阅读说明：本技术 一种高弹阻燃导电纤维及其制备方法 (High-elasticity flame-retardant conductive fiber and preparation method thereof ) 是由 柳玉波 朱飞龙 王轩 于 2021-07-21 设计创作，主要内容包括：本发明公开了一种高弹阻燃导电纤维,包括以下质量份数的各组分：5％水性石墨烯分散液5-20份；5％水性碳纳米管分散液40-60份；水性柔性树脂胶黏剂10-30份；阻燃剂1-5份；消泡剂0.01-1份；分散剂1-5份；润湿剂0.1-1.5份；增稠剂0.1-5份,还公开了其制备方法,本发明适用于导电纤维制备技术领域,工艺简单,能够提高附着力、保持原有纤维的轻柔性；还能够提高导电纤维的附着力和耐磨性能；同时提高了导电纤维的导电性能,制备出系列具有高弹性,电阻均一稳定、附着力高的碳纳米管/石墨烯复合导电纤维；本方法制备导电纤维具有环境友好、操作简易、价格低廉、产品质量稳定可控的优点,产品在电热、防静电、电磁屏蔽以及生物传感器、电池电极等方面有更好的应用价值。(The invention discloses a high-elasticity flame-retardant conductive fiber which comprises the following components in parts by mass: 5-20 parts of 5% aqueous graphene dispersion liquid; 40-60 parts of 5% aqueous carbon nanotube dispersion liquid; 10-30 parts of water-based flexible resin adhesive; 1-5 parts of a flame retardant; 0.01-1 part of defoaming agent; 1-5 parts of a dispersant; 0.1-1.5 parts of wetting agent; 0.1-5 parts of thickening agent and a preparation method thereof, the invention is suitable for the technical field of conductive fiber preparation, has simple process, can improve the adhesive force and keep the light flexibility of the original fiber; the adhesive force and the wear resistance of the conductive fiber can be improved; meanwhile, the conductivity of the conductive fiber is improved, and a series of carbon nanotube/graphene composite conductive fibers with high elasticity, uniform and stable resistance and high adhesive force are prepared; the conductive fiber prepared by the method has the advantages of environmental friendliness, simplicity in operation, low price, stable and controllable product quality, and the product has better application value in the aspects of electric heating, static electricity prevention, electromagnetic shielding, biosensors, battery electrodes and the like.)

1. The high-elasticity flame-retardant conductive fiber is characterized by being prepared from composite flame-retardant slurry, wherein the composite flame-retardant slurry comprises the following components in parts by mass:

5-20 parts of 5% aqueous graphene dispersion liquid; 40-60 parts of 5% aqueous carbon nanotube dispersion liquid; 10-30 parts of water-based flexible resin adhesive; 1-5 parts of a flame retardant; 0.01-1 part of defoaming agent; 1-5 parts of a dispersant; 0.1-1.5 parts of wetting agent; 0.1-5 parts of thickening agent.

2. The high-elastic flame-retardant conductive fiber according to claim 1, wherein: the composite flame-retardant slurry comprises the following components in parts by weight:

17 parts of 5% aqueous graphene dispersion liquid; 50 parts of 5% aqueous carbon nanotube dispersion liquid; 25 parts of water-based flexible resin adhesive; 2.5 parts of a flame retardant; 0.5 part of defoaming agent; 2 parts of a dispersing agent; 0.5 part of wetting agent; 3 parts of a thickening agent.

3. The high-elastic flame-retardant conductive fiber according to claim 1, wherein: the 5% aqueous graphene dispersion is a single-layer or 3-5-layer graphene solution.

4. The high-elastic flame-retardant conductive fiber according to claim 1, wherein: the 5% aqueous carbon nanotube dispersion liquid is a single-walled carbon nanotube, and the wetting agent is a polyether modified organosilicon wetting agent.

5. The high-elastic flame-retardant conductive fiber according to claim 1, wherein: the aqueous resin adhesive is aqueous acrylic resin, aqueous polyurethane or a compound of the aqueous acrylic resin and the aqueous polyurethane.

6. The high-elastic flame-retardant conductive fiber according to claim 1, wherein: the flame retardant comprises at least one of dimethyl methylphosphonate, a flame retardant PN-1, a flame retardant PN-2 and superfine antimony trioxide.

7. The high-elastic flame-retardant conductive fiber according to claim 1, wherein: the thickener is cellulose and hydrophobic modified polyurethane thickener, and the defoamer is at least one of 901W, BYK019 and BYK 025.

8. The high-elastic flame-retardant conductive fiber according to claim 1, wherein: the dispersant includes at least one of an acrylic block polymer, an anionic polyacrylamide, BYK025, and BYK 9076.

9. The preparation method of the high-elasticity flame-retardant conductive fiber is characterized by comprising the following steps of:

preparation of slurry: adding the raw materials of each component into a stirring grinder, pre-dispersing at the stirring speed of 800-1500 rpm, adding zirconia beads for grinding, and preparing aqueous CNTs-graphene composite flame-retardant slurry with the average particle size controlled at 500nm for later use, wherein the volume ratio of the zirconia beads is 65-80%, the diameter is 1.0mm or 2.0mm, the grinding speed is 750-1000 rpm, and the grinding time is 25-45 min;

preparing conductive fibers: carrying out corona treatment on the substrate fiber to enable the surface of the substrate fiber to generate free radicals or ionic groups, setting parameters of a dyeing machine, adjusting tension, firstly stretching the fiber to 50-150% of length, carrying out primary dyeing through sizing, stretching the fiber to 200-300% of length, and carrying out secondary sizing dyeing to prepare the carbon nanotube/graphene conductive fiber; wherein, the first sizing and dyeing process is carried out, and the stretching length is 120%; and the second sizing dyeing line has a stretching length of 300 percent, and the corona treatment is carried out in a corona discharge electric field with the voltage of 3000-12000V and the power of 10-500W.

10. The method for preparing the high-elastic flame-retardant conductive fiber according to claim 9, wherein the method comprises the following steps: the base material fiber is selected from one of high stretch yarn polyester, chinlon, aramid fiber and acrylic fiber, and the specification is one of 150D/48F, 300D/96F and 300D/144F.

Technical Field

The invention belongs to the technical field of conductive fiber preparation, and particularly relates to a high-elasticity flame-retardant conductive fiber and a preparation method thereof.

Background

The conductive fibers applied to the traditional electric heating fabrics are mainly metal, metal compound fibers, carbon fibers, organic conductive fibers and the like, the metal, metal compound fibers, carbon fibers and the like generally have the defects of hard fibers, no elasticity, poor comfort and the like, and the organic conductive fibers are relatively soft and have high elasticity, but have relatively poor conductivity, resistance uniformity and stability and poor kneading resistance. Meanwhile, the traditional electric heating fabric has no flame retardant property, an insulating film is often required to be covered when the electric heating body is prepared, the heating power temperature is adjusted through external control, and the danger of overheating caused by faults or extreme use conditions exists. Therefore, it is desirable to provide a highly elastic conductive fiber with flame retardant function, while simultaneously achieving flexibility, elasticity, comfort and safety of use.

At present, two common methods for preparing the high-elasticity conductive fiber are provided, firstly, the conductive material and the high-elasticity polymer slice are directly mixed and spun, but the prepared conductive fiber has poor resistance uniformity, complex process and relatively high cost.

Secondly, rigid conductive fibers are prepared by a coating method, and then the rigid conductive high-performance fibers are combined with flexible rubber and the like in a composite weaving mode, so that the process is relatively complex and the conductivity is limited.

In CNIO838537OA, polyurethane is subjected to processes such as carbon nanotube dispersion liquid impregnation, and conductive substances are doped on the surface of a chemical synthetic fiber to obtain a carbon nanotube polyurethane elastic conductive fiber, although the conductivity and strength are improved to some extent, the elasticity of the fiber is basically lost, and the conductivity and resistance stability under deformation cannot be ensured.

In CN107904734B, firstly, a fiber material is prepared in a coating-swelling-reducing mode, and then, rigid conductive high-performance fibers and flexible rubber are combined in a composite weaving mode to weave a composite woven fabric with a uniform structure and high stability.

CN111287003ACN111287003A adopts simple dyeing process, improves the safety of the fiber in application by adding PTC functional components, does not fundamentally solve the problems of the conductivity and the resistance uniformity of the fiber, and the prepared conductive fiber has no elasticity and is limited in application.

Disclosure of Invention

The invention aims to overcome the defects of the prior art and provides a high-elasticity flame-retardant conductive fiber and a preparation method thereof.

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

the high-elasticity flame-retardant conductive fiber comprises the following components in parts by mass:

5-20 parts of 5% aqueous graphene dispersion liquid; 40-60 parts of 5% aqueous carbon nanotube dispersion liquid; 10-30 parts of water-based flexible resin adhesive; 1-5 parts of a flame retardant; 0.01-1 part of defoaming agent; 1-5 parts of a dispersant; 0.1-1.5 parts of wetting agent; 0.1-5 parts of thickening agent.

Preferably, the composite flame-retardant slurry comprises the following components in parts by mass:

17 parts of 5% aqueous graphene dispersion liquid; 50 parts of 5% aqueous carbon nanotube dispersion liquid; 25 parts of water-based flexible resin adhesive; 2.5 parts of a flame retardant; 0.5 part of defoaming agent; 2 parts of a dispersing agent; 0.5 part of wetting agent; 3 parts of a thickening agent.

Preferably, the 5% aqueous graphene dispersion is a single-layer or 3-5-layer graphene solution.

Preferably, the 5% aqueous carbon nanotube dispersion liquid is a single-walled carbon nanotube, and the wetting agent is a polyether modified silicone wetting agent.

Preferably, the aqueous resin adhesive is aqueous acrylic resin, aqueous polyurethane or a compound of the aqueous acrylic resin and the aqueous polyurethane.

Preferably, the flame retardant comprises at least one of dimethyl methylphosphonate, a flame retardant PN-1, a flame retardant PN-2 and superfine antimony trioxide.

Preferably, the thickener is a cellulose-based or hydrophobically modified polyurethane thickener, and the defoamer is at least one of a defoamer 901W, a defoamer BYK019 and a defoamer BYK 025.

Preferably, the dispersant comprises at least one of an acrylic block polymer, an anionic polyacrylamide, BYK025 and BYK 9076.

A preparation method of high-elastic flame-retardant conductive fibers comprises the following steps:

preparation of slurry: adding the raw materials of each component into a stirring grinder, pre-dispersing at the stirring speed of 800-1500 rpm, adding zirconia beads for grinding, and preparing aqueous CNTs-graphene composite flame-retardant slurry with the average particle size controlled at 500nm for later use, wherein the volume ratio of the zirconia beads is 65-80%, the diameter is 1.0mm or 2.0mm, the grinding speed is 750-1000 rpm, and the grinding time is 25-45 min;

preparing conductive fibers: carrying out corona treatment on the substrate fiber to enable the surface of the substrate fiber to generate free radicals or ionic groups, setting parameters of a dyeing machine, adjusting tension, firstly stretching the fiber to 50-150% of length, carrying out primary dyeing through sizing, stretching the fiber to 200-300% of length, and carrying out secondary sizing dyeing to prepare the carbon nanotube/graphene conductive fiber; wherein, the first sizing and dyeing process is carried out, and the stretching length is 120%; and the second sizing dyeing line has a stretching length of 300 percent, and the corona treatment is carried out in a corona discharge electric field with the voltage of 3000-12000V and the power of 10-500W.

Preferably, the base material fiber is selected from one of high stretch yarn terylene, chinlon, aramid fiber and acrylic fiber, and the specification is one of 150D/48F, 300D/96F and 300D/144F.

In summary, due to the adoption of the technical scheme, the invention has the beneficial effects that:

1. the invention forms the conductive coating on the surface of the single fiber by utilizing simple and traditional dip-coating, printing and dyeing technology and the like, and the process is simple;

2. compared with the single resin adhesive, the flexible resin adhesive is adopted for compounding, so that the adhesive force is improved, and the light flexibility of the original fiber is kept;

3. through corona treatment, the invention improves the phase hydrophilic property of the fiber, thereby improving the adhesive force and wear resistance of the conductive fiber;

4. according to the invention, sizing is carried out for 2 times by adjusting different tensions, and the preparation process of the conductive fiber greatly improves the uniform resistance stability of the high-elasticity conductive fiber under the stretching condition, and simultaneously improves the conductivity of the conductive fiber, so that a series of carbon nanotube/graphene composite conductive fibers with high elasticity, uniform and stable resistance and high adhesive force are prepared;

5. according to the invention, the flame retardant is added, so that the flame retardant property of the fiber is greatly improved, and the use safety performance of the conductive fabric is improved; the resistance of the high-elastic conductive fiber prepared by the method can reach 100-900 omega/cm, the resistance range difference of a single fiber can be controlled within 50 omega/cm, the resistance stability is high, the change rate of the tensile rebound resistance is less than 5 percent, and the dry friction adhesive force reaches the level 3 of the standard GB/T3920-2008 grade evaluation; the conductive fiber prepared by the method has the advantages of environmental friendliness, simplicity in operation, low price and stable and controllable product quality, and the product has better application value in the aspects of electric heating, static electricity prevention, electromagnetic shielding, biosensors, battery electrodes and the like.

Drawings

FIG. 1 is a flow chart of a method for preparing a high-elastic flame-retardant conductive fiber according to the present invention.

Reference numerals: 1. raw material fibers; 2. a feed liquid groove; 3. an oven; 4. and (3) functional fibers.

Detailed Description

The following description further illustrates a specific embodiment of the high-elastic flame-retardant conductive fiber and the preparation method thereof according to the present invention with reference to fig. 1. The high elastic flame retardant conductive fiber and the method for preparing the same according to the present invention are not limited to the following examples.

Example 1:

the embodiment provides a specific structure of a high-elastic flame-retardant conductive fiber, as shown in fig. 1, which includes the following components in parts by mass:

5-20 parts of 5% aqueous graphene dispersion liquid; 40-60 parts of 5% aqueous carbon nanotube dispersion liquid; 10-30 parts of water-based flexible resin adhesive; 1-5 parts of a flame retardant; 0.01-1 part of defoaming agent; 1-5 parts of a dispersant; 0.1-1.5 parts of wetting agent; 0.1-5 parts of thickening agent.

Further, the composite flame-retardant slurry comprises the following components in parts by weight:

17 parts of 5% aqueous graphene dispersion liquid; 50 parts of 5% aqueous carbon nanotube dispersion liquid; 25 parts of water-based flexible resin adhesive; 2.5 parts of a flame retardant; 0.5 part of defoaming agent; 2 parts of a dispersing agent; 0.5 part of wetting agent; 3 parts of a thickening agent.

The 5% aqueous graphene dispersion is a single-layer or 3-5-layer graphene solution.

The 5% aqueous carbon nanotube dispersion liquid is a single-wall carbon nanotube, and the wetting agent is a polyether modified organic silicon wetting agent.

The aqueous resin adhesive is aqueous acrylic resin, aqueous polyurethane or a compound of the aqueous acrylic resin and the aqueous polyurethane.

Further, the flame retardant comprises at least one of dimethyl methylphosphonate, a flame retardant PN-1, a flame retardant PN-2 and superfine antimony trioxide.

Further, the thickener is cellulose, hydrophobic modified polyurethane thickener, and at least one of defoamer 901W, BYK019 and BYK 025.

Further, the dispersant includes at least one of an acrylic block polymer, an anionic polyacrylamide, BYK025, and BYK 9076.

Example 2:

this example shows a specific structure of a method for preparing a high-elastic flame-retardant conductive fiber, as shown in fig. 1, including the following steps:

preparation of slurry: adding the raw materials of each component into a stirring grinder, pre-dispersing at the stirring speed of 800-1500 rpm, adding zirconia beads for grinding, and preparing the aqueous CNTs-graphene composite flame-retardant slurry with the average particle size controlled at 500nm for later use, wherein the volume ratio of the zirconia beads is 65-80%, the diameter is 1.0mm or 2.0mm, the grinding speed is 750-1000 rpm, and the grinding time is 25-45 min;

preparing conductive fibers: carrying out corona treatment on the substrate fiber to enable the surface of the substrate fiber to generate free radicals or ionic groups, setting parameters of a dyeing machine, adjusting tension, firstly stretching the fiber to 50-150% of length, carrying out primary dyeing through sizing, stretching the fiber to 200-300% of length, carrying out secondary sizing and dyeing to prepare the carbon nano tube/graphene conductive fiber; wherein, the first sizing and dyeing process is carried out, and the stretching length is 120%; and the second sizing dyeing line has a stretching length of 300%, and the corona treatment is carried out in a corona discharge electric field with a voltage of 3000-12000V and a power of 10-500W.

Furthermore, the base material fiber is selected from one of high stretch yarn terylene, chinlon, aramid fiber and acrylic fiber, and the specification is one of 150D/48F, 300D/96F and 300D/144F.

The working principle is as follows: as shown in fig. 1, 1 is raw material fiber, 2 is a material liquid tank, 3 is an oven, and 4 is functional fiber;

firstly, adding raw materials of each component into a stirring grinder, pre-dispersing at the stirring speed of 800-1500 rpm, adding zirconia beads for grinding, and preparing aqueous CNTs-graphene composite flame retardant slurry with the average particle size controlled at 500nm for later use;

then, carrying out corona treatment on the substrate fiber to enable the surface of the substrate fiber to generate free radicals or ionic groups, setting parameters of a dyeing machine, adjusting tension, firstly stretching the fiber to 50-150% of length, carrying out primary dyeing through sizing, stretching the fiber to 200-300% of length, carrying out secondary sizing and dyeing to prepare the carbon nano tube/graphene conductive fiber; wherein, the first sizing and dyeing process is carried out, and the stretching length is 120%; sizing and dyeing the yarn for the second time, wherein the stretching length is 300 percent;

the invention forms the conductive coating on the surface of the single fiber by utilizing simple and traditional dip-coating, printing and dyeing technology and the like, and the process is simple;

compared with the single resin adhesive, the flexible resin adhesive is adopted for compounding, so that the adhesive force is improved, and the light flexibility of the original fiber is kept;

through corona treatment, the invention improves the phase hydrophilic property of the fiber, thereby improving the adhesive force and wear resistance of the conductive fiber;

according to the invention, sizing is carried out for 2 times by adjusting different tensions, and the preparation process of the conductive fiber greatly improves the uniform resistance stability of the high-elasticity conductive fiber under the stretching condition, and simultaneously improves the conductivity of the conductive fiber, so that a series of carbon nanotube/graphene composite conductive fibers with high elasticity, uniform and stable resistance and high adhesive force are prepared;

according to the invention, the flame retardant is added, so that the flame retardant property of the fiber is greatly improved, and the use safety performance of the conductive fabric is improved; the resistance of the high-elastic conductive fiber prepared by the method can reach 100-900 omega/cm, the resistance range difference of a single fiber can be controlled within 50 omega/cm, the resistance stability is high, the change rate of the tensile rebound resistance is less than 5 percent, and the dry friction adhesive force reaches the level 3 of the standard GB/T3920-2008 grade evaluation; the conductive fiber prepared by the method has the advantages of environmental friendliness, simplicity in operation, low price, stable and controllable product quality, and the product has better application value in the aspects of electric heating, static electricity prevention, electromagnetic shielding, biosensors, battery electrodes and the like

The foregoing is a more detailed description of the invention in connection with specific preferred embodiments and it is not intended that the invention be limited to these specific details. For those skilled in the art to which the invention pertains, several simple deductions or substitutions can be made without departing from the spirit of the invention, and all shall be considered as belonging to the protection scope of the invention.