CN113005565A - Preparation method of high-strength bio-based composite fiber and composite fiber - Google Patents
Preparation method of high-strength bio-based composite fiber and composite fiber Download PDFInfo
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Images
Classifications
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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
- D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
- D01F8/18—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from other substances
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B15/00—Preparation of other cellulose derivatives or modified cellulose, e.g. complexes
- C08B15/02—Oxycellulose; Hydrocellulose; Cellulosehydrate, e.g. microcrystalline cellulose
- C08B15/04—Carboxycellulose, e.g. prepared by oxidation with nitrogen dioxide
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/06—Wet spinning methods
-
- 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
- D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
- D01F8/02—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from cellulose, cellulose derivatives, or proteins
Abstract
The invention discloses a preparation method of high-strength bio-based composite fiber and the composite fiber. The preparation method comprises the following steps: (1) preparing a graphene oxide solution: preparing a graphene oxide aqueous solution with the concentration of 8-15 g/L; (2) modification of graphene oxide: adding a proper amount of modifier B into the graphene oxide solution for modification to obtain solution C; (3) modifying cellulose, and dissolving in ionic water to obtain solution E; (4) preparing a spinning solution: mixing the solution C with the solution E to obtain a spinning solution; (5) preparing graphene oxide fibers; (6) and (3) placing the graphene oxide fiber in a reducing agent F, and reducing for 6-24h at the temperature of 20-120 ℃ to obtain the graphene composite fiber. The invention optimizes the structure of the fiber, and the prepared graphene fiber has obviously improved strength and good conductivity.
Description
Technical Field
The invention belongs to the field of graphene fiber preparation, and particularly relates to a preparation method of a high-strength bio-based composite fiber and the composite fiber.
Background
Along with the shortage of resources and the increase of cost, the development of the biomass fiber has profound significance for realizing low-carbon economy, energy conservation and emission reduction, the dependence of the biomass fiber on petroleum can be reduced, and the cost is greatly reduced. The development of biomass fibers at present mainly centers on two aspects: firstly, the raw material resources are exploited and new production technology is developed. For example, the biomass synthetic fibers such as polylactic acid, polybutylene succinate and polytrimethylene terephthalate are prepared by utilizing resources such as agricultural products and crop wastes and adopting a biosynthesis technology; the biomass regenerated fiber is produced by using marine biomasses such as chitin, seaweed and the like and various proteins as raw materials. Secondly, multidisciplinary cross fusion, and the composite fiber with excellent performance is designed and prepared. For example, the novel biomass fiber has the performances of water resistance, pollution resistance, high strength or flame retardance. The advantages of renewable and degradable utilization of the biomass material are fully exerted, and special new functions are given to the fiber.
The graphene has unique electrical, optical, thermal, mechanical and other properties and surprising antibacterial properties. Therefore, the graphene fiber is endowed with various performances such as electric conduction, heat conduction, flame retardance, antibiosis, ultraviolet protection, far infrared emission, electricity storage and the like, and can be used in multiple fields such as textile production, electronic communication, energy storage, signal conduction and the like. The most common method for preparing graphene fibers is to prepare graphene oxide fibers from graphene oxide by wet spinning, and then reduce the graphene oxide fibers to graphene fibers. Due to the reasons that the size and the shape of the graphene obtained by the chemical synthesis method are irregular, the graphene sheets are stacked disorderly and the like, the strength of the graphene fiber is not high, and the application of the graphene fiber is greatly hindered.
Disclosure of Invention
The purpose of the invention is as follows: the invention provides a preparation method of a high-strength bio-based composite fiber, which is characterized in that graphene and cellulose are respectively modified, so that the content of functional groups of the graphene and the cellulose is increased, and the graphene and the cellulose are tightly combined through chemical bonds; and simultaneously, the cellulose fills gaps among graphene sheets, so that the fiber is more compact. The strength of the composite fiber prepared by the method is improved.
The technical scheme is as follows: the preparation method of the high-strength bio-based composite fiber comprises the following steps:
(1) preparing a graphene oxide solution: preparing a graphene oxide aqueous solution with the concentration of 5-15g/L, and adjusting the pH value to 5-12 to obtain a spinning solution;
(2) modification of graphene oxide: adding a proper amount of modifier B into the graphene oxide solution, stirring at 20-80 ℃, and reacting for 1-24h to obtain a solution C containing modified graphene oxide; the modifier B is one or more of KH550, 4-aminobenzoic acid, isocyanate, polymethyl methacrylate, 2-bromoisobutyryl bromide and the like, and the addition amount of the modifier B is 1-10% of the mass of the graphene oxide;
(3) modification of cellulose: mixing cellulose with a proper amount of modifier D1, wherein the reaction temperature is 20-80 ℃, and the reaction time is 1-24 h; stirring for reaction, and adding a modifier D2, wherein the reaction temperature is 20-80 ℃, and the reaction time is 1-24 h; washing and drying the reaction product, and dissolving the reaction product in ionized water to obtain a solution E containing modified fibers, wherein the concentration of the modified cellulose in the solution E is 5-15 g/L; the modifier D1 is selected from one or more of ethanol, propanol, isopropanol, sulfuric acid, n-butyric acid, acetic acid, maleic anhydride and sodium hydroxide; the modifier D2 is one or more of sodium chloroacetate, sodium hypochlorite, chloroacetic acid, 2,6, 6-tetramethylpiperidine oxide and ethylene diamine tetraacetic acid;
(4) preparing a spinning solution: mixing the solution C and the solution E, and stirring for 0.5-6h at 20-70 ℃ to obtain a spinning solution; the mixing ratio of the solution C to the solution E is modified graphene oxide: the mass ratio of the modified cellulose is 100: 1-100: 30;
(5) preparing graphene oxide fibers: injecting the spinning solution into a coagulating bath at a speed of 0.1-1mL/min through a spinning nozzle of 0.2-1mm, and drying to obtain graphene oxide fibers;
(6) and (3) placing the graphene oxide fiber in a reducing agent F, and reducing for 6-24h at the temperature of 20-120 ℃ to obtain the graphene composite fiber.
In the step (3), the cellulose is wood fiber, cotton linter fiber or pulp fiber.
In the step (3), the modifier D1 is a mixed solution of sodium hydroxide solution and ethanol; the mass ratio of the sodium hydroxide to the cellulose is 5: 4-12.
The modifier D2 is sodium chloroacetate, and the mass ratio of the sodium chloroacetate to the cellulose is 1: 1-2.
In the step (1), adding a solution A to adjust the pH, wherein the solution A is one or more of KOH, NaOH or ammonia water.
In the step (2), the modifier B is KH 550.
In the step (5), the coagulating bath is one or more of aqueous solution of sodium hydroxide, aqueous solution of sodium chloride, aqueous solution of potassium chloride, aqueous solution of calcium chloride, ammonia water, ethanol, acetic acid, ethyl acetate, acetone and the like.
The coagulating bath is a mixed solution of acetic acid and ethanol with equal volume.
In the step (6), the reducing agent F is one or more of hydroiodic acid, hydrazine hydrate, sodium borohydride, hydrobromic acid, acetic acid, trifluoroacetic acid and vitamin C.
Preferably, the reducing agent F is hydroiodic acid
The invention also provides the composite fiber prepared by the preparation method.
Preferably, in the step (1), the concentration of the graphene oxide solution is 8-15 g/L; in the step (3), the concentration of the solution E is 8-15 g/L.
In the present invention, "%" is a mass percentage unless otherwise specified.
Has the advantages that: (1) according to the invention, the modified biomass fiber and the modified graphene are compounded through chemical bonds to prepare the bio-based composite fiber, so that the problem of low strength of the graphene fiber is solved, and the obtained fiber has high strength and good conductivity and can be applied to the fields of electric conduction, energy storage and the like; (2) according to the invention, graphene oxide is chemically modified, functional groups are grafted on the graphene oxide, cellulose is further subjected to carboxylation modification and functional groups such as carboxyl, the graphene oxide fiber is obtained by wet spinning after the graphene oxide fiber and the carboxyl are mixed, the graphene fiber is obtained by reduction, long-chain cellulose is used as a tie and is connected with graphene by strong acting forces such as chemical bonds, hydrogen bonds and the like, the binding force between graphene sheets is enhanced, meanwhile, the cellulose is inserted between graphene layers, the stacking of graphene is reduced, the orientation of the graphene sheets is improved, and the structure of the fiber is optimized; (3) the modified cellulose is prepared from natural fibers, so that the dependence on chemical raw materials is reduced, the component structure of the composite fiber is optimized, and the binding force of graphene and cellulose is effectively enhanced.
Drawings
FIG. 1 is a cross-sectional SEM image of a composite fiber obtained in example 2
FIG. 2 is an SEM image of the composite fiber obtained in example 2;
Detailed Description
Example 1: the preparation method of the high-strength bio-based composite fiber comprises the following steps:
(1) preparing a graphene oxide solution: preparing 8g/L graphene oxide (prepared by a Hummers method) aqueous solution, and adding ammonia water to adjust the pH value to 5.
(2) Modification of graphene oxide: KH550 accounting for 1% of the mass of the graphene oxide is added into the graphene oxide solution, and the mixture is stirred for 8 hours at 25 ℃ to obtain a solution C containing modified graphene oxide.
(3) Modification of cellulose: 5g of cotton linter fibers were mixed with 40mL of a 10% aqueous sodium hydroxide solution and 100mL of an absolute ethanol solution, and reacted at 40 ℃ for 4 hours with stirring. 5g of sodium chloroacetate are added and the reaction is stirred at 70 ℃ for 3 h. Washing with absolute ethyl alcohol, drying, and preparing the modified cotton linter fiber into a solution E with the concentration of 8g/L by using water as a solvent.
(4) Preparing a spinning solution: and mixing the solution C and the solution E according to the mass of the graphene oxide and the cellulose, wherein the mass of the graphene oxide and the cellulose is 100:1, and stirring for 1h at room temperature to obtain the spinning solution.
(5) Preparing graphene oxide fibers: and injecting the spinning solution into a coagulating bath through a 0.2mm spinning nozzle at the speed of 0.2mL/min to obtain the graphene oxide-based gel fiber. The coagulation bath was an equal volume of acetic acid/ethanol mixed solution.
(6) Reduction of graphene oxide fibers: the graphene oxide-based fibers are immersed in hydroiodic acid (mass concentration of 47%) and reduced at 60 ℃ for 12 h.
The strength of the fiber after reduction is 417MPa, and the conductivity is 5270S/m.
Example 2: the preparation method of the high-strength bio-based composite fiber comprises the following steps:
(1) preparing a graphene oxide solution: preparing 10g/L graphene oxide aqueous solution (prepared by a Hummers method), and adding ammonia water to adjust the pH value to 8.
(2) Modification of graphene oxide: adding KH550 accounting for 5% of the mass of the graphene oxide into the graphene oxide solution, and stirring for 5 hours at 25 ℃ to obtain a solution C containing modified graphene oxide.
(3) Modification of cellulose: 5g of cotton linter fibers were mixed with 40mL of 20% sodium hydroxide and 100mL of absolute ethanol solution and reacted at 50 ℃ with stirring for 2 h. 10g of sodium chloroacetate are added and the reaction is stirred at 60 ℃ for 4 h. Washing with absolute ethyl alcohol, drying, and preparing the modified cotton linter fiber into a solution E with the concentration of 10g/L by using water as a solvent.
(4) Preparing a spinning solution: and mixing the solution C and the solution E according to the mass of the graphene oxide and the cellulose, wherein the mass of the graphene oxide and the cellulose is 100:15, and stirring for 1h at room temperature. Obtaining the spinning solution.
(5) Preparing graphene oxide fibers: and (3) injecting the spinning solution into a coagulating bath at the speed of 0.2mL/min through a spinning nozzle of 0.25mm to obtain the graphene oxide-based gel fiber, wherein the coagulating bath is an acetic acid/ethanol mixed solution with the same volume.
(6) Reduction of graphene oxide fibers: the graphene oxide-based fiber is immersed in hydroiodic acid (47% by mass) and reduced at 60 ℃ for 12 hours. The cross-sectional scanning electron microscope image of the composite fiber obtained in this example is shown in fig. 1, and the surface of the composite fiber is shown in fig. 2.
The strength of the fiber after reduction is 475MPa, and the conductivity is 5100S/m.
Example 3: the preparation method of the high-strength bio-based composite fiber comprises the following steps:
(1) preparing a graphene oxide solution: preparing 15g/L graphene oxide (prepared by a Hummers method) aqueous solution. Ammonia was added to adjust the pH to 12.
(2) Modification of graphene oxide: adding KH550 accounting for 10% of the mass of the graphene oxide into the graphene oxide solution, and stirring for 4 hours at 25 ℃ to obtain a solution C.
(3) Modification of cellulose: 5g of cotton linter fibers were mixed with 40mL of 30% sodium hydroxide and 100mL of absolute ethanol solution and reacted at 40 ℃ with stirring for 1 h. 10g of sodium chloroacetate are added and the reaction is stirred at 80 ℃ for 2 h. Washing with absolute ethyl alcohol, drying, and preparing the modified cotton linter fiber into a solution E with the concentration of 15g/L by using water as a solvent.
(4) Preparing a spinning solution: and mixing the solution C and the solution E according to the mass of the graphene oxide and the cellulose, wherein the mass of the graphene oxide and the cellulose is 100:30, and stirring for 1h at room temperature to obtain the spinning solution.
(5) Preparing graphene oxide fibers: and injecting the spinning solution into a coagulating bath through a spinning nozzle of 0.3mm at the speed of 0.2mL/min to obtain the graphene oxide-based gel fiber. The coagulation bath was an equal volume of acetic acid/ethanol mixed solution.
(6) Reduction of graphene oxide fibers: the graphene oxide-based fibers were immersed in 47% hydroiodic acid (47% by mass) and reduced at 60 ℃ for 12 hours.
The strength of the fiber after reduction is 397MPa and the conductivity is 5040S/m.
Comparative example 1: (1) preparing a graphene oxide solution: a10 g/L aqueous solution of graphene oxide (prepared by the Hummers method) was prepared. Ammonia was added to adjust the pH to 8.
(2) Modification of graphene oxide: none.
(3) Modification of cellulose: none.
(4) Preparing a spinning solution: mixing the unmodified graphene oxide solution and cellulose according to the mass ratio of graphene oxide to cellulose of 100:10, and stirring for 1h at room temperature. Obtaining the spinning solution.
(5) Preparing graphene oxide fibers: and injecting the spinning solution into a coagulating bath through a 0.2mm spinning nozzle at the speed of 0.2mL/min to obtain the graphene oxide-based gel fiber. The coagulation bath was an equal volume of acetic acid/ethanol mixed solution.
(6) Reduction of graphene oxide fibers: the graphene oxide-based fiber is immersed in hydroiodic acid (47% by mass) and reduced at 60 ℃ for 12 hours.
The strength of the fiber after reduction is 279MPa, and the conductivity is 5940S/m.
The results are compared as follows:
TABLE 1 comparison of the properties of the fibers obtained under different preparation conditions
In summary, it can be seen from the results in table 1 that the graphene composite fiber prepared by using the modified graphene and the cellulose greatly improves the mechanical properties of the material, obviously improves the fiber strength, and has good conductivity.
Finally, it should be noted that the above list is only a few specific embodiments of the present invention. It is obvious that the invention is not limited to the above embodiment examples, but that many variations are possible. All modifications which can be derived or suggested by a person skilled in the art from the disclosure of the present invention are to be considered within the scope of the invention.
Claims (10)
1. A preparation method of high-strength bio-based composite fiber is characterized by comprising the following steps:
(1) preparing a graphene oxide solution: preparing a graphene oxide aqueous solution with the concentration of 5-15g/L, and adjusting the pH value to 5-12 to obtain a spinning solution;
(2) modification of graphene oxide: adding a proper amount of modifier B into the graphene oxide solution, stirring at 20-80 ℃, and reacting for 1-24h to obtain a solution C containing modified graphene oxide; the modifier B is one or more of KH550, 4-aminobenzoic acid, isocyanate, polymethyl methacrylate and 2-bromoisobutyryl bromide, and the addition amount of the modifier B is 1-10% of the mass of the graphene oxide;
(3) modification of cellulose: mixing cellulose with a proper amount of modifier D1, wherein the reaction temperature is 20-80 ℃, and the reaction time is 1-24 h; stirring for reaction, and adding a modifier D2, wherein the reaction temperature is 20-80 ℃, and the reaction time is 1-24 h; washing and drying the reaction product, and dissolving the reaction product in ionized water to obtain a solution E containing modified fibers, wherein the concentration of the modified cellulose in the solution E is 5-15 g/L; the modifier D1 is selected from one or more of ethanol, propanol, isopropanol, sulfuric acid, n-butyric acid, acetic acid, maleic anhydride and sodium hydroxide; the modifier D2 is one or more of sodium chloroacetate, sodium hypochlorite, chloroacetic acid, 2,6, 6-tetramethylpiperidine oxide and ethylene diamine tetraacetic acid;
(4) preparing a spinning solution: mixing the solution C and the solution E, and stirring for 0.5-6h at 20-70 ℃ to obtain a spinning solution; the mixing ratio of the solution C to the solution E is modified graphene oxide: the mass ratio of the modified cellulose is 100: 1-100: 30;
(5) preparing graphene fibers: injecting the spinning solution into a coagulating bath at a speed of 0.1-1mL/min through a spinning nozzle of 0.2-1mm, and drying to obtain graphene oxide fibers;
(6) and (3) placing the graphene oxide fiber in a reducing agent F, and reducing for 6-24h at the temperature of 20-120 ℃ to obtain the graphene composite fiber.
2. The method for preparing high-strength bio-based composite fiber according to claim 1, wherein in the step (3), the cellulose is wood fiber, cotton linter fiber or pulp fiber.
3. The method for preparing high-strength bio-based composite fibers according to claim 1, wherein in the step (3), the modifier D1 is a mixed solution of sodium hydroxide solution and ethanol; the mass ratio of the sodium hydroxide to the cellulose is 5: 4-12.
4. The preparation method of the high-strength bio-based composite fiber according to claim 1, wherein the modifier D2 is sodium chloroacetate, and the mass ratio of the sodium chloroacetate to the cellulose is 1: 1-2.
5. The method for preparing high-strength bio-based composite fiber according to claim 1, wherein in the step (1), solution A is added to adjust the pH, wherein the solution A is one or more of KOH, NaOH or ammonia water.
6. The method for preparing high-strength bio-based composite fiber according to claim 1, wherein in the step (2), the modifier B is KH 550.
7. The method for preparing high strength bio-based composite fiber according to claim 1, wherein in the step (5), the coagulation bath is one or more of aqueous solution of sodium hydroxide, aqueous solution of sodium chloride, aqueous solution of potassium chloride, aqueous solution of calcium chloride, ammonia water, ethanol, acetic acid, ethyl acetate, acetone, etc.
8. The method of claim 7, wherein the coagulation bath is a mixed solution of acetic acid and ethanol in equal volume.
9. The method according to claim 1, wherein in step (6), the reducing agent F is one or more of hydroiodic acid, hydrazine hydrate, sodium borohydride, hydrobromic acid, acetic acid, trifluoroacetic acid, and vitamin C.
10. A composite fiber produced by the production method as claimed in any one of claims 1 to 9.
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| CN113802200A (en) * | 2021-08-30 | 2021-12-17 | 兰州大学 | Functionalized graphene oxide/bacterial cellulose composite fiber and preparation method and application thereof |
| CN114959948A (en) * | 2022-02-25 | 2022-08-30 | 南京工业大学 | Preparation method of high-performance graphene fiber and graphene fiber |
| CN115449922A (en) * | 2022-09-26 | 2022-12-09 | 马鞍山皖烯新材料科技有限公司 | Preparation method of high-performance graphene fiber |
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| CN109868527A (en) * | 2019-01-28 | 2019-06-11 | 北京服装学院 | A kind of preparation method of modified graphene fiber |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113802200A (en) * | 2021-08-30 | 2021-12-17 | 兰州大学 | Functionalized graphene oxide/bacterial cellulose composite fiber and preparation method and application thereof |
| CN114959948A (en) * | 2022-02-25 | 2022-08-30 | 南京工业大学 | Preparation method of high-performance graphene fiber and graphene fiber |
| CN114959948B (en) * | 2022-02-25 | 2023-10-27 | 南京工业大学 | Preparation method of high-performance graphene fiber and graphene fiber |
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