阅读说明：本技术 一种石墨烯聚酰亚胺复合纤维及其制备方法 (Graphene polyimide composite fiber and preparation method thereof ) 是由 沙嫣 沙晓林 马立国 于 2021-08-26 设计创作，主要内容包括：本发明公开了一种石墨烯聚酰亚胺复合纤维及其制备方法,该方法包含：步骤1,按比例称取各原料；步骤2,将石墨烯、改性剂加入到N,N’-二甲基乙酰胺中,搅拌均匀制备石墨烯分散液；步骤3,将4,4-二氨基二苯加入到步骤2所得的溶液中,持续搅拌直至完全溶解,然后加入均苯四甲酸二酐,持续搅拌,再将混合溶液充入氮气保护,调整温度进行低温缩聚反应,制备纺丝液；步骤4,将纺丝液加入到反应釜中,通过干湿法进行纺丝,再将初生丝送入烘箱中烘干,得到石墨烯聚酰亚胺纤维。本发明还提供了通过该方法制备的石墨烯聚酰亚胺复合纤维。本发明制备的石墨烯聚酰亚胺复合纤维具备高强度、耐高温等功能,能够扩展聚酰亚胺纤维的应用范围。(The invention discloses a graphene polyimide composite fiber and a preparation method thereof, wherein the method comprises the following steps: step 1, weighing raw materials in proportion; step 2, adding graphene and a modifier into N, N' -dimethylacetamide, and uniformly stirring to prepare a graphene dispersion solution; step 3, adding 4, 4-diaminodiphenyl into the solution obtained in the step 2, continuously stirring until the solution is completely dissolved, then adding pyromellitic dianhydride, continuously stirring, introducing nitrogen into the mixed solution for protection, adjusting the temperature, and carrying out low-temperature polycondensation reaction to prepare a spinning solution; and 4, adding the spinning solution into a reaction kettle, spinning by a dry-wet method, and then sending the as-spun yarn into an oven for drying to obtain the graphene polyimide fiber. The invention also provides the graphene polyimide composite fiber prepared by the method. The graphene polyimide composite fiber prepared by the invention has the functions of high strength, high temperature resistance and the like, and can expand the application range of the polyimide fiber.)

1. A preparation method of graphene polyimide composite fibers is characterized by comprising the following steps:

step 1, weighing raw materials in proportion; each raw material comprises 4, 4-diaminodiphenyl ether, pyromellitic dianhydride, N' -dimethylacetamide, a graphene material and a modifier;

step 2, adding graphene and a modifier into N, N' -dimethylacetamide, and uniformly stirring to prepare a graphene dispersion solution;

step 3, adding 4, 4-diaminodiphenyl into the solution obtained in the step 2, continuously stirring until the solution is completely dissolved, then adding pyromellitic dianhydride, continuously stirring, introducing nitrogen into the mixed solution for protection, adjusting the temperature, and carrying out low-temperature polycondensation reaction to prepare a spinning solution;

and 4, adding the spinning solution into a reaction kettle, spinning by a dry-wet method, and then sending the as-spun yarn into an oven for drying to obtain the graphene polyimide fiber.

2. The method for preparing the graphene polyimide composite fiber according to claim 1, wherein in the step 1, the amount of the raw materials is 30-49% by mass of 4, 4-diaminodiphenyl ether, 20-40% by mass of pyromellitic dianhydride, 10-40% by mass of N, N' -dimethylacetamide, 0.1-10% by mass of a graphene material, and 0.1-5% by mass of a modifier.

3. The method for preparing the graphene polyimide composite fiber according to claim 2, wherein the modifier is any one or more of polyvinyl alcohol, polyethylene glycol, polyvinylpyrrolidone and silane coupling agent.

4. The method for preparing the graphene polyimide composite fiber according to claim 2, wherein the graphene material is graphene or graphene oxide prepared by any one or more methods of a mechanical stripping method, a chemical vapor deposition method and a redox method.

5. The method for preparing graphene polyimide composite fibers according to claim 1, wherein in the step 3, 4-diaminodiphenyl is slowly added to the solution obtained in the step 2, stirring is continued until the solution is completely dissolved, pyromellitic dianhydride is slowly added, stirring is continued, the mixed solution is filled with nitrogen for protection, the temperature is adjusted to 0-10 ℃, and low-temperature polycondensation reaction is carried out to prepare the spinning solution.

6. The method for preparing the graphene polyimide composite fiber according to claim 1, wherein in the step 4, the spinning is performed by a dry-wet method, and a coagulation bath adopts a 10-30% ethanol solution by volume fraction and is at a temperature of 20-40 ℃.

7. The method for preparing the graphene polyimide composite fiber according to claim 1, wherein in the step 4, the as-spun yarn is sent into an oven to be dried, and is firstly dried at 200 ℃ for 1-2h, and then dried at 300-400 ℃ for 1-2 h.

8. A graphene polyimide composite fiber prepared by the method according to any one of claims 1 to 7.

Technical Field

The invention relates to a graphene composite antiviral fiber and a preparation method thereof, and particularly relates to a graphene polyimide composite 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.

Polyimide (PI) is a polymer material widely used in the fields of electronics, power, aerospace, and the like due to its excellent thermal, dielectric, and mechanical properties. The polyimide fiber has higher elastic modulus, is second to the carbon fiber and is a reinforcing material of an advanced composite material. However, the polyimide fibers are not commercially available due to the difficulty in preparation, high production cost, and the like. Currently, the main application of polyimide fiber is to be used as a high temperature resistant filter material in the field of environmental protection. In addition, the polyimide fiber can also be applied to fireproof flame-retardant clothes, heat-insulating protective clothes and the like, is comfortable to wear, has good safety and long service life, and is the most ideal fiber material for manufacturing protective clothes. The polyimide composite fiber prepared by the graphene modification technology has better breaking strength and high temperature resistance, and can be used in military and other composite material protection fields.

Disclosure of Invention

The invention aims to provide a graphene composite fiber and a preparation method thereof, which are used for preparing a graphene polyimide fiber with high strength, high temperature resistance and other functions, improving the additional value of the polyimide fiber and expanding the application range of the polyimide fiber.

In order to achieve the above object, the present invention provides a method for preparing a graphene polyimide composite fiber, wherein the method comprises: step 1, weighing raw materials in proportion; each raw material comprises 4, 4-diaminodiphenyl ether, pyromellitic dianhydride, N' -dimethylacetamide, a graphene material and a modifier; step 2, adding graphene and a modifier into N, N' -dimethylacetamide, and uniformly stirring to prepare a graphene dispersion solution; step 3, adding 4, 4-diaminodiphenyl into the solution obtained in the step 2, continuously stirring until the solution is completely dissolved, then adding pyromellitic dianhydride, continuously stirring, introducing nitrogen into the mixed solution for protection, adjusting the temperature, and carrying out low-temperature polycondensation reaction to prepare a spinning solution; and 4, adding the spinning solution into a reaction kettle, spinning by a dry-wet method, and then sending the as-spun yarn into an oven for drying to obtain the graphene polyimide fiber.

In the preparation method of the graphene polyimide composite fiber, in the step 1, the amount of the raw materials is 30-49% by mass of 4, 4-diaminodiphenyl ether, 20-40% by mass of pyromellitic dianhydride, 10-40% by mass of N, N' -dimethylacetamide, 0.1-10% by mass of a graphene material, and 0.1-5% by mass of a modifier.

In the preparation method of the graphene polyimide composite fiber, the modifier is any one or more of polyvinyl alcohol, polyethylene glycol, polyvinylpyrrolidone and silane coupling agent.

In the preparation method of the graphene polyimide composite fiber, the graphene material is graphene or graphene oxide prepared by any one or more methods of a mechanical stripping method, a chemical vapor deposition method and a redox method.

In the step 3, 4-diaminodiphenyl is slowly added to the solution obtained in the step 2, the mixture is continuously stirred until the mixture is completely dissolved, pyromellitic dianhydride is slowly added, the mixture is continuously stirred, nitrogen is filled into the mixed solution for protection, the temperature is adjusted to 0-10 ℃, and low-temperature polycondensation reaction is carried out to prepare the spinning solution.

In the step 4, spinning is performed by a dry-wet method, and a coagulating bath adopts an ethanol solution with the volume fraction of 10-30% and the temperature is 20-40 ℃.

In the step 4, the spun yarn is sent into an oven to be dried, and is firstly dried at 200 ℃ for 1-2h, and then is dried at 300-400 ℃ for 1-2 h.

The invention also provides the graphene polyimide composite fiber prepared by the method.

The graphene polyimide composite fiber and the preparation method thereof provided by the invention have the following advantages:

the graphene polyimide fiber with the functions of high strength, high temperature resistance and the like is prepared, the additional value of the polyimide fiber is improved, and the application range of the polyimide fiber is expanded.

The high-strength high-temperature-resistant graphene polyimide 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 a graphene polyimide composite fiber, which comprises the following steps:

step 1, weighing raw materials in proportion; each raw material comprises 4, 4-diaminodiphenyl ether (ODA), pyromellitic dianhydride (PMDA), N' -dimethylacetamide (DMAc), a graphene material and a modifier; step 2, adding graphene and a modifier into N, N' -dimethylacetamide, and uniformly stirring to prepare a graphene dispersion solution; the graphene content of the solution is 1-15% and the modifier content is 0.1-5% by mass percent. Step 3, adding 4, 4-diaminodiphenyl into the solution obtained in the step 2, continuously stirring until the solution is completely dissolved, then adding pyromellitic dianhydride, continuously stirring, introducing nitrogen into the mixed solution for protection, adjusting the temperature, and carrying out low-temperature polycondensation reaction to prepare a spinning solution; and 4, adding the spinning solution into a reaction kettle, spinning by a dry-wet method, and then sending the as-spun yarn into an oven for drying to obtain the graphene polyimide fiber.

Preferably, in the step 1, the amount of the raw materials is 30-49% by mass of 4, 4-diaminodiphenyl ether, 20-40% by mass of pyromellitic dianhydride, 10-40% by mass of N, N' -dimethylacetamide, 0.1-10% by mass of graphene material and 0.1-5% by mass of modifier.

The modifier is one or more of polyvinyl alcohol, polyethylene glycol, polyvinylpyrrolidone (PVP), silane coupling agent, etc.

The graphene material is graphene or graphene oxide prepared by any one or more methods of a mechanical stripping method, a chemical vapor deposition method, a redox method and the like.

And 3, slowly adding 4, 4-diaminodiphenyl into the solution obtained in the step 2, continuously stirring until the solution is completely dissolved, then slowly adding pyromellitic dianhydride, continuously stirring, introducing nitrogen into the mixed solution for protection, adjusting the temperature to 0-10 ℃, and carrying out low-temperature polycondensation reaction to prepare the spinning solution.

In the step 4, spinning is carried out by a dry-wet method, and the coagulating bath adopts 10-30% of ethanol solution by volume fraction and is at the temperature of 20-40 ℃.

And 4, conveying the primary filaments into an oven for drying, firstly drying at 200 ℃ for 1-2h, and then drying at 300-400 ℃ for 1-2 h.

The equipment and spinning process conditions parameters, etc. employed in the present invention are known to those skilled in the art.

The invention also provides the graphene polyimide composite fiber prepared by the method.

The graphene polyimide composite fiber and the preparation method thereof provided by the present invention are further described with reference to the following examples.

Example 1

A method for preparing a graphene polyimide composite fiber, comprising:

step 1, weighing raw materials in proportion; the raw materials comprise 4, 4-diaminodiphenyl ether, pyromellitic dianhydride, N' -dimethylacetamide, a graphene material and a modifier.

Preferably, the amount of each raw material is 30% by mass of 4, 4-diaminodiphenyl ether, 40% by mass of pyromellitic dianhydride, 29.8% by mass of N, N' -dimethylacetamide, 0.1% by mass of graphene material and 0.1% by mass of modifier.

The modifier is polyethylene glycol.

The graphene material is prepared by a mechanical stripping method.

And 2, adding the graphene and the modifier into N, N' -dimethylacetamide, and uniformly stirring to prepare the graphene dispersion liquid.

And 3, slowly adding 4, 4-diaminodiphenyl into the solution obtained in the step 2, continuously stirring until the solution is completely dissolved, then slowly adding pyromellitic dianhydride, continuously stirring, introducing nitrogen into the mixed solution for protection, adjusting the temperature to 0-10 ℃, and carrying out low-temperature polycondensation reaction to prepare the spinning solution.

And 4, adding the spinning solution into a reaction kettle, spinning by a dry-wet method, wherein the coagulating bath adopts 10-30% of ethanol solution by volume fraction, and the temperature is 20-40 ℃. And then the primary yarn is sent into an oven to be dried, firstly dried for 1-2h at 200 ℃, and then dried for 1-2h at 400 ℃ of 300-. And obtaining the graphene polyimide fiber.

The embodiment also provides the graphene polyimide composite fiber prepared by the method.

Example 2

A method for preparing a graphene polyimide composite fiber, comprising:

step 1, weighing raw materials in proportion; the raw materials comprise 4, 4-diaminodiphenyl ether, pyromellitic dianhydride, N' -dimethylacetamide, a graphene material and a modifier.

Preferably, the use amount of each raw material is 35% by mass of 4, 4-diaminodiphenyl ether, 23% by mass of pyromellitic dianhydride, 40% by mass of N, N' -dimethylacetamide, 1% by mass of graphene material and 1% by mass of modifier.

The modifier is polyvinylpyrrolidone.

The graphene material is graphene oxide prepared by a mechanical stripping method.

And 2, adding the graphene and the modifier into N, N' -dimethylacetamide, and uniformly stirring to prepare the graphene dispersion liquid.

And 3, slowly adding 4, 4-diaminodiphenyl into the solution obtained in the step 2, continuously stirring until the solution is completely dissolved, then slowly adding pyromellitic dianhydride, continuously stirring, introducing nitrogen into the mixed solution for protection, adjusting the temperature to 0-10 ℃, and carrying out low-temperature polycondensation reaction to prepare the spinning solution.

And 4, adding the spinning solution into a reaction kettle, spinning by a dry-wet method, wherein the coagulating bath adopts 10-30% of ethanol solution by volume fraction, and the temperature is 20-40 ℃. And then the primary yarn is sent into an oven to be dried, firstly dried for 1-2h at 200 ℃, and then dried for 1-2h at 400 ℃ of 300-. And obtaining the graphene polyimide fiber.

The embodiment also provides the graphene polyimide composite fiber prepared by the method.

Example 3

A method for preparing a graphene polyimide composite fiber, comprising:

step 1, weighing raw materials in proportion; the raw materials comprise 4, 4-diaminodiphenyl ether, pyromellitic dianhydride, N' -dimethylacetamide, a graphene material and a modifier.

Preferably, the use amount of each raw material is 48% of 4, 4-diaminodiphenyl ether, 35% of pyromellitic dianhydride, 10% of N, N' -dimethylacetamide, 5% of graphene material and 2% of modifier by mass percentage.

The modifier is polyvinyl alcohol.

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

And 2, adding the graphene and the modifier into N, N' -dimethylacetamide, and uniformly stirring to prepare the graphene dispersion liquid.

And 3, slowly adding 4, 4-diaminodiphenyl into the solution obtained in the step 2, continuously stirring until the solution is completely dissolved, then slowly adding pyromellitic dianhydride, continuously stirring, introducing nitrogen into the mixed solution for protection, adjusting the temperature to 0-10 ℃, and carrying out low-temperature polycondensation reaction to prepare the spinning solution.

And 4, adding the spinning solution into a reaction kettle, spinning by a dry-wet method, wherein the coagulating bath adopts 10-30% of ethanol solution by volume fraction, and the temperature is 20-40 ℃. And then the primary yarn is sent into an oven to be dried, firstly dried for 1-2h at 200 ℃, and then dried for 1-2h at 400 ℃ of 300-. And obtaining the graphene polyimide fiber.

The embodiment also provides the graphene polyimide composite fiber prepared by the method.

Example 4

A method for preparing a graphene polyimide composite fiber, comprising:

step 1, weighing raw materials in proportion; the raw materials comprise 4, 4-diaminodiphenyl ether, pyromellitic dianhydride, N' -dimethylacetamide, a graphene material and a modifier.

Preferably, the using amount of each raw material is 33% by mass of 4, 4-diaminodiphenyl ether, 25% by mass of pyromellitic dianhydride, 30% by mass of N, N' -dimethylacetamide, 8% by mass of graphene material and 4% by mass of modifier.

The modifier is a silane coupling agent.

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

And 2, adding the graphene and the modifier into N, N' -dimethylacetamide, and uniformly stirring to prepare the graphene dispersion liquid.

And 3, slowly adding 4, 4-diaminodiphenyl into the solution obtained in the step 2, continuously stirring until the solution is completely dissolved, then slowly adding pyromellitic dianhydride, continuously stirring, introducing nitrogen into the mixed solution for protection, adjusting the temperature to 0-10 ℃, and carrying out low-temperature polycondensation reaction to prepare the spinning solution.

And 4, adding the spinning solution into a reaction kettle, spinning by a dry-wet method, wherein the coagulating bath adopts 10-30% of ethanol solution by volume fraction, and the temperature is 20-40 ℃. And then the primary yarn is sent into an oven to be dried, firstly dried for 1-2h at 200 ℃, and then dried for 1-2h at 400 ℃ of 300-. And obtaining the graphene polyimide fiber.

The embodiment also provides the graphene polyimide composite fiber prepared by the method.

Example 5

A method for preparing a graphene polyimide composite fiber, comprising:

step 1, weighing raw materials in proportion; the raw materials comprise 4, 4-diaminodiphenyl ether, pyromellitic dianhydride, N' -dimethylacetamide, a graphene material and a modifier.

Preferably, the use amount of each raw material is 49% by mass of 4, 4-diaminodiphenyl ether, 20% by mass of pyromellitic dianhydride, 16% by mass of N, N' -dimethylacetamide, 10% by mass of graphene material and 5% by mass of a modifier.

The modifier is polyethylene glycol and polyvinylpyrrolidone.

The graphene material is prepared by a redox method.

And 2, adding the graphene and the modifier into N, N' -dimethylacetamide, and uniformly stirring to prepare the graphene dispersion liquid.

And 3, slowly adding 4, 4-diaminodiphenyl into the solution obtained in the step 2, continuously stirring until the solution is completely dissolved, then slowly adding pyromellitic dianhydride, continuously stirring, introducing nitrogen into the mixed solution for protection, adjusting the temperature to 0-10 ℃, and carrying out low-temperature polycondensation reaction to prepare the spinning solution.

And 4, adding the spinning solution into a reaction kettle, spinning by a dry-wet method, wherein the coagulating bath adopts 10-30% of ethanol solution by volume fraction, and the temperature is 20-40 ℃. And then the primary yarn is sent into an oven to be dried, firstly dried for 1-2h at 200 ℃, and then dried for 1-2h at 400 ℃ of 300-. And obtaining the graphene polyimide fiber.

The embodiment also provides the graphene polyimide composite fiber prepared by the method.

The results of experimental proportions and physical property data of the graphene polyimide composite fibers obtained in the embodiments of the present invention are shown in table 1 below.

TABLE 1 test results.

The invention discloses a graphene polyimide composite fiber and a preparation method thereof, and aims to prepare the graphene polyimide composite fiber by utilizing an improved graphene oxide solution preparation and dispersion system and an improved polyimide fiber production system, so that the graphene polyimide composite fiber has the functions of high strength, high temperature resistance and the like, and the application range of the graphene polyimide fiber is expanded.

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.