Conductive fiber and conductive fabric, and preparation method and application thereof

Abstract

The application discloses a kind of conductive fiber and conductive fabric and its preparation method and application, the conductive fiber includes (a) fiber matrix, (b) inorganic material and / or polymer combined on the surface of the fiber matrix and (c) conductive material combined with the inorganic material and / or polymer.The conductive fiber and conductive fabric of the application have stable and uniform high conductivity, and can maintain good conductivity and mechanical properties after more than 50 bending and stretching, and can be widely used in antistatic, conductive, sensing and other fields, such as wireless sensor and the like.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of textile materials, and more particularly, to a conductive fiber and a conductive fabric and a preparation method and application thereof. BACKGROUND

[0002] The research and application of conductive fibers have gradually matured. Conductive fibers and their textiles can not only be used to eliminate static electricity and absorb electromagnetic waves, but also can be made into super capacitors for detecting and transmitting electrical signals. Therefore, conductive fibers have been very successfully and widely used in smart textiles.

[0003] Traditional natural fibers, chemical fibers, viscose fibers and the like are not conductive, so a proper method should be adopted to introduce a conductive component to improve the conductivity of the fibers, thereby imparting the fibers with conductive properties. Existing conductive fibers mainly include carbon black conductive fibers, metal conductive fibers and metal composite conductive fibers. Carbon black conductive fibers refer to polymer fibers containing carbon black particles. The conductive component of carbon black is generally dispersed in the fiber or combined on the surface of the fiber through a physical method. Metal conductive fibers can be divided into stainless steel fibers, polymer fibers doped with metals such as silver and nickel. The metal conductive fibers have good conductive properties, but the interface bonding between the fiber matrix and the conductive reinforcing phase and the oxidation of the metal conductive component can lead to unstable conductive properties. Metal composite conductive fibers refer to polymer fibers doped with ZnO, CuI, ITO, ATO, polyaniline, polypyrrole and polyacetylene, but the metal conductive elements also have the disadvantages of high cost, poor fatigue resistance, difficult blending process and easy clogging; and when the polyaniline, polypyrrole and polyacetylene are introduced into the fibers, the conductive polymer component has a viscosity that is much higher than that of carbon black and metal in the spinning process, making the processing difficult.

[0004] So far, the combination of conductive materials and fiber matrix is still a key problem. SUMMARY

[0005] In order to improve the above technical problems, the present application provides a conductive fiber and a conductive fabric, and a preparation method thereof. The preparation method can fully graft a conductive substance on the surface of natural and / or man-made fibers and natural and / or man-made fabrics, and prepare fibers and fabrics with high conductivity.

[0006] The technical solution adopted by the present application is that;

[0007] A conductive fiber, the conductive fiber comprising (a) a fiber matrix, (b) an inorganic material and / or a polymer combined on the surface of the fiber matrix, and (c) a conductive material combined with the inorganic material and / or the polymer;

[0008] The inorganic material is selected from at least one of silicon dioxide, titanium dioxide, iron oxide, aluminum oxide, a compound as shown in Formula 3 below or a hydrolysis condensate thereof, or distearoyloxyisopropoxyaluminate or a hydrolysis condensate thereof;

[0009]

[0010] M is Si or Ti;

[0011] In formula 3, R a 、R b 、R c and R d The same or different, independently selected from H, Cl, unsubstituted or optionally substituted by one, two or more R e Substituted C 1-12 Alkyl, vinyl, -OC 1-12 Alkyl, C 6-20 aromatic groups;

[0012] Each R e The same or different, independently selected from unsubstituted or optionally substituted by one, two or more R f Substituted -C(=O)OH, C 1-12 Alkyl, C 6-20 Aromatic group, -OC 1-12 Alkyl, -NH-C 1-12 Alkyl, amino, -SH;

[0013] Each R f The same or different, independently selected from C 1-12 Alkyl, amino, -OC 1-12 Alkyl, vinyl or C 1-12 Alkyl-substituted vinyl, 3-20 membered heterocyclic group;

[0014] And R a 、R b 、R c and R d At least one of them is -OC 1-12 Alkyl or Cl;

[0015] The polymer monomer of the polymer is selected from at least one of the following substances: the compound represented by Formula 1, the compound represented by Formula 2, ethylene glycol, triethylenetetramine or diethylenetriamine; or the polymer is selected from at least one of polyurethane, polyvinyl acetate, polyimide and epoxy resin;

[0016]

[0017] In formula 1, R 1 and R 2identically or differently, independently of one another, selected from H, alkyl; R 3 selected from H or C 1-6 alkyl; R 4 selected from -OH, -COOR 8 , -CON(R 9 )(R 10 ) or aryl, R 8 selected from H, alkyl or epoxyalkyl, R 9 and R 10 identically or differently, independently of one another, selected from H, alkyl, or hydroxy-substituted alkyl;

[0018] in formula 2, R 5 and R 6 are identical or different, independently of one another, selected from H or alkyl, R 5 and R 6 are identical or different, independently of one another, selected from H or alkyl, R 7 selected from -O- or -N(R 11 )-, R 11 selected from H or alkyl;

[0019] The electrically conductive material comprises an electrically conductive polymer and / or an electrically conductive metallic material.

[0020] According to the present application, the electrically conductive fiber further comprises (d) an electrically conductive material bound to the surface of the fiber matrix.

[0021] According to the present application, the fiber matrix is selected from cellulose fibers, selected from bamboo fibers, cotton fibers, viscose fibers, silk fibers, spandex, polyester fibers, polyamide fibers, polyester fibers, a-olefin polymer fibers, polyacrylonitrile, chlorofiber or polyvinyl alcohol fibers, etc.

[0022] According to the present application, the surface of the fiber matrix is further modified with a reactive chemical group selected from at least one of hydroxyl, carboxyl, amino, epoxy, double bond, ether bond, aldehyde group, sulfonate, nitro, etc.; through the reactive chemical group, reacting with the substances in component (b) and / or component (d) to form ester bond, amide bond and / or ether bond, realizing chemical bond combination.

[0023] According to the present application, in formula 1, R 1 and R 2 are identical or different, independently of one another, selected from H, C 1-6 alkyl; R 3 selected from H, methyl or ethyl; R 4 selected from -OH, -COOR 8 , -CON(R 9 )(R 10 ) or phenyl, R 8 selected from H, C 1-6Alkyl or epoxy C 1-6 Alkyl, R 9 Selected from H, R 10 Selected from C 1-6 alkyl.

[0024] Illustratively, the compound represented by Formula 1 is acrylic acid, methacrylic acid, methyl methacrylate, ethyl methacrylate, glycidyl methacrylate, vinyl alcohol, styrene, N-isopropylacrylamide or N-(2-hydroxypropyl)methacrylamide.

[0025] According to the present invention, in Formula 2, R 5 and R 6 The same or different, independently selected from H or C 1-6 Alkyl, R 5 and R 6 Optionally, it can be annulated to form a benzene ring; R 7 Selected from -O- or -N(R 11 )-,R 11 is selected from H or alkyl.

[0026] Illustratively, the compound represented by Formula 2 is maleic anhydride or phthalic anhydride.

[0027] According to the present invention, the conductive material is selected from the conductive polymer, the conductive metal material, or a composite of the conductive polymer and the conductive metal material.

[0028] The present invention provides a conductive fabric, which is woven by the conductive fibers mentioned above.

[0029] The present invention provides a conductive fabric, comprising (a') a fabric substrate, (b') an inorganic material and / or a polymer bonded to a surface of the fabric substrate, and (c') a conductive material bonded to the polymer and / or inorganic material;

[0030] The inorganic material is selected from at least one of silicon dioxide, titanium dioxide, iron oxide, aluminum oxide, a compound as shown in Formula 3 below or a hydrolysis condensate thereof, or distearoyloxyisopropoxyaluminate or a hydrolysis condensate thereof;

[0031]

[0032] M is at least one of Si and Ti;

[0033] In formula 3, R a 、R b 、R c and R d The same or different, independently selected from H, Cl, unsubstituted or optionally substituted by one, two or more R e Substituted C1-12 alkyl, vinyl, -O-C 1-12 alkyl, C 6-20 aryl;

[0034] each R e identical or different, are independently of each other selected from the group consisting of unsubstituted or optionally substituted -C(=O)-OH, C f alkyl, C 1-12 alkyl, C 6-20 aryl, -O-C 1-12 alkyl, -NH-C 1-12 alkyl, amino, -SH;

[0035] each R f identical or different, are independently of each other selected from the group consisting of C 1-12 alkyl, amino, -O-C 1-12 alkyl, vinyl or C 1-12 alkyl-substituted vinyl, 3-20 membered heterocyclyl;

[0036] and R a , R b , R c and R d , at least one is -O-C 1-12 alkyl or Cl;

[0037] The polymerization monomer of the polymer is selected from at least one of the following: a compound shown in Formula 1, a compound shown in Formula 2, ethylene glycol, triethylene tetramine or diethylene triamine, etc.; or the polymer is selected from at least one of polyurethane, polyvinyl acetate, polyimide, epoxy resin;

[0038]

[0039] In Formula 1, R 1 and R 2 are identical or different, and are independently of each other selected from H, alkyl; R 3 is selected from H or C 1-6 alkyl; R 4 is selected from -OH, -COOR 8 , -CON(R 9 )(R 10 ) or aryl, R 8 is selected from H, alkyl or epoxyalkyl, R 9 and R 10 are identical or different, and are independently of each other selected from H or alkyl;

[0040] In Formula 2, R 5 and R 6 are identical or different, and are independently of each other selected from H or alkyl, R 5 and R6 Optionally, it can be annulated to form an aromatic ring; R 7 Selected from -O- or -N(R 11 )-,R 11 Selected from H or alkyl;

[0041] The conductive material includes a conductive polymer and / or a conductive metal material.

[0042] Preferably, the conductive fabric further comprises (d') a conductive material bonded to the surface of the fabric base.

[0043] According to the present invention, the surface of the fabric substrate is further modified with reactive chemical groups, and the reactive chemical groups are selected from at least one of hydroxyl, carboxyl, amino, epoxy, double bond, ether bond, aldehyde, sulfonate, nitro, etc.; through the reactive chemical groups, ester bonds, amide bonds and / or ether bonds are formed by reacting with the substances in component (b') and / or component (d'), thereby achieving chemical bond bonding.

[0044] According to the present invention, in Formula 1, R 1 and R 2 The same or different, independently selected from H, C 1-6 Alkyl; R 3 is selected from H, methyl or ethyl; R 4 Selected from -OH, -COOR 8 、-CON(R 9 )(R 10 ) or phenyl, R 8 Selected from H, C 1-6 Alkyl or epoxy C 1-6 Alkyl, R 9 Selected from H, R 10 Selected from C 1-6 alkyl.

[0045] Illustratively, the compound represented by Formula 1 is acrylic acid, methacrylic acid, methyl methacrylate, ethyl methacrylate, glycidyl methacrylate, vinyl alcohol, styrene, N-isopropylacrylamide or N-(2-hydroxypropyl)methacrylamide.

[0046] According to the present invention, in Formula 2, R 5 and R 6 The same or different, independently selected from H or C 1-6 Alkyl, R 5 and R 6 Optionally, it can be annulated to form a benzene ring; R 7 Selected from -O- or -N(R 11 )-,R 11 is selected from H or alkyl.

[0047] Exemplarily, the compound shown in formula 2 is maleic anhydride or phthalic anhydride.

[0048] According to the present application, the conductive material is selected from the conductive polymer, the conductive metal material, or a composite of the conductive polymer and the conductive metal material.

[0049] The present application also provides a preparation method of the conductive fiber, which comprises:

[0050] 1) preparing a fiber substrate;

[0051] 2) reacting the fiber substrate in step 1) with a polymer and / or an inorganic material to obtain a fiber substrate with inorganic material and / or polymer on the surface;

[0052] 3) reacting the fiber substrate with inorganic material and / or polymer on the surface in step 2) with a conductive polymer monomer and / or a conductive metal material precursor to obtain the conductive fiber.

[0053] In step 1), a step of introducing a reactive chemical group on the fiber substrate is further included.

[0054] Step 2) is specifically: reacting the fiber substrate in step 1), in particular the fiber substrate containing the reactive chemical group, with a solution comprising a polymer, a polymer monomer and / or an inorganic material to obtain a fiber substrate with inorganic material and / or polymer on the surface.

[0055] Step 3) is specifically: adding a conductive polymer monomer in the solution of the fiber substrate with inorganic material and / or polymer on the surface in step 2), optionally adding one or more of an initiator, an oxidant, a catalyst, a reducing agent, a dispersing agent, and performing in-situ polymerization to prepare the conductive fiber.

[0056] For example, a conductive polymer monomer, an initiator, a catalyst and a dispersing agent are added in the solution of the fiber substrate with inorganic material and / or polymer on the surface in step 2), and in-situ polymerization is performed to prepare the conductive fiber.

[0057] According to the present application, the conductive polymer monomer is selected from at least one of aniline, pyrrole, thiophene, acetylene, phenylacetylene, benzene, etc.

[0058] The present application also provides a preparation method of the conductive fabric, which is the same as the preparation method of the conductive fiber except that the fiber substrate is replaced by a fabric substrate.

[0059] The application also provides the use of the conductive fiber and / or the conductive fabric, which is preferably used in the fields of antistatic, conductive, sensing, etc.

[0060] Advantages

[0061] The conductive fiber and the conductive fabric of the application have stable and uniform high conductivity. Specifically, the conductive fiber and the conductive fabric of the application can maintain good conductivity and mechanical properties after being bent and stretched for more than 50 times. For example, after being bent and stretched for more than 50 times, the fabric has an R0 of not less than 250 KΩ (even not less than 260 KΩ, more even not less than 265 KΩ), an R25 of not less than 250 KΩ (even not less than 260 KΩ, more even not less than 265 KΩ), and an R50 of not less than 250 KΩ (even not less than 260 KΩ, more even not less than 265 KΩ, and even not less than 270 KΩ). The conductive fiber and the conductive fabric of the application can be widely used in the fields of antistatic, conductive, sensing, etc., such as the field of wireless sensors, etc.

[0062] Explanation of terms

[0063] The term "C 1-12 "alkyl" means straight-chain and branched-chain alkyl groups having 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 or 12 carbon atoms, for example "C 1-6 "alkyl" is to be understood as meaning straight-chain and branched-chain alkyl groups having 1, 2, 3, 4, 5, 6 carbon atoms ("C 1-6 "alkyl"), for example methyl, ethyl, propyl, butyl, pentyl, hexyl, isopropyl, isobutyl, sec-butyl, t-butyl.

[0064] The application uses "alkyl" alone or as a suffix is intended to include both branched and straight-chain saturated aliphatic hydrocarbon groups having from 1 to 20 carbon atoms (or, if a specific number of carbon atoms is provided, that specific number). For example, "C 1-6 "alkyl" means straight-chain and branched-chain alkyl groups having 1, 2, 3, 4, 5, 6, 7 or 8 carbon atoms.

[0065] The term "aryl" or "C 6-20Aryl" refers to an aromatic ring structure consisting of 6 to 20 carbon atoms. For example, aromatic ring structures comprising 6, 7, and 8 carbon atoms can be monocyclic aromatic groups such as phenyl; ring structures comprising 8, 9, 10, 11, 12, 13, or 14 carbon atoms can be polycyclic such as naphthyl. The aryl ring can be substituted at one or more ring positions with those substituents described above. The term "aryl" also includes polycyclic ring systems having two or more rings wherein two or more carbons are shared by two adjacent rings (the rings are "fused"), wherein at least one ring is aromatic and other rings can be, for example, cycloalkyl, cycloalkenyl, cycloalkynyl, aryl, and / or heterocyclyl. Examples of polycyclic rings include, but are not limited to, 2,3-dihydro-l,4-benzodioxinyl and 2,3-dihydro-l- benzofuranyl.

[0066] The term "3-20 membered heterocyclyl" means a saturated, monovalent monocyclic, bicyclic, or bridged ring cycloalkane comprising 1-5 heteroatoms independently selected from N, O, and S, having a total ring atom count of 3-20 (e.g., 3, 4, 5, 6, 7, 8, 9, 10, etc.), preferably "3-10 membered heterocyclyl". The term "3-10 membered heterocyclyl" means a saturated, monovalent monocyclic, bicyclic, or bridged ring cycloalkane comprising 1-5, preferably 1-3 heteroatoms selected from N, O, and S. The heterocyclyl group can be attached to the remainder of the molecule through any of the carbon atoms or the nitrogen atom, if present. In particular, the heterocyclyl group can include, but is not limited to: 4-membered rings such as azetidinyl, oxetanyl; 5-membered rings such as tetrahydrofuranyl, dioxolanyl, pyrrolidinyl, imidazolidinyl, pyrazolidinyl, pyrrolinyl; or 6-membered rings such as tetrahydropyranyl, piperidinyl, morpholinyl, dithianyl, thiomorpholinyl, piperazinyl, or trithianyl; or 7-membered rings such as diazepanyl. Optionally, the heterocyclyl group can be benzo-fused. The heterocyclyl group can be bicyclic, such as, but not limited to, 5,5-membered rings such as hexahydrocyclopenta[c]pyrrol-2(lH)-yl ring, or 5,6-membered rings such as hexahydropyrrolo[l,2-a]pyrazin-2(lH)-yl ring. The heterocyclyl group can be spirocyclic, such as, but not limited to, spiro[3,3]ring, such as spiro[3,3]cyclohexane, spiro[3,4]ring, spiro[3,5]ring, spiro[4,4]ring, spiro[4,5]ring, spiro[5,5]ring, such as 2,7-diazaspiro[3,5]nonane, 2,6-diazaspiro[3,4]octane. The ring containing nitrogen atom can be partially unsaturated, i.e. it can contain one or more double bonds, such as, but not limited to, 2,5-dihydro-lH-pyrrolyl, 4H-[l,3,4]thiadiazinyl, 4,5-dihydrooxazolyl or 4H-[l,4]thiazinyl, or it can be benzo-fused, such as, but not limited to, dihydroisoquinolinyl. According to the present application, the heterocyclyl group is non-aromatic. When the 3-20 membered heterocyclyl group is attached to other groups to form a compound of the present application, it can be attached to other groups through a carbon atom of the 3-20 membered heterocyclyl group or through a heteroatom of the 3-20 membered heterocyclyl ring. For example, when the 3-20 membered heterocyclyl group is selected from piperazinyl, it can be attached to other groups through a nitrogen atom of the piperazinyl group. Or when the 3-20 membered heterocyclyl group is selected from piperidinyl, it can be attached to other groups through a nitrogen atom of the piperidinyl ring and a carbon atom para to the nitrogen atom. BRIEF DESCRIPTION OF DRAWINGS

[0067] Figure 1 Flow chart of the process for preparing the conductive fabric of the present application;

[0068] Figure 2 Infrared spectrum of the polyaniline grafted bamboo fiber in Example 1;

[0069] Figure 3 Scanning electron micrograph of the polyaniline / bamboo fiber conductive fabric in Example 3. DETAILED DESCRIPTION

[0070] [conductive fibers]

[0071] As described above, the present application provides a conductive fiber comprising (a) a fiber base, (b) an inorganic material and / or a polymer bound to the surface of the fiber base, and (c) a conductive material bound to the inorganic material and / or the polymer;

[0072] The inorganic material is selected from at least one of silicon dioxide, titanium dioxide, iron oxide, aluminum oxide, a compound represented by Formula 3 below or a hydrolysis condensate thereof, or distearyl oxyisopropoxy aluminate or a hydrolysis condensate thereof.

[0073]

[0074] M is at least one of Si and Ti;

[0075] In Formula 3, R a , R b , R c , and R d are the same or different from each other and are independently selected from H, Cl, C e , which is unsubstituted or optionally substituted with one, two or more R 1-12alkyl, vinyl, -O-C 1-12 alkyl, C 6-20 aryl;

[0076] each R e are the same or different, each independently selected from the group consisting of unsubstituted or optionally substituted -C(=O)OH, C f alkyl, C 1-12 alkyl, C 6-20 aryl, -O-C 1-12 alkyl, -NH-C 1-12 alkyl, amino, -SH;

[0077] each R f are the same or different, each independently selected from the group consisting of C 1-12 alkyl, amino, -O-C 1-12 alkyl, vinyl or C 1-12 alkyl-substituted vinyl, 3-20 membered heterocyclyl;

[0078] and R a , R b , R c and R d , at least one of R 1-12 is -O-C 1 alkyl or Cl;

[0079] polymer is selected from at least one of polyurethane, polyvinyl acetate, polyimide or epoxy resin;

[0080]

[0081] in Formula 1, R 1 and R 2 are the same or different, each independently selected from the group consisting of H, alkyl; R 3 is selected from H or C 1-6 alkyl; R 4 is selected from -OH, -COOR 8 , -CON(R 9 )(R 10 ) or aryl, R 8 is selected from H, alkyl or epoxyalkyl, R 9 and R 10 are the same or different, each independently selected from the group consisting of H, alkyl, or hydroxyl-substituted alkyl;

[0082] in Formula 2, R 5 and R 6 are the same or different, each independently selected from the group consisting of H or alkyl, R 5 and R6 Optionally, it can be annulated to form an aromatic ring; R 7 Selected from -O- or -N(R 11 )-,R 11 Selected from H or alkyl;

[0083] The conductive material includes a conductive polymer and / or a conductive metal material.

[0084] According to the present invention, the conductive fiber further comprises (d) a conductive material bonded to the surface of the fiber matrix.

[0085] (a) Fiber matrix

[0086] The fiber matrix has a gram weight of 100 to 350 g / m 2 ; Exemplarily 110 to 320 g / m 2 , for example, 100, 110, 112.8, 120, 150, 200, 250, 280, 300, 316.8, 320, 330, 340 or 350 g / m 2 .

[0087] The fiber matrix is, for example, selected from cellulose fibers, specifically bamboo fibers, cotton fibers, viscose fibers, silk fibers, spandex, terylene fibers, polyamide fibers, polyester fibers, α-olefin polymer fibers, polyacrylonitrile fibers, polyvinyl alcohol fibers, etc. For example, the bamboo fibers include bamboo pulp fibers, bamboo fibrils, bamboo charcoal fibers, and composite fibers containing bamboo fibers; modified bamboo fibers obtained by chemically modifying bamboo fibers (e.g., surface modification using a silane coupling agent) are also included.

[0088] For example, the surface of the fiber matrix is ​​further modified with reactive chemical groups, and the reactive chemical groups can be selected from at least one of hydroxyl, carboxyl, amino, epoxy, double bond, ether bond, aldehyde, sulfonate, nitro, etc.; through the reactive chemical groups, it can react with the substances in component (b) and / or component (d) to form ester bonds, amide bonds and / or ether bonds, etc., to achieve chemical bond bonding.

[0089] The surface of the fiber matrix can be modified with reactive chemical groups by chemical reaction, ultraviolet irradiation or plasma treatment.

[0090] Chemical reaction methods include chemical group conversion (eg, oxidation of hydroxyl groups to carboxyl groups, oxidation of hydroxyl groups to aldehydes, esterification of carboxyl groups to ester groups).

[0091] The chemical reaction, for example, reacts the fiber matrix with a coupling agent to prepare a fiber matrix whose surface is modified with reactive chemical groups.

[0092] The coupling agent includes at least one of a silane coupling agent, a titanate coupling agent, an aluminate coupling agent, an epoxy group-containing coupling agent, a double bond-containing coupling agent, a mercapto silane coupling agent, and the like.

[0093] The silane coupling agent is, for example, at least one selected from the group consisting of γ-aminopropyltriethoxysilane (NH2CH2CH2CH2Si(OC2H5)3), γ-aminopropyltrimethoxysilane (C6H 17 NH2(CH2)2NH(CH2)3SiCH3(OCH3)2), N-β-(aminoethyl)-γ-aminopropyltrimethoxysilane, γ-aminopropylmethyldiethoxysilane, and the like.

[0094] The titanate coupling agent is, for example, at least one selected from the group consisting of isopropyl tri(dioctyl pyrophosphato) titanate, triisostearyl titanate, tetraisopropyl di(dioctyl phosphite) titanate, isopropyl dioleatoxy (dioctyl phosphatoxy) titanate, and the like.

[0095] The aluminate coupling agent includes, but is not limited to, di-stearyl oxyisopropoxy aluminate.

[0096] The epoxy group-containing coupling agent includes, but is not limited to, an epoxy group-containing trimethoxysilane coupling agent such as β-(3, 4-epoxycyclohexyl)-ethyl triethoxysilane.

[0097] The double bond-containing coupling agent is, for example, at least one selected from the group consisting of vinyl triethoxysilane, vinyl trimethoxysilane, methyl vinyl diethoxysilane, methyl vinyl dimethoxysilane, vinyl triisopropoxysilane, vinyl trichlorosilane, vinyl tri(β-methoxyethoxy)silane, methacryloxypropyl trimethoxysilane, methacryloxypropyl triethoxysilane, and the like.

[0098] The mercapto silane coupling agent is, for example, at least one selected from the group consisting of mercaptopropyl trimethoxysilane, 3-mercaptopropyl triethoxysilane, 3-mercaptopropyl methyl dimethoxysilane, 3-mercaptopropyl methyl diethoxysilane, and the like.

[0099] (b) inorganic material and / or polymer bound to the surface of the fiber substrate

[0100] The inorganic material and / or polymer is bound to the surface of the fiber substrate by a chemical bond.

[0101] The inorganic material is bound to the surface of the fiber substrate in the form of particles.

[0102] For example, the average particle diameter of the inorganic material is 10 nm to 100 μm.

[0103] The inorganic material includes micro-particles of a compound represented by Formula 3, such as silica particles, silica particles containing a reactive chemical group, titanium dioxide particles, titanium dioxide particles containing a reactive chemical group, etc., which are formed by hydrolysis of a compound represented by Formula 3.

[0104] The polymer is bound to the surface of the fiber substrate in the form of polymer particles or a polymer layer.

[0105] In Formula 1, R 1 and R 2 are the same or different and are each independently selected from H, C 1-6 alkyl; R 3 is selected from H, methyl or ethyl; R 4 is selected from -OH, -COOR 8 , -CON(R 9 )(R 10 ) or phenyl, R 8 is selected from H, C 1-6 alkyl or epoxy C 1-6 alkyl, R 9 is selected from H, R 10 is selected from C 1-6 alkyl (e.g., isopropyl).

[0106] The compound represented by Formula 1 is, for example, acrylic acid, methacrylic acid, methyl methacrylate, ethyl methacrylate, glycidyl methacrylate, vinyl alcohol, styrene, N-isopropyl acrylamide or N-(2-hydroxypropyl) methacrylamide, etc.

[0107] In Formula 2, R 5 and R 6 are the same or different and are each independently selected from H or C 1-6 alkyl, R 5 and R 6 may also optionally form a ring to form a benzene ring; R 7 is selected from -O- or -N(R 11 )-, R 11 is selected from H or alkyl.

[0108] The compound represented by Formula 2 is, for example, maleic anhydride or phthalic anhydride, etc.

[0109] Exemplarily, the polymer is selected from at least one of polyethylene glycol, polyvinyl alcohol, or an ammonia-containing polymer (such as triethylene tetramine, diethylene triamine, polyurethane), or can be selected from at least one monomer polymerized to form a homopolymer or copolymer selected from N-isopropyl acrylamide, acrylic acid, methacrylic acid, methyl methacrylate, ethyl methacrylate, maleic anhydride, glycidyl methacrylate, styrene, oxirane, etc. Exemplarily, it can be selected from at least one of poly(N-isopropyl acrylamide-acrylic acid), poly(styrene-acrylic acid), poly(N-isopropyl acrylamide-methacrylic acid), poly(N-isopropyl acrylamide-styrene-acrylic acid), poly(styrene-methacrylic acid), poly(oxirane-acrylic acid), etc.

[0110] (c) a conductive material combined with the inorganic material and / or polymer

[0111] wherein the conductive material is combined with the inorganic material and / or polymer by one of the following forces: i) chemical bond; ii) forming interpenetrating network with component b; iii) penetrating into component b; iv) charge interaction; etc.

[0112] The conductive material is, for example, selected from the conductive polymer, the conductive metal material, or a composite of the conductive polymer and the conductive metal material.

[0113] Exemplarily, the conductive polymer is selected from at least one of polyaniline, polypyrrole, polythiophene, poly(3,4-ethylenedioxythiophene)-polystyrene sulfonic acid, polyacetylene, polyphenylacetylene, poly-p-phenylene, and derivatives thereof, etc.

[0114] The conductive metal material is selected from at least one of gold, silver, copper.

[0115] wherein the conductive polymer is combined on the surface of the inorganic material and / or polymer by chemical bond; and / or, the conductive metal material is combined on the surface of the inorganic material and / or polymer by physical adsorption, forming interpenetrating network with component b or penetrating into component b; and / or, the conductive metal material is combined on the surface of the inorganic material and / or polymer by coordination interaction between the conductive metal material and component b.

[0116] wherein the conductive polymer is combined on the surface of the inorganic material and / or polymer by in-situ polymerization.

[0117] Exemplarily, the conductive metal material is reacted with a silane coupling agent before being combined on the surface of the inorganic material and / or polymer.

[0118] The composite of the conductive polymer and the conductive metal material is combined with the component b in an in-situ formation. In the composite, the weight ratio of the conductive metal material and the conductive polymer and the weight ratio of the fiber substrate are 0.000001-100:1, preferably 0.0001-10:1.

[0119] (d) the conductive material combined on the surface of the fiber substrate

[0120] In the present application, the conductive fiber further comprises a conductive material directly combined on the surface of the fiber substrate.

[0121] In the present application, the conductive fiber further comprises a conductive material directly combined on the surface of the fiber substrate.

[0122] For example, the conductive material is combined on the surface of the fiber substrate by in-situ polymerization.

[0123] The conductive material has the above meaning. Specifically, the conductive material combined on the surface of the fiber substrate is selected from the conductive polymer or the composite of the conductive polymer and the conductive metal material.

[0124] [conductive fabrics]

[0125] The present application provides a conductive fabric woven by the conductive fiber described above. For example, the conductive fabric is woven by the conductive fiber described above by any weaving technology.

[0126] For example, the fabric can comprise a fabric woven by the conductive fiber in any way (woven, knitted) in various structures, and also comprises a fabric in which the conductive fiber is inserted or woven in other fibers (such as polyester, nylon and acrylic).

[0127] The present application further provides a conductive fabric, which comprises (a') a fabric substrate, (b') an inorganic material and / or a polymer combined on the surface of the fabric substrate, and (c') a conductive material combined with the polymer and / or the inorganic material.

[0128] The inorganic material is selected from at least one of silicon dioxide, titanium dioxide, iron oxide, aluminum oxide, a compound represented by formula 3 below or a hydrolysis condensate thereof, or distearyl oxyisopropoxy aluminate or a hydrolysis condensate thereof.

[0129]

[0130] M is at least one of Si and Ti;

[0131] In formula 3, R a , R b , R c and R didentical or different, are independently of each other selected from H, Cl, unsubstituted or optionally substituted with one, two or more R e substituted C 1-12 alkyl, vinyl, -O-C 1-12 alkyl, C 6-20 aryl;

[0132] each R e identical or different, are independently of each other selected from unsubstituted or optionally substituted with one, two or more R f substituted -C(=O)OH, C 1-12 alkyl, C 6-20 aryl, -O-C 1-12 alkyl, -NH-C 1-12 alkyl, amino, -SH;

[0133] each R f identical or different, are independently of each other selected from C 1-12 alkyl, amino, -O-C 1-12 alkyl, vinyl or C 1-12 alkyl-substituted vinyl, 3-20-membered heterocyclyl;

[0134] and R a , R b , R c and R d , at least one is -O-C 1-12 alkyl or Cl;

[0135] The polymerization monomer of the polymer is selected from at least one of the following: a compound shown in Formula 1, a compound shown in Formula 2, ethylene glycol, triethylene tetramine or diethylene triamine, etc.; or, the polymer is selected from at least one of polyurethane, polyvinyl acetate, polyimide or epoxy resin;

[0136]

[0137] In Formula 1, R 1 and R 2 are identical or different, and are independently of each other selected from H, alkyl; R 3 is selected from H or C 1-6 alkyl; R 4 is selected from -OH, -COOR 8 , -CON(R 9 )(R 10 ) or aryl, R 8 is selected from H, alkyl or epoxyalkyl, R 9 and R 10 are identical or different, and are independently of each other selected from H or alkyl;

[0138] In Formula 2, R5 and R 6 are the same or different, independently of one another, selected from H or alkyl, R 5 and R 6 may also optionally form a ring to form an aromatic ring; R 7 is selected from -O- or -N(R 11 )-, R 11 is selected from H or alkyl.

[0139] wherein the inorganic material includes micro-particles of a compound represented by Formula 3, such as silica particles, silica particles containing a reactive chemical group, titanium dioxide particles, titanium dioxide particles containing a reactive chemical group, and the like, formed by hydrolysis of a compound represented by Formula 3.

[0140] wherein the above-mentioned polymer or polymerized monomers of the polymer and cross-linking agent form micro-particles such as poly(N-isopropyl acrylamide) microgel particles, poly(N-isopropyl acrylamide-acrylic acid) copolymer particles, poly(N-isopropyl acrylamide-methacrylic acid) copolymer particles, poly(N-isopropyl acrylamide-acrylamide) copolymer particles, poly(N-isopropyl acrylamide-acrylic acid-acrylamide) copolymer particles, poly(N-isopropyl acrylamide-styrene) copolymer particles, poly(N-isopropyl acrylamide-styrene-acrylic acid) copolymer particles, poly(N-isopropyl acrylamide-methacrylate) copolymer particles, poly(N-isopropyl acrylamide-N-(2-hydroxypropyl) methacrylamide) copolymer particles, and the like.

[0141] The electrically conductive material includes an electrically conductive polymer and / or an electrically conductive metal material.

[0142] Preferably, the electrically conductive fabric further includes (d') an electrically conductive material bound to the surface of the fabric substrate.

[0143] wherein the inorganic material, the polymer, and the electrically conductive material have the same definitions as the inorganic material, the polymer, and the electrically conductive material in the electrically conductive fiber described above.

[0144] Illustratively, the fabric substrate can be a fabric woven from at least one of polyester, spandex, and acrylic.

[0145] wherein the surface of the fabric substrate is further modified with a reactive chemical group selected from at least one of a hydroxyl group, a carboxyl group, an amino group, an epoxy group, a double bond, an ether bond, an aldehyde group, a sulfonate group, a nitro group, and the like; and the chemical bond is formed by the reaction of the reactive chemical group with the substance in component (b') and / or component (d') to form an ester bond, an amide bond, and / or an ether bond.

[0146] [preparation of conductive fibers]

[0147] The present application also provides a method for preparing the conductive fiber as described above, which comprises:

[0148] 1) preparing a fiber substrate;

[0149] 2) reacting the fiber substrate in step 1) with a polymer (or a polymerized monomer of the polymer) and / or an inorganic material (or a precursor of inorganic oxide) to obtain a fiber substrate with inorganic material and / or polymer on the surface; 3) reacting the fiber substrate with inorganic material and / or polymer on the surface in step 2) with a conductive polymer monomer and / or a precursor of conductive metal material to obtain the conductive fiber.

[0150] The method for preparing the conductive fiber further comprises step 4): after the reaction is completed, the conductive fiber is taken out and washed with deionized water until the solution is clear; drying; to obtain the conductive fiber.

[0151] In step 1), it further comprises the step of introducing a reactive chemical group on the fiber substrate. Specifically, the aforementioned method can be used to introduce a reactive chemical group on the fiber substrate.

[0152] Step 2) is specifically: reacting the fiber substrate in step 1), especially the fiber substrate containing a reactive chemical group, with a solution containing a polymer, a polymer monomer and / or an inorganic material to obtain a fiber substrate with inorganic material and / or polymer on the surface.

[0153] In step 2), the inorganic material is reacted with a coupling agent before the reaction. Exemplarily, the coupling agent has the same definition as the coupling agent described above.

[0154] In step 2), the fiber substrate containing a reactive chemical group is soaked in a solvent containing at least one of a polymer, a polymer monomer and an inorganic material.

[0155] In step 2), the fiber substrate containing a reactive chemical group, a catalyst, is stirred uniformly and then soaked in a solvent containing at least one of a polymer, a polymer monomer and an inorganic material.

[0156] Wherein, the combination of the fiber substrate with the inorganic material and / or the polymer means that the inorganic material, the polymer and the fiber substrate have undergone a chemical reaction; specifically including: the chemical reaction of the polymer with the surface of the fiber substrate to form a polymer layer, or the combination of the polymer particles with the surface of the fiber substrate; or the combination of the particles formed by the condensation reaction of the inorganic material (such as silicon dioxide, titanium dioxide) and the coupling agent with the surface of the fiber substrate.

[0157] The combination of the polymer and the surface of the fiber substrate includes the reaction of the functional groups of the polymer with the reactive chemical groups on the surface of the fiber, such as the reaction of carboxyl groups with hydroxyl groups or amino groups, the reaction of epoxy groups with amino groups or hydroxyl groups, and the like. Specifically, the direct reaction and combination of polymers such as polyurethane, polyethylene glycol, polyvinyl acetate, polyvinyl alcohol, polyimide, polyacrylamide, epoxy resin, poly(N-isopropyl acrylamide), poly(N-isopropyl acrylamide-acrylic acid) copolymer, poly(N-isopropyl acrylamide-methacrylic acid) copolymer, and the like with the fiber substrate.

[0158] The precursor of the inorganic oxide has a structure shown in Formula 3.

[0159] The combination of the inorganic material (such as silicon dioxide, titanium dioxide) and the surface of the fiber substrate can be achieved through the reaction between the above-mentioned chemical groups, or through the condensation reaction of hydroxyl groups (such as the condensation reaction of silicon hydroxyl groups).

[0160] The reaction temperature in Step 1) and Step 2) is -15-150°C, preferably -5-50°C. For example, -15°C, 0°C, 10°C, 20°C, 30°C, 40°C, 50°C, 60°C, 80°C, 100°C, 120°C, 150°C

[0161] In Step 2), the polymer monomer can be combined with the surface of the fiber substrate in the form of in-situ polymerization. In the solution containing the polymer monomer, the ratio of the polymer monomer to the solvent is (100:0)-(0.001:100). For example, the polymer monomer is selected from at least one of N-isopropyl acrylamide, acrylic acid, methacrylic acid, methyl methacrylate, ethyl methacrylate, maleic anhydride, glycidyl methacrylate, styrene, polyethylene glycol, and the like. For example, the solvent includes ethanol, methanol, tetrahydrofuran, N,N-dimethylformamide, dioxane, C 5-12 at least one of saturated alkanes, toluene, benzene, xylene, water, and the like.

[0162] In Step 3), the combination of the fiber substrate with the surface of the inorganic material and / or polymer with the conductive material includes the combination of the inorganic material and / or polymer with the conductive material, and the combination of the fiber substrate with the conductive material; specifically, it includes: the in-situ polymerization of the conductive polymer monomer to the surface of the inorganic material and / or polymer, or the in-situ polymerization of the conductive polymer monomer to the surface of the fiber substrate, or the reaction of the particles formed by the condensation reaction of the conductive metal material and the coupling agent with the inorganic material and / or polymer, or the combination of the particles formed by the condensation reaction of the conductive metal material and the coupling agent with the surface of the fiber substrate.

[0163] The step 3) is specifically: adding conductive polymer monomer into the solution of the fiber substrate with inorganic material and / or polymer on the surface combined in step 2), optionally adding one or more of initiator, oxidant, catalyst, reducing agent, dispersant, and carrying out in-situ polymerization to prepare conductive fiber.

[0164] For example, the conductive polymer monomer, initiator, catalyst and dispersant are added into the solution of the fiber substrate with inorganic material and / or polymer on the surface combined in step 2), and in-situ polymerization is carried out to prepare conductive fiber.

[0165] The conductive polymer monomer is for example selected from at least one of aniline, pyrrole, thiophene, acetylene, phenylacetylene, benzene, etc.

[0166] The initiator is for example selected from at least one of ammonium persulfate, potassium persulfate, azobisisobutyronitrile, azobis isobutyl amidine hydrochloride, benzoyl peroxide, etc.

[0167] The oxidant is for example selected from at least one of ferric trichloride, potassium dichromate, potassium permanganate, perchloric acid, etc.

[0168] The catalyst can include esterification reaction catalyst, amidation reaction catalyst; for example, acid, base, lithium aluminum hydride, trimethylaluminum, alkyl lithium or compound with groups of formula I-III as follows:

[0169]

[0170] The acid can be hydrochloric acid, phosphoric acid or sulfuric acid;

[0171] The base can be dodecyl tertiary amine, sodium bicarbonate or sodium hydroxide;

[0172] The catalyst containing group of formula I can be 1-(3-dimethylaminopropyl)-3-ethyl carbodiimide hydrochloride;

[0173] The catalyst containing group of formula III can be N-hydroxysuccinimide or N-hydroxylthiosuccinimide.

[0174] The reducing agent is for example selected from at least one of sodium borohydride, glucose, citric acid, glycerol, ethylene glycol, etc.

[0175] The dispersant is for example selected from at least one of polyvinylpyrrolidone, dodecyl quaternary ammonium, sodium dodecyl sulfate, sodium dodecyl benzene sulfonate, potassium dodecyl sulfate, potassium dodecyl benzene sulfonate, polystyrene maleic anhydride, Tween, Span (such as Span 60, Span 80), stearic acid, etc.

[0176] Specifically, the step 3) and the step 4) can include: adding conductive polymer monomers (such as aniline, pyrrole, thiophene, etc.), and polymerization initiators, dispersants into the solution of the fiber substrate with the inorganic material and / or polymer combined on the surface in the step 2), mixing uniformly, reacting sufficiently, taking out the reaction product, washing, drying, etc., to obtain the conductive fiber.

[0177] In the step 3), the conductive metal material precursor can be the product after the conductive metal material reacts with the silane coupling agent.

[0178] Specifically, the step 3) and the step 4) can include: adding conductive metal material particles containing reactive groups into the solution of the fiber substrate with the inorganic material and / or polymer combined on the surface in the step 2), adding a reducing agent, and the conductive metal material particles are deposited on the surface of the fiber substrate; heating, reacting sufficiently, taking out the reaction product, washing, drying, etc., to obtain the conductive fiber.

[0179] In the system containing the conductive polymer monomers, the volume ratio of the conductive polymer monomers to the solvent is 100:0-0.01:100, preferably 100:10-1:100.

[0180] Exemplarily, the volume ratio of the solvent to the coupling agent is 0.1-100:1. For example, 0.1:1, 0.2:1, 1:1, 2:1, 3:1, 4:1, 5:1, 6:1, 7:1, 8:1, 10:1, 40:1, 60:1, 80:1, 100:1.

[0181] Exemplarily, the mass ratio of the conductive polymer monomers to the fiber substrate is 0.000001-10:1.

[0182] The reaction in the steps 1), 2) and 3) can also be carried out in an inert atmosphere, such as nitrogen atmosphere or argon atmosphere, etc.

[0183] [ preparation of conductive fabrics

[0184] The preparation method of the conductive fabric of the present application is the same as the preparation method of the conductive fiber described above except that the substrate is different, that is, the fiber substrate in the preparation method of the conductive fiber described above is replaced by the fabric substrate.

[0185] [application of conductive fibers and conductive fabrics]

[0186] The present application also provides the application of the conductive fiber and / or the conductive fabric described above, which is preferably applied in the fields of antistatic, conductive, sensing, etc., preferably in the fields of wires, antistatic clothes, heating fabrics, motion sensing, and remote control products (such as remote control of object movement, remote control of electronic switch), electromagnetic shielding devices, wireless sensors, etc.

[0187] The technical solutions of the present application will be further described in detail below in connection with specific examples. It should be understood that the following examples are only illustrative and explanatory of the present application and should not be interpreted as limiting the scope of protection of the present application. Any technology realized based on the above description of the present application is covered within the scope of protection intended by the present application.

[0188] Unless otherwise specified, the raw materials and reagents used in the following examples are commercially available or can be prepared by known methods.

[0189] Examples 1-19 of the present application are prepared using the following flow:

[0190] As shown in Figure 1 Step S1, first graft a coupling agent on the surface of the fiber substrate or fabric substrate. For example, in a preferred embodiment of the present application, the hydroxyl groups on the surface of the fiber substrate or fabric substrate are connected to the silicon-oxygen bond in the coupling agent (such as γ-aminopropyl triethoxysilane), so that the surface of the fiber substrate or fabric substrate has an amino group.

[0191] Step S2, graft a polymer or inorganic material on the surface of the fiber substrate or fabric substrate treated with the coupling agent, to obtain a fiber substrate or fabric substrate with inorganic material and / or polymer bonded on the surface; for example, the above fabric substrate can be soaked in a solvent containing a polymer.

[0192] Step S3, mix the product in Step S2 uniformly with a conductive polymer monomer, so that the conductive polymer is bonded in situ on the surface of the inorganic material and / or polymer, to prepare a conductive fiber or conductive fabric.

[0193] Example 1

[0194] In a 500ml 2% poly(N-isopropyl acrylamide-acrylic acid) microgel solution, 1-(3-dimethylaminopropyl)-3-ethyl carbodiimide hydrochloride is added to make the concentration of poly(N-isopropyl acrylamide-acrylic acid) 0.075%, then the bamboo fiber fabric is soaked in the solution at 5°C for 5 minutes, taken out, washed and dried. In 3L deionized water at 5°C, polyvinylpyrrolidone (PVP) is added and stirred uniformly to make the mass concentration of PVP 0.1%, aniline and hydrochloric acid are added to the reaction system, the concentration of aniline is 0.01%, the above bamboo fiber fabric is put into the reaction system, 12g ammonium persulfate is added and stirred uniformly, then added to the reaction system and reacted thoroughly, the bamboo fiber fabric is taken out, washed with deionized water and dried, to prepare a conductive bamboo fiber fabric.

[0195] Fourier transform infrared spectrometer is used for observation, and the success of the polyaniline grafting process is verified, and the test results are shown in Figure 2 Figure 2 ​is the Fourier transform infrared spectrum of the conductive bamboo fiber. The frequency range is 1000 cm -1 to 4000 cm -1 . The stretching vibration band of polysaccharide acetal (C-O) in the fiber matrix before and after aniline treatment is 1017.3 cm -1 , and the stretching vibration band of hydroxyl (-OH) in cellulose or lignin is 3326.7 cm -1 . There are strong absorption peaks near 1017.3 cm -1 and 3326.7 cm -1 . The results show that the oxidative polymerization of aniline on the surface of the fabric does not change the properties of the fabric. At the same time, the C-H bending vibration peak of disubstituted benzene is at 805.2 cm -1 , the characteristic absorption peak of quinone structure is at 1141.7 cm -1 , the C-N stretching vibration peak of benzene ring is at 1300.8 cm -1 , and the C=C stretching vibration peak of benzene structure is observed at 1495.6 cm -1 and 1581.4 cm -1 . The results show that the fabric contains polyaniline after in-situ polymerization treatment. The surface resistance is 10 7 Ω.

[0196] Example 2

[0197] First, the bamboo fiber fabric with a grammage of 112.8 g / m 2 is washed with deionized water; then treated with 0.01 mol / L NaOH solution, and then immersed in a mixed solution of anhydrous ethanol and γ-aminopropyl triethoxysilane with a volume ratio of 1:1 for 12 hours to prepare an aminated fabric; 5 ml of 2% poly(N-isopropyl acrylamide-acrylic acid) solution is added to 100 ml of deionized water, and 1-(3-dimethylaminopropyl)-3-ethyl carbodiimide hydrochloride and N-hydroxysuccinimide are added to make the concentrations 0.075% and 0.09% respectively, and then the aminated fabric is added and reacted at room temperature for 1 hour. The environmental temperature is set to 5°C; 3L of deionized water is added to a flask, 50ml of polyvinylpyrrolidone solution with a concentration of 0.02g / ml is added, 50ml of aniline hydrochloride solution with a concentration of 2% (the volume ratio of hydrochloric acid to aniline is 2.5:1) is dissolved in the flask, and the poly(N-isopropyl acrylamide-acrylic acid)-fabric is immersed in the above solution and stirred for 30 minutes, and ammonium persulfate is added to make the solution concentration reach 0.0053g / ml. Stirring is continued at 0°C for 12 hours, the fabric is taken out and washed with deionized water until the solution is clear, and the fabric is dried after washing to prepare a conductive fabric.

[0198] The obtained polyaniline / bamboo fiber conductive fabric was scanned by SEM, and it was found that polyaniline was densely and uniformly coated on the surface of the bamboo fiber of the base fabric. The obtained fiber was dark green, and the volume resistivity was 5.8 Ω·cm.

[0199] Example 3

[0200] First, the bamboo fiber fabric with a grammage of 120.1 g / m 2 The bamboo fiber fabric was washed with deionized water; the fabric was treated with 0.01 mol / L KOH solution, immersed in a mixed solution of anhydrous ethanol and γ-aminopropyl triethoxysilane with a volume ratio of 10:1 for 12 hours, then 5 ml of 0.2% silica particle solution was added, and the reaction was carried out at room temperature for 5 hours, then the fabric was taken out and washed; the environmental temperature was set to 5°C; 3L deionized water was added to a flask, 50ml of 2% pyrrole hydrochloric acid solution was dissolved in the flask, the above fabric was immersed in the above solution and stirred for 30 minutes, potassium persulfate was added to make the solution concentration reach 0.0053g / ml. Stirring was continued at 10°C for 12 hours, the fabric was taken out and washed with deionized water until the solution was clear, the fabric was dried after washing, and a conductive fabric was prepared. The volume resistivity of the conductive fabric was 0.92759 Ω·cm.

[0201] Example 4

[0202] First, the bamboo fiber fabric with a grammage of 162.4 g / m 2 The bamboo fiber fabric was washed with deionized water and acetone; the fabric was immersed in a mixed solution of anhydrous ethanol and γ-aminopropyl trimethoxysilane with a volume ratio of 1:1 for 12 hours to prepare an aminated fabric; 5 ml of 2% poly(N-isopropyl acrylamide-acrylic acid) solution was added to 100 ml of deionized water, 1-(3-dimethylaminopropyl)-3-ethyl carbodiimide hydrochloride and N-hydroxysuccinimide were added to make the concentrations reach 0.075% and 0.09% respectively, and then the aminated fabric was added and reacted at room temperature for 1 hour. The environmental temperature was set to 5°C; 3L deionized water was added to a flask, 50ml of 0.02g / ml polyvinylpyrrolidone solution was added, 50ml of 2% 3,4-ethylenedioxythiophene hydrochloric acid solution was dissolved in the flask, the poly(N-isopropyl acrylamide-acrylic acid)-fabric was immersed in the above solution and stirred for 30 minutes, ammonium persulfate was added to make the solution concentration reach 0.0053g / ml. Stirring was continued at 0°C for 12 hours, the fabric was taken out and washed with deionized water until the solution was clear, the fabric was dried after washing, and a conductive fabric was prepared. The volume resistivity of the conductive fabric was 0.92761 Ω·cm.

[0203] Example 5

[0204] First, the bamboo fiber fabric with a grammage of 208.6 g / m 2The bamboo fiber fabric was washed with deionized water; the fabric was treated with 0.01 mol / L NaOH solution, and was immersed in a mixed solution of heptane and γ-aminopropyl triethoxysilane with a volume ratio of 1:1 for 12 hours to prepare an aminated fabric; 5 ml of 2% poly(N-isopropyl acrylamide-acrylic acid) solution was added to 100 ml of deionized water, 1-(3-dimethylaminopropyl)-3-ethyl carbodiimide hydrochloride and N-hydroxysuccinimide were added to make the concentrations 0.075% and 0.09% respectively, and then the aminated fabric was added to react at room temperature for 1 hour. The ambient temperature was set to 0°C; 3L of deionized water was added to a flask, 50 ml of polyvinylpyrrolidone solution with a concentration of 0.2 g / ml was added, 50 ml of aniline hydrochloride solution (hydrochloric acid and aniline with a volume ratio of 2.5:1) with a concentration of 2% was dissolved in the flask, the poly(N-isopropyl acrylamide-acrylic acid)-fabric was immersed in the above solution and stirred for 30 minutes, and ammonium persulfate was added to make the solution concentration reach 0.0053 g / ml. Stirring was continued at 0°C for 12 hours, the fabric was taken out and washed with deionized water until the solution was clear, the fabric was dried after washing, and a conductive fabric was prepared. The volume resistivity was 0.64856 Ω·cm.

[0205] Example 6

[0206] First, the bamboo fiber fabric with a grammage of 244.7 g / m 2 The bamboo fiber fabric was washed with deionized water; the fabric was treated with 0.01 mol / L NaOH solution, and was immersed in a mixed solution of heptane and γ-aminopropyl triethoxysilane with a volume ratio of 1:1 for 12 hours to prepare an aminated fabric; 5 ml of 2% poly(N-isopropyl acrylamide-acrylic acid) solution was added to 100 ml of deionized water, 1-(3-dimethylaminopropyl)-3-ethyl carbodiimide hydrochloride and N-hydroxysuccinimide were added to make the concentrations 0.075% and 0.09% respectively, and then the aminated fabric was added to react at room temperature for 1 hour. The ambient temperature was set to 0°C; 3L of deionized water was added to a flask, 50 ml of polyvinylpyrrolidone solution with a concentration of 0.2 g / ml was added, 50 ml of aniline hydrochloride solution (hydrochloric acid and aniline with a volume ratio of 2.5:1) with a concentration of 2% was dissolved in the flask, the poly(N-isopropyl acrylamide-acrylic acid)-fabric was immersed in the above solution and stirred for 30 minutes, and ammonium persulfate was added to make the solution concentration reach 0.0053 g / ml. Stirring was continued at 0°C for 12 hours, the fabric was taken out and washed with deionized water until the solution was clear, the fabric was dried after washing, and a conductive fabric was prepared. The volume resistivity was 0.64856 Ω·cm.

[0207] Example 7

[0208] First, the bamboo fiber fabric with a grammage of 274.28 g / m 2The bamboo fiber fabric is washed with deionized water; the fabric is treated with 0.01 mol / L NaOH solution, and immersed in a mixed solution of anhydrous ethanol and γ-aminopropyl triethoxysilane with a volume ratio of 1:1 for 12 hours; 5 ml of 2% poly(N-isopropyl acrylamide-acrylic acid) solution is added to 100 ml of deionized water, 1-(3-dimethylaminopropyl)-3-ethyl carbodiimide hydrochloride and 0.095 g of N-hydroxysuccinimide are added to make the concentrations 0.075% and 0.09% respectively, and then the aminated fabric is added and reacted at room temperature for 1 hour. The ambient temperature is set to 5°C; 3L of deionized water is added to a flask, 50 ml of polyvinylpyrrolidone solution with a concentration of 0.02 g / ml is added, 50 ml of aniline hydrochloric acid solution (hydrochloric acid: aniline = 2.5:1) with a concentration of 2% is dissolved in the flask, the poly(N-isopropyl acrylamide-acrylic acid)-fabric is immersed in the above solution and stirred for 30 minutes, and ammonium persulfate is added to make the solution concentration 0.0053 g / ml. Stirring is continued at 0°C for 12 hours, the fabric is taken out and washed with deionized water until the solution is clear, and the fabric is dried after washing to prepare a conductive fabric. The volume resistivity of the conductive fabric is 0.38696 Ω·cm.

[0209] Example 8

[0210] First, the bamboo fiber fabric with a grammage of 316.8 g / m 2 The bamboo fiber fabric is washed with deionized water; the fabric is treated with 0.01 mol / L NaOH solution, and immersed in a mixed solution of anhydrous ethanol and γ-aminopropyl triethoxysilane with a volume ratio of 1:1 for 12 hours; 5 ml of 2% poly(N-isopropyl acrylamide-acrylic acid) solution is added to 100 ml of deionized water, 1-(3-dimethylaminopropyl)-3-ethyl carbodiimide hydrochloride and 0.095 g of N-hydroxysuccinimide are added to make the concentrations 0.075% and 0.09% respectively, and then the aminated fabric is added and reacted at room temperature for 1 hour. The ambient temperature is set to 5°C; 3L of deionized water is added to a flask, 50 ml of polyvinylpyrrolidone solution with a concentration of 0.02 g / ml is added, 50 ml of aniline hydrochloric acid solution (hydrochloric acid: aniline = 2.5:1) with a concentration of 2% is dissolved in the flask, the poly(N-isopropyl acrylamide-acrylic acid)-fabric is immersed in the above solution and stirred for 30 minutes, and ammonium persulfate is added to make the solution concentration 0.0053 g / ml. Stirring is continued at 0°C for 12 hours, the fabric is taken out and washed with deionized water until the solution is clear, and the fabric is dried after washing to prepare a conductive fabric. The volume resistivity of the conductive fabric is 0.37686 Ω·cm.

[0211] Example 9

[0212] The bamboo fabric was first washed with 200 mL of deionized water. The fabric was immersed in a mixed solution of acetone and N-(β-aminoethyl)-γ-aminopropylmethyldimethoxysilane (NH2(CH2)2NH(CH2)3SiCH3(OCH3)2) in a volume ratio of 1:5 for 12 hours. Then, the above fabric was added and reacted at room temperature for 1 hour. The ambient temperature was set to 5°C. 3 L of deionized water was added to a flask, 50 mL of a polyvinylpyrrolidone solution with a concentration of 0.02 g / mL was added, 50 mL of a pyrrole hydrochloride solution (hydrochloric acid: pyrrole = 5:1) with a concentration of 2% was dissolved in the flask, the above fabric was immersed in the solution and stirred for 30 minutes, ammonium persulfate was added to make the solution concentration 0.0053 g / mL. The solution was continuously stirred at 30°C for 12 hours. The fabric was taken out and washed with deionized water until the solution was clear. The fabric was dried after washing.

[0213] Example 10

[0214] The bamboo fabric was first washed with 200 mL of deionized water. The fabric was immersed in a mixed solution of acetone and N-(β-aminoethyl)-γ-aminopropylmethyldimethoxysilane (NH2(CH2)2NH(CH2)3SiCH3(OCH3)2) in a volume ratio of 1:5 for 12 hours. Then, the above fabric was added and reacted at room temperature for 1 hour. The ambient temperature was set to 5°C. 3 L of deionized water was added to a flask, 50 mL of a polyvinylpyrrolidone solution with a concentration of 0.02 g / mL was added, 50 mL of a pyrrole hydrochloride solution (hydrochloric acid: pyrrole = 5:1) with a concentration of 2% was dissolved in the flask, the above fabric was immersed in the solution and stirred for 30 minutes, ammonium persulfate was added to make the solution concentration 0.0053 g / mL. The solution was continuously stirred at 30°C for 12 hours. The fabric was taken out and washed with deionized water until the solution was clear. The fabric was dried after washing. 17 The bamboo fabric was first washed with 200 mL of deionized water. The fabric was immersed in a mixed solution of acetone and N-(β-aminoethyl)-γ-aminopropylmethyldimethoxysilane (NH2(CH2)2NH(CH2)3SiCH3(OCH3)2) in a volume ratio of 1:5 for 12 hours. Then, the above fabric was added and reacted at room temperature for 1 hour. The ambient temperature was set to 5°C. 3 L of deionized water was added to a flask, 50 mL of a polyvinylpyrrolidone solution with a concentration of 0.02 g / mL was added, 50 mL of a pyrrole hydrochloride solution (hydrochloric acid: pyrrole = 5:1) with a concentration of 2% was dissolved in the flask, the above fabric was immersed in the solution and stirred for 30 minutes, ammonium persulfate was added to make the solution concentration 0.0053 g / mL. The solution was continuously stirred at 30°C for 12 hours. The fabric was taken out and washed with deionized water until the solution was clear. The fabric was dried after washing.

[0215] Example 11

[0216] First, 100g of bamboo fiber fabric was washed with 200mL of deionized water; treated with 0.01mol / L NaOH solution, and the fabric was soaked in a solution of γ-aminopropyltriethoxysilane (NH2CH2CH2CH2Si(OC2H5)3 for 12 hours; 5ml of 2% poly (N-isopropylacrylamide-acrylic acid) solution was added to 100ml of deionized water, and 1% 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride and 10ml of N-hydroxysulfosuccinimide solution were added. Then, the above fabric was added and reacted for 1 hour. Set the ambient temperature to 5°C; add 3L of deionized water to a flask, add 50ml of a 0.02g / ml polyvinylpyrrolidone solution, and dissolve 50ml of a 2% aniline hydrochloric acid solution (hydrochloric acid:aniline = 2.5:1) in the flask. Immerse the poly(N-isopropylacrylamide-styrene) fabric in this solution and stir continuously for 30 minutes. Add ammonium persulfate to bring the solution concentration to 0.0053g / ml. Stir continuously at 0°C for 12 hours. Remove the fabric and wash it with deionized water until the solution is clear. Then, dry the fabric after washing.

[0217] Example 12

[0218] The bamboo fiber fabric was first washed with deionized water; treated with 0.01 mol / L sodium carbonate solution, and then soaked in anhydrous ethanol and γ-aminopropyltrimethoxysilane (C6H 17 The fabric was then placed in a 1:1 solution of poly(N-isopropylacrylamide-acrylic acid) (PO3Si) at a volume ratio of 1:1 for 12 hours. A 2% poly(N-isopropylacrylamide-acrylic acid) solution was added to 100 mL of deionized water, followed by 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride and 0.5 g of N-hydroxysulfosuccinimide at a mass ratio of 1:2. The fabric was then added to the solution and allowed to react for 2 hours. The ambient temperature was set at 5°C. A flask was filled with 3 L of deionized water, 50 mL of a 0.02 g / mL Tween 60 solution, and 50 mL of a 2% pyrrole solution. The fabric was then immersed in the solution, stirring continuously for 30 minutes. Ammonium persulfate was then added to bring the solution concentration to 0.0053 g / mL. Stirring was continued at 0°C for 12 hours. The fabric was removed and washed with deionized water until the solution was clear. The fabric was then dried. The volume resistivity of the conductive fabric was 6 Ωcm.

[0219] Example 13

[0220] The bamboo fiber fabric was first washed with deionized water; treated with a 0.01 mol / L NaOH solution, and then immersed in a mixed solution of anhydrous ethanol and γ-aminopropyltriethoxysilane in a 1:1 volume ratio for 12 hours. 5 ml of a 2% poly(N-isopropylacrylamide-acrylic acid) solution was added to 100 ml of deionized water, and 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride and 0.095 g of N-hydroxysulfosuccinimide in a mass ratio of 1:2 were added to reach concentrations of 0.075% and 0.09%, respectively, before being added to the amination fabric and reacted for 1 hour. Set the ambient temperature to 5°C; add 3L of deionized water to a flask, add 50ml of a 0.02g / ml polyvinylpyrrolidone solution, and dissolve 50ml of a 2% 3,4-ethylenedioxythiophene-styrenesulfonic acid solution in the flask. Immerse the poly(N-isopropylacrylamide-acrylic acid) fabric in the solution and stir continuously for 30 minutes. Then, add ammonium persulfate to a concentration of 0.0053g / ml. Stir continuously at 0°C for 12 hours. Remove the fabric and wash it with deionized water until the solution is clear. The fabric is then dried. The volume resistivity of the conductive fabric is 11Ωcm.

[0221] Example 14

[0222] The bamboo fiber fabric was first washed with deionized water and treated with 0.01 mol / L NaOH solution. The fabric was then immersed in anhydrous ethanol and γ-aminopropyltrimethoxysilane (C6H 17 The process involved incubating the fabric in a 100 mL mixed solution of 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride (1:2 by weight) at a 1:1 ratio for 12 hours. Five milliliters of a 2% poly(styrene-acrylic acid) solution was added to 100 mL of deionized water, followed by 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride at a 1:2 ratio to achieve a 0.9% concentration. The fabric was then added to the amination reaction for one hour. The ambient temperature was set at 5°C. Three liters of deionized water were added to a flask, along with 50 mL of a 0.02 g / mL polyvinylpyrrolidone solution and 50 mL of a 2% pyrrole hydrochloride solution (hydrochloric acid:pyrrole = 2.5:1). The fabric was then immersed in the solution, stirring continuously for 30 minutes. Ammonium persulfate was then added to achieve a 0.0053 g / mL concentration. Stirring was continued at 0°C for 12 hours. The fabric was then removed and washed with deionized water until the solution was clear. The fabric was then dried to produce a conductive fabric. The volume resistivity of the conductive fabric is 100 Ωcm.

[0223] Example 15

[0224] First, wash the bamboo fiber fabric with deionized water and dry it; put it into 0.01mol / L NaOH solution for 15 minutes, then take it out and wash it with deionized water and dry it; cut the fabric into 5*5cm2 The long strip is prepared by in-situ polymerization; the fabric is soaked in a mixed solution of anhydrous ethanol and γ-aminopropyl triethoxysilane with a volume ratio of 1:1 for 12 hours to make the hydroxyl group in the fibers of the fabric condense with the siloxyl group, thereby preparing an aminated fabric; and the aminated fabric is washed with deionized water. 5 ml of a 2% poly(N-isopropyl acrylamide-methacrylic acid) solution is added to 100 ml of deionized water, 1-(3-dimethylaminopropyl)-3-ethyl carbodiimide hydrochloride and 0.095 g of N-hydroxysuccinimide with a mass ratio of 1:2 are added, and then the aminated fabric is added and left to stand for 1 hour. The ambient temperature is set to 5°C; 200 ml of deionized water and a magnetic stirrer are added to a single-necked flask, 0.1 g of polyvinylpyrrolidone is dissolved in 50 ml of deionized water for 30 minutes and then added to the single-necked flask, 2% of an aniline hydrochloric acid solution (hydrochloric acid: aniline = 2.5:1) is dissolved in the single-necked flask, the dry poly(N-isopropyl acrylamide-methacrylic acid)-fabric is immersed in the above solution and stirred for 30 minutes, 1.2 g of ammonium persulfate is dissolved in 50 ml of deionized water and stirred uniformly, and then added to the single-necked flask, and stirring is continued at 0°C for 12 hours. The fabric is taken out and washed with deionized water until the solution is clear, the fabric is dried after washing, and an electrically conductive fabric is prepared.

[0225] Example 16

[0226] The bamboo fiber fabric is first washed clean with deionized water and dried; it is placed in a 0.01 mol / L NaOH solution for 15 minutes, then taken out and washed clean with deionized water and dried, and the fabric is cut into 5*5 cm 2The long strip of 5*5 cm2is prepared by in-situ polymerization; the fabric is soaked in a mixed solution of anhydrous ethanol and γ-aminopropyl triethoxysilane with a volume ratio of 1:1 for 12 hours to enable condensation reaction between hydroxyl groups and siloxyl groups in the fibers of the fabric, thereby preparing an aminated fabric; and the aminated fabric is washed with deionized water. 5 milliliters of a 2% poly(N-isopropyl acrylamide-styrene-acrylic acid) solution is added to 100 milliliters of deionized water, 1-(3-dimethylaminopropyl)-3-ethyl carbodiimide hydrochloride and 0.095g N-hydroxysuccinimide with a mass ratio of 1:2 are added, and then the aminated fabric is added and left to stand for 1 hour. The ambient temperature is set to 5°C; 200 milliliters of deionized water and a magnetic stirrer are added to a single-necked flask for continuous stirring, 0.1g of polyvinylpyrrolidone is dissolved in 50 milliliters of deionized water for 30 minutes and then added to the single-necked flask, 2% aniline hydrochloric acid solution (hydrochloric acid: aniline = 2.5:1) is dissolved in the single-necked flask, the dry poly(N-isopropyl acrylamide-styrene-acrylic acid)-fabric is immersed in the above solution for continuous stirring for 30 minutes, 1.2 grams of ammonium persulfate is dissolved in 50 milliliters of deionized water and stirred uniformly before being added to the single-necked flask, and the mixture is continuously stirred at 0°C for 12 hours. The fabric is taken out and washed with deionized water until the solution is clear, the fabric is dried after washing, and an electrically conductive fabric is prepared. The volume resistivity of the electrically conductive fabric is 21 Ωcm.

[0227] Example 17

[0228] The bamboo fiber fabric is first washed clean with deionized water and dried; it is placed in a 0.01 mol / L sodium carbonate solution for 15 minutes, then taken out, washed clean with deionized water and dried, and the fabric is cut into 5*5 cm2long strips. 2 The long strip of 5*5 cm2is prepared by in-situ polymerization; the fabric is soaked in a mixed solution of anhydrous ethanol and γ-aminopropyl triethoxysilane with a volume ratio of 1:1 for 12 hours to enable condensation reaction between hydroxyl groups and siloxyl groups in the fibers of the fabric, thereby preparing an aminated fabric; and the aminated fabric is washed with deionized water. 5 milliliters of a 2% poly(N-isopropyl acrylamide-styrene-acrylic acid) solution is added to 100 milliliters of deionized water, 1-(3-dimethylaminopropyl)-3-ethyl carbodiimide hydrochloride and N-hydroxysuccinimide with a mass ratio of 1:2 are added, and then the aminated fabric is added and left to stand for 1 hour. The ambient temperature is set to 5°C; 200 milliliters of deionized water and a magnetic stirrer are added to a single-necked flask for continuous stirring, 0.1g of polyvinylpyrrolidone is dissolved in 50 milliliters of deionized water for 30 minutes and then added to the single-necked flask, 2% aniline hydrochloric acid solution (hydrochloric acid: aniline = 2.5:1) is dissolved in the single-necked flask, the dry poly(N-isopropyl acrylamide-styrene-acrylic acid)-fabric is immersed in the above solution for continuous stirring for 30 minutes, 1.2 grams of ammonium persulfate is dissolved in 50 milliliters of deionized water and stirred uniformly before being added to the single-necked flask, and the mixture is continuously stirred at 0°C for 12 hours. The fabric is taken out and washed with deionized water until the solution is clear, the fabric is dried after washing, and an electrically conductive fabric is prepared. The volume resistivity of the electrically conductive fabric is 21 Ωcm.

[0229] Example 18

[0230] First, wash the bamboo fiber fabric with deionized water and dry it; put it into 0.01mol / L NaOH solution for 15 minutes, then take it out and wash it with deionized water and dry it; cut the fabric into 5*5cm 2 The fabric was prepared by in-situ polymerization of the long strips. The fabric was immersed in a 1:1 volume ratio of anhydrous ethanol and methacryloxypropyltrimethoxysilane for 12 hours to induce a condensation reaction between the hydroxyl groups and the siloxy groups in the fibers, thereby preparing an amino-modified fabric. The fabric was then washed with deionized water. The fabric was then dispersed in 50 ml of an aqueous solution, and 50 ml of an aqueous solution of 2% N-isopropylacrylamide and 0.2% acrylic acid was added. Polymerization was initiated by adding 2 mg of potassium persulfate. After a 4-hour reaction, the fabric was removed and cleaned. A single-necked flask was filled with 200 ml of deionized water and stirred continuously with a magnetic stirrer. 0.1 g of polyvinyl pyrrolidone was dissolved in 50 ml of deionized water for 30 minutes and then added to the flask. A 2% aniline solution was then added to the flask and a dry fabric was immersed in the solution and stirred continuously for 30 minutes. 1.2 g of ammonium persulfate was dissolved in 50 ml of deionized water, stirred uniformly, and then added to the flask. Stirring was continued at room temperature for 12 hours. The fabric was removed and washed with deionized water until the solution was clear. The fabric was then washed and dried to produce a conductive fabric. The volume resistivity of the conductive fabric was 3.1 Ωcm.

[0231] Example 19

[0232] The bamboo fiber fabric is washed with deionized water and dried, and then is placed in a 0.1 mol / L NaOH solution for 5 minutes, taken out, washed with deionized water and dried. The fabric is cut into 5*5 cm2strips and subjected to in-situ polymerization. The fabric is soaked in a mixed solution of anhydrous ethanol and N-β-(aminoethyl)-γ-aminopropyl trimethoxysilane with a volume ratio of 100:1 for 12 hours to allow condensation reaction between the hydroxyl groups and the siloxyl groups in the fibers of the fabric, thereby preparing an aminated fabric. The aminated fabric is washed with deionized water. 5 ml of a 2% poly(ethylene oxide-acrylic acid) solution is added to 100 ml of deionized water, and then 1-(3-dimethylaminopropyl)-3-ethyl carbodiimide hydrochloride and N-hydroxysuccinimide with a mass ratio of 1:1 are added. After standing for 2 hours, 0.1 g of sodium dodecyl benzene sulfonate is dissolved in 50 ml of deionized water, and then is added to the single-necked flask. A 2% aniline sulfuric acid solution (sulfuric acid: aniline = 2.5:1) is added to the single-necked flask. The dried poly(ethylene oxide-acrylic acid)-fabric is soaked in the above solution and stirred for 30 minutes. 1.2 g of ammonium persulfate is dissolved in 50 ml of deionized water, and then is added to the single-necked flask. The single-necked flask is continuously stirred at 60°C for 6 hours. The fabric is taken out and washed with deionized water until the solution is clear. The fabric is dried after washing, thereby preparing a conductive fabric. The volume resistivity of the conductive fabric is 89 Ωcm.

[0233] Example 20

[0234] In 500 ml of a 2% poly(N-isopropyl acrylamide-acrylic acid) microgel solution, 1-(3-dimethylaminopropyl)-3-ethyl carbodiimide hydrochloride aqueous solution 500 ml is added, and then 10 g of spandex fiber fabric is soaked in the solution at 5°C for 5 minutes, taken out, washed and dried. In 3 L of deionized water, polyvinylpyrrolidone (PVP) is added at 5°C and stirred until the PVP mass concentration reaches 0.1%. Aniline and hydrochloric acid are added to the reaction system, and the aniline concentration is 1%. The above spandex fiber fabric is placed in the reaction system, 12 g of ammonium persulfate is added and stirred uniformly, and then is added to the reaction system. After sufficient reaction, the bamboo fiber fabric is taken out, washed with deionized water and dried, thereby preparing a conductive spandex fiber fabric.

[0235] Example 21

[0236] The spandex fabric is washed with deionized water, treated with 0.01 mol / L NaOH solution, 5 ml of 2% poly(N-isopropylacrylamide-acrylic acid) solution is added to 100 ml of deionized water, 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride and N-hydroxysuccinimide are added in a mass ratio of 1:1 to make the concentration 0.075%, then the spandex fabric is added and reacted for 1 hour. The ambient temperature is set to 5°C, 3 L of deionized water is added to a flask, 50 ml of polyvinylpyrrolidone solution with a concentration of 0.02 g / ml is added, 50 ml of aniline solution with a concentration of 2% is added to the flask, the poly(N-isopropylacrylamide-acrylic acid)-fabric is immersed in the above solution and stirred for 30 minutes, ammonium persulfate is added to make the solution concentration 0.0053 g / ml. Stirring is continued at 0°C for 12 hours, the fabric is taken out and washed with deionized water until the solution is clear, the fabric is dried after washing to prepare a conductive fabric.

[0237] Example 1

[0238] The fabric prepared in Example 1 is connected to a lead wire at different parts, then connected to a multimeter or oscilloscope, and when stretched, it shows obvious changes in electrical signals.

[0239] The above describes embodiments of the present application. However, the present application is not limited to the above-described embodiments. Any modifications, equivalent replacements, improvements, etc. made within the spirit and principles of the present application should be included in the scope of protection of the present application.

Claims

1. An electrically conductive fiber, characterized by, The conductive fiber is composed of (a) a fiber substrate, (b) an inorganic material combined on the surface of the fiber substrate, and (c) a conductive material combined with the substance in component (b); The inorganic material is selected from at least one of silicon dioxide, titanium dioxide, iron oxide or aluminum oxide; the conductive material is selected from a conductive polymer, a conductive metal material, or a composite of the conductive polymer and the conductive metal material; the conductive polymer is combined on the surface of the inorganic material through a chemical bond; and / or, the conductive metal material forms an interpenetrating network or penetrates into component b through physical adsorption; and / or, the conductive metal material is combined on the surface of the inorganic material through coordination between the conductive metal material and component b; The surface of the fiber substrate is modified with a reactive chemical group selected from at least one of a hydroxyl group, a carboxyl group, an amino group, an epoxy group, a double bond, an ether bond, an aldehyde group, a sulfonate group, and a nitro group; a chemical bond is achieved by the reactive chemical group reacting with the substance in component (b) to form an ester bond, an amide bond and / or an ether bond; The substance in component (b) is combined on the surface of the fiber substrate through a chemical bond, and the inorganic material is combined on the surface of the fiber substrate in the form of particles.

2. An electrically conductive fiber, characterized by, The conductive fiber is composed of (a) a fiber substrate, (b) a polymer combined on the surface of the fiber substrate, or a polymer and an inorganic material combined on the surface of the fiber substrate, and (c) a conductive material combined with the substance in component (b); The inorganic material is selected from at least one of silicon dioxide, titanium dioxide, iron oxide or aluminum oxide; The polymer monomer at least includes a compound shown in formula 1, Formula 1 In formula 1, R 1 and R 2 are the same or different, independently of each other, selected from H, alkyl; R 3 is selected from H or C 1-6 alkyl; R 4 is selected from -CON(R 9 )(R 10 ), R 9 and R 10 are the same or different, independently of each other, selected from H or alkyl; The polymer monomer further includes at least one of a compound shown in formula 1', a compound shown in formula 2, ethylene glycol, triethylene tetramine or diethylene triamine; Formula 1' Formula 2 In formula 1', R 1 and R 2 are the same or different, independently of each other, selected from H, alkyl; R 3 is selected from H or C 1-6 alkyl; R 4a is selected from -OH, -COOR 8 or aryl, R 8 is selected from H, alkyl or epoxyalkyl; In formula 2, R 5 and R 6 are the same or different, each independently selected from H or alkyl; or R 5 and R 6 form a ring to form an aromatic ring; R 7 is selected from -O- or -N(R 11 )-, R 11 is selected from H or alkyl; Alternatively, the polymer is selected from at least one of polyurethane, polyvinyl acetate, polyimide, and epoxy resin; The conductive material is selected from a conductive polymer, a conductive metal material, or a composite of the conductive polymer and the conductive metal material; the conductive polymer is combined on the surface of the inorganic material and / or the polymer through a chemical bond; and / or, the conductive metal material forms an interpenetrating network or penetrates into component b through physical adsorption; and / or, the conductive metal material is combined on the surface of the inorganic material and / or the polymer through coordination between the conductive metal material and component b; The surface of the fiber substrate is modified with a reactive chemical group selected from at least one of a hydroxyl group, a carboxyl group, an amino group, an epoxy group, a double bond, an ether bond, an aldehyde group, a sulfonate group, and a nitro group; a chemical bond is achieved by the reactive chemical group reacting with the substance in component (b) to form an ester bond, an amide bond and / or an ether bond; The substance in component (b) is combined on the surface of the fiber substrate through a chemical bond; The polymer is combined on the surface of the fiber substrate in the form of polymer particles; the inorganic material is combined on the surface of the fiber substrate in the form of particles; The micro-particles of the polymer or polymerized monomers of the polymer and cross-linking agent include poly(N isopropyl acrylamide acrylic acid) copolymer particles, poly(N isopropyl acrylamide methacrylic acid) copolymer particles, poly(N isopropyl acrylamide acrylic acid acrylamide) copolymer particles, poly(N isopropyl acrylamide styrene) copolymer particles, poly(N isopropyl acrylamide styrene acrylic acid) copolymer particles, poly(N isopropyl acrylamide methacrylic acid ester) copolymer particles.

3. The electrically conductive fiber according to claim 1 or 2, characterized in that, The conductive fiber further includes (d) a conductive material combined on the surface of the fiber substrate.

4. The electrically conductive fiber according to claim 1 or 2, characterized by The fiber substrate is selected from bamboo fiber, cotton fiber, viscose fiber, silk, spandex, polyamide fiber, polyester fiber, a-olefin polymer fiber, polyacrylonitrile, chlorofiber or polyvinyl alcohol fiber.

5. The electrically conductive fiber of claim 2, wherein In formula 1', R 1 and R 2 are the same or different, independently of each other, selected from H, C 1-6 alkyl; R 3 is selected from H, methyl or ethyl; R 4a is selected from -OH, -COOR 8 or phenyl, R 8 is selected from H, C 1-6 alkyl or epoxy C 1-6 alkyl.

6. The electrically conductive fiber of claim 5, wherein, The polymer monomer of the polymer includes N-isopropyl acrylamide, and a combination of at least one of the following monomers: acrylic acid, methacrylic acid, methyl methacrylate, ethyl methacrylate, glycidyl methacrylate, vinyl alcohol or styrene; In formula 2, R 5 and R 6 are the same or different, each independently selected from H or C 1-6 alkyl, or R 5 and R 6 form a ring to form a benzene ring; R 7 is selected from -O- or -N(R 11 )-, R 11 is selected from H or alkyl.

7. The electrically conductive fiber of claim 6, wherein, The compound shown in formula 2 is maleic anhydride or phthalic anhydride.

8. The electrically conductive fiber of claim 2, wherein, The polymer is at least selected from at least one of poly (N-isopropyl acrylamide-acrylic acid) copolymer and poly (N-isopropyl acrylamide-methacrylic acid) copolymer.

9. The electrically conductive fiber of claim 2, wherein, The polymer is composed of at least one of poly (N-isopropyl acrylamide-acrylic acid) copolymer and poly (N-isopropyl acrylamide-methacrylic acid) copolymer, and at least one of the following polymers: polyurethane, polyvinyl acetate, polyimide and epoxy resin.

10. An electrically conductive fabric, characterized in that, It is woven by the conductive fiber according to any one of claims 1-9.

11. An electrically conductive fabric, characterized in that, The conductive fabric is composed of (a') fabric substrate, (b') inorganic material combined on the surface of the fabric substrate, and (c') conductive material combined with the substance in component (b'); The inorganic material is selected from silicon dioxide, titanium dioxide, iron oxide or aluminum oxide; The conductive material is selected from conductive polymer, conductive metal material, or selected from the composite of the conductive polymer and the conductive metal material; the conductive polymer is combined on the surface of the inorganic material by chemical bond; and / or, the conductive metal material forms interpenetrating network or penetrates into component b by physical adsorption; and / or, the conductive metal material is combined on the surface of the inorganic material and / or polymer by coordination between component b; The surface of the fabric substrate is modified with a reactive chemical group selected from at least one of hydroxyl, carboxyl, amino, epoxy, double bond, ether bond, aldehyde group, sulfonate, nitro; the reactive chemical group reacts with the substance in component (b') to form ester bond, amide bond and / or ether bond to realize chemical bond; The substance in component (b') is combined on the surface of the fabric substrate by chemical bond, and the inorganic material is combined on the surface of the fabric substrate in the form of particles.

12. An electrically conductive fabric, characterized in that, The conductive fabric is composed of (a') fabric substrate, (b') polymer combined on the surface of the fabric substrate, or polymer and inorganic material combined on the surface of the fabric substrate, and (c') conductive material combined with the substance in component (b'); The inorganic material is selected from at least one of silicon dioxide, titanium dioxide, iron oxide or aluminum oxide; The polymer monomer of the polymer at least includes a compound shown in formula 1, Formula 1 In formula 1, R 1 and R 2 are the same or different, independently of each other, selected from H, alkyl; R 3 is selected from H or C 1-6 alkyl; R 4 is selected from -CON(R 9 )(R 10 ), R 9 and R 10 are the same or different, independently of each other, selected from H or alkyl; The polymer monomer of the polymer further includes at least one of the following substances: a compound shown in formula 1', a compound shown in formula 2, ethylene glycol, triethylene tetramine or diethylene triamine; Formula 1' Formula 2 In formula 1', R 1 and R 2 are the same or different, independently of each other, selected from H, alkyl; R 3 is selected from H or C 1-6 alkyl; R 4a is selected from -OH, -COOR 8 or aryl, R 8 is selected from H, alkyl or epoxyalkyl; In formula 2, R 5 and R 6 are the same or different, each independently selected from H or alkyl; or R 5 and R 6 form a ring to form an aromatic ring; R 7 is selected from -O- or -N(R 11 )-, R 11 is selected from H or alkyl; Alternatively, the polymer is selected from at least one of polyurethane, polyvinyl acetate, polyimide and epoxy resin; The conductive material is selected from a conductive polymer, a conductive metal material, or a composite of the conductive polymer and the conductive metal material; the conductive polymer is combined on the surface of the inorganic material and / or the polymer through a chemical bond; and / or, the conductive metal material forms an interpenetrating network or penetrates into component b through physical adsorption; and / or, the conductive metal material is combined on the surface of the inorganic material and / or the polymer through coordination between the conductive metal material and component b; The surface of the fabric substrate is modified with a reactive chemical group selected from at least one of a hydroxyl group, a carboxyl group, an amino group, an epoxy group, a double bond, an ether bond, an aldehyde group, a sulfonate group, and a nitro group; the reactive chemical group reacts with a substance in component (b') to form an ester bond, an amide bond, and / or an ether bond, to achieve chemical bond combination; The substance in component (b') is combined on the surface of the fabric substrate through a chemical bond; The polymer is combined on the surface of the fabric substrate in the form of polymer particles, and the inorganic material is combined on the surface of the fabric substrate in the form of particles; The micro-particles of the polymer or polymerized monomers of the polymer and cross-linking agent include poly(N isopropyl acrylamide acrylic acid) copolymer particles, poly(N isopropyl acrylamide methacrylic acid) copolymer particles, poly(N isopropyl acrylamide acrylic acid acrylamide) copolymer particles, poly(N isopropyl acrylamide styrene) copolymer particles, poly(N isopropyl acrylamide styrene acrylic acid) copolymer particles, poly(N isopropyl acrylamide methacrylate) copolymer particles.

13. The conductive fabric according to claim 11 or 12, characterized in that, The conductive fabric further comprises (d') a conductive material combined on the surface of the fabric substrate.

14. The method of making the conductive fiber of claim 1, wherein, The method comprises: 1) preparing a fiber substrate; 2) reacting the fiber substrate in step 1) with an inorganic material or a precursor of an inorganic oxide to obtain a fiber substrate with the inorganic material combined on the surface; 3) reacting the fiber substrate with the inorganic material combined on the surface in step 2) with a conductive polymer monomer to obtain the conductive fiber; In step 1), a step of introducing a reactive chemical group on the fiber substrate is further included.

15. The process for making the conductive fiber of claim 2, characterized by, The method comprises: 1) preparing a fiber substrate; 2) reacting the fiber substrate in step 1) with a polymer to obtain a fiber substrate with the polymer combined on the surface, or reacting the fiber substrate in step 1) with a polymer and an inorganic material, or with a polymer and a precursor of an inorganic oxide, to obtain a fiber substrate with the inorganic material and the polymer combined on the surface; 3) reacting the fiber substrate with the polymer combined on the surface in step 2), or the fiber substrate with the inorganic material and the polymer combined on the surface in step 2), with a conductive polymer monomer to obtain the conductive fiber; In step 1), a step of introducing a reactive chemical group on the fiber substrate is further included.

16. The method of making an electrically conductive fiber according to claim 14 or 15, wherein, Step 3) is specifically: adding the conductive polymer monomer into the solution of the fiber substrate with the inorganic material and / or the polymer combined on the surface in step 2), optionally adding one or more of an initiator, an oxidizing agent, a catalyst, a reducing agent, and a dispersing agent, and performing in-situ polymerization to prepare the conductive fiber.

17. The method of making an electrically conductive fiber according to claim 14 or 15, wherein, Step 3) is specifically: adding the conductive polymer monomer, an initiator, a catalyst, and a dispersing agent into the solution of the fiber substrate with the inorganic material and / or the polymer combined on the surface in step 2), and performing in-situ polymerization to prepare the conductive fiber; The conductive polymer monomer is selected from at least one of aniline, pyrrole, thiophene, acetylene, phenylacetylene, and benzene.

18. The method of making the conductive fabric of claim 11 or 13, wherein, The preparation method of the conductive fabric is the same as the preparation method of the conductive fiber in any one of claims 14, 16-17, except that the substrate is different, that is, the fiber matrix in the preparation method of the conductive fiber in any one of claims 14, 16-17 is replaced by a fabric matrix.

19. A method of making the electrically conductive fabric of any one of claims 12 or 13, characterized in that, The preparation method of the conductive fabric is the same as the preparation method of the conductive fiber in any one of claims 15-17, except that the substrate is different, that is, the fiber matrix in the preparation method of the conductive fiber in any one of claims 15-17 is replaced by a fabric matrix.

20. Use of the electrically conductive fiber according to any one of claims 1 to 9 or the electrically conductive fabric according to any one of claims 10 to 13, characterized in that, It is applied to the fields of antistatic, conductive or sensing.

21. The use according to claim 20, characterized in that, It is applied to the fields of wires, antistatic clothes, heating fabrics, motion sensing, remote control products, electromagnetic shielding devices or wireless sensors.

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