CN115233330B - Preparation method of graphene conductive composite fiber - Google Patents
Preparation method of graphene conductive composite fiber Download PDFInfo
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- CN115233330B CN115233330B CN202210918397.7A CN202210918397A CN115233330B CN 115233330 B CN115233330 B CN 115233330B CN 202210918397 A CN202210918397 A CN 202210918397A CN 115233330 B CN115233330 B CN 115233330B
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- 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
- D01F6/52—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 of polymers of unsaturated carboxylic acids or unsaturated esters
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/09—Addition of substances to the spinning solution or to the melt for making electroconductive or anti-static filaments
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
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Abstract
The invention discloses a preparation method of graphene conductive composite fibers, which relates to the technical field of composite fibers and comprises the following steps: (1) obtaining a mixed suspension; (2) obtaining a reactant; (3) obtaining modified graphene; (4) obtaining modified graphene oxide; (5) preparing modified graphene oxide dispersion liquid; (6) obtaining an acrylic acid mixed solution; (7) obtaining spinning solution; (8) forming graphene conductive composite fibers; the graphene conductive composite fiber prepared by the method has excellent conductivity and mechanical property, has higher conductivity and fiber strength, and has average conductivity of more than 6S/cm.
Description
Technical Field
The invention belongs to the field of composite fibers, and particularly relates to a preparation method of a graphene conductive composite fiber.
Background
Conductive fibers are always research hot spots of functional fibers, generally refer to fibers with resistivity smaller than 108 Ω & cm, have the functions of conducting electricity, heating electricity, preventing electromagnetic radiation and the like, and are generally and intensively applied to the fields of antistatic clothing, electromagnetic radiation preventing clothing and the like used in special occasions. The main method for manufacturing the conductive fiber comprises the steps of coating the surface of a conventional fiber with a conductive component, mixing a conductive material with a fiber raw material, and preparing the conductive fiber through a spinning process. The method for coating the conductive layer on the surface of the fiber is to coat the conductive material containing metal, carbon black or metal compound on the surface of the fiber to prepare the conductive fiber, or to adsorb conductive polymers such as polyaniline on the surface of the fiber by an in-situ polymerization method to obtain the conductive fiber. Blend spinning the conductive particles (mainly carbon black or metal compounds) are blended with the host polymer of the non-conductive component to prepare the composite conductive fiber through a melt or wet spinning process.
In the prior art, application number 201410220720.9 discloses a preparation method of graphene conductive composite fibers, which is characterized by comprising the following steps: surface modification procedure of textile fiber: soaking textile fibers in a silane coupling agent KH560 solution with the concentration of 1% -30% for 2-3 hours, and drying in a drying oven at 50-65 ℃ to obtain surfactant modified textile fibers; preparing a graphene dispersion system: preparing graphene from graphene oxide aqueous solution prepared by a Hummer's method by a chemical reduction method, and preparing a uniform and stable graphene dispersion system under the action of a dispersing agent, wherein the concentration of the uniform and stable graphene dispersion system is 0.1% -5%; the preparation process of the graphene composite fiber comprises the following steps: and soaking the modified textile fiber in a graphene dispersion system for 2-3 hours, and drying in a drying box at 50-65 ℃ to obtain the graphene conductive composite fiber. The process is simple and reasonable, the operation is easy, the yield is high, the graphene consumption is small, the dispersion system is uniform and stable, the reduction degree is good, and the conductive and anti-radiation performances are good. The conductive fiber prepared in the prior art has relatively poor mechanical properties, so that the conductive fiber is easy to break in the use process, thereby limiting the application of the conductive fiber.
Accordingly, there is a need for further improvements in the art.
Disclosure of Invention
The invention aims to provide a preparation method of graphene conductive composite fibers, which aims to solve the defects in the prior art.
The technical scheme adopted by the invention is as follows:
the preparation method of the graphene conductive composite fiber comprises the following steps:
(1) Sequentially adding 3-aminopropyl triethoxysilane and ethanol into distilled water, adjusting the temperature to 55 ℃, keeping the temperature and stirring for 15min, then adding graphene, and performing ultrasonic treatment for 30-40min to obtain a mixed suspension;
(2) Carrying out high-speed centrifugation on the prepared mixed suspension, and then filtering to obtain a reactant;
(3) Washing the obtained reactant by adopting ethanol and distilled water for 15-20min, and then drying to obtain modified graphene;
(4) Mixing the prepared modified graphene with an oxidizing solution, and performing oxidation treatment to obtain modified graphene oxide;
(5) Uniformly dispersing the modified graphene oxide into ethyl acetate to prepare a modified graphene oxide dispersion liquid;
(6) Adding acrylic acid and modified rosin into ethyl acetate according to the mass ratio of 10-12:3-5:20-25, and preparing to obtain an acrylic acid mixed solution;
(7) Adding the modified graphene oxide dispersion liquid into an acrylic acid mixed solution, and uniformly stirring to obtain a spinning stock solution;
(8) Extruding the spinning solution obtained by the preparation at the speed of 8-10mL/h set by a double-pipe microinjection pump, spraying out the stock solution trickle through a needle head into a coagulation bath of glacial acetic acid, so that the stock solution trickle reaches critical concentration, and separating out in the coagulation bath to form the graphene conductive composite fiber.
As a further technical scheme: the mixing mass ratio of the 3-aminopropyl triethoxysilane to the ethanol to the distilled water is 3-5:10-12:15-20.
As a further technical scheme: the mixing mass ratio of the ethanol to the graphene is 5:3;
the ethanol is absolute ethanol.
As a further technical scheme: the mixing mass ratio of the modified graphene to the oxidizing liquid is 1:10-15 parts;
the oxidizing solution is prepared from the following components in parts by weight: 1-3 parts of polyepoxysuccinic acid, 1-3 parts of phytic acid, 4-6 parts of sulfuric acid, 8-10 parts of nitric acid and 100 parts of deionized water.
As a further technical scheme: the weight ratio of the polyepoxysuccinic acid to the phytic acid is 1:1.
As a further technical scheme: the temperature of the oxidation treatment is 70 ℃;
the time of the oxidation treatment was 1 hour.
As a further technical scheme: the mass fraction of the modified graphene oxide dispersion liquid is 3-5%;
the mass fraction of acrylic acid in the acrylic acid mixed solution is 18-25%;
the mass fraction of the modified rosin resin is 3-6%.
As a further technical scheme: the preparation method of the modified rosin resin comprises the following steps:
heating rosin resin to be molten, adding bisphenol A accounting for 10% of the mass of the rosin resin into the molten rosin resin, stirring for 10min, adding a catalyst, continuously stirring for 40min, cooling to 75 ℃, continuously stirring for 1 h, adding polyethyleneimine accounting for 1.5% of the mass of the rosin resin, adjusting the temperature to 118 ℃, preserving heat, stirring for 30min, vacuumizing for 40min, and naturally cooling to room temperature to obtain the modified rosin resin.
As a further technical scheme: the catalyst is acrylic acid-9-anthracene methyl ester;
wherein the addition amount of the catalyst is 0.5% of the mass of the rosin resin.
As a further technical scheme: the mixing mass ratio of the modified graphene oxide dispersion liquid and the acrylic acid mixed solution is 1:3-5;
wherein, the mixing and stirring speed of the modified graphene oxide dispersion liquid and the acrylic acid mixed solution is 150r/min, and the stirring time is 35min.
Graphene is the only two-dimensional free-state atomic crystal found at present, has a perfect large pi conjugated system and the thinnest structure with single-layer atomic thickness, and is used for constructing sp such as zero-dimensional fullerene, one-dimensional carbon nano tube, three-dimensional bulk graphite and the like 2 The basic structure of the hybrid carbon can generate a certain barrier effect by introducing the modified graphene oxide, so that the contact resistance is effectively reduced, compared with unmodified graphene, the hybrid carbon can not generate stable interaction with a polymer, the contact resistance can not be obviously reduced, and the conductivity of the fiber can not be better improved
The modified graphene oxide is introduced to play a role in reducing contact resistance in the polymer, so that the temperature resistance of the polymer is obviously improved. And with the addition of the modified graphene oxide, the mechanical property of the modified graphene oxide is obviously enhanced, the internal density of the prepared conductive fiber is improved by matching with the effect of the modified rosin resin, and the toughness of the conductive fiber is greatly improved.
The conductive fiber prepared by the coordination of the modified graphene oxide and the modified rosin resin forms a stable conductive network structure inside.
The beneficial effects are that:
the graphene conductive composite fiber prepared by the method has excellent conductivity and mechanical property, has higher conductivity and fiber strength, has average conductivity of more than 6S/cm, remarkably improves the conductivity of the graphene conductive composite fiber by modifying graphene, and can further improve the mechanical property, particularly greatly improve breaking strength by introducing modified rosin resin.
Drawings
FIG. 1 is a graph comparing the impact of mass fractions of different modified rosin resins on breaking strength of graphene conductive composite fibers.
Detailed Description
Example 1
The preparation method of the graphene conductive composite fiber comprises the following steps:
(1) Sequentially adding 3-aminopropyl triethoxysilane and ethanol into distilled water, adjusting the temperature to 55 ℃, keeping the temperature and stirring for 15min, then adding graphene, and performing ultrasonic treatment for 30min to obtain a mixed suspension;
(2) Carrying out high-speed centrifugation on the prepared mixed suspension, and then filtering to obtain a reactant;
(3) Washing the obtained reactant by adopting ethanol and distilled water for 15min, and then drying to obtain modified graphene;
(4) Mixing the prepared modified graphene with an oxidizing solution, and performing oxidation treatment to obtain modified graphene oxide;
(5) Uniformly dispersing the modified graphene oxide into ethyl acetate to prepare a modified graphene oxide dispersion liquid;
(6) Adding acrylic acid and modified rosin into ethyl acetate according to the mass ratio of 10:3:20 to prepare an acrylic acid mixed solution;
(7) Adding the modified graphene oxide dispersion liquid into an acrylic acid mixed solution, and uniformly stirring to obtain a spinning stock solution;
(8) Extruding the spinning solution obtained by the preparation at the speed of 8mL/h set by a double-pipe microinjection pump, spraying out the stock solution trickle through a needle head into a coagulating bath of glacial acetic acid, so that the stock solution trickle reaches a critical concentration, and separating out in the coagulating bath to form the graphene conductive composite fiber.
The mixing mass ratio of the 3-aminopropyl triethoxysilane to the ethanol to the distilled water is 3:10:15.
The mixing mass ratio of the ethanol to the graphene is 5:3;
the ethanol is absolute ethanol.
The mixing mass ratio of the modified graphene to the oxidizing liquid is 1:10;
the oxidizing solution is prepared from the following components in parts by weight: 1 part of polyepoxysuccinic acid, 1 part of phytic acid, 4 parts of sulfuric acid, 8 parts of nitric acid and 100 parts of deionized water.
The weight ratio of the polyepoxysuccinic acid to the phytic acid is 1:1.
The temperature of the oxidation treatment is 70 ℃;
the time of the oxidation treatment was 1 hour.
The mass fraction of the modified graphene oxide dispersion liquid is 3%;
the mass fraction of acrylic acid in the acrylic acid mixed solution is 18%;
the mass fraction of the modified rosin resin is 3%.
The preparation method of the modified rosin resin comprises the following steps:
heating rosin resin to be molten, adding bisphenol A accounting for 10% of the mass of the rosin resin into the molten rosin resin, stirring for 10min, adding a catalyst, continuously stirring for 40min, cooling to 75 ℃, continuously stirring for 1 h, adding polyethyleneimine accounting for 1.5% of the mass of the rosin resin, adjusting the temperature to 118 ℃, preserving heat, stirring for 30min, vacuumizing for 40min, and naturally cooling to room temperature to obtain the modified rosin resin.
The catalyst is acrylic acid-9-anthracene methyl ester;
wherein the addition amount of the catalyst is 0.5% of the mass of the rosin resin.
The mixing mass ratio of the modified graphene oxide dispersion liquid to the acrylic acid mixed solution is 1:3;
wherein, the mixing and stirring speed of the modified graphene oxide dispersion liquid and the acrylic acid mixed solution is 150r/min, and the stirring time is 35min.
Example 2
The preparation method of the graphene conductive composite fiber comprises the following steps:
(1) Sequentially adding 3-aminopropyl triethoxysilane and ethanol into distilled water, adjusting the temperature to 55 ℃, keeping the temperature and stirring for 15min, then adding graphene, and performing ultrasonic treatment for 32min to obtain a mixed suspension;
(2) Carrying out high-speed centrifugation on the prepared mixed suspension, and then filtering to obtain a reactant;
(3) Washing the obtained reactant by adopting ethanol and distilled water for 18min, and then drying to obtain modified graphene;
(4) Mixing the prepared modified graphene with an oxidizing solution, and performing oxidation treatment to obtain modified graphene oxide;
(5) Uniformly dispersing the modified graphene oxide into ethyl acetate to prepare a modified graphene oxide dispersion liquid;
(6) Acrylic acid and modified rosin are added into ethyl acetate according to the mass ratio of 11:4:22 to prepare an acrylic acid mixed solution;
(7) Adding the modified graphene oxide dispersion liquid into an acrylic acid mixed solution, and uniformly stirring to obtain a spinning solution;
(8) Extruding the spinning solution obtained by the preparation at the speed of 9mL/h set by a double-pipe microinjection pump, spraying out the stock solution trickle through a needle head into a coagulation bath of glacial acetic acid, so that the stock solution trickle reaches a critical concentration, and separating out in the coagulation bath to form the graphene conductive composite fiber.
The mixing mass ratio of the 3-aminopropyl triethoxysilane to the ethanol to the distilled water is 4:11:16.
The mixing mass ratio of the ethanol to the graphene is 5:3;
the ethanol is absolute ethanol.
The mixing mass ratio of the modified graphene to the oxidizing liquid is 1:12;
the oxidizing solution is prepared from the following components in parts by weight: 2 parts of polyepoxysuccinic acid, 2 parts of phytic acid, 5 parts of sulfuric acid, 9 parts of nitric acid and 100 parts of deionized water.
The weight ratio of the polyepoxysuccinic acid to the phytic acid is 1:1.
The temperature of the oxidation treatment is 70 ℃;
the time of the oxidation treatment was 1 hour.
The mass fraction of the modified graphene oxide dispersion liquid is 4%;
the mass fraction of the acrylic acid in the acrylic acid mixed solution is 20%;
the mass fraction of the modified rosin resin is 4%.
The preparation method of the modified rosin resin comprises the following steps:
heating rosin resin to be molten, adding bisphenol A accounting for 10% of the mass of the rosin resin into the molten rosin resin, stirring for 10min, adding a catalyst, continuously stirring for 40min, cooling to 75 ℃, continuously stirring for 1 h, adding polyethyleneimine accounting for 1.5% of the mass of the rosin resin, regulating the temperature to 118 ℃, preserving heat, stirring for 30min, vacuumizing for 40min, and naturally cooling to room temperature to obtain the modified rosin resin. The catalyst is acrylic acid-9-anthracene methyl ester;
wherein the addition amount of the catalyst is 0.5% of the mass of the rosin resin.
The mixing mass ratio of the modified graphene oxide dispersion liquid to the acrylic acid mixed solution is 1:4;
wherein, the mixing and stirring speed of the modified graphene oxide dispersion liquid and the acrylic acid mixed solution is 150r/min, and the stirring time is 35min.
Example 3
The preparation method of the graphene conductive composite fiber comprises the following steps:
(1) Sequentially adding 3-aminopropyl triethoxysilane and ethanol into distilled water, adjusting the temperature to 55 ℃, keeping the temperature and stirring for 15min, then adding graphene, and performing ultrasonic treatment for 38min to obtain a mixed suspension;
(2) Carrying out high-speed centrifugation on the prepared mixed suspension, and then filtering to obtain a reactant;
(3) Washing the obtained reactant by adopting ethanol and distilled water for 16min, and then drying to obtain modified graphene;
(4) Mixing the prepared modified graphene with an oxidizing solution, and performing oxidation treatment to obtain modified graphene oxide;
(5) Uniformly dispersing the modified graphene oxide into ethyl acetate to prepare a modified graphene oxide dispersion liquid;
(6) Adding acrylic acid and modified rosin into ethyl acetate according to the mass ratio of 11:4:24 to prepare an acrylic acid mixed solution;
(7) Adding the modified graphene oxide dispersion liquid into an acrylic acid mixed solution, and uniformly stirring to obtain a spinning stock solution;
(8) Extruding the spinning solution obtained by the preparation at the speed of 9mL/h set by a double-pipe microinjection pump, spraying out the stock solution trickle through a needle head into a coagulating bath of glacial acetic acid, so that the stock solution trickle reaches a critical concentration, and separating out in the coagulating bath to form the graphene conductive composite fiber.
The mixing mass ratio of the 3-aminopropyl triethoxysilane to the ethanol to the distilled water is 4:11:18.
The mixing mass ratio of the ethanol to the graphene is 5:3;
the ethanol is absolute ethanol.
The mixing mass ratio of the modified graphene to the oxidizing liquid is 1:12;
the oxidizing solution is prepared from the following components in parts by weight: 2 parts of polyepoxysuccinic acid, 2 parts of phytic acid, 5 parts of sulfuric acid, 9 parts of nitric acid and 100 parts of deionized water.
The weight ratio of the polyepoxysuccinic acid to the phytic acid is 1:1.
The temperature of the oxidation treatment is 70 ℃;
the time of the oxidation treatment was 1 hour.
The mass fraction of the modified graphene oxide dispersion liquid is 4%;
the mass fraction of acrylic acid in the acrylic acid mixed solution is 22%;
the mass fraction of the modified rosin resin is 5%.
The preparation method of the modified rosin resin comprises the following steps:
heating rosin resin to be molten, adding bisphenol A accounting for 10% of the mass of the rosin resin into the molten rosin resin, stirring for 10min, adding a catalyst, continuously stirring for 40min, cooling to 75 ℃, continuously stirring for 1 h, adding polyethyleneimine accounting for 1.5% of the mass of the rosin resin, adjusting the temperature to 118 ℃, preserving heat, stirring for 30min, vacuumizing for 40min, and naturally cooling to room temperature to obtain the modified rosin resin.
The catalyst is acrylic acid-9-anthracene methyl ester;
wherein the addition amount of the catalyst is 0.5% of the mass of the rosin resin.
The mixing mass ratio of the modified graphene oxide dispersion liquid to the acrylic acid mixed solution is 1:4;
wherein, the mixing and stirring speed of the modified graphene oxide dispersion liquid and the acrylic acid mixed solution is 150r/min, and the stirring time is 35min.
Example 4
The preparation method of the graphene conductive composite fiber comprises the following steps:
(1) Sequentially adding 3-aminopropyl triethoxysilane and ethanol into distilled water, adjusting the temperature to 55 ℃, keeping the temperature and stirring for 15min, then adding graphene, and performing ultrasonic treatment for 40min to obtain a mixed suspension;
(2) Carrying out high-speed centrifugation on the prepared mixed suspension, and then filtering to obtain a reactant;
(3) Washing the obtained reactant with ethanol and distilled water for 20min, and then drying to obtain modified graphene;
(4) Mixing the prepared modified graphene with an oxidizing solution, and performing oxidation treatment to obtain modified graphene oxide;
(5) Uniformly dispersing the modified graphene oxide into ethyl acetate to prepare a modified graphene oxide dispersion liquid;
(6) Acrylic acid and modified rosin are added into ethyl acetate according to the mass ratio of 12:5:25 to prepare an acrylic acid mixed solution;
(7) Adding the modified graphene oxide dispersion liquid into an acrylic acid mixed solution, and uniformly stirring to obtain a spinning solution;
(8) Extruding the spinning solution obtained by the preparation at the speed of 10mL/h set by a double-pipe microinjection pump, spraying out the stock solution trickle through a needle head into a coagulation bath of glacial acetic acid, so that the stock solution trickle reaches a critical concentration, and separating out in the coagulation bath to form the graphene conductive composite fiber.
The mixing mass ratio of the 3-aminopropyl triethoxysilane to the ethanol to the distilled water is 5:12:20.
The mixing mass ratio of the ethanol to the graphene is 5:3;
the ethanol is absolute ethanol.
The mixing mass ratio of the modified graphene to the oxidizing liquid is 1:15;
the oxidizing solution is prepared from the following components in parts by weight: 3 parts of polyepoxysuccinic acid, 3 parts of phytic acid, 6 parts of sulfuric acid, 10 parts of nitric acid and 100 parts of deionized water.
The weight ratio of the polyepoxysuccinic acid to the phytic acid is 1:1.
The temperature of the oxidation treatment is 70 ℃;
the time of the oxidation treatment was 1 hour.
The mass fraction of the modified graphene oxide dispersion liquid is 5%;
the mass fraction of the acrylic acid in the acrylic acid mixed solution is 25%;
the mass fraction of the modified rosin resin is 3-6%.
The preparation method of the modified rosin resin comprises the following steps:
heating rosin resin to be molten, adding bisphenol A accounting for 10% of the mass of the rosin resin into the molten rosin resin, stirring for 10min, adding a catalyst, continuously stirring for 40min, cooling to 75 ℃, continuously stirring for 1 h, adding polyethyleneimine accounting for 1.5% of the mass of the rosin resin, regulating the temperature to 118 ℃, preserving heat, stirring for 30min, vacuumizing for 40min, and naturally cooling to room temperature to obtain the modified rosin resin. The catalyst is acrylic acid-9-anthracene methyl ester;
wherein the addition amount of the catalyst is 0.5% of the mass of the rosin resin.
The mixing mass ratio of the modified graphene oxide dispersion liquid to the acrylic acid mixed solution is 1:5;
wherein, the mixing and stirring speed of the modified graphene oxide dispersion liquid and the acrylic acid mixed solution is 150r/min, and the stirring time is 35min.
Comparative example 1: the difference from example 1 is that the graphene is not modified;
comparative example 2: the difference from example 1 is that no modified rosin resin was added to the spinning dope;
experiment
Fiber strength (experimental grip 10mm, draw speed 10 mm/min) of examples and comparative examples was tested using YG (B) 026H-250 fiber strength tester from Wenzhou Darong textile instruments, inc.:
TABLE 1
| Breaking strength/CN | |
| Example 1 | 32.5 |
| Example 2 | 33.1 |
| Example 3 | 33.7 |
| Example 4 | 32.8 |
| Comparative example 1 | 26.4 |
| Comparative example 2 | 22.1 |
As can be seen from table 1, the mechanical properties of the graphene conductive composite fiber prepared by the method provided by the invention are obviously improved, and the mechanical properties of the graphene conductive composite fiber can be further improved by introducing the modified rosin resin.
The diameters of cellulose fibers and graphene cellulose fibers were measured by a thickness gauge in an environment with a temperature of 25 ℃ and a humidity of 65%; selecting a test fiber with a length of 1cm, testing the conductivity of the fiber in the length by adopting a digital universal meter (UNIT UT 33D), wherein the test voltage range is-10V to +10V, the interval voltage is 0.5V, and testing the conductivity:
TABLE 2
As can be seen from table 2, the conductive performance of the graphene conductive composite fiber of the invention is greatly improved.
Fiber linear density testing, namely testing the linear density of the fiber by using a weighing method;
TABLE 3 Table 3
| Linear density dtex | |
| Example 1 | 3.15 |
| Example 2 | 3.08 |
| Example 3 | 3.11 |
| Example 4 | 3.13 |
As can be seen from table 3, the graphene conductive composite fiber prepared by the method has higher linear density, which indicates that the internal compactness is better, so that the graphene conductive composite fiber can show excellent mechanical properties.
Based on the sample of example 1, the influence of different mass fractions of modified rosin resin on breaking strength of the graphene conductive composite fiber is compared, as shown in fig. 1.
The foregoing description of the preferred embodiments of the invention should not be taken as limiting the scope of the invention, but rather should be understood to mean an equivalent embodiment, modified or changed in accordance with the teachings of the invention, without departing from the spirit of the invention.
Claims (9)
1. A preparation method of graphene conductive composite fibers is characterized by comprising the following steps: the method comprises the following steps:
(1) Sequentially adding 3-aminopropyl triethoxysilane and ethanol into distilled water, adjusting the temperature to 55 ℃, keeping the temperature and stirring for 15min, then adding graphene, and performing ultrasonic treatment for 30-40min to obtain a mixed suspension;
(2) Carrying out high-speed centrifugation on the prepared mixed suspension, and then filtering to obtain a reactant;
(3) Washing the obtained reactant by adopting ethanol and distilled water for 15-20min, and then drying to obtain modified graphene;
(4) Mixing the prepared modified graphene with an oxidizing solution, and performing oxidation treatment to obtain modified graphene oxide;
(5) Uniformly dispersing the modified graphene oxide into ethyl acetate to prepare a modified graphene oxide dispersion liquid;
(6) Adding acrylic acid and modified rosin resin into ethyl acetate according to the mass ratio of 10-12:3-5:20-25, and preparing to obtain an acrylic acid mixed solution;
(7) Adding the modified graphene oxide dispersion liquid into an acrylic acid mixed solution, and uniformly stirring to obtain a spinning stock solution;
(8) Extruding the spinning solution obtained by the preparation at the speed of 8-10mL/h set by a double-pipe microinjection pump, spraying out the stock solution trickle through a needle head into a coagulating bath of glacial acetic acid, so that the stock solution trickle reaches a critical concentration, and separating out in the coagulating bath to form the graphene conductive composite fiber;
the preparation method of the modified rosin resin in the step (6) comprises the following steps: heating rosin resin to be molten, adding bisphenol A accounting for 10% of the mass of the rosin resin into the molten rosin resin, stirring for 10min, adding a catalyst, continuously stirring for 40min, cooling to 75 ℃, continuously stirring for 1 h, adding polyethyleneimine accounting for 1.5% of the mass of the rosin resin, regulating the temperature to 118 ℃, preserving heat, stirring for 30min, vacuumizing for 40min, and naturally cooling to room temperature to obtain the modified rosin resin.
2. The method for preparing the graphene conductive composite fiber according to claim 1, wherein the method comprises the following steps: the mixing mass ratio of the 3-aminopropyl triethoxysilane to the ethanol to the distilled water is 3-5:10-12:15-20.
3. The method for preparing the graphene conductive composite fiber according to claim 2, wherein the method comprises the following steps: the mixing mass ratio of the ethanol to the graphene is 5:3;
the ethanol is absolute ethanol.
4. The method for preparing the graphene conductive composite fiber according to claim 1, wherein the method comprises the following steps: the mixing mass ratio of the modified graphene to the oxidizing liquid is 1:10-15 parts;
the oxidizing solution is prepared from the following components in parts by weight: 1-3 parts of polyepoxysuccinic acid, 1-3 parts of phytic acid, 4-6 parts of sulfuric acid, 8-10 parts of nitric acid and 100 parts of deionized water.
5. The method for preparing the graphene conductive composite fiber according to claim 4, wherein the method comprises the following steps: the weight ratio of the polyepoxysuccinic acid to the phytic acid is 1:1.
6. The method for preparing the graphene conductive composite fiber according to claim 1, wherein the method comprises the following steps: the temperature of the oxidation treatment is 70 ℃;
the time of the oxidation treatment was 1 hour.
7. The method for preparing the graphene conductive composite fiber according to claim 1, wherein the method comprises the following steps: the mass fraction of the modified graphene oxide dispersion liquid is 3-5%;
the mass fraction of acrylic acid in the acrylic acid mixed solution is 18-25%;
the mass fraction of the modified rosin resin is 3-6%.
8. The method for preparing the graphene conductive composite fiber according to claim 1, wherein the method comprises the following steps: the catalyst is acrylic acid-9-anthracene methyl ester;
wherein the addition amount of the catalyst is 0.5% of the mass of the rosin resin.
9. The method for preparing the graphene conductive composite fiber according to claim 1, wherein the method comprises the following steps: the mixing mass ratio of the modified graphene oxide dispersion liquid to the acrylic acid mixed solution is 1:3-5;
wherein, the mixing and stirring speed of the modified graphene oxide dispersion liquid and the acrylic acid mixed solution is 150r/min, and the stirring time is 35min.
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| CN103966844B (en) * | 2014-05-23 | 2016-03-23 | 青岛大学 | A kind of preparation method of graphene conductive composite fibre |
| CN104264260B (en) * | 2014-07-28 | 2016-04-13 | 四川大学 | A kind of graphene/nanometer cellulose composite fiber and preparation method thereof |
| CN109135144B (en) * | 2018-07-11 | 2021-07-20 | 四川羽玺新材料股份有限公司 | Graphene/acrylic resin composite film and preparation method thereof |
| CN109096750A (en) * | 2018-07-18 | 2018-12-28 | 桐城市明丽碳化硼制品有限公司 | A kind of graphene film and preparation method thereof |
| CN108976719A (en) * | 2018-07-23 | 2018-12-11 | 原晋波 | A kind of high strength graphite alkenyl heat conducting film and preparation method thereof |
| CN110885516A (en) * | 2019-12-17 | 2020-03-17 | 含山县仁盛鞋业有限公司 | Preparation method of wear-resistant plastic sandal material |
| CN111303574A (en) * | 2020-02-19 | 2020-06-19 | 长沙而道新能源科技有限公司 | Modified graphene epoxy acrylate resin and preparation method thereof |
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2022
- 2022-08-01 CN CN202210918397.7A patent/CN115233330B/en active Active
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