a UV box for unilateral irradiation (365nm), taken out after 15s, and washed with ethyl acetate to prepare a unilateral hydrophobic non-woven fabric.
  • conductive wet-sensitive non-woven fabric Disperse 1g of hydrophilic polymer material (calculated based on solid content) and 5g of conductive graphene in water, prepare a 5% water dispersion, and use ultrasonic dispersion to obtain Stable dispersion.
  • the hydrophobic non-woven fabric prepared in step (1) is immersed in the aqueous dispersion. Due to the hydrophobicity of the hydrophobic layer, only the unmodified side can be infiltrated into the aqueous dispersion. After taking it out, use water to wash a small amount of liquid adhered to the hydrophobic layer. Put it into an oven at 170°C and dry for 3 minutes.
  • hydrophilic polymer material is prepared by the following steps: dissolving 90 g of methacryloxyethyl trimethylammonium chloride, 10 g of ⁇ -methacryloxypropyl trimethoxysilane, and 5 g of azobisisobutyronitrile
  • the hydrophilic polymer material was obtained by reacting in 1000g ethanol at 80°C for 2h.
  • a Janus structure conductive wet textile with humidity responsiveness is prepared by the following steps:
  • polyvinyl silicone oil vinyl content of 10%, 500CS
  • the hydrophobic non-woven fabric prepared in step (1) is immersed in the aqueous dispersion. Due to the hydrophobicity of the hydrophobic layer, only the unmodified side can infiltrate the aqueous dispersion. A small amount of liquid adhered to the hydrophobic layer was washed, and dried in an oven at 170°C for 3 minutes to prepare a conductive wet non-woven fabric.
  • hydrophilic polymer material is prepared by the following steps: dissolve 90g methacrylic acid, 10g ⁇ -methacryloxypropyltrimethoxysilane, 1g azobisisobutyronitrile in 500g ethanol, and react at 65°C for 16h. Hydrophilic polymer material.

Abstract

An electrically-conductive humidity-sensitive textile having a Janus structure and humidity responsiveness, which is prepared by the following steps: (1) uniformly mixing a polyvinyl silicone oil, pentaerythritol tetrakis(3-mercaptopropionate), benzoin dimethyl ether, and a solvent to prepare a hydrophobic layer solution, immersing a pretreated textile into the hydrophobic layer solution, taking out the textile and press-rolling same, irradiating a single side of the textile with ultraviolet for 1s - 100s, and washing the textile, so as to obtain a hydrophobic textile; and (2) dissolving a hydrophilic polymer material and an electrically-conductive material in water to prepare an aqueous dispersion, treating the hydrophobic textile with the aqueous dispersion, and drying the treated hydrophobic textile, so as to obtain an electrically-conductive humidity-sensitive textile. Loading an electrically-conductive material and a temperature-responsive and humidity-responsive polymer material on the surface of the textile by means of a specifically designed route imparts functionality to the textile, providing potential use in the field of smart textiles.

Description

一种具有湿度响应性的Janus结构导电感湿纺织品A Janus structure conductive wet textile with humidity responsiveness 技术领域：Technical field:
本发明属于高分子材料技术领域和功能纺织品技术领域，具体涉及一种具有湿度响应性的Janus结构导电感湿纺织品。The invention belongs to the technical field of polymer materials and the technical field of functional textiles, and specifically relates to a Janus structure conductive wet-sensing textile with humidity responsiveness.
背景技术：Background technique:
随着生活水平的提高及电子信息产品依赖程度不断增强，具有导电功能的纺织品成为了可穿戴设备的基础性设施。纺织品不再是单纯的保暖美观功能，更是智能设备的一种载体。常见的导电纺织品单纯具有导电功能，而不具备温度、湿度等响应性。With the improvement of living standards and the increasing dependence on electronic information products, textiles with conductive functions have become the basic facilities of wearable devices. Textiles are no longer simply a function of keeping warm and beautiful, but also a carrier of smart devices. Common conductive textiles simply have a conductive function, but do not have responsiveness such as temperature and humidity.
发明内容：Summary of the invention:
本发明的目的在于克服现有技术的不足，提供一种具有湿度响应性的Janus结构导电感湿纺织品，本发明通过将导电材料与温度、湿度响应性高分子材料通过特定的路线设计负载于纺织品表面，赋予纺织品功能性，在智能纺织品领域有着潜在用途。The purpose of the present invention is to overcome the shortcomings of the prior art and provide a Janus structure conductive wet-sensing textile with humidity responsiveness. The present invention loads the textile on the textile through a specific route design with conductive materials and temperature and humidity responsive polymer materials. The surface imparts functionality to textiles and has potential uses in the field of smart textiles.
本发明的目的在于提供一种具有湿度响应性的Janus结构导电感湿纺织品，由如下步骤制备得到：The purpose of the present invention is to provide a Janus structure conductive wet textile with humidity responsiveness, which is prepared by the following steps:
(1)单侧疏水纺织品制备：将多乙烯基硅油、四(3-巯基丙酸)季戊四醇酯、安息香双甲醚和溶剂混合均匀配制成质量分数为0.5～2％的疏水层溶液，所述的多乙烯基硅油中的乙烯基与四(3-巯基丙酸)季戊四醇酯的巯基的摩尔比为0.8～1.2，安息香双甲醚的加入量按照每1mol巯基加入0.005～0.02mol安息香双甲醚的量加入量，将预处理后的纺织品浸入疏水层溶液中10～60s，纺织品取出后进行压扎，使纺织品的轧余率控制在80～170％，然后将纺织品进行紫外光单侧照射10～100s，将纺织品洗净后制得单侧疏水纺织品；(1) Preparation of one-sided hydrophobic textile: mix polyvinyl silicone oil, tetrakis (3-mercaptopropionic acid) pentaerythritol ester, benzoin dimethyl ether and solvent to form a hydrophobic layer solution with a mass fraction of 0.5-2%. The molar ratio of the vinyl group in the polyvinyl silicone oil to the mercapto group of the pentaerythritol tetrakis (3-mercaptopropionic acid) pentaerythritol ester is 0.8 to 1.2, and the amount of benzoin dimethyl ether added is 0.005 to 0.02 mol benzoin dimethyl ether per 1 mol mercapto group. Dip the pre-treated textile into the hydrophobic layer solution for 10-60 seconds. After the textile is taken out, it will be pressed to control the scalping rate of the textile to 80-170%, and then the textile will be irradiated with ultraviolet light on one side for 10 ~100s, the one-sided hydrophobic textile is obtained after washing the textile;
(2)导电感湿纺织品制备：将1～20质量份亲水性高分子材料和0.1～5质量份导电材料分散于水中，混合均匀后配制成质量分数为1～5％的水分散液，水分散液通过浸渍或涂布的方法处理步骤(1)制备的单侧疏水纺织品，处理后的单侧疏水纺织品烘干制得导电感湿纺织品。所述的溶剂选自乙酸乙酯、甲苯、醋酸丁酯和四氢呋喃中的一种。(2) Preparation of conductive wet textiles: Disperse 1-20 parts by mass of hydrophilic polymer materials and 0.1-5 parts by mass of conductive materials in water, mix them evenly, and prepare a water dispersion with a mass fraction of 1 to 5%. The water dispersion is dipped or coated to treat the unilateral hydrophobic textile prepared in step (1), and the treated unilateral hydrophobic textile is dried to obtain a conductive wet textile. The solvent is selected from one of ethyl acetate, toluene, butyl acetate and tetrahydrofuran.
Figure PCTCN2019125137-appb-000001
Figure PCTCN2019125137-appb-000001
Figure PCTCN2019125137-appb-000002
Figure PCTCN2019125137-appb-000002
水分散液通过浸渍的方法处理步骤(1)制备的疏水纺织品，处理后的疏水纺织品烘干制得导电感湿纺织品的具体步骤是：将步骤(1)制备的疏水纺织品浸入水分散液中，由于疏水纺织品上疏水层的疏水性，只有未改性侧能够浸润水分散液，纺织品取出后使用水将疏水层粘附的少量液体洗净，放入烘箱120～170℃烘干3～120min制得。The aqueous dispersion is dipped into the hydrophobic textile prepared in step (1), and the treated hydrophobic textile is dried to obtain a conductive wet textile. The specific steps are: immerse the hydrophobic textile prepared in step (1) in the aqueous dispersion, Due to the hydrophobicity of the hydrophobic layer on the hydrophobic textile, only the unmodified side can infiltrate the water dispersion. After the textile is taken out, use water to wash a small amount of liquid adhered to the hydrophobic layer, and put it in an oven at 120～170℃ to dry for 3～120min. Got.
水分散液通过涂布的方法处理步骤(1)制备的疏水层纺织品，处理后的疏水纺织品烘干制得导电感湿纺织品的具体步骤是：将水分散液按照一定的图案涂布于纺织品亲水侧，由于疏水纺织品上疏水层的疏水性，只有未改性侧能够吸收水分散液获得改性效果，放入烘箱120～170℃烘干3～120min制得特定图案或线路的适度响应性导湿纺织品。The aqueous dispersion is applied to the hydrophobic layer textile prepared in step (1), and the treated hydrophobic textile is dried to obtain a conductive wet textile. The specific steps are: coating the aqueous dispersion on the textile in a certain pattern. On the water side, due to the hydrophobicity of the hydrophobic layer on the hydrophobic textile, only the unmodified side can absorb the water dispersion to obtain the modified effect. Put it in an oven at 120～170℃ for 3～120min to obtain a moderate responsiveness of specific patterns or lines. Moisture-conducting textiles.
优选地，所述的预处理后的纺织品的预处理步骤是：将纺织品放入水中清洗以去除纺织品上的尘土和油渍，然后烘干即得预处理后的纺织品。Preferably, the pretreatment step of the pretreated textile is: washing the textile in water to remove dust and oil stains on the textile, and then drying to obtain the pretreated textile.
优选地，所述的紫外光波长为365nm。Preferably, the wavelength of the ultraviolet light is 365 nm.
优选地，所述的亲水性高分子材料由如下步骤制备得到：将90～95质量份丙烯酸单体 与5～10质量份γ-甲基丙烯酰氧基丙基三甲氧基硅烷在溶剂中混合均匀，再加入1～5质量份引发剂，在50～80℃下发生聚合反应2～20h制得亲水性高分子材料。Preferably, the hydrophilic polymer material is prepared by the following steps: 90-95 parts by mass of acrylic monomer and 5-10 parts by mass of γ-methacryloxypropyltrimethoxysilane in a solvent The mixture is uniformly mixed, and 1 to 5 parts by mass of initiator are added, and a polymerization reaction occurs at 50 to 80° C. for 2 to 20 hours to prepare a hydrophilic polymer material.
优选地，所述的丙烯酸单体选自丙烯酸二甲胺乙酯、甲基丙烯酸二甲胺乙酯、丙烯酸二乙胺乙酯、甲基丙烯酸二乙胺乙酯、甲基丙烯酸和甲基丙烯酰氧乙基三甲基氯化铵中的一种。Preferably, the acrylic monomer is selected from the group consisting of dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, diethylaminoethyl acrylate, diethylaminoethyl methacrylate, methacrylic acid and methacrylic acid. One of acyloxyethyl trimethylammonium chloride.
优选地，所述的导电材料选自单壁碳纳米管、多壁碳纳米管、石墨烯、膨胀石墨烯、导电石墨和纳米银线中的一种。Preferably, the conductive material is selected from one of single-walled carbon nanotubes, multi-walled carbon nanotubes, graphene, expanded graphene, conductive graphite, and silver nanowires.
优选地，所述的溶剂选自甲醇、乙醇、二氯甲烷、四氢呋喃和乙酸乙酯中的一种。Preferably, the solvent is selected from one of methanol, ethanol, dichloromethane, tetrahydrofuran and ethyl acetate.
优选地，所述的引发剂为偶氮二异丁腈或偶氮二异庚腈。Preferably, the initiator is azobisisobutyronitrile or azobisisoheptonitrile.
优选地，所述的纺织品为无纺布或针织布。Preferably, the textile is a non-woven fabric or knitted fabric.
优选地，所述的处理后的疏水层纺织品烘干具体步骤是：处理后的疏水层纺织品放入烘箱120～170℃烘干3～120min。Preferably, the specific step of drying the treated hydrophobic layer textile is: the treated hydrophobic layer textile is placed in an oven at 120-170° C. and dried for 3 to 120 minutes.
本发明的有益效果是：The beneficial effects of the present invention are:
(1)本发明通过疏水-亲水的Janus结构，将体表产生的水分导出、富集到纺织品表面，获得透气干爽穿着体验；(1) In the present invention, through the hydrophobic-hydrophilic Janus structure, the moisture generated on the body surface is led out and enriched to the surface of the textile to obtain a breathable and dry wearing experience;
(2)在亲水高分子中引入了γ-甲基丙烯酰氧基丙基三甲氧基硅烷，可使高分子在固化时发生交联，同时将导电材料固化，赋予纺织品导电特性，由于固化后的亲水性高分子在不同湿度条件下会发生体积的变化(水凝胶)，造成纺织品的电导率发生变化，从而产生电性能的变化，作为电开关使用，赋予了湿度响应性。(2) The introduction of γ-methacryloxypropyltrimethoxysilane into the hydrophilic polymer can cross-link the polymer during curing and at the same time cure the conductive material to give the textile conductive properties. The latter hydrophilic polymer will undergo volume changes (hydrogels) under different humidity conditions, which will cause changes in the electrical conductivity of the textiles, resulting in changes in electrical properties. It is used as an electrical switch to give moisture responsiveness.
附图说明：Description of the drawings:
图1为实施例1制备得到的导电感湿感湿无纺布湿度变化图；Figure 1 is a diagram showing the humidity change of the conductive and wet-sensing wet non-woven fabric prepared in Example 1;
图2为实施例1制备得到的导电感湿感湿无纺布的电导率随湿度变化图。2 is a graph showing the change in electrical conductivity of the conductive and moisture-sensitive wet non-woven fabric prepared in Example 1 with humidity.
具体实施方式：Detailed ways:
以下实施例是对本发明的进一步说明，而不是对本发明的限制。The following examples are to further illustrate the present invention, but not to limit the present invention.
下面结合具体实例，进一步阐明本发明。应该理解，这些实施例仅用于说明本发明，而不用于限定本发明的保护范围。在实际应用中技术人员根据本发明做出的改进和调整，仍属于本发明的保护范围。The present invention will be further clarified below in conjunction with specific examples. It should be understood that these embodiments are only used to illustrate the present invention, but not to limit the protection scope of the present invention. Improvements and adjustments made by technicians according to the present invention in practical applications still belong to the protection scope of the present invention.
本发明使用的设备和试剂为本技术领域常规市购产品。The equipment and reagents used in the present invention are conventional commercially available products in the technical field.
实施例1：Example 1:
一种具有湿度响应性的Janus结构导电感湿纺织品，由如下步骤制备得到：A Janus structure conductive wet textile with humidity responsiveness is prepared by the following steps:
(1)单侧疏水无纺布制备：：将多乙烯基硅油(10％乙烯基含量，粘度500CS)、四(3-巯基丙酸)季戊四醇酯按照n 乙烯基/n 巯基＝1比例加料，加入巯基1mol％量的安息香双甲醚，使用乙酸乙酯溶解混合均匀配制成1％的疏水层溶液，将待处理的无纺布浸入疏水层溶液中浸渍10s，取出后用轧机压扎，轧余率控制在100％，然后放入紫外箱中单侧照射(365nm)，10s后取出，使用乙酸乙酯洗净后制得单侧疏水无纺布。 (1) Preparation of one-side hydrophobic non-woven fabric: Add polyvinyl silicone oil (10% vinyl content, viscosity 500CS), tetrakis (3-mercaptopropionic acid) pentaerythritol ester according to the ratio of n vinyl group/n mercapto group = 1, Add 1 mol% of mercapto benzoin dimethyl ether, use ethyl acetate to dissolve and mix uniformly to prepare a 1% hydrophobic layer solution, immerse the non-woven fabric to be treated in the hydrophobic layer solution for 10 seconds, take it out, and press it with a rolling machine. The residual rate is controlled at 100%, and then placed in a UV box for unilateral irradiation (365nm), taken out after 10s, and washed with ethyl acetate to prepare a unilateral hydrophobic non-woven fabric.
(2)导电感湿导湿感湿无纺布的制备：将1g亲水性高分子(按固含量计算)和5g多壁碳纳米管分散于水中，配制质量分数为1％水分散液，使用超声分散，获得稳定的分散液。将步骤(1)制备的单侧疏水无纺布的亲水侧浮于浸入水分散液中，由于疏水无纺布疏水层的疏水性，只有未改性侧能够浸润水分散液，取出后放入烘箱170℃烘干3min制得导电感湿感湿无纺布。其湿度响应如图1所示，从图1可以看出，当测试开始时， 疏液测基本保持着水含量不变，而亲液侧水含量迅速增加，在25s后得到饱和。(2) Preparation of conductive, moisture-sensitive and moisture-conducting non-woven fabric: Disperse 1g of hydrophilic polymer (calculated based on solid content) and 5g of multi-walled carbon nanotubes in water to prepare a 1% water dispersion. Use ultrasonic dispersion to obtain a stable dispersion. The hydrophilic side of the one-sided hydrophobic non-woven fabric prepared in step (1) floats in the water dispersion. Due to the hydrophobicity of the hydrophobic layer of the hydrophobic non-woven fabric, only the unmodified side can be soaked in the water dispersion. Dry it in an oven at 170°C for 3 minutes to prepare a conductive and wet-feeling wet non-woven fabric. The humidity response is shown in Figure 1. It can be seen from Figure 1 that when the test is started, the lyophobic test basically keeps the water content unchanged, while the water content on the lyophilic side increases rapidly and becomes saturated after 25s.
图2表明，当水含量增加时，凝胶体系膨胀，导致掺杂其间的导电材料接触变少，从而电阻增大。Figure 2 shows that when the water content increases, the gel system swells, resulting in less contact with the conductive material between the dopants, and thus the resistance increases.
上述亲水性高分子材料由如下步骤制备得到：将95g甲基丙烯酸二甲胺乙酯、5gγ-甲基丙烯酰氧基丙基三甲氧基硅烷、2g偶氮二异丁腈溶于500g无水乙醇中，65℃反应10h获得亲水性高分子材料。The above-mentioned hydrophilic polymer material is prepared by the following steps: dissolving 95g of dimethylaminoethyl methacrylate, 5g of γ-methacryloxypropyltrimethoxysilane, and 2g of azobisisobutyronitrile in 500g of absolute ethanol In the reaction at 65°C for 10 hours, a hydrophilic polymer material was obtained.
湿度检测：样品尺寸为90mm 2，按照AATCC-15配制盐水，16.6g盐水在20s内滴到纺织品疏水一侧，使用湿度测量仪测定湿度。 Humidity detection: The sample size is 90mm 2 , the brine is prepared according to AATCC-15, 16.6g of brine is dropped on the hydrophobic side of the textile within 20s, and the humidity is measured with a humidity meter.
对比例1Comparative example 1
与实施例1相同，不同之处在于：步骤(2)加入6g亲水性高分子(按固含量计算)，配制质量分数为1％水分散液。结果显示无导电性，无法测定湿度。Same as Example 1, except that: Step (2) adds 6 g of hydrophilic polymer (calculated based on the solid content) to prepare a 1% water dispersion with a mass fraction. The result showed no conductivity, and humidity could not be measured.
对比例2Comparative example 2
与实施例1相同，不同之处在于：步骤(2)加入6g多壁碳纳米管，配制质量分数为1％水分散液。无法成膜。The same as Example 1, except that: Step (2) adds 6 g of multi-walled carbon nanotubes, and prepares a 1% aqueous dispersion with a mass fraction. Can not form a film.
实施例2Example 2
一种具有湿度响应性的Janus结构导电感湿纺织品，由如下步骤制备得到：A Janus structure conductive wet textile with humidity responsiveness is prepared by the following steps:
(1)单侧疏水无纺布制备：将多乙烯基硅油(10％乙烯基含量，500CS)、四(3-巯基丙酸)季戊四醇酯按照n 乙烯基/n 巯基＝1比例加料，加入巯基1mol％量的安息香双甲醚，使用乙酸乙酯溶解混合均匀配制成质量分数为0.5％的疏水层溶液，将待处理的无纺布浸入疏水层溶液中20s，取出后用轧机压扎，轧余率控制在80％，然后放入紫外箱中单侧照射(365nm)， 30s后取出，使用乙酸乙酯洗净后制得单侧疏水无纺布。 (1) Preparation of one-sided hydrophobic non-woven fabric: add polyvinyl silicone oil (10% vinyl content, 500CS), tetrakis (3-mercaptopropionic acid) pentaerythritol ester according to the ratio of n vinyl /n mercapto group = 1, and add mercapto group 1 mol% of benzoin dimethyl ether was dissolved and mixed with ethyl acetate to form a 0.5% hydrophobic layer solution, and the non-woven fabric to be treated was immersed in the hydrophobic layer solution for 20 seconds. After taking it out, it was pressed and rolled with a rolling mill. The residual rate is controlled at 80%, and then placed in a UV box for unilateral irradiation (365nm), taken out after 30 seconds, and washed with ethyl acetate to prepare a unilateral hydrophobic non-woven fabric.
(2)导电感湿无纺布的制备：将1g亲水性高分子材料(按固含量计算)、0.1g纳米银线分散于水中，配制质量分数为3％的水分散液，使用超声分散，获得稳定的分散液，将水分散液按照特定图案涂布于疏水无纺布亲水侧，由于疏水层的疏水性，只有未改性侧能够吸收分散液获得改性效果，放入烘箱120℃烘干120min制得特定图案或线路的湿度响应性导电感湿无纺布。(2) Preparation of conductive moisture-sensitive non-woven fabric: Disperse 1g of hydrophilic polymer material (calculated based on solid content) and 0.1g of nano silver wire in water, prepare a 3% water dispersion, and use ultrasonic dispersion To obtain a stable dispersion, apply the aqueous dispersion to the hydrophilic side of the hydrophobic non-woven fabric according to a specific pattern. Due to the hydrophobicity of the hydrophobic layer, only the unmodified side can absorb the dispersion to obtain the modification effect. Put it into the oven 120 Dry at ℃ for 120min to prepare a humidity-responsive conductive wet non-woven fabric with specific patterns or lines.
上述亲水性高分子材料由如下步骤制备得到：将95g丙烯酸二甲胺乙酯、5gγ-甲基丙烯酰氧基丙基三甲氧基硅烷、5g偶氮二异丁腈溶于500g四氢呋喃中，50℃反应20h获得亲水性高分子材料。The above-mentioned hydrophilic polymer material is prepared by the following steps: 95g of dimethylaminoethyl acrylate, 5g of γ-methacryloxypropyltrimethoxysilane, 5g of azobisisobutyronitrile are dissolved in 500g of tetrahydrofuran at 50°C React for 20h to obtain hydrophilic polymer material.
实施例3Example 3
一种具有湿度响应性的Janus结构导电感湿纺织品，由如下步骤制备得到：A Janus structure conductive wet textile with humidity responsiveness is prepared by the following steps:
(1)单侧疏水无纺布制备：将多乙烯基硅油(10％乙烯基含量，500CS)、四(3-巯基丙酸)季戊四醇酯按照n 乙烯基/n 巯基＝1比例加料，加入巯基1mol％量的安息香双甲醚，使用四氢呋喃溶解混合均匀配制成质量分数为1.5％的溶液，将待处理的无纺布浸入疏水层溶液中10s，取出后用轧机压扎，轧余率控制在100％，然后放入紫外箱中单侧照射(365nm)，15s后取出，使用乙酸乙酯洗净后制得单侧疏水无纺布。 (1) Preparation of one-sided hydrophobic non-woven fabric: add polyvinyl silicone oil (10% vinyl content, 500CS), tetrakis (3-mercaptopropionic acid) pentaerythritol ester according to the ratio of n vinyl /n mercapto group = 1, and add mercapto group 1 mol% of benzoin dimethyl ether, dissolved and mixed with tetrahydrofuran to make a solution with a mass fraction of 1.5%, immerse the non-woven fabric to be treated in the hydrophobic layer solution for 10 seconds, take it out and press it with a rolling mill, and control the residual rate at 100%, and then put it into a UV box for unilateral irradiation (365nm), take it out after 15s, and wash it with ethyl acetate to prepare a unilateral hydrophobic non-woven fabric.
(2)导电感湿无纺布的制备：将1g亲水性高分子材料(按固含量计算)、1g石墨烯分散于水中，配制质量分数为5％水分散液，使用超声分散，获得稳定的分散液。将步骤(1)制备的疏水无纺布浸入水分散液中，由于疏水层的疏水性，只有未改性侧能够浸润水分散液，取出后将疏水层粘附的少量液体洗净，放入烘箱170℃烘干3min制得导电 感湿无纺布。(2) Preparation of conductive and wet non-woven fabric: Disperse 1g of hydrophilic polymer material (calculated based on solid content) and 1g of graphene in water, prepare a 5% water dispersion with mass fraction, and use ultrasonic dispersion to obtain stability The dispersion. Dip the hydrophobic non-woven fabric prepared in step (1) into the aqueous dispersion. Due to the hydrophobicity of the hydrophobic layer, only the unmodified side can soak the aqueous dispersion. After taking it out, wash the small amount of liquid adhering to the hydrophobic layer and put it in Dry in an oven at 170°C for 3 minutes to prepare a conductive wet non-woven fabric.
上述亲水性高分子材料由如下步骤制备得到：将90g丙烯酸二乙胺乙酯、10gγ-甲基丙烯酰氧基丙基三甲氧基硅烷、5g偶氮二异庚腈溶于500g乙醇中，65℃反应10h获得亲水性高分子材料。The above-mentioned hydrophilic polymer material is prepared by the following steps: dissolving 90 g of diethylaminoethyl acrylate, 10 g of γ-methacryloxypropyl trimethoxysilane, and 5 g of azobisisoheptonitrile in 500 g of ethanol, React at 65°C for 10 hours to obtain a hydrophilic polymer material.
实施例4Example 4
一种具有湿度响应性的Janus结构导电感湿纺织品，由如下步骤制备得到：A Janus structure conductive wet textile with humidity responsiveness is prepared by the following steps:
(1)单侧疏水无纺布制备：将多乙烯基硅油(10％乙烯基含量，500CS)、四(3-巯基丙酸)季戊四醇酯按照n 乙烯基/n 巯基＝1比例加料，加入巯基1mol％量的安息香双甲醚，使用醋酸丁酯溶解混合均匀配制成质量分数为1％的溶液，将待处理的无纺布布浸入疏水层溶液中60s，取出后用轧机压扎，轧余率控制在170％，然后放入紫外箱中单侧照射(365nm)，100s后取出，使用乙酸乙酯洗净后制得单侧疏水无纺布。 (1) Preparation of one-sided hydrophobic non-woven fabric: add polyvinyl silicone oil (10% vinyl content, 500CS), tetrakis (3-mercaptopropionic acid) pentaerythritol ester according to the ratio of n vinyl /n mercapto group = 1, and add mercapto group 1 mol% of benzoin dimethyl ether, dissolve and mix uniformly with butyl acetate to prepare a solution with a mass fraction of 1%, immerse the non-woven fabric to be treated in the hydrophobic layer solution for 60s, take it out, and press it with a rolling machine. The rate is controlled at 170%, and then placed in a UV box for single-side irradiation (365nm), taken out after 100s, and washed with ethyl acetate to prepare a single-side hydrophobic non-woven fabric.
(2)导电感湿无纺布的制备：将1g亲水性高分子(按固含量计算)、0.1g纳米银线分散于水中，配制质量分数为5％水分散液，使用超声分散，获得稳定的分散液。将分散液按照特定图案涂布于步骤(1)疏水无纺布亲水侧，由于疏水层的疏水性，只有未改性侧能够吸收分散液获得改性效果，放入烘箱120℃烘干120min制得特定图案或线路的湿度响应性导湿纺织品。(2) Preparation of conductive moisture-sensitive non-woven fabric: Disperse 1g hydrophilic polymer (calculated based on solid content) and 0.1g nano silver wire in water, prepare a 5% water dispersion with mass fraction, and use ultrasonic dispersion to obtain Stable dispersion. Apply the dispersion to the hydrophilic side of the hydrophobic non-woven fabric in step (1) according to a specific pattern. Due to the hydrophobicity of the hydrophobic layer, only the unmodified side can absorb the dispersion to obtain the modification effect. Place it in an oven at 120°C for 120 minutes. The humidity-responsive moisture-conducting textiles with specific patterns or lines are prepared.
上述亲水性高分子材料由如下步骤制备得到：将95g甲基丙烯酸、5gγ-甲基丙烯酰氧基丙基三甲氧基硅烷、5g偶氮二异丁腈溶于500g四氢呋喃中，50℃反应20h获得亲水性高分子材料。The above hydrophilic polymer material is prepared by the following steps: 95g methacrylic acid, 5g γ-methacryloxypropyltrimethoxysilane, 5g azobisisobutyronitrile are dissolved in 500g tetrahydrofuran and reacted at 50°C for 20h. Hydrophilic polymer material.
实施例5Example 5
一种具有湿度响应性的Janus结构导电感湿纺织品，由如下步骤制备得到：A Janus structure conductive wet textile with humidity responsiveness is prepared by the following steps:
(1)单侧疏水无纺布制备：将多乙烯基硅油(乙烯基含量为10％，500CS)、四(3-巯基丙酸)季戊四醇酯按照n 乙烯基/n 巯基＝0.8比例加料，加入巯基0.5mol％量的安息香双甲醚，使用乙酸乙酯溶解混合均匀配制成质量分数为0.5％的疏水层溶液，将待处理的无纺布浸入疏水层溶液中10s，取出后用轧机压扎，轧余率控制在100％，然后放入紫外箱中单侧照射(365nm)，15s后取出，使用乙酸乙酯洗净后制得单侧疏水无纺布。 (1) Preparation of one-side hydrophobic non-woven fabric: Add polyvinyl silicone oil (vinyl content of 10%, 500CS), tetrakis (3-mercaptopropionic acid) pentaerythritol ester according to the ratio of n vinyl group/n mercapto group = 0.8, and add Benzoin dimethyl ether containing 0.5 mol% of mercapto group is dissolved and mixed with ethyl acetate to form a 0.5% hydrophobic layer solution. The non-woven fabric to be treated is immersed in the hydrophobic layer solution for 10 seconds, and then taken out and pressed with a rolling machine. , The scouring rate is controlled at 100%, and then placed in a UV box for unilateral irradiation (365nm), taken out after 15s, and washed with ethyl acetate to prepare a unilateral hydrophobic non-woven fabric.
(2)导电感湿无纺布的制备：将1g亲水性高分子材料(按固含量计算)、5g导电石墨烯分散于水中，配制质量分数为5％水分散液，使用超声分散，获得稳定的分散液。将步骤(1)制备的疏水无纺布浸入水分散液中，由于疏水层的疏水性，只有未改性侧能够浸润水分散液，取出后使用水将疏水层粘附的少量液体洗净，放入烘箱170℃烘干3min制得。(2) Preparation of conductive wet-sensitive non-woven fabric: Disperse 1g of hydrophilic polymer material (calculated based on solid content) and 5g of conductive graphene in water, prepare a 5% water dispersion, and use ultrasonic dispersion to obtain Stable dispersion. The hydrophobic non-woven fabric prepared in step (1) is immersed in the aqueous dispersion. Due to the hydrophobicity of the hydrophobic layer, only the unmodified side can be infiltrated into the aqueous dispersion. After taking it out, use water to wash a small amount of liquid adhered to the hydrophobic layer. Put it into an oven at 170℃ and dry for 3 minutes.
上述亲水性高分子材料由如下步骤制备得到：将90g甲基丙烯酰氧乙基三甲基氯化铵、10gγ-甲基丙烯酰氧基丙基三甲氧基硅烷、5g偶氮二异丁腈溶于1000g乙醇中，80℃反应2h获得亲水性高分子材料。The above-mentioned hydrophilic polymer material is prepared by the following steps: dissolving 90 g of methacryloxyethyl trimethylammonium chloride, 10 g of γ-methacryloxypropyl trimethoxysilane, and 5 g of azobisisobutyronitrile The hydrophilic polymer material was obtained by reacting in 1000g ethanol at 80°C for 2h.
实施例6Example 6
一种具有湿度响应性的Janus结构导电感湿纺织品，由如下步骤制备得到：A Janus structure conductive wet textile with humidity responsiveness is prepared by the following steps:
(1)单侧疏水无纺布制备：将多乙烯基硅油(乙烯基含量为10％，500CS)、四(3-巯基丙酸)季戊四醇酯按照n 乙烯基/n 巯基＝1.2比例加料，加入巯基2mol％量的安息香双甲醚，使用乙酸乙酯溶解配制成质量分数为2％的疏水层溶液，混合均匀，将待处理的无纺布浸入疏水层溶液中10s，取出后用轧机压扎，轧余率控制在100％，然后放入紫外箱中单侧照射(365 nm)，15s后取出，使用乙酸乙酯洗净后制得单侧疏水无纺布。 (1) Preparation of one-side hydrophobic non-woven fabric: add polyvinyl silicone oil (vinyl content of 10%, 500CS), tetrakis (3-mercaptopropionic acid) pentaerythritol ester according to the ratio of n vinyl group/n mercapto group = 1.2, and add Benzoin dimethyl ether with 2mol% of mercapto group is dissolved in ethyl acetate to prepare a hydrophobic layer solution with a mass fraction of 2%, mix evenly, immerse the non-woven fabric to be treated in the hydrophobic layer solution for 10s, take it out and press it with a rolling machine , The reduction rate is controlled at 100%, and then placed in a UV box for unilateral irradiation (365 nm), taken out after 15 seconds, and washed with ethyl acetate to prepare a unilateral hydrophobic non-woven fabric.
(2)导电感湿无纺布的制备：将20g亲水性高分子材料(按固含量计算，调节pH＝8)、5g导电石墨烯分散于水中，配制质量分数为3％水分散液，使用超声分散，获得稳定的分散液，将步骤(1)制备的疏水无纺布浸入水分散液中，由于疏水层的疏水性，只有未改性侧能够浸润水分散液，取出后使用水将疏水层粘附的少量液体洗净，放入烘箱170℃烘干3min制得导电感湿无纺布。(2) Preparation of conductive wet non-woven fabric: Disperse 20g of hydrophilic polymer material (calculated based on solid content, adjust pH=8) and 5g of conductive graphene in water to prepare a 3% water dispersion. Use ultrasonic dispersion to obtain a stable dispersion. The hydrophobic non-woven fabric prepared in step (1) is immersed in the aqueous dispersion. Due to the hydrophobicity of the hydrophobic layer, only the unmodified side can infiltrate the aqueous dispersion. A small amount of liquid adhered to the hydrophobic layer was washed, and dried in an oven at 170°C for 3 minutes to prepare a conductive wet non-woven fabric.
上述亲水性高分子材料由如下步骤制备得到：将90g甲基丙烯酸、10gγ-甲基丙烯酰氧基丙基三甲氧基硅烷、1g偶氮二异丁腈溶于500g乙醇中，65℃反应16h获得亲水性高分子材料。The above hydrophilic polymer material is prepared by the following steps: dissolve 90g methacrylic acid, 10g γ-methacryloxypropyltrimethoxysilane, 1g azobisisobutyronitrile in 500g ethanol, and react at 65°C for 16h. Hydrophilic polymer material.
以上对本发明提供的具有湿度响应性的Janus结构导电感湿纺织品进行了详细的介绍，以上实施例的说明只是用于帮助理解本发明的技术方案及其核心思想，应当指出，对于本技术领域的技术人员来说，在不脱离本发明原理的前提下，还可以对本发明进行若干改进和修饰，这些改进和修饰也落入本发明权利要求的保护范围内。The above is a detailed introduction to the Janus structure conductive wet textile with humidity responsiveness provided by the present invention. The description of the above embodiments is only used to help understand the technical solution of the present invention and its core ideas. It should be pointed out that for the technical field For the skilled person, without departing from the principle of the present invention, several improvements and modifications can be made to the present invention, and these improvements and modifications also fall within the protection scope of the claims of the present invention.

Claims (10)

  1. 一种具有湿度响应性的Janus结构导电感湿纺织品，其特征在于，由如下步骤制备得到：A Janus structure conductive wet-sensing textile with humidity responsiveness, which is characterized in that it is prepared by the following steps:
    (1)单侧疏水纺织品制备：将多乙烯基硅油、四(3-巯基丙酸)季戊四醇酯、安息香双甲醚和溶剂混合均匀配制成质量分数为0.5～2％的疏水层溶液，所述的多乙烯基硅油中的乙烯基与四(3-巯基丙酸)季戊四醇酯的巯基的摩尔比为0.8～1.2，安息香双甲醚的加入量按照每1mol巯基加入0.005～0.02mol安息香双甲醚的量加入量，将预处理后的纺织品浸入疏水层溶液中10～60s，纺织品取出后进行压扎，使纺织品的轧余率控制在80～170％，然后将纺织品进行紫外光单侧照射10～100s，将纺织品洗净后制得单侧疏水纺织品；(1) Preparation of one-sided hydrophobic textile: mix polyvinyl silicone oil, tetrakis (3-mercaptopropionic acid) pentaerythritol ester, benzoin dimethyl ether and solvent to form a hydrophobic layer solution with a mass fraction of 0.5-2%. The molar ratio of the vinyl group in the polyvinyl silicone oil to the mercapto group of the pentaerythritol tetrakis (3-mercaptopropionic acid) pentaerythritol ester is 0.8 to 1.2, and the amount of benzoin dimethyl ether added is 0.005 to 0.02 mol benzoin dimethyl ether per 1 mol mercapto group. Dip the pre-treated textile into the hydrophobic layer solution for 10-60 seconds. After the textile is taken out, it will be pressed to control the scalping rate of the textile to 80-170%, and then the textile will be irradiated with ultraviolet light on one side for 10 ~100s, the one-sided hydrophobic textile is obtained after washing the textile;
    (2)导电感湿纺织品制备：将1～20质量份亲水性高分子材料和0.1～5质量份导电材料分散于水中，混合均匀后配制成质量分数为1～5％的水分散液，水分散液通过浸渍或涂布的方法处理步骤(1)制备的单侧疏水纺织品，处理后的单侧疏水纺织品烘干制得导电感湿纺织品。(2) Preparation of conductive wet textiles: Disperse 1-20 parts by mass of hydrophilic polymer materials and 0.1-5 parts by mass of conductive materials in water, mix them evenly, and prepare a water dispersion with a mass fraction of 1 to 5%. The water dispersion is dipped or coated to treat the unilateral hydrophobic textile prepared in step (1), and the treated unilateral hydrophobic textile is dried to obtain a conductive wet textile.
  2. 根据权利要求1所述的具有湿度响应性的Janus结构导湿感湿纺织品，其特征在于，所述的预处理后的纺织品的预处理步骤是：将纺织品放入水中清洗以去除纺织品上的尘土和油渍，然后烘干即得预处理后的纺织品。The Janus structure moisture-conductive wet textile with humidity responsiveness according to claim 1, wherein the pretreatment step of the pre-treated textile is: washing the textile in water to remove dust on the textile And oil stains, and then dried to obtain pre-treated textiles.
  3. 根据权利要求1所述的具有湿度响应性的Janus结构导湿感湿纺织品，其特征在于，所述的紫外光波长为365nm。The Janus structure moisture-conducting wet-sensing textile with moisture responsiveness according to claim 1, wherein the wavelength of the ultraviolet light is 365 nm.
  4. 根据权利要求1所述的具有湿度响应性的Janus结构导电感湿纺织品，其特征在于，所述的亲水性高分子材料由如下步骤制备得到：将90～95质量份丙烯酸单体与5～10质量份γ-甲基丙烯酰氧基丙基三甲氧基硅烷在溶剂中混合均匀，再加入1～5质量份引发剂，在 50～80℃下发生聚合反应2～20h制得亲水性高分子材料。The Janus structure conductive wet textile with humidity responsiveness according to claim 1, wherein the hydrophilic polymer material is prepared by the following steps: 90-95 parts by mass of acrylic monomer and 5~ 10 parts by mass of γ-methacryloxypropyltrimethoxysilane are mixed uniformly in the solvent, and then 1 to 5 parts by mass of initiator are added, and the polymerization reaction occurs at 50 to 80°C for 2 to 20 hours to obtain hydrophilicity. Polymer Materials.
  5. 根据权利要求4所述的具有湿度响应性的Janus结构导电感湿纺织品，其特征在于，所述的丙烯酸单体选自丙烯酸二甲胺乙酯、甲基丙烯酸二甲胺乙酯、丙烯酸二乙胺乙酯、甲基丙烯酸二乙胺乙酯、甲基丙烯酸和甲基丙烯酰氧乙基三甲基氯化铵中的一种。The Janus structure conductive wet textile with humidity responsiveness according to claim 4, wherein the acrylic monomer is selected from the group consisting of dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, and diethyl acrylate. One of aminoethyl, diethylaminoethyl methacrylate, methacrylic acid and methacryloxyethyl trimethylammonium chloride.
  6. 根据权利要求4所述的具有湿度响应性的Janus结构导电感湿纺织品，其特征在于，所述的导电材料选自单壁碳纳米管、多壁碳纳米管、石墨烯、膨胀石墨烯、导电石墨和纳米银线中的一种。The Janus structure conductive wet-sensitive textile with humidity response according to claim 4, wherein the conductive material is selected from the group consisting of single-walled carbon nanotubes, multi-walled carbon nanotubes, graphene, expanded graphene, conductive One of graphite and nano silver wire.
  7. 根据权利要求4所述的具有湿度响应性的Janus结构导电感湿纺织品，其特征在于，所述的溶剂选自甲醇、乙醇、二氯甲烷、四氢呋喃和乙酸乙酯中的一种。The Janus structure conductive wet textile with humidity responsiveness according to claim 4, wherein the solvent is selected from one of methanol, ethanol, dichloromethane, tetrahydrofuran and ethyl acetate.
  8. 根据权利要求4所述的具有湿度响应性的Janus结构导电感湿纺织品，其特征在于，所述的引发剂为偶氮二异丁腈或偶氮二异庚腈。The Janus structure conductive wet textile with humidity responsiveness according to claim 4, wherein the initiator is azobisisobutyronitrile or azobisisoheptonitrile.
  9. 根据权利要求1所述的具有湿度响应性的Janus结构导电感湿纺织品，其特征在于，所述的纺织品为无纺布或针织布。The Janus structure conductive wet textile with humidity responsiveness according to claim 1, wherein the textile is a non-woven fabric or a knitted fabric.
  10. 根据权利要求1所述的具有湿度响应性的Janus结构导电感湿纺织品，其特征在于，所述的处理后的疏水纺织品放入烘干具体步骤是：处理后的疏水纺织品放入烘箱120～170℃烘干3～120min。The Janus structure conductive wet textile with humidity responsiveness according to claim 1, wherein the specific step of putting the treated hydrophobic textile into drying is: putting the treated hydrophobic textile into an oven 120-170 Dry at ℃ for 3～120min.
PCT/CN2019/125137 2019-11-26 2019-12-13 Electrically-conductive humidity-sensitive textile having a janus structure and humidity responsiveness WO2021103181A1 (en)

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