阅读说明：本技术 一种导电纤维制备装置 (Conductive fiber preparation device ) 是由 边慧光 江瑞 马亚标 郝国强 于 2020-05-13 设计创作，主要内容包括：本发明属于纳米纤维技术领域,具体涉及一种导电纤维制备装置,主体结构包括供料机构、储液仓、喷头、接收机构、电源和接地导线,通过一次法利用静电纺丝技术实现碳纳米管/天然橡胶导电纤维和石墨烯/天然橡胶导电纤维的制备,制备的导电纤维在水浴溶剂的作用下纤维交联,经过导电性测试表明,添加了碳纳米管的导电纤维的导电性提高了5个数量级,添加了石墨烯的导电纤维的导电性提高了8个数量级；其结构简单,制备的导电纤维比表面积大、纤维尺寸均匀、更易实现表面功能化、克服了橡胶纤维的粘连问题,大幅度提高了物理机械性能,在天然橡胶产业化生产和增强增韧材料等方面具有更加广泛的应用。(The invention belongs to the technical field of nano-fibers, and particularly relates to a conductive fiber preparation device, which comprises a main body structure, a feeding mechanism, a liquid storage bin, a spray head, a receiving mechanism, a power supply and a grounding wire, wherein the preparation of carbon nano-tube/natural rubber conductive fibers and graphene/natural rubber conductive fibers is realized by utilizing an electrostatic spinning technology through a one-step method, the prepared conductive fibers are subjected to fiber crosslinking under the action of a water bath solvent, and a conductivity test shows that the conductivity of the conductive fibers added with carbon nano-tubes is improved by 5 orders of magnitude, and the conductivity of the conductive fibers added with graphene is improved by 8 orders of magnitude; the prepared conductive fiber has the advantages of large specific surface area, uniform fiber size, easiness in realizing surface functionalization, overcoming the adhesion problem of rubber fibers, greatly improving the physical and mechanical properties, and having wider application in the aspects of industrial production of natural rubber, reinforced and toughened materials and the like.)

1. A conductive fiber preparation device is characterized in that the main structure comprises a feeding mechanism, a liquid storage bin, a spray head, a receiving mechanism, a power supply and a grounding wire; the feeding mechanism is connected with the liquid storage bin, the bottom end of the liquid storage bin is connected with the spray head, the receiving mechanism is arranged below the spray head, and the power supply is connected with the ground lead after being connected with the spray head and the receiving mechanism respectively.

2. The apparatus for preparing conductive fiber according to claim 1, wherein the feeding mechanism is capable of feeding the spinning solution into the reservoir at a set speed; the capacity of the liquid storage bin is more than or equal to 5 mL; the nozzle is a spinning nozzle and comprises a single-needle nozzle, and the diameter of the nozzle is 0.5-2.5 mm; the receiving mechanism comprises a rotary drum, a rotary frame, a rotary disc and a metal aluminum foil, when the unidirectional orderly arranged fibers are prepared, the rotary drum, the rotary frame or the rotary disc are selected, and when the disorderly arranged fibers are prepared, the metal aluminum foil is selected; the power supply is a high-voltage direct-current power supply.

3. The apparatus for preparing conductive fiber according to claim 1 or 2, wherein the vertical distance between the spraying head 3 and the receiving means 4 is 10-25 cm.

4. The apparatus for preparing conductive fiber according to claim 3, wherein the carbon nanotube/natural rubber conductive fiber and the graphene/natural rubber conductive fiber can be prepared by a single process, and the specific process comprises three steps of preparing a spinning solution, electrospinning and vulcanizing:

preparing a spinning solution: crushing natural rubber, dissolving the crushed natural rubber in an organic solvent to prepare a rubber solution with the weight percentage of 0.5-4 wt%, dissolving the rubber solution by using a high-speed stirrer under the water bath condition at the temperature of 50 ℃ to reach a uniform state, adding a vulcanizing agent, a vulcanization aid and carbon nano tubes or graphene into the rubber solution to form a spinning solution, and placing the spinning solution in an ultrasonic cell crusher for ultrasonic treatment for 20min for later use;

(II) electrostatic spinning: setting a feeding mechanism to convey the spinning solution into a liquid storage bin at the speed of 0.03-0.2ml/min, after the spinning solution stably flows out of a spray head, turning on a power supply, applying static electricity, starting electrostatic spinning under the conditions that the temperature is 23-27 ℃ and the humidity is 50-65%, forming polymer jet flow between the spray head and a receiving mechanism, falling onto the receiving mechanism, and drying to form natural rubber nanofiber;

(III) vulcanization: standing natural rubber nanofiber in a water bath solvent, taking out after 5-10min, vulcanizing at 90-175 ℃ for 7-60min, and cooling to room temperature to obtain the conductive fiber.

5. The apparatus for preparing conductive fiber according to claim 4, wherein the organic solvent in step (one) is one or more selected from cyclohexane, benzene, toluene, xylene, N-dimethylformamide, and tetrahydrofuran; the mass portions of the natural rubber, the vulcanizing agent, the vulcanizing assistant and the carbon nano tube or the graphene are respectively 100, 0.05-30 and 0.01-5; the vulcanizing agent is one or a mixture of several of nano-scale sulfur, metal oxide, organic peroxide, resin and amine, and one or a mixture of two of nano-scale sulfur and organic peroxide is preferably selected; the vulcanization aid is one or a mixture of more of an accelerator, an active agent, an anti-aging agent, a reinforcing agent and a filler, and the mass parts of the accelerator, the active agent, the anti-aging agent, the reinforcing agent and the filler in the vulcanization aid are respectively 0.01-5, 0-5 and 0-5.

6. The apparatus for preparing conductive fiber according to claim 4, wherein the voltage of the static electricity involved in the step (two) is 10 to 30 kv.

7. The apparatus for preparing conductive fiber according to claim 4, wherein the solvent of the water bath involved in the step (III) is liquid paraffin or zinc ethanolate solution.

8. The apparatus for preparing conductive fiber according to any one of claims 4 to 7, wherein the morphology of the conductive fiber prepared is adjusted by adjusting electrospinning parameters including concentration of the spinning solution, volatility of the organic solvent, electrostatic voltage, transport speed of the spinning solution, vertical distance between the nozzle and the receiving mechanism, diameter of the nozzle, ambient temperature and humidity.

The technical field is as follows:

the invention belongs to the technical field of nano fibers, and particularly relates to a conductive fiber preparation device which can be used for preparing carbon nano tubes/natural rubber conductive fibers and graphene/natural rubber conductive fibers by a one-step method.

Background art:

the conductive fiber is chemical fiber or metal fiber, carbon fiber, etc. spun by mixing conductive medium into polymer, has excellent performance of eliminating and preventing static far higher than that of antistatic fiber, and has lasting specific resistance value and no influence of humidity. The conductive material is classified into a uniform type, a coated type and a composite type according to the distribution state of the conductive components. The fiber is generally prepared by adding conductive media such as carbon black, graphite, metal powder or metal compounds and the like into the fiber by adopting methods such as mixing and dissolving, evaporation, electroplating, composite spinning and the like. The crystal can be shielded by electrostatic induction, and the fabric mixed with a small amount of conductive fiber can be used as special work clothes, dust-proof brushes, etc.

Rubber is called strategic material because it is a very important material in national production. The rubber has the characteristics of strong elasticity, good insulativity, plasticity, water and gas resistance, tensile strength, wear resistance and the like, and is widely applied to the fields of industry, agriculture, national defense, traffic, transportation, mechanical manufacture, medicine and health field, daily life and the like. With the continuous development of scientific technology, higher and higher requirements are also put on rubber products, and high-performance rubber products become the development trend of the rubber industry. To meet this trend, the potential of rubber products is constantly developed.

The carbon nanotube in the carbon series filler is an allotrope of carbon, the gap between the tubes is close to the gap of a graphite carbon atom layer, the hybridization type of the carbon atoms forming the carbon nanotube is mainly sp2, and the carbon nanotube is combined with the surrounding carbon atoms through carbon-carbon bonds to form a cylinder. The special structure of the carbon nano tube enables the carbon nano tube to have excellent performances which are not possessed by other materials, such as high strength, high toughness, high electric conductivity, high heat conductivity and the like, so that the carbon nano tube becomes one of nano materials with wide application potential, can effectively improve the comprehensive performance of a matrix, and has attracted wide attention in the world as a one-dimensional nano material with excellent electrical and mechanical properties.

Graphene with a two-dimensional structure in the carbon-based filler is considered to be a nanoscale filler capable of effectively improving the electrical conductivity of the composite material. After the graphene is combined with other materials to form a composite material or a hybrid structure, the electrical property and the mechanical property of the host material can be changed. Researches find that the electron mobility of the graphene is up to 15000cm at normal temperature²·V^-1·S^-1The conductive material is the material with the best conductivity at normal temperature. Each carbon atom in the graphene is connected with three peripheral carbon atoms through a bond, an included angle between the bond and the bond is 120 degrees, except a honeycomb type layered structure in which the bond and other carbon atoms are linked to form a hexagonal ring, the track of each carbon atom perpendicular to the layer surface forms a large pi bond penetrating through all layers of polyatomic layers, and the graphene has excellent conductivity.

The electrostatic spinning technology is the most simple and effective technology for preparing the nano-fiber at present, and the polymer matrixes such as polyvinyl alcohol (PVA), Polyacrylonitrile (PAN), polylactic acid (PLA) and the like are successfully prepared at present. The principle of electrostatic spinning is that under the action of high-voltage electrostatic field, polymer solution overcomes surface tension to form jet stream, and the polymer fiber is finally obtained on a receiving device after the volatile flowing solvent in the air is volatilized. The nanofiber manufactured by electrostatic spinning at present has been widely applied to air filtration, water treatment, heterogeneous catalysis, environmental protection, intelligent fabrics, surface coating, energy collection, transformation and storage, bioactive material encapsulation, drug release, tissue engineering, regenerative medicine and the like.

Chinese patent 201910417828.X discloses a device for preparing metal/polymer composite conductive fibers, comprising a liquid storage tank, a high-frequency signal generator, a power supply, and a collecting plate, wherein: the liquid storage tank is used for containing electrostatic spinning precursor liquid containing metal nanowires, one end of the liquid storage tank is connected with a spraying part, and a propelling part is arranged in the liquid storage tank and used for propelling the electrostatic spinning precursor liquid in the liquid storage tank to the spraying part and spraying the electrostatic spinning precursor liquid out through the spraying part; the output end of the high-frequency signal generator is connected with a first metal polar plate through a lead, the first metal polar plate is placed inside the liquid storage tank, the input end of the high-frequency signal generator is connected with a second metal polar plate through a lead, and the second metal polar plate is fixed at the joint of the outside of the liquid storage tank and the injection component; the first metal polar plate is parallel to the second metal polar plate; one end of the power supply is connected with the injection component through a lead, and the other end of the power supply is grounded; the collecting plate is oppositely arranged in front of the spraying component and is grounded; chinese patent 201520083823.5 discloses a preparation device of attapulgite hybrid conductive fiber, including master batch preparation device: a hybridization reactor for nanometer powder reaction, a single screw extruder, a vacuum drier, a double screw extruder, an online injector, a blower and a granulator; the nano hybrid reactor is communicated with a single-screw extruder; the single-screw extruder is communicated with the double-screw extruder through a vacuum drier; the injector is communicated with the double-screw extruder; the double-screw extruder is communicated with a blower through a pipeline; the blower is communicated with the granulator through a pipeline; and in the prior art, no record exists for preparing the carbon nano tube/natural rubber conductive fiber and the graphene/natural rubber conductive fiber by a one-step method based on an electrostatic spinning technology.

The invention content is as follows:

the invention aims to overcome the defects in the prior art, and seeks to design a conductive fiber preparation device, prepare a conductive fiber with excellent mechanical properties by a simple, quick and effective conductive fiber preparation method, and realize industrial production of the conductive fiber.

In order to achieve the purpose, the main structure of the conductive fiber preparation device comprises a feeding mechanism, a liquid storage bin, a spray head, a receiving mechanism, a power supply and a grounding wire; the feeding mechanism is connected with the liquid storage bin, the bottom end of the liquid storage bin is connected with the spray head, the receiving mechanism is arranged below the spray head, and the power supply is connected with the ground lead after being connected with the spray head and the receiving mechanism respectively.

The feeding mechanism 1 related to the invention can convey the spinning solution into the liquid storage bin according to a set speed; the capacity of the liquid storage bin is more than or equal to 5 mL; the nozzle is a spinning nozzle and comprises a single-needle nozzle, and the diameter of the nozzle is 0.5-2.5 mm; the receiving mechanism comprises a rotary drum, a rotary frame, a rotary disc and a metal aluminum foil, when the unidirectional orderly arranged fibers are prepared, the rotary drum, the rotary frame or the rotary disc are selected, and when the disorderly arranged fibers are prepared, the metal aluminum foil is selected; the power supply is a high-voltage direct-current power supply; the vertical distance between the spray head and the receiving mechanism is 10-25 cm.

The invention relates to a conductive fiber preparation device which can prepare carbon nano tubes/natural rubber conductive fibers and graphene/natural rubber conductive fibers by a one-step method, and the specific process comprises three steps of spinning solution preparation, electrostatic spinning and vulcanization:

preparing a spinning solution: crushing natural rubber, dissolving the crushed natural rubber in an organic solvent to prepare a rubber solution with the weight percentage of 0.5-4 wt%, dissolving the rubber solution by using a high-speed stirrer under the water bath condition at the temperature of 50 ℃ to reach a uniform state, adding a vulcanizing agent, a vulcanization aid and carbon nano tubes or graphene into the rubber solution to form a spinning solution, and placing the spinning solution in an ultrasonic cell crusher for ultrasonic treatment for 20min for later use;

(II) electrostatic spinning: setting a feeding mechanism to convey the spinning solution into a liquid storage bin at the speed of 0.03-0.2ml/min, after the spinning solution stably flows out of a spray head, turning on a power supply, applying static electricity, starting electrostatic spinning under the conditions that the temperature is 23-27 ℃ and the humidity is 50-65%, forming polymer jet flow between the spray head and a receiving mechanism, falling onto the receiving mechanism, and drying to form natural rubber nanofiber;

(III) vulcanization: standing natural rubber nanofiber in a water bath solvent, taking out after 5-10min, vulcanizing at 90-175 ℃ for 7-60min, and cooling to room temperature to obtain the conductive fiber.

The organic solvent involved in the step (one) of the invention is one or a mixture of more of cyclohexane, benzene, toluene, xylene, N-dimethylformamide and tetrahydrofuran; the mass portions of the natural rubber, the vulcanizing agent, the vulcanizing assistant and the carbon nano tube or the graphene are respectively 100, 0.05-30 and 0.01-5; the vulcanizing agent is one or a mixture of several of nano-scale sulfur, metal oxide, organic peroxide, resin and amine, and one or a mixture of two of nano-scale sulfur and organic peroxide is preferably selected; the vulcanization auxiliary agent is one or a mixture of more of an accelerator, an active agent, an anti-aging agent, a reinforcing agent and a filler, and the mass parts of the accelerator, the active agent, the anti-aging agent, the reinforcing agent and the filler in the vulcanization auxiliary agent are respectively 0.01-5, 0-5 and 0-5; the voltage of the static electricity involved in the step (II) is 10-30 kv; and (3) the water bath solvent involved in the step (III) is liquid paraffin or zinc ethanolate solution.

The shape of the conductive fiber related by the invention is adjusted by adjusting electrostatic spinning parameters including the concentration of the spinning solution, the volatility of the organic solvent, the electrostatic voltage, the conveying speed of the spinning solution, the vertical distance between the spray head and the receiving mechanism, the diameter of the spray head, the ambient temperature and the humidity.

Compared with the prior art, the preparation of the carbon nano tube/natural rubber conductive fiber and the graphene/natural rubber conductive fiber is realized by utilizing an electrostatic spinning technology through a one-step method, the specific process is that a vulcanization system and the like are added into a spinning solution for electrostatic spinning, then a set temperature field is added in the spinning process, the volatilization rate of a solvent is improved, water bath receiving is adopted, the temperature of a water bath solvent is kept at 60-70 ℃, the water bath solvent can effectively avoid the flowing adhesion of the rubber fiber, the appearance of the fiber is well kept, the prepared conductive fiber is subjected to fiber crosslinking under the action of the water bath solvent, and the conductivity test shows that the conductivity of the conductive fiber added with the carbon nano tube is improved by 5 orders of magnitude, and the conductivity of the conductive fiber added with the graphene is improved by 8 orders of magnitude; the prepared conductive fiber has the advantages of large specific surface area, uniform fiber size, easiness in realizing surface functionalization, overcoming the adhesion problem of rubber fibers, greatly improving the physical and mechanical properties, and having wider application in the aspects of industrial production of natural rubber, reinforced and toughened materials and the like.

Description of the drawings:

fig. 1 is a schematic diagram of the principle of the main structure of the present invention.

FIG. 2 is a photograph of the three-dimensional morphology of the natural rubber nanofibers according to example 2 of the present invention.

FIG. 3 is a photograph of the three-dimensional morphology of the natural rubber nanofibers according to example 3 of the present invention.

The specific implementation mode is as follows:

the invention is further described below by way of an embodiment example in conjunction with the accompanying drawings.