阅读说明：本技术 一种复合导电面料及其制造方法 (Composite conductive fabric and manufacturing method thereof ) 是由 翁菀蕾 于 2019-09-25 设计创作，主要内容包括：本发明公开了一种复合导电面料及其制造方法,涉及纺织材料技术领域。本发明先用浓硫酸和浓硝酸共同处理碳纳米管,制得功能化碳纳米管,然后,利用树枝状多孔二氧化硅与聚烯丙胺盐酸盐和四氯合钯酸钾共同反应后,再经还原,碳化,碱蚀后制得导电颗粒坯料,将导电颗粒坯料与多巴胺混合,过滤,制得导电颗粒,最后,将导电颗粒与功能化碳纳米管,并加入聚丙烯腈和N,N-二甲基甲酰胺,制得纺丝液,将纺丝液纺织成丝,并制造成面料,即得复合导电面料。本发明制备的复合导电面料具有优异的电导率,且拉伸强度较好。(The invention discloses a composite conductive fabric and a manufacturing method thereof, and relates to the technical field of textile materials. The method comprises the steps of firstly treating carbon nanotubes with concentrated sulfuric acid and concentrated nitric acid to prepare functionalized carbon nanotubes, then carrying out a common reaction on dendritic porous silicon dioxide, polyallylamine hydrochloride and potassium tetrachloropalladate, then carrying out reduction, carbonization and alkaline etching to prepare a conductive particle blank, mixing the conductive particle blank with dopamine, filtering to prepare conductive particles, finally adding polyacrylonitrile and N, N-dimethylformamide to the conductive particles and the functionalized carbon nanotubes to prepare a spinning solution, spinning the spinning solution into filaments, and manufacturing the filaments into a fabric to obtain the composite conductive fabric. The composite conductive fabric prepared by the invention has excellent conductivity and good tensile strength.)

1. The composite conductive fabric is characterized by mainly comprising the following raw material components, by weight, 40 ~ 50 parts of polyacrylonitrile and 5 ~ 8 parts of functionalized carbon nanotubes.

2. The composite conductive fabric as claimed in claim 1, further comprising 8 ~ 12 parts by weight of conductive particles.

3. The composite conductive fabric according to claim 2, wherein the functionalized carbon nanotubes are prepared by reacting carbon nanotubes with concentrated sulfuric acid and concentrated nitric acid.

4. The composite conductive fabric of claim 3, wherein the conductive particles are prepared by reacting modified silica with polyallylamine hydrochloride and potassium tetrachloropalladate, reducing, carbonizing, and performing alkaline etching to obtain conductive particle blanks, and mixing the conductive particle blanks with dopamine to react; the modified silicon dioxide is prepared by treating porous silicon dioxide with concentrated sulfuric acid and ammonia water.

5. The composite conductive fabric as claimed in claim 3, wherein the composite conductive fabric mainly comprises the following raw material components in parts by weight: 40 parts of polyacrylonitrile, 6 parts of functionalized carbon nanotubes and 12 parts of conductive particles.

6. The manufacturing method of the composite conductive fabric is characterized by mainly comprising the following preparation steps:

(1) reacting the carbon nano tube with mixed acid to prepare a functionalized carbon nano tube;

(2) reacting porous silicon dioxide with mixed acid liquor and mixed alkali liquor in sequence to obtain modified silicon dioxide, mixing the modified silicon dioxide with polyallylamine hydrochloride solution, filtering to obtain filter cake, mixing the filter cake with potassium tetrachloropalladate solution, filtering to obtain pretreated modified silicon dioxide, reacting the pretreated modified silicon dioxide with sodium borohydride solution, carbonizing under the condition of nitrogen, mixing the carbonized substance with sodium hydroxide solution for reaction, filtering, mixing with dopamine solution for reaction, filtering, washing and drying to obtain conductive particles;

(3) mixing the functionalized carbon nano tube obtained in the step (1) with the conductive particles obtained in the step (2), adding N, N-dimethylformamide and polyacrylonitrile, stirring and mixing, performing ultrasonic dispersion to obtain a spinning solution, extruding the spinning solution into a coagulating bath through a spinneret orifice, washing with water, oiling, drying, and weaving to obtain a composite conductive fabric;

(4) and (4) performing index analysis on the composite conductive fabric obtained in the step (3).

7. The manufacturing method of the composite conductive fabric as claimed in claim 6, which is characterized by mainly comprising the following preparation steps:

(1) mixing 95% sulfuric acid and 70% nitric acid according to a volume ratio of 3: 1 to obtain a mixed acid solution, mixing the mixed acid solution and the carbon nano tube according to a mass ratio of 10: 1, stirring for reaction, filtering to obtain a functionalized carbon nano tube blank, washing the functionalized carbon nano tube blank with deionized water for 8 ~ 10 times, and drying at the temperature of 85 ℃ for 3 hours;

(2) mixing porous silicon dioxide and mixed acid liquor according to the mass ratio of 1: 8, stirring for reaction, filtering to obtain pretreated porous silicon dioxide, mixing the pretreated porous silicon dioxide and mixed alkali liquor according to the mass ratio of 1: 8, stirring for reaction, filtering to obtain a modified silicon dioxide blank, washing the modified silicon dioxide blank with deionized water for 3 ~ times, drying at the temperature of 70 ℃ for 2 hours to obtain modified silicon dioxide, mixing the modified silicon dioxide with a polyallylamine hydrochloride solution with the mass fraction of 10% according to the mass ratio of 1: 8, soaking at the room temperature for 3 hours, filtering to obtain a filter cake, mixing the filter cake with a potassium tetrachloropalladate solution with the mass fraction of 8% according to the mass ratio of 1: 6, soaking at the room temperature for 2 hours, filtering to obtain pretreated modified silicon dioxide, mixing the pretreated modified silicon dioxide with a sodium borohydride solution with the mass fraction of 2% according to the mass ratio of 1: 10, stirring for reaction, filtering to obtain conductive particles, placing the conductive particle blank in a carbonization furnace, introducing 80 mL/100 min, washing with a sodium borohydride solution with the carbonized particle at the mass fraction of 2% for 2 hours, filtering, soaking at the room temperature of 3 hours, drying at the room temperature of the filter cake, filtering to obtain carbonized particle blank, soaking at the carbonized particle for 2% for 2 hours, soaking at the temperature of 3 hours, drying at the temperature of 3 hours, filtering to obtain carbonized particle, drying at the carbonized particle for 3 hours, and carbonizing at the carbonized particle blank at the temperature of 750 ℃, filtering for 3 hours, and carbonizing at the temperature of 3 hours, drying at the temperature of 3 hours, and carbonizing at;

(3) mixing the substance obtained in the step (1) and the substance obtained in the step (2) in a beaker according to a mass ratio of 1: 2, adding N, N-dimethylformamide 70 ~ times the mass of the substance obtained in the step (1) and polyacrylonitrile 6 ~ times the mass of the substance obtained in the step (1) into the beaker, stirring and mixing for 30min at the temperature of 45 ℃ and the rotating speed of 350r/min, ultrasonically dispersing the material in the beaker for 15min at the frequency of 45kHz to obtain a spinning solution, extruding the spinning solution into a coagulating bath through a spinneret hole, filtering to obtain fibrils, washing the fibrils for 5 times with water, mixing the fibrils and amino silicone oil according to a mass ratio of 1: 8, soaking for 15min at room temperature, filtering to obtain pretreated fibrils, drying the pretreated fibrils for 40min at the temperature of 70 ~ ℃ to obtain yarns, and weaving the yarns in a weaving machine to obtain the composite conductive fabric;

(4) and (4) performing index analysis on the composite conductive fabric obtained in the step (3).

8. The method for manufacturing the composite conductive fabric according to claim 7, wherein the porous silica in the step (2) is prepared by mixing cetyl trimethyl ammonium bromide and water in a mass ratio of 1: 140 in a flask, adding diethyl ether 20 times the mass of cetyl trimethyl ammonium bromide, ethanol 12 times the mass of cetyl trimethyl ammonium bromide and ammonia water 5 ~ 8 times the mass of cetyl trimethyl ammonium bromide into the flask, stirring and mixing to obtain a mixed solution, mixing the mixed solution and ethyl orthosilicate in a mass ratio of 60: 1 in a three-neck flask, adding 3-aminopropyltriethoxysilane 0.08 times the mass of the mixed solution 0.08 ~ 0.10 into the three-neck flask, stirring and reacting, adjusting the pH of the material in the three-neck flask to 7, filtering to obtain a porous silica blank, and drying the porous silica blank at a temperature of 75 ℃ for 2h to obtain the porous silica.

9. The manufacturing method of the composite conductive fabric as claimed in claim 7, wherein the mixed acid solution in the step (2) is prepared by mixing 90% by mass of sulfuric acid and 30% by mass of hydrogen peroxide in a volume ratio of 7: 3, mixing to obtain mixed acid liquor; the mixed alkali liquor in the step (2) is prepared by mixing 20% of ammonia water and 30% of hydrogen peroxide according to a volume ratio of 1: 1, mixing, adding deionized water with the volume of 5 times that of ammonia water, and stirring and mixing to obtain mixed alkali liquor.

10. The manufacturing method of the composite conductive fabric according to claim 7, wherein the coagulation bath in the step (3) is prepared by mixing N, N-dimethylformamide and water in a mass ratio of 1: 1, mixing to obtain the coagulating bath.

Technical Field

The invention relates to the technical field of textile materials, in particular to a composite conductive fabric and a manufacturing method thereof.

Background

In the current day-to-day internet of things technology, the development progress of intelligent clothes is extremely important, but the whole development progress is very slow due to the conductive problem of the fabric.

The conductivity of the fabric depends on the conductivity of the fiber; nowadays, the preparation method of the conductive fiber mainly comprises the following steps: 1. the metal processing method is that the conductive property of metal is utilized, and metal conductive fiber can be prepared by a certain processing means; 2. the spinning method comprises directly spinning conductive polymer (such as polyacetylene, polyaniline, polypyrrole, polythiophene, etc.) or spinning conductive polymer, conductive particles (mainly carbon black or metal compound) and matrix polymer to obtain conductive fiber; 3. physical form of post-treatment, i.e. conductive particles (metal, carbon black, etc.) or metal compounds can be used to prepare conductive fibers by physical methods such as coating, bonding, etc.; 4. post-treatment in chemical form, namely carbonizing common chemical fiber or preparing conductive fiber by chemical methods such as chemical sedimentation, complexation and the like by using conductive polymers and metal ions; 5. the post-treatment in the form of physical and chemical mixing is to immerse ordinary fibers in a solution, make fiber molecules adsorbed or complexed with the solution, and then solidify a conductive substance on the fibers through a chemical reaction to generate conductivity.

Although the methods for preparing the conductive fibers are many at present, the preparation methods have certain defects, the conductive fibers prepared by the three methods 3, 4 and 5 have the defects that the conductive layer on the surface of the fibers is easy to fall off in the using process, so that the fabric cannot have long-acting conductivity, and the fabric woven by the conductive fibers prepared by the two methods 1 and 2 has long-acting conductivity, but the strength of the fabric is greatly influenced. Therefore, a conductive fabric with long-acting conductivity and good strength needs to be researched and developed.

Disclosure of Invention

The invention aims to provide a composite conductive fabric and a manufacturing method thereof, which aim to solve the problems in the prior art.

In order to achieve the purpose, the invention provides the following technical scheme:

the composite conductive fabric is characterized by mainly comprising the following raw material components, by weight, 40 ~ 50 parts of polyacrylonitrile and 5 ~ 8 parts of functionalized carbon nanotubes.

The composite conductive fabric is characterized by further comprising 8 ~ 12 parts by weight of conductive particles.

Preferably, the functionalized carbon nanotube is prepared by the common reaction of concentrated sulfuric acid and concentrated nitric acid on the carbon nanotube.

The conductive particles are prepared by carrying out a common reaction on modified silicon dioxide, polyallylamine hydrochloride and potassium tetrachloropalladate, then carrying out reduction, carbonization and alkaline etching on the obtained product to obtain conductive particle blanks, and mixing and reacting the conductive particle blanks with dopamine to obtain conductive particles; the modified silicon dioxide is prepared by treating porous silicon dioxide with concentrated sulfuric acid and ammonia water

As optimization, the composite conductive fabric mainly comprises the following raw material components in parts by weight: 40 parts of polyacrylonitrile, 6 parts of functionalized carbon nanotubes and 12 parts of conductive particles.

As optimization, the manufacturing method of the composite conductive fabric mainly comprises the following preparation steps:

(1) reacting the carbon nano tube with mixed acid to prepare a functionalized carbon nano tube;

(2) reacting porous silicon dioxide with mixed acid liquor and mixed alkali liquor in sequence to obtain modified silicon dioxide, mixing the modified silicon dioxide with polyallylamine hydrochloride solution, filtering to obtain filter cake, mixing the filter cake with potassium tetrachloropalladate solution, filtering to obtain pretreated modified silicon dioxide, reacting the pretreated modified silicon dioxide with sodium borohydride solution, carbonizing under the condition of nitrogen, mixing the carbonized substance with sodium hydroxide solution for reaction, filtering, mixing with dopamine solution for reaction, filtering, washing and drying to obtain conductive particles;

(3) mixing the functionalized carbon nano tube obtained in the step (1) with the conductive particles obtained in the step (2), adding N, N-dimethylformamide and polyacrylonitrile, stirring and mixing, performing ultrasonic dispersion to obtain a spinning solution, extruding the spinning solution into a coagulating bath through a spinneret orifice, washing with water, oiling, drying, and weaving to obtain a composite conductive fabric;

(4) and (4) performing index analysis on the composite conductive fabric obtained in the step (3).

As optimization, the manufacturing method of the composite conductive fabric mainly comprises the following preparation steps:

(1) mixing 95% sulfuric acid and 70% nitric acid according to a volume ratio of 3: 1 to obtain a mixed acid solution, mixing the mixed acid solution and the carbon nano tube according to a mass ratio of 10: 1, stirring for reaction, filtering to obtain a functionalized carbon nano tube blank, washing the functionalized carbon nano tube blank with deionized water for 8 ~ 10 times, and drying at the temperature of 85 ℃ for 3 hours;

(2) mixing porous silicon dioxide and mixed acid liquor according to the mass ratio of 1: 8, stirring for reaction, filtering to obtain pretreated porous silicon dioxide, mixing the pretreated porous silicon dioxide and mixed alkali liquor according to the mass ratio of 1: 8, stirring for reaction, filtering to obtain a modified silicon dioxide blank, washing the modified silicon dioxide blank with deionized water for 3 ~ times, drying at the temperature of 70 ℃ for 2 hours to obtain modified silicon dioxide, mixing the modified silicon dioxide with a polyallylamine hydrochloride solution with the mass fraction of 10% according to the mass ratio of 1: 8, soaking at the room temperature for 3 hours, filtering to obtain a filter cake, mixing the filter cake with a potassium tetrachloropalladate solution with the mass fraction of 8% according to the mass ratio of 1: 6, soaking at the room temperature for 2 hours, filtering to obtain pretreated modified silicon dioxide, mixing the pretreated modified silicon dioxide with a sodium borohydride solution with the mass fraction of 2% according to the mass ratio of 1: 10, stirring for reaction, filtering to obtain conductive particles, placing the conductive particle blank in a carbonization furnace, introducing 80 mL/100 min, washing with a sodium borohydride solution with the carbonized particle at the mass fraction of 2% for 2 hours, filtering, soaking at the room temperature of 3 hours, drying at the room temperature of the filter cake, filtering to obtain carbonized particle blank, soaking at the carbonized particle for 2% for 2 hours, soaking at the temperature of 3 hours, drying at the temperature of 3 hours, filtering to obtain carbonized particle, drying at the carbonized particle for 3 hours, and carbonizing at the carbonized particle blank at the temperature of 750 ℃, filtering for 3 hours, and carbonizing at the temperature of 3 hours, drying at the temperature of 3 hours, and carbonizing at;

(3) mixing the substance obtained in the step (1) and the substance obtained in the step (2) in a beaker according to a mass ratio of 1: 2, adding N, N-dimethylformamide 70 ~ times the mass of the substance obtained in the step (1) and polyacrylonitrile 6 ~ times the mass of the substance obtained in the step (1) into the beaker, stirring and mixing for 30min at the temperature of 45 ℃ and the rotating speed of 350r/min, ultrasonically dispersing the material in the beaker for 15min at the frequency of 45kHz to obtain a spinning solution, extruding the spinning solution into a coagulating bath through a spinneret hole, filtering to obtain fibrils, washing the fibrils for 5 times with water, mixing the fibrils and amino silicone oil according to a mass ratio of 1: 8, soaking for 15min at room temperature, filtering to obtain pretreated fibrils, drying the pretreated fibrils for 40min at the temperature of 70 ~ ℃ to obtain yarns, and weaving the yarns in a weaving machine to obtain the composite conductive fabric;

(4) and (4) performing index analysis on the composite conductive fabric obtained in the step (3).

Optimally, the preparation method of the porous silica described in the step (2) comprises the steps of mixing cetyl trimethyl ammonium bromide and water in a mass ratio of 1: 140 in a flask, adding diethyl ether with the mass of 20 times that of cetyl trimethyl ammonium bromide, ethanol with the mass of 12 times that of cetyl trimethyl ammonium bromide and ammonia water with the mass of 5 ~ 8 times that of cetyl trimethyl ammonium bromide into the flask, stirring and mixing to obtain a mixed solution, mixing the mixed solution and ethyl orthosilicate in a mass ratio of 60: 1 in a three-neck flask, adding 3-aminopropyl triethoxysilane with the mass of 0.08 ~ 0.10.10 times that of the mixed solution into the three-neck flask, stirring and reacting, adjusting the pH of materials in the three-neck flask to 7, filtering to obtain a porous silica blank, and drying the porous silica blank for 2 hours at the temperature of 75 ℃ to obtain the porous silica.

As optimization, the mixed acid liquid in the step (2) is prepared by mixing 90% by mass of sulfuric acid and 30% by mass of hydrogen peroxide according to a volume ratio of 7: 3, mixing to obtain mixed acid liquor; the mixed alkali liquor in the step (2) is prepared by mixing 20% of ammonia water and 30% of hydrogen peroxide according to a volume ratio of 1: 1, mixing, adding deionized water with the volume of 5 times that of ammonia water, and stirring and mixing to obtain mixed alkali liquor.

Preferably, the coagulating bath in the step (3) is prepared by mixing N, N-dimethylformamide and water in a mass ratio of 1: 1, mixing to obtain the coagulating bath.

Compared with the prior art, the invention has the beneficial effects that:

when polyacrylonitrile fibers are used for manufacturing the composite conductive fabric, functional carbon nanotubes and conductive particles prepared by taking porous silicon dioxide as a template are added into the polyacrylonitrile fibers; firstly, adding conductive particles prepared by using porous silicon dioxide as a template in the preparation of polyacrylonitrile fibril, because the porous silica contains a dendritic pore structure and is treated by the mixed acid solution and the mixed alkali solution, polyallylamine hydrochloride can be adsorbed inside the dendritic pore structure, and tetrachloropalladate ions are further adsorbed inside the dendritic pore structure after being mixed with potassium tetrachloropalladate solution, and then forms the conductive particles containing the metal particles after reduction, carbonization and alkaline etching treatment, after the polyacrylonitrile fibrils are added, because of the dendritic shape of the conductive particles, a plurality of contact sites are provided, can form a complete conductive path after being added into polyacrylonitrile fibrils, reduce the stress borne by the polyacrylonitrile under the stretching action, further improving the conductivity and tensile strength of the composite conductive fabric prepared from the polyacrylonitrile fibril weft raw material; and secondly, functional carbon nano tubes are added into the polyacrylonitrile fibrils, so that on one hand, the functional carbon nano tubes can cooperate with the dendritic conductive particles to form a complete conductive path in the polyacrylonitrile fibrils, thereby further improving the conductivity of the composite conductive fabric prepared from the polyacrylonitrile fibril weft raw material, on the other hand, the functional carbon nano tubes contain carboxyl on the surface, and can be uniformly distributed in the polyacrylonitrile fibrils after being added into the polyacrylonitrile fibrils, thereby further reducing the stress when the polyacrylonitrile fibrils are stretched, and further improving the tensile strength of the composite conductive fabric prepared from the polyacrylonitrile fibril weft raw material.

Detailed Description

The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

In order to more clearly illustrate the method provided by the present invention, the following examples are used to describe in detail, and the method for testing each index of the composite conductive fabric manufactured in the following examples is as follows:

conductivity: the conductivity of the composite conductive fabric obtained in each example and the yarns in the comparative example product were tested by a four-probe method.

Tensile strength: the tensile strength of the yarns in the composite conductive fabric obtained in each example and the comparative example product was tested by using a universal tensile machine.