CN117845360A - A method for preparing high-strength and high-toughness heterocyclic aramid fiber reinforced with single-layer graphene oxide - Google Patents
A method for preparing high-strength and high-toughness heterocyclic aramid fiber reinforced with single-layer graphene oxide Download PDFInfo
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- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/88—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds
- D01F6/90—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds of polyamides
- D01F6/905—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds of polyamides of aromatic polyamides
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Abstract
本发明提供一种单层氧化石墨烯增强的高强高韧杂环芳纶纤维的制备方法。本发明选用杂环对位芳纶，将微量的氧化石墨烯直接引入到杂环对位芳纶聚合物的纺丝液中，刚性大分子结构的氧化石墨烯在芳纶凝固及拉伸过程中，不断与芳纶分子靠近，到一定距离后与芳纶链状分子间形成氢键，固定芳纶分子，防止芳纶回缩以及芳纶分子之间的润滑作用，提升杂环芳纶的拉伸倍率和取向度。经过后续的拉伸、热处理等步骤，得到高度取向的杂环芳纶，断裂强度可达6.28GPa，弹性模量达120GPa，断裂伸长率为5.5％。
The present invention provides a method for preparing a high-strength and high-toughness heterocyclic aramid fiber reinforced with a single layer of graphene oxide. The present invention selects heterocyclic para-aramid, and directly introduces a trace amount of graphene oxide into the spinning solution of the heterocyclic para-aramid polymer. The graphene oxide with a rigid macromolecular structure continuously approaches the aramid molecules during the coagulation and stretching process of the aramid, and forms hydrogen bonds with the aramid chain molecules after a certain distance, fixes the aramid molecules, prevents the aramid from shrinking, and lubricates the aramid molecules, thereby improving the stretching ratio and orientation of the heterocyclic aramid. After subsequent stretching, heat treatment and other steps, a highly oriented heterocyclic aramid is obtained, and the breaking strength can reach 6.28GPa, the elastic modulus can reach 120GPa, and the elongation at break is 5.5%.
Description
Technical Field
The invention relates to a preparation method of graphene oxide reinforced high-strength heterocyclic aramid fiber, which improves the mechanical properties of heterocyclic aramid fiber by adding a trace amount of graphene oxide into spinning solution of heterocyclic aramid polymer.
Background
The aramid fiber mainly comprises two kinds of wholly aromatic polyamide fiber and heterocyclic aromatic polyamide fiber, and can be divided into ortho-aramid fiber, para-aramid fiber (PPTA) and meta-aramid fiber (PMTA). The heterocyclic aromatic polyamide fiber is abbreviated as heterocyclic aramid fiber or aramid fiber III, is a high-performance organic fiber, has the characteristics of high strength and high modulus, and has excellent heat resistance, creep resistance and dielectric property.
At present, the improvement of the mechanical properties of the heterocyclic aramid fiber is mainly carried out by introducing other modified monomers to carry out quaternary copolymerization modification on the basis of the molecular structure of the existing heterocyclic aramid fiber, and the mechanism of the method is that diamine monomers containing polar side groups, such as 2-chloro-p-phenylenediamine, 2, 5-diaminobenzonitrile and the like, are selected, and the introduction of polar groups greatly improves the composite properties of the heterocyclic aramid fiber, so that the use strength of the heterocyclic aramid fiber after gum dipping is improved. However, the introduction of polar side groups reduces the thermal stability of the heterocyclic aramid and limits the application of the heterocyclic aramid in some fields.
Graphene is one of the thinnest and highest strength materials known at present, and has good toughness and good heat conduction performance. By introducing the graphene into the heterocyclic aramid fiber, the mechanical property and the thermal property of the heterocyclic aramid fiber are more excellent, and the application requirements of different fields are met. However, the graphene oxide is directly introduced into the heterocyclic aramid polymer solution, and the blending mode is generally limited to physical blending, so that on one hand, high-concentration doping cannot be realized, and on the other hand, the performance of the heterocyclic aramid polymer solution cannot be effectively improved. And graphene oxide or aminated graphene is added into the polymerization reaction liquid of the heterocyclic aramid fiber as a monomer, so that the reaction is not easy to control, and the stability of the mechanical property of the heterocyclic aramid fiber is finally affected.
Disclosure of Invention
The invention provides a preparation method of high Jiang Zahuan aramid fiber aiming at the problems in the background technology. The invention selects the heterocyclic para-aramid fiber, and introduces a trace amount of graphene oxide into the spinning solution of the heterocyclic para-aramid fiber polymer, wherein the heterocyclic para-aramid fiber is a flexible chain polymer, and the natural state of the heterocyclic para-aramid fiber tends to curl, especially in a solvent, and is in an irregular curled state. And graphene oxide is a lamellar molecule with a rigid macromolecular structure, when lamellar graphene oxide is added between aramid molecular chains, the graphene oxide is continuously close to the aramid molecules in the solidification and stretching processes, and after a certain distance, hydrogen bonds are formed between the graphene oxide lamellar molecules and the aramid chain molecules, and the lamellar graphene oxide plays a role in fixing the aramid molecules to prevent retraction and lubrication between the aramid molecules, so that the stretching multiplying power and the orientation degree of the heterocyclic aramid are improved. The highly oriented heterocyclic aramid fiber is obtained through the subsequent steps of stretching, heat treatment and the like, the breaking strength can reach 6.28GPa, the elastic modulus can reach 120GPa, and the breaking elongation is 5.5%.
Specifically, the invention adopts the following technical scheme: the preparation method of the aramid fiber comprises the following steps:
(1) Dispersing single-layer graphene oxide with the size of 2-5um in a dimethylacetamide solution, adding the dimethylacetamide solution of a heterocyclic para-aramid polymer, regulating the solid content, and uniformly stirring to obtain a solid content of 2wt% of the heterocyclic aramid polymer, wherein the graphene oxide accounts for the mass of the aramid polymerIs a spinning solution of (a); in the step, para-aramid containing heterocycle is adopted, so that the flexibility and polarity of molecules of the aramid are enhanced, and the aramid can be dissolved in DMAC polar solvent; the oxygen-containing functional group in the graphene oxide promotes the polarity of the graphene, so that the graphene oxide can be dissolved in a DMAC polar solvent. Since the solvents are the same, conditions are provided for their blending. The graphene oxide needs a single layer, if the compactness among aramid fiber molecules can be reduced by multiple layers, the size of the graphene oxide is most suitable at about 2-5um, the graphene oxide is suitable for the size of heterocyclic para-aramid fiber molecules, for example, a reinforced cement board, the cement particle size is about 10um, and the most suitable diameter of the reinforced steel bar is 10-30mm; the molecular diameter of the aramid fiber is about 2nm, and the GO is 2-5um in proper size. Too large a size, too many molecular chains of linked aramid fibers will reduce lubrication and fixation.
(2) And (5) spinning the spinning solution after defoaming treatment. During spinning, the polymer solution is sprayed into a coagulating bath through a spinneret tube with the aperture of 0.4-1.0mm to form nascent fibers, wherein the coagulating bath is an alcohol water solution with the volume fraction of 30% -40%; the alcohol is one or more of methanol, ethanol, propanol, sec-butanol and isobutanol; in the step, the density of 30% -40% of the alcohol aqueous solution is equal to or slightly greater than that of the aramid fiber solution prepared in the step 1, so that the primary fiber is ensured to be kept in a good state and pulled out of the coagulation bath with minimum force, and a foundation is laid for subsequent high strength.
(3) The nascent fiber enters a stretching bath which is deionized water, and the stretching ratio is 2.1-2.4 times;
(4) And (3) after washing and drying, carrying out heat treatment for 1-20 minutes in an air atmosphere at 340-440 ℃ to obtain the high-strength aramid fiber. In the step, GO is tightly combined with surrounding aramid fiber molecules to crystallize after high-temperature heat treatment, and the GO single layer has small size and large quantity although the occupied ratio is small, so that a large quantity of amorphous areas are crystallized, and the crystallinity of the fiber and the connection points of the amorphous areas are improved.
In certain embodiments herein, the heterocyclic para-aramid polymer is referred to as poly (p-benzimidazole) terephthalamide, particularly poly (p-phenylene terephthalamide) containing 2- (4-aminophenyl) -5-aminobenzimidazole.
In certain embodiments herein, in step 1, the mass fraction of graphene oxide in the dimethylacetamide solution of graphene oxide is
In certain embodiments herein, in step 4, the water wash is performed with deionized water at 70 ℃.
In certain embodiments herein, in step 4, the drying is performed for 40min under an air atmosphere of 80 ℃ and then for 30min under an air atmosphere of 150 ℃.
The single-layer graphene oxide provided by the invention refers to a graphene oxide raw material with a single-layer rate of more than 99.5%.
Compared with the prior art, the invention has the following steps:
according to the invention, through the physical doping of the single-layer graphene oxide, chemical induction is realized in a high-temperature process, the aramid fiber is modified to generate quality change, the breaking strength can reach 6.28GPa, the elastic modulus reaches 120GPa, the breaking elongation is 5.5%, and the fiber mechanical property is more stable. In addition, the preparation process of the invention is easier to control and the cost is lower.
Drawings
FIG. 1 is a process flow diagram of the present invention.
FIG. 2 is an aramid monofilament load test at different GO ratios.
Detailed Description
The following detailed description of the invention is merely illustrative of the invention, and is not intended to be limiting of the invention.
As shown in fig. 1, a continuous process flow diagram of the present invention is provided, comprising:
(1) Dispersing single-layer graphene oxide with the size of 2-5um in a dimethylacetamide solution, adding the dimethylacetamide solution of a heterocyclic para-aramid polymer, regulating the solid content, and uniformly stirring to obtain a solid content of 2wt% of the heterocyclic aramid polymer, wherein the graphene oxide accounts for the mass of the aramid polymerIs a spinning solution of (a);
in the embodiment of the invention, the heterocyclic para-aramid polymer refers to poly (p-benzimidazole) terephthalamide, in particular to poly (p-phenylene terephthalamide) containing 2- (4-aminophenyl) -5-aminobenzimidazole, and can be prepared by adopting a method described in 201010108545.6, and the structural formula is as follows:
wherein the ratio of m to n is less than or equal to 1.
(2) And (5) spinning the spinning solution after defoaming treatment. During spinning, the polymer solution is sprayed into a coagulating bath through a spinneret tube with the aperture of 0.4-1.0mm to form nascent fibers, wherein the coagulating bath is an alcohol water solution with the volume fraction of 30% -40%; the alcohol is one or more of methanol, ethanol, propanol, sec-butanol and isobutanol;
(3) The nascent fiber enters a stretching bath which is deionized water, and the stretching ratio is 2.1-2.4 times;
(4) And (3) after washing and drying, carrying out heat treatment for 1-20 minutes in an air atmosphere at 340-440 ℃ to obtain the high-strength aramid fiber.
The invention will be further illustrated with reference to examples.
In the following examples, the following formula of the polybenzimidazole terephthalamide was used, unless otherwise specified:
wherein the ratio of m to n is less than or equal to 1.
Example 1:
the graphene oxide is single-layer graphene oxide, the single-layer rate is more than 99.5%, and the warp size is 2-5um. And dispersing the single-layer graphene oxide in a dimethylacetamide solution to obtain graphene oxide dispersion liquid with the solid content of one ten thousandth.
Compounding the graphene oxide dispersion liquid with a polybenzimidazole terephthalamide solution with the solid content of 4wt%, regulating the solid content by using dimethylacetamide, and uniformly stirring to obtain a heterocyclic aramid fiber with the solid content of 2wt% and the graphene oxide accounting for the aramid fiber proportion ofIs a spinning solution of (a).
And (5) spinning the spinning solution after defoaming treatment. During spinning, the polymer solution is sprayed into a coagulating bath which is an ethanol water solution with the volume fraction of 30% through a spinneret tube with the aperture of 0.4mm to form nascent fibers. The as-spun fibers then enter a draw bath of deionized water at a draw ratio of 2.2 times. And then washing with 70 ℃ deionized water. And then carrying out two-stage continuous non-contact drying in an air atmosphere through a tube furnace, wherein the drying is respectively carried out at 80 ℃ for 40min and 150 ℃ for 30min. Finally, continuous non-contact heat treatment is carried out in an air atmosphere through a tube furnace, and the temperature is 340 ℃ for 20 minutes.
The breaking strength of the aramid fiber prepared by the embodiment is 5.69GPa, the elastic modulus is 109.4GPa, and the breaking elongation is 5.2%.
Example 2:
the graphene oxide is single-layer graphene oxide, the single-layer rate is more than 99.5%, and the warp size is 2-5um. And dispersing the single-layer graphene oxide in a dimethylacetamide solution to obtain graphene oxide dispersion liquid with the solid content of one ten thousandth.
Compounding the graphene oxide dispersion liquid with a polybenzimidazole terephthalamide solution with the solid content of 4%, regulating the solid content by using dimethylacetamide, and uniformly stirring to obtain a heterocyclic aramid fiber with the solid content of 2% and the graphene oxide accounting for the aramid fiber proportion ofIs a spinning solution of (a). And (5) spinning the spinning solution after defoaming treatment. During spinning, the polymer solution is sprayed into a coagulating bath which is 40% methanol water solution by volume percentage through a spinneret tube with the aperture of 0.4mm to form nascent fibers. The as-spun fibers then enter a draw bath of deionized water at a draw ratio of 2.3 times. And then washing with 70 ℃ deionized water. And then carrying out two-stage continuous non-contact drying in an air atmosphere through a tube furnace, wherein the drying is respectively carried out at 80 ℃ for 40min and 150 ℃ for 30min. Finally, continuous non-contact heat treatment is carried out in an air atmosphere through a tube furnace, and the temperature is 400 ℃ for 1 minute.
The breaking strength of the aramid fiber prepared by the embodiment is 6.04GPa, the elastic modulus is 118.5GPa, and the breaking elongation is 5.1%.
Example 3:
the graphene oxide is single-layer graphene oxide, the single-layer rate is more than 99.5%, and the warp size is 2-5um. And dispersing the single-layer graphene oxide in a dimethylacetamide solution to obtain graphene oxide dispersion liquid with the solid content of one ten thousandth.
Compounding the graphene oxide dispersion liquid with a polybenzimidazole terephthalamide solution with the solid content of 4%, regulating the solid content by using dimethylacetamide, and uniformly stirring to obtain a heterocyclic aramid fiber with the solid content of 2% and the graphene oxide accounting for the aramid fiber proportion ofIs a spinning solution of (a). And (5) spinning the spinning solution after defoaming treatment. During spinning, the polymer solution is sprayed into a coagulating bath through a spinneret tube with the aperture of 0.4mm to form nascent fibers, wherein the coagulating bath is a 30% volume percent propanol aqueous solution. The as-spun fibers then enter a draw bath of deionized water at a draw ratio of 2.4 times. And then washing with 70 ℃ deionized water. And then carrying out two-stage continuous non-contact drying in an air atmosphere through a tube furnace, wherein the drying is respectively carried out at 80 ℃ for 40min and 150 ℃ for 30min. Finally, continuous non-contact heat treatment is carried out in an air atmosphere through a tube furnace, and the temperature is 340 ℃ for 20 minutes.
The breaking strength of the aramid fiber prepared by the embodiment is 6.28GPa, the weight borne by the monofilament is more than 760g (as shown in figure 2), the elastic modulus reaches 114.2GPa, and the breaking elongation is 5.5%.
Example 4:
the graphene oxide is single-layer graphene oxide, the single-layer rate is more than 99.5%, and the warp size is 2-5um. And dispersing the single-layer graphene oxide in a dimethylacetamide solution to obtain graphene oxide dispersion liquid with the solid content of one ten thousandth.
Compounding the graphene oxide dispersion liquid with a polybenzimidazole terephthalamide solution with the solid content of 4%, regulating the solid content by using dimethylacetamide, and uniformly stirring to obtain a heterocyclic aramid fiber with the solid content of 2% and the graphene oxide accounting for the aramid fiber proportion ofIs a spinning solution of (a). And (5) spinning the spinning solution after defoaming treatment. During spinning, the polymer solution is sprayed into a coagulating bath which is an ethanol water solution with the volume fraction of 30% through a spinneret tube with the aperture of 1.0mm to form nascent fibers. The as-spun fibers then enter a draw bath of deionized water at a draw ratio of 2.3 times. And then washing with 70 ℃ deionized water. Then two-stage continuous non-contact drying is carried out in the air atmosphere by a tube furnace, and the drying is respectively carried out at 80 ℃ for 40minOven-drying at 150deg.C for 30min. Finally, continuous non-contact heat treatment is carried out in an air atmosphere through a tube furnace, and the temperature is 340 ℃ for 20 minutes.
The breaking strength of the aramid fiber prepared by the embodiment is 5.92GPa, the elastic modulus is 107.7GPa, and the breaking elongation is 5.5%.
Example 5:
the graphene oxide is single-layer graphene oxide, the single-layer rate is more than 99.5%, and the warp size is 2-5um. And dispersing the single-layer graphene oxide in a dimethylacetamide solution to obtain graphene oxide dispersion liquid with the solid content of one ten thousandth.
Compounding the graphene oxide dispersion liquid with a polybenzimidazole terephthalamide solution with the solid content of 4%, regulating the solid content by using dimethylacetamide, and uniformly stirring to obtain a heterocyclic aramid fiber with the solid content of 2% and the graphene oxide accounting for the aramid fiber proportion ofIs a spinning solution of (a). And (5) spinning the spinning solution after defoaming treatment. During spinning, the polymer solution is sprayed into a coagulating bath through a spinneret tube with the aperture of 0.5mm to form nascent fibers, wherein the coagulating bath is a 30% methanol/ethanol aqueous solution with the volume fraction, and the volume ratio of the methanol to the ethanol is 1/1. The as-spun fibers then enter a draw bath of deionized water at a draw ratio of 2.2 times. And then washing with 70 ℃ deionized water. And then carrying out two-stage continuous non-contact drying in an air atmosphere through a tube furnace, wherein the drying is respectively carried out at 80 ℃ for 40min and 150 ℃ for 30min. Finally, continuous non-contact heat treatment is carried out in an air atmosphere through a tube furnace, and the temperature is 350 ℃ for 17 minutes. The breaking strength of the aramid fiber prepared by the method is 5.8GPa, the elastic modulus is 128.9GPa, and the breaking elongation is 4.5%.
Example 6:
the graphene oxide is single-layer graphene oxide, the single-layer rate is more than 99.5%, and the warp size is 2-5um. And dispersing the single-layer graphene oxide in a dimethylacetamide solution to obtain graphene oxide dispersion liquid with the solid content of one ten thousandth.
Compounding the graphene oxide dispersion liquid with a polybenzimidazole terephthalamide solution with the solid content of 4%, regulating the solid content by using dimethylacetamide, and uniformly stirring to obtain a heterocyclic aramid fiber with the solid content of 2% and the graphene oxide accounting for the aramid fiber proportion ofIs a spinning solution of (a). And (5) spinning the spinning solution after defoaming treatment. During spinning, the polymer solution is sprayed into a coagulating bath which is an ethanol water solution with the volume fraction of 30% through a spinneret tube with the aperture of 0.5mm to form nascent fibers. The as-spun fibers then enter a draw bath of deionized water at a draw ratio of 2.4 times. And then washing with 70 ℃ deionized water. And then carrying out two-stage continuous non-contact drying in an air atmosphere through a tube furnace, wherein the drying is respectively carried out at 80 ℃ for 40min and 150 ℃ for 30min. Finally, continuous non-contact heat treatment is carried out in an air atmosphere through a tube furnace, and the temperature is 400 ℃ for 5 minutes.
The breaking strength of the aramid fiber prepared by the method is 5.65GPa, the elastic modulus is 125.5GPa, and the breaking elongation is 4.5%.
Comparative example 1
The poly-p-benzimidazole terephthalamide solution with the solid content of 4% is diluted by using dimethylacetamide, the solid content of the obtained heterocyclic aramid is 2% after uniform stirring, and the spinning solution is subjected to wet spinning after defoaming. During spinning, the polymer solution is sprayed into a coagulating bath which is an ethanol water solution with the volume fraction of 30% through a spinneret tube with the aperture of 0.5mm to form nascent fibers. The as-spun fibers then enter a draw bath of deionized water at a draw ratio of 2.0 times. And then washing with 70 ℃ deionized water. And then carrying out two-stage continuous non-contact drying in an air atmosphere through a tube furnace, wherein the drying is respectively carried out at 80 ℃ for 40min and 150 ℃ for 30min. Finally, continuous non-contact heat treatment is carried out in an air atmosphere through a tube furnace, and the temperature is 350 ℃ for 17 minutes. The breaking strength of the aramid fiber prepared by the method is 5.4GPa, the elastic modulus is 122.2GPa, and the breaking elongation is 4.5%.
Claims (6)
1. The preparation method of the single-layer graphene oxide reinforced high-strength high-toughness heterocyclic aramid fiber is characterized by comprising the following steps of:
(1) Dispersing single-layer graphene oxide with the size of 2-5um in a dimethylacetamide solution, adding the dimethylacetamide solution of a heterocyclic para-aramid polymer, regulating the solid content, and uniformly stirring to obtain a solid content of 2wt% of the heterocyclic aramid polymer, wherein the graphene oxide accounts for the mass of the aramid polymerIs a spinning solution of (a);
(2) And (5) spinning the spinning solution after defoaming treatment. During spinning, the polymer solution is sprayed into a coagulating bath through a spinneret tube with the aperture of 0.4-1.0mm to form nascent fibers, wherein the coagulating bath is an alcohol water solution with the volume fraction of 30% -40%; the alcohol is one or more of methanol, ethanol, propanol, sec-butanol and isobutanol;
(3) The nascent fiber enters a stretching bath which is deionized water, and the stretching ratio is 2.1-2.4 times;
(4) And (3) after washing and drying, carrying out heat treatment for 1-20 minutes in an air atmosphere at 340-440 ℃ to obtain the high-strength aramid fiber.
2. The method of claim 1, wherein the heterocyclic para-aramid polymer is poly-paraphenylene terephthalamide containing 2- (4-aminophenyl) -5-aminobenzimidazole.
3. The preparation method according to claim 1, wherein in the step 1, the mass fraction of the graphene oxide in the dimethylacetamide solution of the graphene oxide is
4. The method according to claim 1, wherein in step 4, the washing is performed with deionized water at 70 ℃.
5. The method according to claim 1, wherein in step 4, the drying is performed for 40min in an air atmosphere at 80 ℃ and then for 30min in an air atmosphere at 150 ℃.
6. The high-strength aramid fiber produced by the method of claim 1.
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| CN119685946A (en) * | 2024-12-18 | 2025-03-25 | 浙江大学 | Superfine high-strength meta-aramid fiber and preparation method thereof |
| CN119736732A (en) * | 2024-12-19 | 2025-04-01 | 浙江大学 | A high-strength and conductive heterocyclic aramid composite fiber and preparation method thereof |
| CN119736732B (en) * | 2024-12-19 | 2026-03-24 | 浙江大学 | A high-strength and conductive heterocyclic aramid composite fiber and its preparation method |
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| CN119736732B (en) * | 2024-12-19 | 2026-03-24 | 浙江大学 | A high-strength and conductive heterocyclic aramid composite fiber and its preparation method |
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