阅读说明：本技术 一种石墨烯高强抗冲击芳纶纤维及其制备方法 (Graphene high-strength impact-resistant aramid fiber and preparation method thereof ) 是由 沙嫣 沙晓林 马立国 于 2021-08-24 设计创作，主要内容包括：本发明公开了一种石墨烯高强抗冲击芳纶纤维及其制备方法,该方法包含：步骤1,按比例称取各原料；步骤2,制备石墨烯芳纶纺丝液；步骤3,将纺丝液离心除盐后装入反应罐进行脱泡,得到纺丝原液,然后进行干湿法纺丝；步骤4,将石墨烯芳纶纤维置于等离子体反应室内,抽真空,填充氮气,调整气压,进行等离子体处理后取出；步骤5,配制涂覆浆料,充分搅拌,保持浆料温度,并将改性石墨烯芳纶纤维置入浆槽中,上浆处理,干燥卷绕。本发明还提供了通过该方法制备的石墨烯高强抗冲击芳纶纤维。本发明制备的石墨烯高强抗冲击芳纶纤维,具有高强抗冲击、抗菌、抗紫外等功能,提升了芳纶纤维附加值,扩展了芳纶纤维的使用范围。(The invention discloses a graphene high-strength impact-resistant aramid fiber and a preparation method thereof, wherein the method comprises the following steps: step 1, weighing raw materials in proportion; step 2, preparing a graphene aramid spinning solution; step 3, centrifugally desalting the spinning solution, filling the spinning solution into a reaction tank for defoaming to obtain a spinning solution, and then carrying out dry-wet spinning; step 4, placing the graphene aramid fiber in a plasma reaction chamber, vacuumizing, filling nitrogen, adjusting air pressure, performing plasma treatment, and taking out; and 5, preparing coating slurry, fully stirring, keeping the temperature of the slurry, putting the modified graphene aramid fiber into a slurry tank, performing sizing treatment, drying and winding. The invention also provides the graphene high-strength impact-resistant aramid fiber prepared by the method. The graphene high-strength impact-resistant aramid fiber prepared by the invention has the functions of high strength impact resistance, antibiosis, ultraviolet resistance and the like, the additional value of the aramid fiber is improved, and the application range of the aramid fiber is expanded.)

1. A preparation method of graphene high-strength impact-resistant aramid fiber is characterized by comprising the following steps:

step 1, weighing raw materials in proportion; the raw materials comprise an aramid fiber spinning material, a graphene material, a modifier and water-based slurry;

step 2, preparing a graphene aramid spinning solution;

step 3, centrifuging and desalting the graphene aramid fiber spinning solution obtained in the step 2, then filling the solution into a reaction tank for defoaming to obtain a spinning solution, then carrying out dry-wet spinning, and carrying out processes of spinning, stretching, washing, drying, dry-heat stretching, shaping, oiling and rolling to obtain the graphene aramid fiber composite fiber;

step 4, placing the graphene aramid fiber obtained in the step 3 in a plasma reaction chamber, vacuumizing, filling nitrogen, adjusting air pressure, performing plasma treatment, and taking out to obtain the graphene aramid fiber subjected to surface modification treatment;

and 5, preparing coating slurry, fully stirring, keeping the temperature of the slurry, putting the modified graphene aramid fiber obtained in the step 4 into a slurry tank, performing sizing treatment, and then drying and winding to obtain the high-strength impact-resistant graphene aramid fiber.

2. The preparation method of the graphene high-strength impact-resistant aramid fiber according to claim 1, wherein in the step 1, the raw materials comprise, by mass: 80-99% of aramid fiber spinning material, 0.1-15% of graphene material, 0.1-1% of modifier and 0.1-15% of water-based slurry; the graphene material is graphene or graphene oxide prepared by any one of a mechanical stripping method, a chemical vapor deposition method and a redox method; the modifier is one or more of polyvinyl alcohol, polyethylene glycol, polyvinylpyrrolidone and silane coupling agent; the water-based sizing agent is any one or more of water-based PU resin, water-based acrylic resin, water-based polyester resin, water-based epoxy resin and water-based alkyd resin sizing agent.

3. The preparation method of the graphene high-strength impact-resistant aramid fiber according to claim 1, wherein in the step 2, the aramid fiber spinning material is prepared by taking isophthaloyl dichloride and 2- (4-aminophenyl) -5-aminobenzimidazole as main raw materials, taking N, N-dimethylacetamide as a solvent, firstly adding N, N-dimethylacetamide and lithium chloride into a reaction kettle under the protection of nitrogen, starting stirring, then adding 2- (4-aminophenyl) -5-aminobenzimidazole, cooling to 0-10 ℃ after complete dissolution, then adding isophthaloyl dichloride in batches, keeping the temperature of the reaction system not more than 15-30 ℃, continuing to react for 40min after the addition is finished, and finally adding lithium hydroxide for neutralization to obtain an aramid fiber resin solution with a solid content of 15-30% by mass, and adding a graphene material, and uniformly mixing to obtain the graphene aramid spinning solution.

4. The preparation method of the graphene high-strength impact-resistant aramid fiber according to claim 3, wherein in the step 2, the adopted aramid fiber spinning material comprises the following components in percentage by mass: 50 to 80 percent of N, N-dimethylacetamide, 0.1 to 5 percent of lithium chloride, 1 to 25 percent of 2- (4-aminophenyl) -5-aminobenzimidazole, 1 to 20 percent of isophthaloyl dichloride and 0.1 to 5 percent of lithium hydroxide.

5. The preparation method of the graphene high-strength impact-resistant aramid fiber according to claim 1, wherein in the step 3, the solid content in the spinning solution is 15-30% by mass; the temperature of the spinning dope was 20 ℃.

6. The preparation method of the graphene high-strength impact-resistant aramid fiber according to claim 5, wherein in the step 3, the spinning speed is 10-15 m/min; the dry heat stretching temperature is 290-320 ℃; the heat setting temperature is 270-290 ℃, and the time is 1-5 min.

7. The preparation method of the graphene high-strength impact-resistant aramid fiber according to claim 5, wherein a coagulation bath is adopted in the step 3, the first coagulation bath is an N, N-dimethylacetamide aqueous solution with the concentration of 30-50% by mass, and the temperature is 10-20 ℃; the second coagulating bath is a water-washing coagulating bath of pure water, and the temperature is 70-90 ℃; finally, an air bath with a height of (20. + -. 5) mm.

8. The preparation method of the graphene high-strength impact-resistant aramid fiber as claimed in claim 1, wherein in the step 4, nitrogen is filled, the air pressure is adjusted to 50-70Pa, plasma treatment is performed, the treatment power is 100-150W, and the treatment time is 1-5 min.

9. The preparation method of the graphene high-strength impact-resistant aramid fiber according to claim 1, wherein in the step 5, the graphene material and the modifier are added into the aqueous slurry to prepare the coating slurry, the coating slurry is fully stirred for 30-50min, the temperature of the slurry is kept at 30-50 ℃, the modified graphene aramid fiber is placed into a continuous slurry tank, the sizing treatment is carried out for 5-10s, and then the modified graphene aramid fiber is dried and wound.

10. Graphene high-strength impact-resistant aramid fibers prepared by the method of any one of claims 1 to 9.

Technical Field

The invention relates to a high-strength impact-resistant graphene aramid composite fiber and a preparation method thereof, and particularly relates to a high-strength impact-resistant graphene aramid fiber and a preparation method thereof.

Background

Graphene is a two-dimensional material with carbon atoms arranged in a hexagon, and graphene oxide has a carboxyl group, an epoxy group, a hydroxyl group and other group-containing modifications on the surface layer of graphene. The graphene oxide is simple in preparation process and low in raw material cost, and meanwhile, the graphene oxide is less prone to agglomeration compared with graphene in actual operation, so that the graphene oxide can be widely applied to large-scale industrial production.

Aramid fiber is short for aromatic polyamide fiber, is a novel high-tech synthetic fiber, and is a linear polymer formed by connecting aromatic groups and amide groups. Since the aromatic group replaces the aliphatic group, the flexibility of the molecular chain is reduced and the rigidity is enhanced, reflected in the fiber properties, and the heat resistance and the initial modulus are both significantly increased.

Disclosure of Invention

The invention aims to provide a high-strength impact-resistant graphene aramid composite fiber and a preparation method thereof.

In order to achieve the above object, the present invention provides a method for preparing a graphene high-strength impact-resistant aramid fiber, wherein the method comprises: step 1, weighing raw materials in proportion; the raw materials comprise an aramid fiber spinning material, a graphene material, a modifier and water-based slurry; step 2, preparing a graphene aramid spinning solution; step 3, centrifuging and desalting the graphene aramid fiber spinning solution obtained in the step 2, then filling the solution into a reaction tank for defoaming to obtain a spinning solution, then carrying out dry-wet spinning, and carrying out processes of spinning, stretching, washing, drying, dry-heat stretching, shaping, oiling and rolling to obtain the graphene aramid fiber composite fiber; step 4, placing the graphene aramid fiber obtained in the step 3 in a plasma reaction chamber, vacuumizing, filling nitrogen, adjusting air pressure, performing plasma treatment, and taking out to obtain the graphene aramid fiber subjected to surface modification treatment; and 5, preparing coating slurry, fully stirring, keeping the temperature of the slurry, putting the modified graphene aramid fiber obtained in the step 4 into a slurry tank, performing sizing treatment, and then drying and winding to obtain the high-strength impact-resistant graphene aramid fiber.

The preparation method of the graphene high-strength impact-resistant aramid fiber comprises the following raw materials in step 1 in percentage by mass: 80-99% of aramid fiber spinning material, 0.1-15% of graphene material, 0.1-1% of modifier and 0.1-15% of water-based slurry; the graphene material is graphene or graphene oxide prepared by any one of a mechanical stripping method, a chemical vapor deposition method and a redox method; the modifier is one or more of polyvinyl alcohol, polyethylene glycol, polyvinylpyrrolidone and silane coupling agent; the water-based sizing agent is any one or more of water-based PU resin, water-based acrylic resin, water-based polyester resin, water-based epoxy resin and water-based alkyd resin sizing agent.

The preparation method of the graphene high-strength impact-resistant aramid fiber comprises the step 2, the aramid fiber spinning material is prepared by taking isophthaloyl dichloride and 2- (4-aminophenyl) -5-aminobenzimidazole as main raw materials, taking N, N-dimethylacetamide as a solvent, firstly adding N, N-dimethylacetamide and lithium chloride into a reaction kettle under the protection of nitrogen, starting stirring, then adding 2- (4-aminophenyl) -5-aminobenzimidazole, cooling to 0-10 ℃ after complete dissolution, then adding isophthaloyl dichloride in batches, keeping the temperature of a reaction system not exceeding 15-30 ℃, continuing to react for 40min after the addition is finished, and finally adding lithium hydroxide for neutralization to obtain an aramid resin solution with a solid content of 15-30% by mass percentage, and adding a graphene material, and uniformly mixing to obtain the graphene aramid spinning solution.

The preparation method of the graphene high-strength impact-resistant aramid fiber comprises the following steps of in step 2, wherein the aramid fiber spinning material comprises the following components in percentage by mass: 50 to 80 percent of N, N-dimethylacetamide, 0.1 to 5 percent of lithium chloride, 1 to 25 percent of 2- (4-aminophenyl) -5-aminobenzimidazole, 1 to 20 percent of isophthaloyl dichloride and 0.1 to 5 percent of lithium hydroxide.

In the preparation method of the graphene high-strength impact-resistant aramid fiber, in the step 3, the solid content in the spinning solution is 15-30% by mass; the temperature of the spinning dope was 20 ℃.

According to the preparation method of the graphene high-strength impact-resistant aramid fiber, in the step 3, the spinning speed is 10-15 m/min; the dry heat stretching temperature is 290-320 ℃; the heat setting temperature is 270-290 ℃, and the time is 1-5 min.

The preparation method of the graphene high-strength impact-resistant aramid fiber comprises the following steps of (1) adopting a coagulation bath in the step (3), wherein the first coagulation bath is an N, N-dimethylacetamide aqueous solution with the concentration of 30-50% by mass, and the temperature is 10-20 ℃; the second coagulating bath is a water-washing coagulating bath of pure water, and the temperature is 70-90 ℃; finally, an air bath with a height of (20. + -. 5) mm.

In the step 4, nitrogen is filled, the air pressure is adjusted to 50-70Pa, and plasma treatment is performed at a treatment power of 100-150W for 1-5 min.

In the step 5, the graphene material and the modifier are added into the aqueous slurry to prepare the coating slurry, the coating slurry is fully stirred for 30-50min, the temperature of the slurry is kept at 30-50 ℃, the modified graphene aramid fiber is placed into a continuous slurry tank, the sizing treatment is carried out for 5-10s, and then the drying and winding are carried out.

The invention also provides the graphene high-strength impact-resistant aramid fiber prepared by the method.

The graphene high-strength impact-resistant aramid fiber and the preparation method thereof provided by the invention have the following advantages:

according to the invention, the graphene high-strength impact-resistant aramid fiber is prepared by utilizing an improved graphene oxide solution preparation and dispersion system and an improved aramid fiber production system, so that the aramid composite fiber has the functions of high strength impact resistance, antibiosis, ultraviolet resistance and the like, and the application range of the graphene aramid fiber is expanded.

The aramid composite fiber prepared by the graphene modification technology has better breaking strength and impact resistance, and can be used in the fields of military affairs and other composite material protection.

The high-strength impact-resistant graphene aramid composite fiber prepared by the method is simple in process, easy to operate, low in cost, high in economic benefit and suitable for large-scale industrial production.

Detailed Description

The following further describes embodiments of the present invention.

The invention provides a preparation method of graphene high-strength impact-resistant aramid fiber, which comprises the following steps:

step 1, weighing raw materials in proportion; the raw materials comprise an aramid fiber spinning material, a graphene material, a modifier and water-based slurry; step 2, preparing a graphene aramid spinning solution; step 3, centrifuging and desalting the graphene aramid fiber spinning solution obtained in the step 2, then filling the solution into a reaction tank for defoaming to obtain a spinning solution, then carrying out dry-wet spinning, and carrying out processes of spinning, stretching, washing, drying, dry-heat stretching, shaping, oiling, rolling and the like to obtain the graphene aramid fiber composite fiber; step 4, placing the graphene aramid fiber obtained in the step 3 in a plasma reaction chamber, vacuumizing, filling nitrogen, adjusting air pressure, performing plasma treatment, and taking out to obtain the graphene aramid fiber subjected to surface modification treatment; and 5, preparing coating slurry, fully stirring, keeping the temperature of the slurry, putting the modified graphene aramid fiber obtained in the step 4 into a slurry tank, performing sizing treatment, and then drying and winding to obtain the high-strength impact-resistant graphene aramid fiber.

Preferably, the raw materials in the step 1 comprise, by mass: 80-99% of aramid fiber spinning material, namely aramid fiber spinning solution, 0.1-15% of graphene material, 0.1-1% of modifier and 0.1-15% of water-based slurry; the graphene material is graphene or graphene oxide prepared by any one of a mechanical stripping method, a chemical vapor deposition method, a redox method and the like; the modifier is one or more of polyvinyl alcohol, polyethylene glycol, polyvinylpyrrolidone (PVP), silane coupling agent and the like; the water-based sizing agent is one or more of water-based PU resin (polyurethane), water-based acrylic resin, water-based polyester resin, water-based epoxy resin, water-based alkyd resin sizing agent and the like.

In the step 2, the adopted aramid fiber spinning material takes isophthaloyl dichloride and 2- (4-aminophenyl) -5-aminobenzimidazole as main raw materials, taking N, N-dimethylacetamide as a solvent, firstly adding N, N-dimethylacetamide and lithium chloride into a reaction kettle under the protection of nitrogen, stirring, adding 2- (4-aminophenyl) -5-aminobenzimidazole, cooling to 0-minus 10 ℃ after complete dissolution, then adding m-phthaloyl chloride in batches, keeping the temperature of the reaction system not to exceed 15-30 ℃, continuing the reaction for 40min after the addition is finished, finally adding lithium hydroxide for neutralization, obtaining an aramid fiber resin solution with the solid content of 15-30% by mass, adding a graphene material, and uniformly mixing to obtain the graphene aramid fiber spinning solution.

In the step 2, the aramid fiber spinning material comprises the following components in percentage by mass: 50 to 80 percent of N, N-dimethylacetamide, 0.1 to 5 percent of lithium chloride, 1 to 25 percent of 2- (4-aminophenyl) -5-aminobenzimidazole, 1 to 20 percent of isophthaloyl dichloride and 0.1 to 5 percent of lithium hydroxide.

In the step 3, the solid content in the spinning solution is 15-30% by mass percent; the temperature of the spinning dope was 20 ℃.

In the step 3, the spinning speed is 10-15 m/min; the dry heat stretching temperature is 290-320 ℃; the heat setting temperature is 270-290 ℃, and the time is 1-5 min.

Adopting a coagulation bath in the step 3, wherein the first coagulation bath is an N, N-dimethylacetamide aqueous solution with the concentration of 30-50% by mass, and the temperature is 10-20 ℃; the second coagulating bath is a water-washing coagulating bath of pure water, and the temperature is 70-90 ℃; finally, an air bath with a height of (20. + -. 5) mm.

In step 4, nitrogen is filled, the pressure is adjusted to 50-70Pa, and plasma treatment is carried out with the treatment power of 100-150W and the treatment time of 1-5 min.

And step 5, adding the graphene material and the modifier into the aqueous slurry, preparing coating slurry, fully stirring for 30-50min, keeping the temperature of the slurry at 30-50 ℃, placing the modified graphene aramid fiber into a continuous slurry tank, performing sizing treatment for 5-10s, and then drying and winding.

The equipment used in the present invention is known to those skilled in the art.

The invention also provides the graphene high-strength impact-resistant aramid fiber prepared by the method.

The graphene high-strength impact-resistant aramid fiber and the preparation method thereof provided by the invention are further described below with reference to the examples.

Example 1

A preparation method of graphene high-strength impact-resistant aramid fiber comprises the following steps:

step 1, weighing raw materials in proportion; the raw materials comprise an aramid fiber spinning material, a graphene material, a modifier and water-based slurry.

Preferably, each raw material comprises the following components in percentage by mass: 99% of aramid fiber spinning material, 0.1% of graphene material, 0.1% of modifier and 0.8% of water-based slurry.

The graphene material is prepared by a mechanical stripping method.

The modifier is a mixture of polyvinyl alcohol and polyethylene glycol according to the mass ratio of 1: 1.

The aqueous sizing agent is aqueous PU resin.

And 2, preparing the graphene aramid spinning solution.

The aramid fiber spinning material is prepared with isophthaloyl dichloride and 2- (4-aminophenyl) -5-aminobenzimidazole as main material, taking N, N-dimethylacetamide as a solvent, firstly adding N, N-dimethylacetamide and lithium chloride into a reaction kettle under the protection of nitrogen, stirring, adding 2- (4-aminophenyl) -5-aminobenzimidazole, cooling to 0-minus 10 ℃ after complete dissolution, then adding m-phthaloyl chloride in batches, keeping the temperature of the reaction system not to exceed 15-30 ℃, continuing the reaction for 40min after the addition is finished, finally adding lithium hydroxide for neutralization, obtaining an aramid fiber resin solution with the solid content of 15-30% by mass, adding a graphene material, and uniformly mixing to obtain the graphene aramid fiber spinning solution.

The aramid fiber spinning material comprises the following components in percentage by mass: 80% of N, N-dimethylacetamide, 0.1% of lithium chloride, 1% of 2- (4-aminophenyl) -5-aminobenzimidazole, 18.8% of isophthaloyl dichloride and 0.1% of lithium hydroxide.

Step 3, centrifuging and desalting the graphene aramid fiber spinning solution obtained in the step 2, and then filling the graphene aramid fiber spinning solution into a reaction tank for defoaming to obtain a spinning stock solution, wherein the solid content in the spinning stock solution is 15-30% by mass; the temperature of the spinning dope was 20 ℃. And then carrying out dry-wet spinning, and carrying out processes of spinning, stretching, washing, drying, dry-hot stretching, sizing, oiling and rolling to obtain the graphene aramid composite fiber.

The spinning speed is 10-15 m/min; the dry heat stretching temperature is 290-320 ℃; the heat setting temperature is 270-290 ℃, and the time is 1-5 min.

Adopting a coagulation bath in the step 3, wherein the first coagulation bath is an N, N-dimethylacetamide aqueous solution with the concentration of 30-50% by mass, and the temperature is 10-20 ℃; the second coagulating bath is a water-washing coagulating bath of pure water, and the temperature is 70-90 ℃; finally, an air bath with a height of (20. + -. 5) mm.

And 4, placing the graphene aramid fiber obtained in the step 3 in a plasma reaction chamber, vacuumizing, filling nitrogen, adjusting the air pressure to 50-70Pa, performing plasma treatment, and taking out to obtain the graphene aramid fiber subjected to surface modification treatment. The power of the plasma treatment is 100-150W, and the treatment time is 1-5 min.

And 5, adding the graphene material and the modifier into the aqueous slurry, preparing coating slurry, fully stirring for 30-50min, keeping the temperature of the slurry at 30-50 ℃, placing the modified graphene aramid fiber obtained in the step 4 into a continuous slurry tank, performing sizing treatment for 5-10s, and then drying and winding to obtain the high-strength impact-resistant graphene aramid fiber.

The embodiment also provides the graphene high-strength impact-resistant aramid fiber prepared by the method.

Example 2

A preparation method of graphene high-strength impact-resistant aramid fiber comprises the following steps:

step 1, weighing raw materials in proportion; the raw materials comprise an aramid fiber spinning material, a graphene material, a modifier and water-based slurry.

Preferably, each raw material comprises the following components in percentage by mass: 80.8% of aramid fiber spinning material, 4% of graphene material, 0.2% of modifier and 15% of water-based slurry.

The graphene material is prepared by a chemical vapor deposition method.

The modifier is a mixture of polyvinylpyrrolidone and polyethylene glycol according to a mass ratio of 2: 1.

The aqueous sizing agent is aqueous acrylic resin.

And 2, preparing the graphene aramid spinning solution.

The aramid fiber spinning material is prepared with isophthaloyl dichloride and 2- (4-aminophenyl) -5-aminobenzimidazole as main material, taking N, N-dimethylacetamide as a solvent, firstly adding N, N-dimethylacetamide and lithium chloride into a reaction kettle under the protection of nitrogen, stirring, adding 2- (4-aminophenyl) -5-aminobenzimidazole, cooling to 0-minus 10 ℃ after complete dissolution, then adding m-phthaloyl chloride in batches, keeping the temperature of the reaction system not to exceed 15-30 ℃, continuing the reaction for 40min after the addition is finished, finally adding lithium hydroxide for neutralization, obtaining an aramid fiber resin solution with the solid content of 15-30% by mass, adding a graphene material, and uniformly mixing to obtain the graphene aramid fiber spinning solution.

The aramid fiber spinning material comprises the following components in percentage by mass: 70% of N, N-dimethylacetamide, 1% of lithium chloride, 8% of 2- (4-aminophenyl) -5-aminobenzimidazole, 20% of isophthaloyl dichloride and 1% of lithium hydroxide.

Step 3, centrifuging and desalting the graphene aramid fiber spinning solution obtained in the step 2, and then filling the graphene aramid fiber spinning solution into a reaction tank for defoaming to obtain a spinning stock solution, wherein the solid content in the spinning stock solution is 15-30% by mass; the temperature of the spinning dope was 20 ℃. And then carrying out dry-wet spinning, and carrying out processes of spinning, stretching, washing, drying, dry-hot stretching, sizing, oiling and rolling to obtain the graphene aramid composite fiber.

The spinning speed is 10-15 m/min; the dry heat stretching temperature is 290-320 ℃; the heat setting temperature is 270-290 ℃, and the time is 1-5 min.

Adopting a coagulation bath in the step 3, wherein the first coagulation bath is an N, N-dimethylacetamide aqueous solution with the concentration of 30-50% by mass, and the temperature is 10-20 ℃; the second coagulating bath is a water-washing coagulating bath of pure water, and the temperature is 70-90 ℃; finally, an air bath with a height of (20. + -. 5) mm.

And 4, placing the graphene aramid fiber obtained in the step 3 in a plasma reaction chamber, vacuumizing, filling nitrogen, adjusting the air pressure to 50-70Pa, performing plasma treatment, and taking out to obtain the graphene aramid fiber subjected to surface modification treatment. The power of the plasma treatment is 100-150W, and the treatment time is 1-5 min.

And 5, adding the graphene material and the modifier into the aqueous slurry, preparing coating slurry, fully stirring for 30-50min, keeping the temperature of the slurry at 30-50 ℃, placing the modified graphene aramid fiber obtained in the step 4 into a continuous slurry tank, performing sizing treatment for 5-10s, and then drying and winding to obtain the high-strength impact-resistant graphene aramid fiber.

The embodiment also provides the graphene high-strength impact-resistant aramid fiber prepared by the method.

Example 3

A preparation method of graphene high-strength impact-resistant aramid fiber comprises the following steps:

step 1, weighing raw materials in proportion; the raw materials comprise an aramid fiber spinning material, a graphene material, a modifier and water-based slurry.

Preferably, each raw material comprises the following components in percentage by mass: 83.5% of aramid fiber spinning material, 8% of graphene material, 0.5% of modifier and 8% of water-based slurry.

The graphene material is prepared by a redox method.

The modifier is a mixture of a silane coupling agent and polyethylene glycol according to the mass ratio of 1: 2.

The aqueous sizing agent is aqueous polyester resin.

And 2, preparing the graphene aramid spinning solution.

The aramid fiber spinning material is prepared with isophthaloyl dichloride and 2- (4-aminophenyl) -5-aminobenzimidazole as main material, taking N, N-dimethylacetamide as a solvent, firstly adding N, N-dimethylacetamide and lithium chloride into a reaction kettle under the protection of nitrogen, stirring, adding 2- (4-aminophenyl) -5-aminobenzimidazole, cooling to 0-minus 10 ℃ after complete dissolution, then adding m-phthaloyl chloride in batches, keeping the temperature of the reaction system not to exceed 15-30 ℃, continuing the reaction for 40min after the addition is finished, finally adding lithium hydroxide for neutralization, obtaining an aramid fiber resin solution with the solid content of 15-30% by mass, adding a graphene material, and uniformly mixing to obtain the graphene aramid fiber spinning solution.

The aramid fiber spinning material comprises the following components in percentage by mass: 57% of N, N-dimethylacetamide, 3% of lithium chloride, 22% of 2- (4-aminophenyl) -5-aminobenzimidazole, 15% of isophthaloyl dichloride and 3% of lithium hydroxide.

Step 3, centrifuging and desalting the graphene aramid fiber spinning solution obtained in the step 2, and then filling the graphene aramid fiber spinning solution into a reaction tank for defoaming to obtain a spinning stock solution, wherein the solid content in the spinning stock solution is 15-30% by mass; the temperature of the spinning dope was 20 ℃. And then carrying out dry-wet spinning, and carrying out processes of spinning, stretching, washing, drying, dry-hot stretching, sizing, oiling and rolling to obtain the graphene aramid composite fiber.

The spinning speed is 10-15 m/min; the dry heat stretching temperature is 290-320 ℃; the heat setting temperature is 270-290 ℃, and the time is 1-5 min.

Adopting a coagulation bath in the step 3, wherein the first coagulation bath is an N, N-dimethylacetamide aqueous solution with the concentration of 30-50% by mass, and the temperature is 10-20 ℃; the second coagulating bath is a water-washing coagulating bath of pure water, and the temperature is 70-90 ℃; finally, an air bath with a height of (20. + -. 5) mm.

And 4, placing the graphene aramid fiber obtained in the step 3 in a plasma reaction chamber, vacuumizing, filling nitrogen, adjusting the air pressure to 50-70Pa, performing plasma treatment, and taking out to obtain the graphene aramid fiber subjected to surface modification treatment. The power of the plasma treatment is 100-150W, and the treatment time is 1-5 min.

And 5, adding the graphene material and the modifier into the aqueous slurry, preparing coating slurry, fully stirring for 30-50min, keeping the temperature of the slurry at 30-50 ℃, placing the modified graphene aramid fiber obtained in the step 4 into a continuous slurry tank, performing sizing treatment for 5-10s, and then drying and winding to obtain the high-strength impact-resistant graphene aramid fiber.

The embodiment also provides the graphene high-strength impact-resistant aramid fiber prepared by the method.

Example 4

A preparation method of graphene high-strength impact-resistant aramid fiber comprises the following steps:

step 1, weighing raw materials in proportion; the raw materials comprise an aramid fiber spinning material, a graphene material, a modifier and water-based slurry.

Preferably, each raw material comprises the following components in percentage by mass: 89% of aramid fiber spinning material, 10% of graphene material, 0.9% of modifier and 0.1% of water-based slurry.

The graphene material is graphene oxide prepared by a chemical vapor deposition method.

The modifier is a mixture of polyvinyl alcohol and polyvinylpyrrolidone in a mass ratio of 1: 3.

The aqueous sizing agent is aqueous epoxy resin.

And 2, preparing the graphene aramid spinning solution.

The aramid fiber spinning material is prepared with isophthaloyl dichloride and 2- (4-aminophenyl) -5-aminobenzimidazole as main material, taking N, N-dimethylacetamide as a solvent, firstly adding N, N-dimethylacetamide and lithium chloride into a reaction kettle under the protection of nitrogen, stirring, adding 2- (4-aminophenyl) -5-aminobenzimidazole, cooling to 0-minus 10 ℃ after complete dissolution, then adding m-phthaloyl chloride in batches, keeping the temperature of the reaction system not to exceed 15-30 ℃, continuing the reaction for 40min after the addition is finished, finally adding lithium hydroxide for neutralization, obtaining an aramid fiber resin solution with the solid content of 15-30% by mass, adding a graphene material, and uniformly mixing to obtain the graphene aramid fiber spinning solution.

The aramid fiber spinning material comprises the following components in percentage by mass: 71% of N, N-dimethylacetamide, 4% of lithium chloride, 20% of 2- (4-aminophenyl) -5-aminobenzimidazole, 1% of isophthaloyl dichloride and 4% of lithium hydroxide.

Step 3, centrifuging and desalting the graphene aramid fiber spinning solution obtained in the step 2, and then filling the graphene aramid fiber spinning solution into a reaction tank for defoaming to obtain a spinning stock solution, wherein the solid content in the spinning stock solution is 15-30% by mass; the temperature of the spinning dope was 20 ℃. And then carrying out dry-wet spinning, and carrying out processes of spinning, stretching, washing, drying, dry-hot stretching, sizing, oiling and rolling to obtain the graphene aramid composite fiber.

The spinning speed is 10-15 m/min; the dry heat stretching temperature is 290-320 ℃; the heat setting temperature is 270-290 ℃, and the time is 1-5 min.

Adopting a coagulation bath in the step 3, wherein the first coagulation bath is an N, N-dimethylacetamide aqueous solution with the concentration of 30-50% by mass, and the temperature is 10-20 ℃; the second coagulating bath is a water-washing coagulating bath of pure water, and the temperature is 70-90 ℃; finally, an air bath with a height of (20. + -. 5) mm.

And 4, placing the graphene aramid fiber obtained in the step 3 in a plasma reaction chamber, vacuumizing, filling nitrogen, adjusting the air pressure to 50-70Pa, performing plasma treatment, and taking out to obtain the graphene aramid fiber subjected to surface modification treatment. The power of the plasma treatment is 100-150W, and the treatment time is 1-5 min.

And 5, adding the graphene material and the modifier into the aqueous slurry, preparing coating slurry, fully stirring for 30-50min, keeping the temperature of the slurry at 30-50 ℃, placing the modified graphene aramid fiber obtained in the step 4 into a continuous slurry tank, performing sizing treatment for 5-10s, and then drying and winding to obtain the high-strength impact-resistant graphene aramid fiber.

The embodiment also provides the graphene high-strength impact-resistant aramid fiber prepared by the method.

Example 5

A preparation method of graphene high-strength impact-resistant aramid fiber comprises the following steps:

step 1, weighing raw materials in proportion; the raw materials comprise an aramid fiber spinning material, a graphene material, a modifier and water-based slurry.

Preferably, each raw material comprises the following components in percentage by mass: 80% of aramid fiber spinning material, 15% of graphene material, 1% of modifier and 4% of water-based slurry.

The graphene material is graphene oxide prepared by a redox method.

The modifier is a mixture of polyvinylpyrrolidone and a silane coupling agent according to the mass ratio of 3: 1.

The aqueous sizing agent is aqueous alkyd resin.

And 2, preparing the graphene aramid spinning solution.

The aramid fiber spinning material is prepared with isophthaloyl dichloride and 2- (4-aminophenyl) -5-aminobenzimidazole as main material, taking N, N-dimethylacetamide as a solvent, firstly adding N, N-dimethylacetamide and lithium chloride into a reaction kettle under the protection of nitrogen, stirring, adding 2- (4-aminophenyl) -5-aminobenzimidazole, cooling to 0-minus 10 ℃ after complete dissolution, then adding m-phthaloyl chloride in batches, keeping the temperature of the reaction system not to exceed 15-30 ℃, continuing the reaction for 40min after the addition is finished, finally adding lithium hydroxide for neutralization, obtaining an aramid fiber resin solution with the solid content of 15-30% by mass, adding a graphene material, and uniformly mixing to obtain the graphene aramid fiber spinning solution.

The aramid fiber spinning material comprises the following components in percentage by mass: 50% of N, N-dimethylacetamide, 5% of lithium chloride, 25% of 2- (4-aminophenyl) -5-aminobenzimidazole, 15% of isophthaloyl dichloride and 5% of lithium hydroxide.

Step 3, centrifuging and desalting the graphene aramid fiber spinning solution obtained in the step 2, and then filling the graphene aramid fiber spinning solution into a reaction tank for defoaming to obtain a spinning stock solution, wherein the solid content in the spinning stock solution is 15-30% by mass; the temperature of the spinning dope was 20 ℃. And then carrying out dry-wet spinning, and carrying out processes of spinning, stretching, washing, drying, dry-hot stretching, sizing, oiling and rolling to obtain the graphene aramid composite fiber.

The spinning speed is 10-15 m/min; the dry heat stretching temperature is 290-320 ℃; the heat setting temperature is 270-290 ℃, and the time is 1-5 min.

Adopting a coagulation bath in the step 3, wherein the first coagulation bath is an N, N-dimethylacetamide aqueous solution with the concentration of 30-50% by mass, and the temperature is 10-20 ℃; the second coagulating bath is a water-washing coagulating bath of pure water, and the temperature is 70-90 ℃; finally, an air bath with a height of (20. + -. 5) mm.

And 4, placing the graphene aramid fiber obtained in the step 3 in a plasma reaction chamber, vacuumizing, filling nitrogen, adjusting the air pressure to 50-70Pa, performing plasma treatment, and taking out to obtain the graphene aramid fiber subjected to surface modification treatment. The power of the plasma treatment is 100-150W, and the treatment time is 1-5 min.

And 5, adding the graphene material and the modifier into the aqueous slurry, preparing coating slurry, fully stirring for 30-50min, keeping the temperature of the slurry at 30-50 ℃, placing the modified graphene aramid fiber obtained in the step 4 into a continuous slurry tank, performing sizing treatment for 5-10s, and then drying and winding to obtain the high-strength impact-resistant graphene aramid fiber.

The embodiment also provides the graphene high-strength impact-resistant aramid fiber prepared by the method.

The composite fibers prepared in the examples were tested, and the physical property data obtained by the tests are shown in table 1 below.

TABLE 1 test results.

The key technology of the graphene high-strength impact-resistant aramid fiber and the preparation method thereof is to prepare the graphene high-strength impact-resistant aramid fiber, firstly prepare a graphene aramid fiber spinning solution, secondly spin through spinning equipment to obtain the graphene aramid fiber, and finally obtain the high-strength impact-resistant graphene aramid fiber through fiber surface coating. The graphene high-strength impact-resistant aramid fiber prepared by the invention has the functions of high strength impact resistance, antibiosis, ultraviolet resistance and the like, improves the additional value of the aramid fiber and expands the application range of the aramid fiber.

While the present invention has been described in detail with reference to the preferred embodiments, it should be understood that the above description should not be taken as limiting the invention. Various modifications and alterations to this invention will become apparent to those skilled in the art upon reading the foregoing description. Accordingly, the scope of the invention should be determined from the following claims.