CN112680811B - Graphene/polyacrylonitrile composite fiber, spinning solution and preparation method thereof - Google Patents
Graphene/polyacrylonitrile composite fiber, spinning solution and preparation method thereof Download PDFInfo
- Publication number
- CN112680811B CN112680811B CN201910989867.7A CN201910989867A CN112680811B CN 112680811 B CN112680811 B CN 112680811B CN 201910989867 A CN201910989867 A CN 201910989867A CN 112680811 B CN112680811 B CN 112680811B
- Authority
- CN
- China
- Prior art keywords
- graphene
- polyacrylonitrile
- solution
- spinning
- submicron
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 217
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 215
- 229920002239 polyacrylonitrile Polymers 0.000 title claims abstract description 156
- 238000009987 spinning Methods 0.000 title claims abstract description 67
- 239000000835 fiber Substances 0.000 title claims abstract description 29
- 239000002131 composite material Substances 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 239000007788 liquid Substances 0.000 claims abstract description 47
- 239000002243 precursor Substances 0.000 claims abstract description 25
- 238000002156 mixing Methods 0.000 claims abstract description 9
- 238000000034 method Methods 0.000 claims abstract description 7
- 239000000243 solution Substances 0.000 claims description 113
- VGTPCRGMBIAPIM-UHFFFAOYSA-M sodium thiocyanate Chemical compound [Na+].[S-]C#N VGTPCRGMBIAPIM-UHFFFAOYSA-M 0.000 claims description 107
- 239000007864 aqueous solution Substances 0.000 claims description 46
- 238000010008 shearing Methods 0.000 claims description 28
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 15
- 239000002904 solvent Substances 0.000 claims description 15
- 238000004090 dissolution Methods 0.000 claims description 13
- 230000008961 swelling Effects 0.000 claims description 13
- 238000003756 stirring Methods 0.000 claims description 11
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 10
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 10
- 229910001867 inorganic solvent Inorganic materials 0.000 claims description 10
- 239000003049 inorganic solvent Substances 0.000 claims description 10
- 239000003960 organic solvent Substances 0.000 claims description 10
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 10
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 5
- FDPIMTJIUBPUKL-UHFFFAOYSA-N dimethylacetone Natural products CCC(=O)CC FDPIMTJIUBPUKL-UHFFFAOYSA-N 0.000 claims description 5
- 150000002148 esters Chemical class 0.000 claims description 5
- 229910017604 nitric acid Inorganic materials 0.000 claims description 5
- 235000005074 zinc chloride Nutrition 0.000 claims description 5
- 239000011592 zinc chloride Substances 0.000 claims description 5
- 230000000844 anti-bacterial effect Effects 0.000 abstract description 3
- 239000002861 polymer material Substances 0.000 abstract description 2
- 239000006185 dispersion Substances 0.000 description 24
- 238000009210 therapy by ultrasound Methods 0.000 description 24
- 239000008346 aqueous phase Substances 0.000 description 16
- 239000000843 powder Substances 0.000 description 8
- 238000013329 compounding Methods 0.000 description 6
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000000903 blocking effect Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 239000011550 stock solution Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 238000004804 winding Methods 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 238000002166 wet spinning Methods 0.000 description 1
Landscapes
- Carbon And Carbon Compounds (AREA)
Abstract
The invention belongs to the field of high polymer materials, and particularly relates to a graphene/polyacrylonitrile composite fiber, a spinning solution and a preparation method thereof. The spinning solution for preparing the composite fiber is a solution in which polyacrylonitrile is uniformly dissolved and nano graphene and submicron graphene are uniformly dispersed. The preparation of the spinning solution comprises the steps of firstly taking and uniformly mixing a part of solution in which polyacrylonitrile is uniformly dissolved and a solution in which nano graphene and submicron graphene are uniformly dispersed, so as to prepare spinning precursor solution; and then taking part or all of the spinning precursor liquid and the rest solution which is uniformly dissolved with polyacrylonitrile, and uniformly mixing to obtain the spinning solution. The graphene/polyacrylonitrile composite fiber with antistatic, high strength, antibacterial and other functions can be obtained by utilizing the dope spinning of the graphene/polyacrylonitrile composite fiber prepared by the method.
Description
Technical Field
The invention belongs to the field of high polymer materials, and particularly relates to a graphene/polyacrylonitrile composite fiber, a spinning solution thereof and a preparation method thereof.
Background
Graphene is a nanomaterial with high conductivity discovered in recent years, and can be used as a filler to remarkably improve the conductivity, strength and the like of a polymer. However, we have found that when graphene/polyacrylonitrile fiber is produced by dope blending wet spinning, the size of graphene directly affects the spinning performance of the dope, the size of graphene is larger than 1 micron, the dope is difficult to extrude, the spinning pressure is high, phenomena such as hole blocking, wire breakage and rod winding during spinning are serious, the size of graphene must be strictly controlled, but the size of graphene is too small, and the obtained graphene/polyacrylonitrile fiber has poor functionality, so that the size of graphene needs to be studied in detail.
According to the invention, the nano graphene (with the size of 50-300nm and the thickness of 1-1.5 nm) and the submicron graphene (with the size of 400-800nm and the thickness of 1-1.5 nm) are compounded according to a certain proportion and then added into the polyacrylonitrile stock solution, so that the obtained stock solution has better spinnability, and the spun fiber has better antistatic property and higher mechanical strength.
Disclosure of Invention
The invention aims to provide a graphene/polyacrylonitrile composite fiber which has excellent performances such as high antistatic property, high strength and antibacterial property.
The invention also provides a spinning solution for preparing the graphene/polyacrylonitrile composite fiber, which has good spinning performance, is beneficial to molding, and has good antistatic, mechanical and antibacterial properties.
The invention also provides a preparation method of the spinning dope of the graphene/polyacrylonitrile composite fiber, which is simple and convenient to operate, has low requirements on equipment and process conditions, and saves cost.
The technical scheme of the invention is that the graphene/polyacrylonitrile composite fiber is a copolymer of polyacrylonitrile, nano graphene and submicron graphene.
The mass ratio of the total amount of the nano graphene and the submicron graphene to the polyacrylonitrile is 0.008-0.035: 1, preferably 0.015 to 0.028:1, more preferably 0.016 to 0.02:1.
the mass ratio of the nano graphene to the submicron graphene is 1:1 to 9, preferably 1:2 to 5, more preferably 1:2 to 3.
The size of the nano graphene is 50-300nm, preferably less than 100nm, and the thickness is 1-1.5 nm.
The size of the submicron graphene is 400-800nm, and the thickness is 1-1.5 nm.
The spinning solution for preparing the graphene/polyacrylonitrile composite fiber is a solution in which polyacrylonitrile is uniformly dissolved and nano graphene and submicron graphene are uniformly dispersed.
In the spinning solution system, the mass percentage concentration of the polyacrylonitrile is 10-13%, preferably 10-12%; the mass ratio of the total amount of the nano graphene and the submicron graphene to the polyacrylonitrile is 0.008-0.035: 1, preferably 0.015 to 0.028:1, more preferably 0.016 to 0.02:1.
the mass ratio of the nano graphene to the submicron graphene is 1:1 to 9, preferably 1:2 to 5, more preferably 1:2 to 3.
The size of the nano graphene is 50-300nm, preferably less than 100nm, and the thickness is 1-1.5 nm.
The size of the submicron graphene is 400-800nm, and the thickness is 1-1.5 nm.
The solvent used in the spinning solution system comprises an organic solvent or an inorganic solvent, wherein the organic solvent comprises dimethylformamide, dimethylacetamide, dimethyl sulfoxide, acetone or carbonic ester and the like, and the inorganic solvent comprises sodium thiocyanate aqueous solution, concentrated nitric acid or zinc chloride aqueous solution and the like, preferably the sodium thiocyanate aqueous solution, and the mass percentage concentration of the sodium thiocyanate aqueous solution is 35% -50%, preferably 44% -48%, more preferably 45% -46%.
The preparation method of the spinning solution of the graphene/polyacrylonitrile composite fiber comprises the following steps: firstly, uniformly mixing a part of solution in which polyacrylonitrile is uniformly dissolved with a solution in which nano graphene and submicron graphene are uniformly dispersed, and preparing spinning precursor liquid; and then taking part or all of the spinning precursor liquid and the rest solution which is uniformly dissolved with polyacrylonitrile, and uniformly mixing to obtain the spinning solution. Preferably, a portion of the spinning precursor solution is mixed homogeneously with the remaining solution of polyacrylonitrile homogeneously dissolved therein.
Specifically, firstly adding a solution with part of polyacrylonitrile uniformly dissolved into a solution with nano graphene and submicron graphene uniformly dispersed, and applying ultrasonic and high shearing actions while adding until the solution is uniformly mixed to prepare spinning precursor liquid; and adding part or all of the spinning precursor liquid into the rest solution uniformly dissolved with polyacrylonitrile, and applying ultrasonic and high shearing actions while adding until the spinning precursor liquid is uniformly mixed to obtain the spinning solution. It is preferable to add a part of the spinning precursor liquid to the remaining solution in which polyacrylonitrile is uniformly dissolved.
In the spinning precursor liquid system, the mass percentage concentration of the polyacrylonitrile is 0.5-3%, and the mass ratio of the total amount of the nano graphene and the submicron graphene to the polyacrylonitrile is 0.5-9: 1, preferably 0.5 to 2:1, more preferably 1 to 1.5:1.
the mass ratio of the nano graphene to the submicron graphene is 1:1 to 9, preferably 1:2 to 5, more preferably 1:2 to 3.
The size of the nano graphene is 50-300nm, preferably less than 100nm, and the thickness is 1-1.5 nm.
The size of the submicron graphene is 400-800nm, and the thickness is 1-1.5 nm.
In the spinning solution system, the mass percentage concentration of the polyacrylonitrile is 10-13%, preferably 10-12%; the mass ratio of the total amount of the nano graphene and the submicron graphene to the polyacrylonitrile is 0.008-0.035: 1, preferably 0.015 to 0.028:1, more preferably 0.016 to 0.02:1.
the mass ratio of the nano graphene to the submicron graphene is 1:1 to 9, preferably 1:2 to 5, more preferably 1:2 to 3.
The size of the nano graphene is 50-300nm, preferably less than 100nm, and the thickness is 1-1.5 nm.
The size of the submicron graphene is 400-800nm, and the thickness is 1-1.5 nm.
The solvent used in the spinning precursor liquid system and the spinning dope system comprises an organic solvent or an inorganic solvent, wherein the organic solvent comprises dimethylformamide, dimethylacetamide, dimethyl sulfoxide, acetone or carbonic ester and the like, the inorganic solvent comprises sodium thiocyanate aqueous solution, concentrated nitric acid or zinc chloride aqueous solution and the like, preferably sodium thiocyanate aqueous solution, and the mass percentage concentration of the sodium thiocyanate aqueous solution is 35% -50%, preferably 44% -48%, more preferably 45% -46%.
The mass percentage concentration of the polyacrylonitrile in the uniformly dissolved polyacrylonitrile solution is 13 percent.
The preparation of the solution in which polyacrylonitrile is uniformly dissolved comprises: adding a pre-solvent into polyacrylonitrile, stirring and swelling, and then adding a post-solvent for high-shear dissolution to obtain a solution in which the polyacrylonitrile is uniformly dissolved. Preferably, the pre-solvent is the same type as the post-solvent, and the post-solvent has a higher concentration than the pre-solvent.
The swelling reaction time is 0.5-1 hour, and the high shear dissolution time is 1-2 hours.
The solvents used for the front solvent and the rear solvent comprise organic solvents or inorganic solvents, wherein the organic solvents comprise dimethylformamide, dimethylacetamide, dimethyl sulfoxide, acetone or carbonic ester and the like, the inorganic solvents comprise sodium thiocyanate aqueous solution, concentrated nitric acid or zinc chloride aqueous solution and the like, preferably sodium thiocyanate aqueous solution, and the mass percentage concentration of the sodium thiocyanate aqueous solution is 35% -50%, preferably 44% -48%, more preferably 45% -46%.
The preparation of the solution in which the nano graphene and the submicron graphene are uniformly dispersed comprises: and uniformly dispersing the nano graphene and the submicron graphene in a solvent under the action of high shear and ultrasonic to obtain a solution in which the nano graphene and the submicron graphene are uniformly dispersed.
In a solution system in which nano graphene and submicron graphene are uniformly dispersed, the mass ratio of the nano graphene to the submicron graphene is 1:1 to 9, preferably 1:2 to 5, more preferably 1:2 to 3.
The size of the nano graphene is 50-300nm, preferably less than 100nm, and the thickness is 1-1.5 nm.
The size of the submicron graphene is 400-800nm, and the thickness is 1-1.5 nm.
The solvent comprises an organic solvent or an inorganic solvent, the organic solvent comprises dimethylformamide, dimethylacetamide, dimethyl sulfoxide, acetone or carbonic ester and the like, the inorganic solvent comprises sodium thiocyanate aqueous solution, concentrated nitric acid or zinc chloride aqueous solution and the like, preferably sodium thiocyanate aqueous solution, and the mass percentage concentration of the sodium thiocyanate aqueous solution is 35% -50%, preferably 44% -48%, more preferably 45% -46%.
As the preferable scheme of the invention, firstly adding a sodium thiocyanate aqueous solution with part of polyacrylonitrile uniformly dissolved into the sodium thiocyanate aqueous solution with nano graphene and submicron graphene uniformly dispersed, and applying ultrasonic and high shearing actions while adding until the solution is uniformly mixed to obtain spinning precursor liquid; adding part of spinning precursor liquid into the rest sodium thiocyanate aqueous solution uniformly dissolved with polyacrylonitrile, and applying ultrasonic and high shearing actions while adding until the spinning precursor liquid is uniformly mixed to prepare spinning solution;
in a sodium thiocyanate aqueous solution uniformly dissolved with polyacrylonitrile, the mass percentage of the polyacrylonitrile is 13%;
in the spinning precursor liquid, the mass percentage concentration of the polyacrylonitrile is 0.5-3%, and the mass ratio of the total amount of the nano graphene and the submicron graphene to the polyacrylonitrile is 0.5-9: 1, preferably 0.5 to 2:1, more preferably 1 to 1.5:1, a step of;
in the spinning solution, the mass percentage concentration of the polyacrylonitrile is 10-13%, preferably 10-12%; the mass ratio of the total amount of the nano graphene and the submicron graphene to the polyacrylonitrile is 0.008-0.035: 1, preferably 0.015 to 0.028:1, more preferably 0.016 to 0.02:1, a step of;
in the spinning precursor liquid and the spinning solution, the mass ratio of the nano graphene to the submicron graphene is 1:1 to 9, preferably 1:2 to 5, more preferably 1:2 to 3;
the size of the nano graphene is 50-300nm, preferably less than 100nm, and the thickness is 1-1.5 nm;
the size of the submicron graphene is 400-800nm, and the thickness is 1-1.5 nm.
The preparation of the sodium thiocyanate aqueous solution uniformly dissolved with polyacrylonitrile comprises the following steps: adding a pre-sodium thiocyanate aqueous solution into polyacrylonitrile, stirring and swelling, and then adding a post-sodium thiocyanate aqueous solution for high-shear dissolution to obtain a solution in which the polyacrylonitrile is uniformly dissolved. The mass percentage concentration of the front sodium thiocyanate aqueous solution is 39%, and the mass percentage concentration of the rear sodium thiocyanate aqueous solution is 58%.
The swelling reaction time is 0.5-1 hour, and the high shear dissolution time is 1-2 hours.
The preparation of the sodium thiocyanate aqueous solution with the nano graphene and the submicron graphene uniformly dispersed comprises the following steps: under the action of high shear and ultrasound, firstly, uniformly dispersing nano graphene and submicron graphene in an aqueous solution, and then adding sodium thiocyanate to obtain the sodium thiocyanate aqueous solution in which the nano graphene and submicron graphene are uniformly dispersed.
In a solution system in which nano graphene and submicron graphene are uniformly dispersed, the mass ratio of the nano graphene to the submicron graphene is 1:1 to 9, preferably 1:2 to 5, more preferably 1:2 to 3.
The size of the nano graphene is 50-300nm, preferably less than 100nm, and the thickness is 1-1.5 nm.
The size of the submicron graphene is 400-800nm, and the thickness is 1-1.5 nm.
Compared with the prior art, the invention has the beneficial effects that:
(1) The spinning solution of the graphene/polyacrylonitrile composite fiber prepared by the method has good spinnability, and can not cause hole blocking, broken filaments and winding rods under a reasonable spinning process.
(2) Different proportions of nano graphene and submicron graphene can be adjusted to obtain graphene/polyacrylonitrile fibers with different antistatic properties and strengths.
(3) The specific resistance of the graphene/polyacrylonitrile composite fiber prepared by the spinning solution reaches 10 6 -10 7 Compared with pure polyacrylonitrileThe specific resistance of the fiber is improved by 5-6 orders of magnitude.
(4) The strength of the graphene/polyacrylonitrile composite fiber prepared by the spinning solution can be improved by more than 20% compared with that of pure polyacrylonitrile fiber.
Detailed Description
The present invention will be described in detail with reference to specific examples. The following examples will assist those skilled in the art in further understanding the present invention, but are not intended to limit the invention in any way. It should be noted that several modifications and improvements can be made by those skilled in the art without departing from the inventive concept. These are all within the scope of the present invention.
The size of the nano graphene in the following embodiment is 50-300nm, preferably less than 100nm, and the thickness is 1-1.5 nm; the size of the submicron graphene is 400-800nm, and the thickness is 1-1.5 nm.
Example 1
(1) Adding sodium thiocyanate water solution with the mass percent concentration of about 39% into polyacrylonitrile powder, mechanically stirring for 0.5-1h for swelling, and then adding sodium thiocyanate water solution with the mass percent concentration of about 58% for high-shear dissolution treatment for 1-2h to obtain polyacrylonitrile/sodium thiocyanate solution with the mass percent concentration of about 13% and sodium thiocyanate concentration of about 45-46%;
(2) Compounding nano graphene and submicron graphene into uniformly dispersed aqueous phase graphene dispersion liquid according to a mass ratio of 1:3 through high shearing and ultrasonic treatment, and then adding sodium thiocyanate to enable the mass percentage concentration of the sodium thiocyanate in the aqueous phase graphene dispersion liquid to be about 45% -46%;
(3) Adding a proper amount of the polyacrylonitrile/sodium thiocyanate solution obtained in the step (1) into the graphene dispersion liquid obtained in the step (2), and obtaining a graphene/polyacrylonitrile/sodium thiocyanate solution with the mass percent concentration of about 3% and the mass percent concentration of about 3.5% of graphene through high shearing and ultrasonic treatment;
(4) Adding a proper amount of the graphene/polyacrylonitrile/sodium thiocyanate solution obtained in the step (3) into the polyacrylonitrile/sodium thiocyanate solution obtained in the step (1), and obtaining about 13% of the concentration of the polyacrylonitrile by mass percent through high shearing and ultrasonic treatment, wherein the mass ratio of the total amount of nano graphene and submicron graphene to the polyacrylonitrile is 0.02:1 graphene/polyacrylonitrile/sodium thiocyanate solution.
Example 2
(1) Adding a proper amount of sodium thiocyanate aqueous solution with the mass percent concentration of about 39% into polyacrylonitrile powder, mechanically stirring for 0.5-1h for swelling, and then adding the sodium thiocyanate aqueous solution with the mass percent concentration of about 58% for high-shear dissolution treatment for 1-2h to obtain a polyacrylonitrile/sodium thiocyanate solution with the mass percent concentration of about 13% and the mass percent concentration of about 45-46%;
(2) Compounding nano graphene and submicron graphene into uniformly dispersed aqueous phase graphene dispersion liquid according to a mass ratio of 1:4 through high shearing and ultrasonic treatment, and then adding sodium thiocyanate to enable the mass percentage concentration of the sodium thiocyanate in the aqueous phase graphene dispersion liquid to be about 45% -46%;
(3) Adding a proper amount of the polyacrylonitrile/sodium thiocyanate solution obtained in the step (1) into the graphene dispersion liquid obtained in the step (2), and carrying out high-shearing and ultrasonic treatment to obtain a graphene/polyacrylonitrile/sodium thiocyanate solution with the mass percent concentration of the polyacrylonitrile of about 2% and the mass percent concentration of the graphene of about 3%;
(4) Adding a proper amount of the graphene/polyacrylonitrile/sodium thiocyanate solution obtained in the step (3) into the polyacrylonitrile/sodium thiocyanate solution obtained in the step (1), and obtaining about 13% of the concentration of the polyacrylonitrile by mass percent through high shearing and ultrasonic treatment, wherein the mass ratio of the total amount of nano graphene and submicron graphene to the polyacrylonitrile is 0.02:1 graphene/polyacrylonitrile/sodium thiocyanate solution.
Example 3
(1) Adding a proper amount of sodium thiocyanate aqueous solution with the mass percent concentration of about 39% into polyacrylonitrile powder, mechanically stirring for 0.5-1h for swelling, and then adding the sodium thiocyanate aqueous solution with the mass percent concentration of about 58% for high-shear dissolution treatment for 1-2h to obtain a polyacrylonitrile/sodium thiocyanate solution with the mass percent concentration of about 13% of polyacrylonitrile and the mass percent concentration of about 45-46%;
(2) Compounding nano graphene and submicron graphene into uniformly dispersed aqueous phase graphene dispersion liquid according to a mass ratio of 1:9 through high shearing and ultrasonic treatment, and then adding sodium thiocyanate to enable the mass percentage concentration of the sodium thiocyanate in the aqueous phase graphene dispersion liquid to be about 45% -46%;
(3) Adding a proper amount of the polyacrylonitrile/sodium thiocyanate solution obtained in the step (1) into the graphene dispersion liquid obtained in the step (2), and obtaining a graphene/polyacrylonitrile/sodium thiocyanate solution with the mass percent concentration of about 3.5% and the mass percent concentration of about 4% of graphene through high shearing and ultrasonic treatment;
(4) Adding a proper amount of the graphene/polyacrylonitrile/sodium thiocyanate solution obtained in the step (3) into the polyacrylonitrile/sodium thiocyanate solution obtained in the step (1), and obtaining about 13% of the concentration of the polyacrylonitrile by mass percent through high shearing and ultrasonic treatment, wherein the mass ratio of the total amount of nano graphene and submicron graphene to the polyacrylonitrile is 0.02:1 graphene/polyacrylonitrile/sodium thiocyanate solution.
Example 4
(1) Adding a proper amount of sodium thiocyanate aqueous solution with the mass percent concentration of about 39% into polyacrylonitrile powder, mechanically stirring for 0.5-1h for swelling, and then adding the sodium thiocyanate aqueous solution with the mass percent concentration of about 58% for high-shear dissolution treatment for 1-2h to obtain a polyacrylonitrile/sodium thiocyanate solution with the mass percent concentration of about 13% and the mass percent concentration of about 45-46%;
(2) Compounding nano graphene and submicron graphene into uniformly dispersed aqueous phase graphene dispersion liquid according to a mass ratio of 1:2.5 through high shearing and ultrasonic treatment, and then adding sodium thiocyanate to enable the mass percentage concentration of the sodium thiocyanate in the aqueous phase graphene dispersion liquid to be about 45% -46%;
(3) Adding a proper amount of the polyacrylonitrile/sodium thiocyanate solution obtained in the step (1) into the graphene dispersion liquid obtained in the step (2), and obtaining a graphene/polyacrylonitrile/sodium thiocyanate solution with the mass percent concentration of about 3% and the mass percent concentration of about 3.5% of graphene through high shearing and ultrasonic treatment;
(4) Adding a proper amount of the graphene/polyacrylonitrile/sodium thiocyanate solution obtained in the step (3) into the polyacrylonitrile/sodium thiocyanate solution obtained in the step (1), and obtaining about 13% of the concentration of the polyacrylonitrile by mass percent through high shearing and ultrasonic treatment, wherein the mass ratio of the total amount of nano graphene and submicron graphene to the polyacrylonitrile is 0.02:1 graphene/polyacrylonitrile/sodium thiocyanate solution.
Example 5
(1) Adding a proper amount of sodium thiocyanate aqueous solution with the mass percent concentration of about 39% into polyacrylonitrile powder, mechanically stirring for 0.5-1h for swelling, and then adding the sodium thiocyanate aqueous solution with the mass percent concentration of about 58% for high-shear dissolution treatment for 1-2h to obtain a polyacrylonitrile/sodium thiocyanate solution with the mass percent concentration of about 13% and the mass percent concentration of about 45-46%;
(2) Compounding nano graphene and submicron graphene into uniformly dispersed aqueous phase graphene dispersion liquid according to a mass ratio of 1:3 through high shearing and ultrasonic treatment, and then adding sodium thiocyanate to enable the mass percentage concentration of the sodium thiocyanate in the aqueous phase graphene dispersion liquid to be about 45% -46%;
(3) Adding a proper amount of the polyacrylonitrile/sodium thiocyanate solution obtained in the step (1) into the graphene dispersion liquid obtained in the step (2), and obtaining a graphene/polyacrylonitrile/sodium thiocyanate solution with the mass percent concentration of about 3.5% of the polyacrylonitrile and the mass percent concentration of about 2% of the graphene through high shearing and ultrasonic treatment;
(4) Adding a proper amount of the graphene/polyacrylonitrile/sodium thiocyanate solution obtained in the step (3) into the polyacrylonitrile/sodium thiocyanate solution obtained in the step (1), and obtaining about 13% of the concentration of the polyacrylonitrile by mass percent through high shearing and ultrasonic treatment, wherein the mass ratio of the total amount of nano graphene and submicron graphene to the polyacrylonitrile is 0.035:1 graphene/polyacrylonitrile/sodium thiocyanate solution.
Example 6
(1) Adding a proper amount of sodium thiocyanate aqueous solution with the mass percent concentration of about 39% into polyacrylonitrile powder, mechanically stirring for 0.5-1h for swelling, and then adding a sodium thiocyanate aqueous solution with the mass percent of about 58% for high-shear dissolution treatment for 1-2h to obtain a polyacrylonitrile/sodium thiocyanate solution with the mass percent concentration of about 13% of polyacrylonitrile and the mass percent concentration of about 45% -46%;
(2) Nano graphene and submicron graphene are subjected to high shear and ultrasonic treatment according to a mass ratio of 1:9, compounding into uniformly dispersed aqueous phase graphene dispersion liquid, and then adding sodium thiocyanate to enable the mass percentage concentration of the sodium thiocyanate in the aqueous phase graphene dispersion liquid to be about 45% -46%;
(3) Adding a proper amount of the polyacrylonitrile/sodium thiocyanate solution obtained in the step (1) into the graphene dispersion liquid obtained in the step (2), and obtaining a graphene/polyacrylonitrile/sodium thiocyanate solution with the mass percent concentration of about 3.5% and the mass percent concentration of about 4.5% of graphene through high shearing and ultrasonic treatment;
(4) Adding a proper amount of the graphene/polyacrylonitrile/sodium thiocyanate solution obtained in the step (3) into the polyacrylonitrile/sodium thiocyanate solution obtained in the step (1), and obtaining about 13% of the concentration of the polyacrylonitrile by mass percent through high shearing and ultrasonic treatment, wherein the mass ratio of the total amount of nano graphene and submicron graphene to the polyacrylonitrile is 0.035:1 graphene/polyacrylonitrile/sodium thiocyanate solution.
Example 7
(1) Adding a proper amount of sodium thiocyanate aqueous solution with the mass percent concentration of about 39% into polyacrylonitrile powder, mechanically stirring for 0.5-1h for swelling, and then adding a sodium thiocyanate aqueous solution with the mass percent of about 58% for high-shear dissolution treatment for 1-2h to obtain a polyacrylonitrile/sodium thiocyanate solution with the mass percent concentration of about 13% of polyacrylonitrile and the mass percent concentration of about 45% -46%;
(2) Preparing nano graphene into uniformly dispersed aqueous phase graphene dispersion liquid through high shearing and ultrasonic treatment, and then adding sodium thiocyanate to enable the mass percentage concentration of the sodium thiocyanate in the aqueous phase graphene dispersion liquid to be about 45% -46%;
(3) Adding a proper amount of the polyacrylonitrile/sodium thiocyanate solution obtained in the step (1) into the graphene dispersion liquid obtained in the step (2), and obtaining a graphene/polyacrylonitrile/sodium thiocyanate solution with the mass percent concentration of about 3.5% of the polyacrylonitrile and the mass percent concentration of about 3% of the graphene through high shearing and ultrasonic treatment;
(4) Adding a proper amount of the graphene/polyacrylonitrile/sodium thiocyanate solution obtained in the step (3) into the polyacrylonitrile/sodium thiocyanate solution obtained in the step (1), and carrying out high-shear and ultrasonic treatment to obtain the graphene/sodium thiocyanate solution with the mass percentage concentration of about 12% of polyacrylonitrile, wherein the mass ratio of the total amount of nano graphene and submicron graphene to the polyacrylonitrile is 0.02:1 graphene/polyacrylonitrile/sodium thiocyanate solution.
Example 8
(1) Adding a proper amount of sodium thiocyanate aqueous solution with the mass percent concentration of about 39% into polyacrylonitrile powder, mechanically stirring for 0.5-1h for swelling, and then adding a sodium thiocyanate aqueous solution with the mass percent of about 58% for high-shear dissolution treatment for 1-2h to obtain a polyacrylonitrile/sodium thiocyanate solution with the mass percent concentration of about 13% of polyacrylonitrile and the mass percent concentration of about 45% -46%;
(2) Preparing submicron graphene into uniformly dispersed aqueous phase graphene dispersion liquid through high shearing and ultrasonic treatment, and then adding sodium thiocyanate to enable the mass percentage concentration of the sodium thiocyanate in the aqueous phase graphene dispersion liquid to be about 45% -46%;
(3) Adding a proper amount of the polyacrylonitrile/sodium thiocyanate solution obtained in the step (1) into the graphene dispersion liquid obtained in the step (2), and obtaining a graphene/polyacrylonitrile/sodium thiocyanate solution with the mass percent concentration of about 3.5% and the mass percent concentration of about 4.5% of graphene through high shearing and ultrasonic treatment;
(4) Adding a proper amount of the graphene/polyacrylonitrile/sodium thiocyanate solution obtained in the step (3) into the polyacrylonitrile/sodium thiocyanate solution obtained in the step (1), and obtaining about 13% of the concentration of the polyacrylonitrile by mass percent through high shearing and ultrasonic treatment, wherein the mass ratio of the total amount of nano graphene and submicron graphene to the polyacrylonitrile is 0.035:1 graphene/polyacrylonitrile/sodium thiocyanate solution.
The spinning solutions obtained in examples 1 to 6 all have good spinnability, and compared with the pure polyacrylonitrile fiber (comparative example) in the prior art, the specific resistance of the graphene/polyacrylonitrile fiber prepared by adopting the spinning solution is improved by 3-5 orders of magnitude, and the strength is improved by more than 20%, as shown in table 1.
TABLE 1 graphene/Polyacrylonitrile fiber Performance data prepared with the spinning dope of the examples
| Examples | Specific resistance (omega cm) | Intensity (cN/dtex) |
| Example 1 | 2.9×10 7 | 5.02 |
| Example 2 | 3.2×10 7 | 4.89 |
| Example 3 | 7.6×10 7 | 4.25 |
| Example 4 | 3.2×10 6 | 5.00 |
| Example 5 | 6.3×10 7 | 5.12 |
| Example 6 | 4.8×10 7 | 4.79 |
| Example 7 | 7.9×10 9 | 4.82 |
| Example 8 | 6.5×10 10 | 4.63 |
| Comparative example | 9.6×10 12 | 3.82 |
Claims (7)
1. The graphene/polyacrylonitrile composite fiber is characterized in that a spinning solution of the graphene/polyacrylonitrile composite fiber is a solution in which polyacrylonitrile is uniformly dissolved and nano graphene and submicron graphene are uniformly dispersed;
the preparation method of the spinning solution comprises the following steps: firstly, uniformly mixing a part of solution in which polyacrylonitrile is uniformly dissolved with a solution in which nano graphene and submicron graphene are uniformly dispersed, and preparing spinning precursor liquid; then taking part or all of the spinning precursor liquid and the rest solution which is uniformly dissolved with polyacrylonitrile, and uniformly mixing to prepare spinning solution;
the mass ratio of the total amount of the nano graphene and the submicron graphene to the polyacrylonitrile is 0.008-0.035: 1, the mass ratio of the nano graphene to the submicron graphene is 1:1 to 9;
the size of the nano graphene is 50-300nm, and the thickness is 1-1.5 nm;
the size of the submicron graphene is 400-800nm, and the thickness is 1-1.5 nm.
2. The spinning solution for preparing the graphene/polyacrylonitrile composite fiber according to claim 1 is characterized in that the mass percentage concentration of the polyacrylonitrile in the spinning solution system is 10% -13%.
3. The method for preparing the spinning dope of the graphene/polyacrylonitrile composite fiber according to claim 2, wherein the steps include: firstly, uniformly mixing a part of solution in which polyacrylonitrile is uniformly dissolved with a solution in which nano graphene and submicron graphene are uniformly dispersed, and preparing spinning precursor liquid; and then taking part or all of the spinning precursor liquid and the rest solution which is uniformly dissolved with polyacrylonitrile, and uniformly mixing to obtain the spinning solution.
4. A method of preparing as claimed in claim 3, wherein the steps comprise: firstly, adding a solution with part of polyacrylonitrile uniformly dissolved into the solution with the nano graphene and the submicron graphene uniformly dispersed, and applying ultrasonic and high shearing actions while adding until the solution is uniformly mixed to prepare spinning precursor liquid; and adding part or all of the spinning precursor liquid into the rest solution uniformly dissolved with polyacrylonitrile, and applying ultrasonic and high shearing actions while adding until the spinning precursor liquid is uniformly mixed to obtain the spinning solution.
5. The preparation method according to claim 3 or 4, wherein in the spinning precursor liquid system, the mass percentage concentration of polyacrylonitrile is 0.5% -3%, and the mass ratio of the total amount of nano graphene and submicron graphene to polyacrylonitrile is 0.5-9: 1, a step of;
in the spinning solution system, the mass percentage concentration of the polyacrylonitrile is 10% -13%, and the mass ratio of the total amount of the nano graphene and the submicron graphene to the polyacrylonitrile is 0.008-0.035: 1, a step of;
the solvent used in the spinning precursor liquid system and the spinning solution system comprises an organic solvent or an inorganic solvent, wherein the organic solvent comprises dimethylformamide, dimethylacetamide, dimethyl sulfoxide, acetone or carbonic ester, and the inorganic solvent comprises sodium thiocyanate aqueous solution, concentrated nitric acid or zinc chloride aqueous solution.
6. The method according to claim 3 or 4, wherein the preparation of the solution in which polyacrylonitrile is uniformly dissolved comprises: adding a pre-sodium thiocyanate aqueous solution into polyacrylonitrile, stirring and swelling, and then adding a post-sodium thiocyanate aqueous solution for high-shear dissolution to obtain a solution in which the polyacrylonitrile is uniformly dissolved.
7. The method according to claim 3 or 4, wherein the preparation of the solution in which the nano-graphene and the sub-micro-graphene are uniformly dispersed comprises: and uniformly dispersing the nano graphene and the submicron graphene in a solvent under the action of high shear and ultrasonic to obtain a solution in which the nano graphene and the submicron graphene are uniformly dispersed.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910989867.7A CN112680811B (en) | 2019-10-17 | 2019-10-17 | Graphene/polyacrylonitrile composite fiber, spinning solution and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910989867.7A CN112680811B (en) | 2019-10-17 | 2019-10-17 | Graphene/polyacrylonitrile composite fiber, spinning solution and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN112680811A CN112680811A (en) | 2021-04-20 |
| CN112680811B true CN112680811B (en) | 2024-02-27 |
Family
ID=75444845
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910989867.7A Active CN112680811B (en) | 2019-10-17 | 2019-10-17 | Graphene/polyacrylonitrile composite fiber, spinning solution and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112680811B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115928241B (en) * | 2022-03-11 | 2024-06-07 | 北京服装学院 | Green structural color fiber containing graphene and polyacrylonitrile and preparation method thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20100099586A (en) * | 2009-03-03 | 2010-09-13 | 한국과학기술연구원 | Graphene composite nanofiber and the preparation method thereof |
| CN102560746A (en) * | 2011-12-29 | 2012-07-11 | 中国科学院宁波材料技术与工程研究所 | Preparation method of polyacrylonitrile/graphene composite-based carbon fiber |
| CN104862807A (en) * | 2015-04-09 | 2015-08-26 | 浙江泰索科技有限公司 | High thermal conductivity acrylic fiber and preparation method thereof |
| CN104862828A (en) * | 2015-04-09 | 2015-08-26 | 浙江泰索科技有限公司 | High thermal conductivity carbon fiber and preparation method thereof |
| WO2016188310A1 (en) * | 2015-05-22 | 2016-12-01 | 济南圣泉集团股份有限公司 | Multifunctional viscose fibre and preparation method therefor |
| CN109914037A (en) * | 2019-03-29 | 2019-06-21 | 中原工学院 | A kind of preparation method of non-woven nano-graphene/polyacrylonitrile non-woven fabrics |
-
2019
- 2019-10-17 CN CN201910989867.7A patent/CN112680811B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20100099586A (en) * | 2009-03-03 | 2010-09-13 | 한국과학기술연구원 | Graphene composite nanofiber and the preparation method thereof |
| CN102560746A (en) * | 2011-12-29 | 2012-07-11 | 中国科学院宁波材料技术与工程研究所 | Preparation method of polyacrylonitrile/graphene composite-based carbon fiber |
| CN104862807A (en) * | 2015-04-09 | 2015-08-26 | 浙江泰索科技有限公司 | High thermal conductivity acrylic fiber and preparation method thereof |
| CN104862828A (en) * | 2015-04-09 | 2015-08-26 | 浙江泰索科技有限公司 | High thermal conductivity carbon fiber and preparation method thereof |
| WO2016188310A1 (en) * | 2015-05-22 | 2016-12-01 | 济南圣泉集团股份有限公司 | Multifunctional viscose fibre and preparation method therefor |
| CN109914037A (en) * | 2019-03-29 | 2019-06-21 | 中原工学院 | A kind of preparation method of non-woven nano-graphene/polyacrylonitrile non-woven fabrics |
Non-Patent Citations (1)
| Title |
|---|
| 石墨烯微片的尺寸和形态对聚丙烯基纳米复合材料导电导热性能的影响;余浩斌等;中国塑料;第32卷(第3期);第51页摘要 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN112680811A (en) | 2021-04-20 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107383405B (en) | Composite proton exchange membrane and preparation method thereof | |
| CN100535209C (en) | Method of preparing Lyocell fiber containing carbon nano tube | |
| EP2011815B1 (en) | The use of aqueous solution of sodium-hydroxide and sulfourea in producing cellulose products in pilot-scale | |
| CN103993380A (en) | Method for preparing high-strength chitosan fiber | |
| DE112018001356T5 (en) | Modified fiber product, manufacturing method thereof and use thereof | |
| CN103613790B (en) | A kind of preparation method of cellulose base matrix material | |
| WO2021015078A1 (en) | Cellulose fiber containing carbon nanotube, and method for producing same | |
| JP6316577B2 (en) | Method for producing carbon nanotube-containing fiber and carbon nanotube-containing fiber | |
| CN106435830A (en) | High strength chitosan complex fiber and preparing method thereof | |
| WO2007128268A2 (en) | Method for the production of multicomponent cellulose fibers | |
| CN106435797B (en) | A kind of preparation method of cellulose/carbon nano composite fibre | |
| JP2010510405A (en) | Cellulose dissolution and processing | |
| KR20190140281A (en) | Carbon nanotube nanocomposite conducting multifiber and manufacturing method the same | |
| CN102432892B (en) | Method for dissolving cellulose and method for preparing regenerated fiber | |
| DE102011080548A1 (en) | Precursor fibers based on renewable raw materials | |
| CN112680811B (en) | Graphene/polyacrylonitrile composite fiber, spinning solution and preparation method thereof | |
| CN106381564A (en) | Preparation method of functional regeneration cellulose fiber | |
| US20190032250A1 (en) | Wet spinning method for producing a lignin-containing fiber as a precursor for a carbon fiber | |
| CN113832560B (en) | Clay-cellulose-alginic acid composite flame-retardant large fiber and preparation and application thereof | |
| CN109913965B (en) | In-situ self-assembly cellulose/graphene composite fiber of co-alkali system and preparation method thereof | |
| CN108866665A (en) | Antibacterial cellulose composite fibre and preparation method thereof | |
| CN106179497A (en) | A kind of preparation method of metal nanoparticles loaded nano-fiber composite film | |
| CN110042499A (en) | The preparation method of the alginate fibre of electric conductivity enhancing | |
| JP7154816B2 (en) | Ultrafine short fibers and a composite in which said ultrafine short fibers are dispersed in a resin composition | |
| CN106189376A (en) | Carbon nanotube dust pretreating process |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |