CN108866669B - Preparation method of modified carbon nanotube/conductive polyacrylonitrile fiber - Google Patents
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- CN108866669B CN108866669B CN201810819296.8A CN201810819296A CN108866669B CN 108866669 B CN108866669 B CN 108866669B CN 201810819296 A CN201810819296 A CN 201810819296A CN 108866669 B CN108866669 B CN 108866669B
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- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/44—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds
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- D01F1/09—Addition of substances to the spinning solution or to the melt for making electroconductive or anti-static filaments
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Abstract
The invention provides a preparation method of modified carbon nano tube/conductive polyacrylonitrile fiber, which comprises the following steps: (1) dissolving the acid modified carbon nano tube in n-hexane solution of tetramethyl tetravinylcyclotetrasiloxane, blowing nitrogen, performing ultrasonic treatment, and placing the mixture in a container60Irradiating in gamma rays of a Co radioactive source, washing and drying after irradiation to obtain a crude product of graft copolymerization; (2) heating and refluxing the crude product of the graft copolymerization obtained in the step (1) to constant weight by taking acetone as a solvent, and drying insoluble substances to obtain a grafted carbon nanotube; (3) and (3) mixing the grafted carbon nano tube obtained in the step (2), PAN and DMF to prepare spinning solution, and spinning the spinning solution to obtain the modified carbon nano tube/conductive polyacrylonitrile fiber. The amorphous carbon on the surface of the original carbon nano tube can be oxidized by nitric acid under the catalysis of hydrochloric acid to generate carbon dioxide for removal. After the amorphous carbon layer on the surface is removed, the outer surface of the carbon nano tube is continuously oxidized by nitric acid to generate hydroxyl and carboxyl.
Description
Technical Field
The invention relates to the field of fiber preparation, in particular to a preparation method of modified carbon nanotube/conductive polyacrylonitrile fiber.
Background
The carbon nano tube has extremely high strength, the theoretical calculation value is 100 times of that of steel, meanwhile, the carbon nano tube has extremely high toughness and is very soft, the carbon nano tube is considered as a future super fiber, and meanwhile, the carbon nano tube also has conductivity. The growth characteristics of the carbon nanotubes are that a plurality of carbon nanotubes are agglomerated and intertwined with each other, in addition, the surface characteristics of the carbon nanotubes are similar to those of graphite, the carbon nanotubes are insoluble in most solvents and have poor wetting performance, and if untreated carbon nanotubes are added into a polymer, the problems of poor bonding property with a matrix, poor dispersibility and the like can occur. Therefore, how to uniformly disperse the carbon nanotubes in the matrix of the composite material, and the tight bonding with the matrix is the first consideration in the preparation of carbon nanotube reinforced composite materials.
Because the steric hindrance of the polymer molecular chain can not make the carboxyl on the surface of the carbon nano tube effectively react, the grafting rate is very low, so that the patent adopts the method of effectively modifying the carbon nano tube to achieve the satisfactory grafting rate.
Disclosure of Invention
The invention provides a preparation method of a modified carbon nano tube/conductive polyacrylonitrile fiber, which solves the problem of low grafting rate of the existing carbon nano tube.
The technical scheme for realizing the invention is as follows: a preparation method of modified carbon nano tube/conductive polyacrylonitrile fiber comprises the following steps:
(1) dissolving acid-modified carbon nanotube in n-hexane solution of tetramethyltetravinylcyclotetrasiloxane, blowing nitrogen for 15min, performing ultrasonic treatment, and placing in60Irradiating in gamma rays of a Co radioactive source, washing and drying after irradiation to obtain a crude product of graft copolymerization;
(2) heating and refluxing the crude product of the graft copolymerization obtained in the step (1) to constant weight by taking acetone as a solvent, and drying insoluble substances to obtain a grafted carbon nanotube;
(3) and (3) mixing the grafted carbon nano tube obtained in the step (2), PAN (polyacrylonitrile) and DMF (dimethyl formamide) to prepare spinning solution, and spinning the spinning solution to obtain the modified carbon nano tube/conductive polyacrylonitrile fiber.
The concentration of the n-hexane solution of tetramethyltetravinylcyclotetrasiloxane in the step (1) is 0.005-0.01 g/ml.
The ultrasonic treatment in the step (1) is carried out under the conditions of temperature of 20 ℃, power of 125W and time of 12-20 h.
The gamma ray irradiation conditions in the step (1) are as follows: the radiance is 1KGy/h, and the irradiation time is 30-36 h.
In the step (2), the reflux temperature is 50-55 ℃, and the drying temperature is 90-100 ℃.
The preparation method of the acid modified carbon nano tube in the step (1) comprises the following steps: placing the carbon nano tube in 3 mol/L nitric acid, refluxing and stirring at 60 ℃ for 24h, cooling to room temperature, centrifuging to obtain a precipitate, dissolving the precipitate in 120 ℃ and 5 mol/L hydrochloric acid, treating for 6h, cooling to room temperature, centrifuging to obtain a precipitate, washing with deionized water until the pH is 7, washing with acetone for three times, and placing in a vacuum drying oven at 60 ℃ and 10mbar until the weight is constant.
The mass ratio of the grafted carbon nanotube to the PAN in the step (3) is (10-15): (85-90).
The spinning process in the step (3) is as follows: extruding the spinning solution under the pressure of 0.3MPa of nitrogen, reaching a spinning nozzle through a metering pump, entering a sodium thiocyanate aqueous solution coagulating bath through the spinning nozzle for solidification, entering a boiling water bath for washing after solidification, drying through a high-temperature drying cylinder, and performing package forming to obtain the modified carbon nanotube/conductive polyacrylonitrile fiber.
The carbon nanotube acidification principle is as follows:
the invention has the beneficial effects that: the carbon nano tube is mainly oxidized by nitric acid in the mixed acid purification process, and the hydrochloric acid is used for catalyzing the oxidation reaction of the nitric acid and dissolving metal ions. The catalyst Ni/Mo/MgO is firstly oxidized by nitric acid and then reacts with hydrochloric acid to generate NiCl2、MgCl2And (MoO)2)Cl2These compounds are soluble in the mixed acid and can be removed by filtration. The amorphous carbon on the surface of the original carbon nano tube can be oxidized by nitric acid under the catalysis of hydrochloric acid to generate carbon dioxide for removal. After the amorphous carbon layer on the surface is removed, the outer surface of the carbon nano tube is continuously oxidized by nitric acid to generate hydroxyl and carboxyl.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the drawings without creative efforts.
FIG. 1 is a schematic diagram of carbon nanotube acidification.
FIG. 2 is an infrared spectrum of the carbon nanotube acidified according to example 1.
FIG. 3 is a Raman spectrum of the acidified carbon nanotube of example 1.
FIG. 4 is a schematic diagram of carbon nanotube radiation grafting.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments of the present invention, and it should be understood 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 obtained by a person skilled in the art without inventive effort based on the embodiments of the present invention, are within the scope of the present invention.
Example 1
A preparation method of modified carbon nano tube/conductive polyacrylonitrile fiber comprises the following steps:
weighing a certain amount of carbon nano tube, dissolving the carbon nano tube in 3 mol/L nitric acid at 60 ℃, refluxing and stirring for 24h, cooling to room temperature, centrifuging to obtain a precipitate, dissolving the precipitate in 120 ℃ and 5 mol/L hydrochloric acid for 6h, cooling to room temperature, centrifuging to obtain a precipitate, washing with deionized water until the pH is 7, washing with acetone for three times, placing in a vacuum drying oven at 60 ℃ (10 mbar) to constant weight, weighing a certain weight of the carbon nano tube, placing in a transparent ampere bottle, pouring 100ml (0.005 g/ml) of tetramethyl tetravinylcyclotetrasiloxane n-hexane solution, blowing in nitrogen for 15min to remove dissolved oxygen, ultrasonically treating at 20 ℃ and 125W, placing in a vacuum drying oven at 60 ℃ (60In gamma rays of a Co radioactive source, the radiance is 1KGy/h, after 30h of irradiation, the irradiated reaction materials are taken out, washed by deionized water for many times and then placed in an oven to be dried to constant weight, and the crude product of graft copolymerization is obtained. Weighing a certain amount of crude graft copolymerization product, placing the crude graft copolymerization product in a Soxhlet extractor, heating and refluxing to constant weight (to remove tetramethyl tetravinyl silane) by taking acetone as a solvent, wherein the refluxing temperature is 50 ℃, the drying temperature is 90 ℃, and drying the residual insoluble substances to constant weight to obtain the graft copolymer.
Weight W when sample is dry before radiation treatment1After radiation washing and extraction, the sample is dried and then weighed W2The graft ratio was calculated to obtain the graft ratio (%) = (W)2-W1)/W1× 100% the relationship between radiation dose and grafting ratio can be seen from the graph.
Preparing modified carbon nanotube conductive polyacrylonitrile fiber by a wet method, mixing the prepared modified carbon nanotube conductive powder with PAN according to a proportion, wherein the mass ratio of the grafted carbon nanotube to the PAN is 10: 90, adding a proper amount of DMF (N, N-dimethyl amide) into a slurry storage tank, filling nitrogen with a certain pressure (0.3 MPa) after stirring by a pressing jacket to extrude the spinning solution to a spinning nozzle through a metering pump, then feeding the spinning solution into a sodium thiocyanate aqueous solution (with 25% solubility) coagulation bath through the spinning nozzle, properly solidifying the coagulation bath, then feeding the coagulation bath into a boiling water bath through a roller, and controlling the front speed and the rear speed to ensure that the fiber is drawn to a certain extent and simultaneously washing the fiber to a certain extent. And (4) washing the drum with the next step of water, washing the DMF solvent in the fiber, drying the fiber by using a high-temperature drying drum, and finally performing package forming.
The resistivity of the modified carbon nano tube conductive polyacrylonitrile fiber prepared by the method is 5.86 × 108Ω · cm, average breaking strength 5.88cN/tex, average elongation at break 7.21%.
Example 2
A preparation method of modified carbon nano tube/conductive polyacrylonitrile fiber comprises the following steps:
weighing a certain amount of carbon nano tube, dissolving the carbon nano tube in 3 mol/L nitric acid at 60 ℃, refluxing and stirring for 24 hours, cooling to room temperature, centrifuging to obtain a precipitate, dissolving the precipitate in 120 ℃ 5 mol/L hydrochloric acid for 6 hours, cooling to room temperature, centrifuging to obtain a precipitate, washing with deionized water until the pH is 7, washing with acetone for three times, placing in a vacuum drying oven at 60 ℃ (10 mbar) to constant weight, weighing a certain weight of the carbon nano tube, placing in a transparent ampere bottle, pouring 100ml (0.008 g/ml) of tetramethyl tetravinylcyclotetrasiloxane n-hexane solution, blowing in nitrogen for 15 minutes to remove dissolved oxygen, ultrasonically treating at 20 ℃, 125W, placing in a vacuum drying oven at 60 ℃ (1060In gamma rays of a Co radioactive source, the radiance is 1KGy/h, after 32h of irradiation, the irradiated reaction materials are taken out, washed by deionized water for multiple times and then placed inDrying in a drying oven to constant weight to obtain a crude product of graft copolymerization. Weighing a certain amount of crude graft copolymerization product, placing the crude graft copolymerization product in a Soxhlet extractor, heating and refluxing to constant weight (to remove tetramethyl tetravinyl silane) by taking acetone as a solvent, wherein the refluxing temperature is 53 ℃, the drying temperature is 95 ℃, and drying the residual insoluble substances to constant weight to obtain the graft copolymer.
Weight W when sample is dry before radiation treatment1After radiation washing and extraction, the sample is dried and then weighed W2The graft ratio was calculated to obtain the graft ratio (%) = (W)2-W1)/W1× 100% the relationship between radiation dose and grafting ratio can be seen from the graph.
Preparing modified carbon nanotube conductive polyacrylonitrile fiber by a wet method, mixing the prepared modified carbon nanotube conductive powder with PAN according to a proportion, wherein the mass ratio of the grafted carbon nanotube to the PAN is 12: 88, adding a proper amount of DMF (N, N-dimethyl amide) and filling the mixture into a slurry storage tank, compressing a jacket for stirring, introducing nitrogen with a certain pressure (0.3 MPa) to extrude the spinning solution to a spinning nozzle through a metering pump, introducing the spinning solution into a sodium thiocyanate aqueous solution (with 28% solubility) coagulation bath through the spinning nozzle, properly solidifying the coagulation bath, introducing the solidified coagulation bath into a boiling water bath through a roller, and controlling the front speed and the rear speed to ensure that the fiber is drawn to a certain extent and simultaneously washing the fiber to a certain extent. And (4) washing the drum with the next step of water, washing the DMF solvent in the fiber, drying the fiber by using a high-temperature drying drum, and finally performing package forming.
Example 3
A preparation method of modified carbon nano tube/conductive polyacrylonitrile fiber comprises the following steps:
weighing a certain amount of carbon nano tube, dissolving the carbon nano tube in 3 mol/L nitric acid at 60 ℃, refluxing and stirring for 24h, cooling to room temperature, centrifuging to obtain a precipitate, dissolving the precipitate in 120 ℃ and 5 mol/L hydrochloric acid for 6h, cooling to room temperature, centrifuging to obtain a precipitate, washing with deionized water until the pH is 7, washing with acetone for three times, placing in a vacuum drying oven at 60 ℃ (10 mbar) to constant weight, weighing a certain weight of the carbon nano tube, placing in a transparent ampere bottle, pouring 100ml (0.01 g/ml) of tetramethyl tetravinylcyclotetrasiloxane n-hexane solution, blowing in nitrogen for 15min to remove dissolved oxygen, performing ultrasonic treatment at 20 ℃ and 125W, placing in a vacuum drying oven at 6060In gamma rays of a Co radioactive source, the radiance is 1KGy/h, after 6h of irradiation, the irradiated reaction materials are taken out, washed by deionized water for many times and then placed in an oven to be dried to constant weight, and the crude product of graft copolymerization is obtained. Weighing a certain amount of crude graft copolymerization product, placing the crude graft copolymerization product in a Soxhlet extractor, heating and refluxing to constant weight (to remove tetramethyl tetravinyl silane) by taking acetone as a solvent, wherein the refluxing temperature is 55 ℃, the drying temperature is 100 ℃, and drying the residual insoluble substances to constant weight to obtain the graft copolymer.
Weight W when sample is dry before radiation treatment1After radiation washing and extraction, the sample is dried and then weighed W2The graft ratio was calculated to obtain the graft ratio (%) = (W)2-W1)/W1× 100% the relationship between radiation dose and grafting ratio can be seen from the graph.
Preparing modified carbon nanotube conductive polyacrylonitrile fiber by a wet method, mixing the prepared modified carbon nanotube conductive powder with PAN according to a proportion, wherein the mass ratio of the grafted carbon nanotube to the PAN is 15: 85, adding a proper amount of DMF (N, N-dimethyl amide) into a slurry storage tank, filling nitrogen with a certain pressure (0.3 MPa) after stirring by a pressing jacket to extrude the spinning solution to a spinning nozzle through a metering pump, then feeding the spinning solution into a sodium thiocyanate aqueous solution (with the solubility of 30%) coagulation bath through the spinning nozzle, carrying out proper solidification on the coagulation bath, then feeding the spinning solution into a boiling water bath through a roller, and controlling the front speed and the rear speed to ensure that the fiber is drawn to a certain extent and simultaneously washing the fiber to a certain extent. And (4) washing the drum with the next step of water, washing the DMF solvent in the fiber, drying the fiber by using a high-temperature drying drum, and finally performing package forming.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (7)
1. A preparation method of modified carbon nano tube/conductive polyacrylonitrile fiber is characterized by comprising the following steps:
(1) dissolving the acid modified carbon nano tube in n-hexane solution of tetramethyl tetravinylcyclotetrasiloxaneBlowing nitrogen gas into the solution for 15min, treating with ultrasonic wave, and placing in60Irradiating in gamma rays of a Co radioactive source, washing and drying after irradiation to obtain a crude product of graft copolymerization; the conditions of gamma ray irradiation were: the radiance is 1KGy/h, and the irradiation time is 30-36 h;
(2) heating and refluxing the crude product of the graft copolymerization obtained in the step (1) to constant weight by taking acetone as a solvent, and drying insoluble substances to obtain a grafted carbon nanotube;
(3) and (3) mixing the grafted carbon nano tube obtained in the step (2), PAN and DMF to prepare spinning solution, and spinning the spinning solution to obtain the modified carbon nano tube/conductive polyacrylonitrile fiber.
2. The method for preparing modified carbon nanotube/polyacrylonitrile fiber according to claim 1, wherein the concentration of n-hexane solution of tetramethyltetravinylcyclotetrasiloxane in the step (1) is 0.005-0.01 g/ml.
3. The method for preparing the modified carbon nanotube/conductive polyacrylonitrile fiber according to claim 1, wherein: the ultrasonic treatment in the step (1) is carried out under the conditions that the temperature is 20 ℃, the power is 125W, and the time is 12-20 h.
4. The method for preparing the modified carbon nanotube/conductive polyacrylonitrile fiber according to claim 1, wherein: in the step (2), the reflux temperature is 50-55 ℃, and the drying temperature is 90-100 ℃.
5. The method for preparing the modified carbon nanotube/conductive polyacrylonitrile fiber according to any one of claims 1 to 4, wherein the method for preparing the acid-modified carbon nanotube in the step (1) is as follows: placing the carbon nano tube in 3 mol/L nitric acid, refluxing and stirring at 60 ℃ for 24h, cooling to room temperature, centrifuging to obtain a precipitate, dissolving the precipitate in 120 ℃ and 5 mol/L hydrochloric acid, treating for 6h, cooling to room temperature, centrifuging to obtain a precipitate, washing with deionized water until the pH is 7, washing with acetone for three times, and placing in a vacuum drying oven at 60 ℃ and 10mbar until the weight is constant.
6. The method for preparing the modified carbon nanotube/conductive polyacrylonitrile fiber according to any one of claims 1 to 4, wherein the mass ratio of the grafted carbon nanotube to the PAN in the step (3) is (10-15): (85-90).
7. The method for preparing the modified carbon nanotube/conductive polyacrylonitrile fiber according to any one of claims 1 to 4, wherein the spinning process in the step (3) is as follows: extruding the spinning solution under the pressure of 0.3MPa of nitrogen, reaching a spinning nozzle through a metering pump, entering a sodium thiocyanate aqueous solution coagulating bath through the spinning nozzle for solidification, entering a boiling water bath for washing after solidification, drying through a high-temperature drying cylinder, and performing package forming to obtain the modified carbon nanotube/conductive polyacrylonitrile fiber.
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| CN109518306A (en) * | 2018-12-12 | 2019-03-26 | 深圳烯湾科技有限公司 | Modified carbon nano tube fiber and its preparation method and application |
| CN114427125A (en) * | 2020-10-29 | 2022-05-03 | 中国石油化工股份有限公司 | Carbon nano tube antistatic acrylic fiber and preparation method thereof |
| CN112864435B (en) * | 2021-01-08 | 2022-09-30 | 腾强科技(北京)有限责任公司 | Preparation method and application of composite fiber membrane of carbon nanotube grafted polyacrylonitrile fiber |
| CN112981582A (en) * | 2021-02-09 | 2021-06-18 | 华中科技大学 | Temperature control fiber integrating heat superconducting and refrigerating functions and preparation method and application thereof |
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