CN113737310A - Graphene polyimide composite fiber and preparation method thereof - Google Patents
Graphene polyimide composite fiber and preparation method thereof Download PDFInfo
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- CN113737310A CN113737310A CN202110989497.4A CN202110989497A CN113737310A CN 113737310 A CN113737310 A CN 113737310A CN 202110989497 A CN202110989497 A CN 202110989497A CN 113737310 A CN113737310 A CN 113737310A
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 112
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 112
- 239000004642 Polyimide Substances 0.000 title claims abstract description 63
- 229920001721 polyimide Polymers 0.000 title claims abstract description 63
- 239000000835 fiber Substances 0.000 title claims abstract description 62
- 239000002131 composite material Substances 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000000243 solution Substances 0.000 claims abstract description 58
- 238000000034 method Methods 0.000 claims abstract description 54
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 46
- 239000003607 modifier Substances 0.000 claims abstract description 34
- 238000009987 spinning Methods 0.000 claims abstract description 34
- 238000003756 stirring Methods 0.000 claims abstract description 31
- VLDPXPPHXDGHEW-UHFFFAOYSA-N 1-chloro-2-dichlorophosphoryloxybenzene Chemical compound ClC1=CC=CC=C1OP(Cl)(Cl)=O VLDPXPPHXDGHEW-UHFFFAOYSA-N 0.000 claims abstract description 29
- 239000002994 raw material Substances 0.000 claims abstract description 26
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000011259 mixed solution Substances 0.000 claims abstract description 12
- 238000006068 polycondensation reaction Methods 0.000 claims abstract description 12
- 239000006185 dispersion Substances 0.000 claims abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims abstract description 9
- 238000005303 weighing Methods 0.000 claims abstract description 9
- 238000001035 drying Methods 0.000 claims abstract description 7
- 239000000463 material Substances 0.000 claims description 26
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- ZHDTXTDHBRADLM-UHFFFAOYSA-N hydron;2,3,4,5-tetrahydropyridin-6-amine;chloride Chemical compound Cl.NC1=NCCCC1 ZHDTXTDHBRADLM-UHFFFAOYSA-N 0.000 claims description 16
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 6
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 6
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 6
- 239000002202 Polyethylene glycol Substances 0.000 claims description 5
- 229920001223 polyethylene glycol Polymers 0.000 claims description 5
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 4
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 4
- 238000005229 chemical vapour deposition Methods 0.000 claims description 4
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 4
- 230000015271 coagulation Effects 0.000 claims 1
- 238000005345 coagulation Methods 0.000 claims 1
- 230000001112 coagulating effect Effects 0.000 description 7
- 239000007788 liquid Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000008901 benefit Effects 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- 239000011157 advanced composite material Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 230000000840 anti-viral effect Effects 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 238000007380 fibre production Methods 0.000 description 1
- 239000002657 fibrous material Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000012779 reinforcing material Substances 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
Classifications
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/88—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
- D01F6/94—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 other polycondensation products
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
Abstract
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.
Description
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.
Claims (8)
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.
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| CN115595124A (en) * | 2022-11-11 | 2023-01-13 | 东莞市鸿亿导热材料有限公司（Cn） | Preparation method of graphene phase-change composite material, product and application thereof |
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