CN102828267B - Preparation method of conductive high-strength graphene-reinforced polymer fiber - Google Patents
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- 238000002360 preparation method Methods 0.000 title claims abstract description 19
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- 239000006185 dispersion Substances 0.000 claims abstract description 20
- 238000003756 stirring Methods 0.000 claims abstract description 20
- 229920000642 polymer Polymers 0.000 claims abstract description 17
- 239000002994 raw material Substances 0.000 claims abstract description 13
- 238000009987 spinning Methods 0.000 claims abstract description 12
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- 239000007864 aqueous solution Substances 0.000 claims description 13
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 11
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 11
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- 238000000465 moulding Methods 0.000 claims description 9
- QNILTEGFHQSKFF-UHFFFAOYSA-N n-propan-2-ylprop-2-enamide Chemical compound CC(C)NC(=O)C=C QNILTEGFHQSKFF-UHFFFAOYSA-N 0.000 claims description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 8
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- 235000011121 sodium hydroxide Nutrition 0.000 claims description 8
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical group [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 7
- 239000002202 Polyethylene glycol Substances 0.000 claims description 7
- 239000001110 calcium chloride Substances 0.000 claims description 7
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 7
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- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 6
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- 229920002125 Sokalan® Polymers 0.000 claims description 6
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 6
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 claims description 6
- 239000004584 polyacrylic acid Substances 0.000 claims description 6
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- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 6
- 238000007711 solidification Methods 0.000 claims description 6
- 230000008023 solidification Effects 0.000 claims description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 5
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 claims description 5
- 229940071870 hydroiodic acid Drugs 0.000 claims description 5
- HDZGCSFEDULWCS-UHFFFAOYSA-N monomethylhydrazine Chemical compound CNN HDZGCSFEDULWCS-UHFFFAOYSA-N 0.000 claims description 4
- HKOOXMFOFWEVGF-UHFFFAOYSA-N phenylhydrazine Chemical compound NNC1=CC=CC=C1 HKOOXMFOFWEVGF-UHFFFAOYSA-N 0.000 claims description 4
- 229940067157 phenylhydrazine Drugs 0.000 claims description 4
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 claims description 3
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims description 3
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 3
- 239000004952 Polyamide Substances 0.000 claims description 3
- 235000019270 ammonium chloride Nutrition 0.000 claims description 3
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- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 3
- 239000001488 sodium phosphate Substances 0.000 claims description 3
- 229910000162 sodium phosphate Inorganic materials 0.000 claims description 3
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims description 3
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- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 8
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 5
- 229940068984 polyvinyl alcohol Drugs 0.000 description 5
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Abstract
The invention discloses a preparation method of conductive high-strength graphene-reinforced polymer fiber, which comprises the following steps of: (1) dissolving a graphene oxide raw material in solvent, and carrying out ultrasonic treatment to obtain graphene oxide dispersion; (2) dissolving a polymer in solvent to obtain a polymer solution; and (3) adding the graphene oxide dispersion obtained in the step (1) to the polymer solution obtained in the step (2) under stirring, continuing stirring after complete addition, adding a reducing agent, centrifuging or carrying out rotary evaporation treatment, concentrating, transferring to a spinning device, continuously extruding from a spinning head at uniform speed, forming after entering a solidifying solution, and collecting to a roller to obtain continuous graphene-reinforced polymer fiber. The preparation method is simple and convenient, low in cost and multiple in used polymer variety, and is suitable for large-scale industrialized production; and the produced fiber has excellent mechanical property and better conductivity, and can be used for power transmission, antistatic textile, engineering material engineering material and other fields.
Description
Technical field
The present invention relates to the polymer fiber that Graphene strengthens, relate in particular to a kind of conduction, high strength, the preparation method of the polymer fiber that the Graphene of high tenacity strengthens.
Background technology
Graphene be one deck by carbon atom with sp
2hydridization is connected and the two-dimensional material that forms.From the A. K. Geim of 2004 Nian Bei Britain (K. S. Novoselov, et al. Science, 2004,
306, 666-669) find to have caused so far that science and industrial quarters pay close attention to widely.This material have the intensity that known materials is the highest (Science, 2008,
321, 385-388), excellent electric conductivity and thermal conductivity.Take native graphite as raw material, the batch production of Graphene can realize by chemical oxidation-reducing process (Tung, V. C., et al. Nature Nanotechnol., 2009,
4, 25 – 29).The Graphene that this method is produced has been widely used in various composites, thereby increases the mechanical property of material, conduction and heat conductivility.But up to now, the composite that this Graphene strengthens is only confined to membrane material, and it can be applied to the Material Field of other shapes not yet report.Fiber, as a kind of common material type, is widely used in national defense and military and various civil area.The polymer fiber that Graphene strengthens, can be by the adding of a small amount of Graphene, thereby realize fiber at mechanics, the larger raising of conduction and heat conduction aspect performance.
Summary of the invention
The object of the invention is for existing technical deficiency, the preparation method of the polymer fiber that a kind of high-intensity Graphene of conduction strengthens is provided
The preparation method of the polymer fiber that the high-intensity Graphene of conduction strengthens comprises the following steps:
1) the graphene oxide raw material of 1 weight portion is dissolved in to the solvent of 50～5000 weight portions, in the ultra sonic bath of 1～50Hz, processes 0.1～1 hour, obtain graphene oxide dispersion liquid;
2) by the polymer dissolution of 1～1000 weight portion in the solvent of 20～4000000 weight portions, obtain polymer solution;
3) graphene oxide dispersion liquid step 1) being obtained joins step 2) in the polymer solution that obtains, add while stirring, add rear continuation to stir completely 0.1～48 hour, add 1 weight portion reductant, centrifugal or revolve and steam to process, concentrated, proceed in device for spinning, from diameter, be that 5～1000 μ m spinnerets, continuously and smoothly extrudes, enter after stopping 1S～100h moulding in solidification liquid and collect on roller bearing, obtain the polymer fiber that continuous Graphene strengthens.
Described solvent is that one or more mixing of water, DMF, DMA, 1-METHYLPYRROLIDONE, methyl alcohol, ethanol, isopropyl alcohol, n-butanol or ethylene glycol form.Described polymer is that one or more mixing in polyvinyl alcohol, polyethylene glycol, Carboxymethyl Cellulose, polyacrylic acid, poly hydroxy ethyl acrylate, poly-N-isopropyl acrylamide, polyamide, polyacrylamide or polystyrene form.Described reductant is hydrazine, methyl hydrazine, phenylhydrazine, NaOH, KOH, ammoniacal liquor or hydroiodic acid.Described solidification liquid is that one or more mixing of calcium chloride water, sodium hydrate aqueous solution, aqueous sodium persulfate solution, calcium chloride water, sodium nitrate aqueous solution, calcium nitrate aqueous solution, sodium phosphate aqueous solution, aqueous ammonium chloride solution, ammoniacal liquor, acetone, methyl alcohol, oxolane or ethyl acetate form.
The beneficial effect that the present invention compared with prior art has:
1) raw material adopts graphene oxide, and raw material is easy to get, cost is low;
2) directly graphene oxide and polymer are carried out to blend in solution, do not need deoxygenation, do not need to add catalyst etc., whole process is very simple.
3) adopt the method for solution spinning to prepare the polymer fiber that Graphene strengthens, easy and simple to handle;
4) polymer fiber that the Graphene making strengthens has good intensity and toughness;
5) polymer fiber that the Graphene making strengthens has good antistatic behaviour.
Accompanying drawing explanation
Fig. 1 is the digital camera photo of the polymer fiber of Graphene enhancing;
Fig. 2 (a) is the polymer fiber stereoscan photograph that Graphene strengthens;
Fig. 2 (b) is the polymer fiber stereoscan photograph that the Graphene of amplification strengthens.
The specific embodiment
The preparation method of the polymer fiber that the high-intensity Graphene of conduction strengthens comprises the following steps:
1) the graphene oxide raw material of 1 weight portion is dissolved in to the solvent of 50～5000 weight portions, in the ultra sonic bath of 1～50Hz, processes 0.1～1 hour, obtain graphene oxide dispersion liquid;
2) by the polymer dissolution of 1～1000 weight portion in the solvent of 20～4000000 weight portions, obtain polymer solution;
3) graphene oxide dispersion liquid step 1) being obtained joins step 2) in the polymer solution that obtains, add while stirring, add rear continuation to stir completely 0.1～48 hour, add reductant, centrifugal or revolve and steam to process, concentrated, proceed in device for spinning, from diameter, be that 5～1000 μ m spinnerets, continuously and smoothly extrudes, enter after stopping 1S～100h moulding in solidification liquid and collect on roller bearing, obtain the polymer fiber that continuous Graphene strengthens.
Described solvent is that one or more mixing of water, DMF, DMA, 1-METHYLPYRROLIDONE, methyl alcohol, ethanol, isopropyl alcohol, n-butanol or ethylene glycol form.Described polymer is that one or more mixing in polyvinyl alcohol, polyethylene glycol, Carboxymethyl Cellulose, polyacrylic acid, poly hydroxy ethyl acrylate, poly-N-isopropyl acrylamide, polyamide, polyacrylamide or polystyrene form.Described reductant is hydrazine, methyl hydrazine, phenylhydrazine, NaOH, KOH, ammoniacal liquor or hydroiodic acid.Described solidification liquid is that one or more mixing of calcium chloride water, sodium hydrate aqueous solution, aqueous sodium persulfate solution, calcium chloride water, sodium nitrate aqueous solution, calcium nitrate aqueous solution, sodium phosphate aqueous solution, aqueous ammonium chloride solution, ammoniacal liquor, acetone, methyl alcohol, oxolane or ethyl acetate form.
Below by embodiment, the present invention is specifically described; the present embodiment is only for the present invention is described further; can not be interpreted as limiting the scope of the invention, those skilled in the art makes some nonessential changes and adjusts according to the content of foregoing invention and all belongs to protection scope of the present invention.
Embodiment 1
1) the graphene oxide raw material of 1 weight portion is dissolved in to the water of 50 weight portions, in the ultra sonic bath of 1Hz, processes 0.1 hour, obtain graphene oxide dispersion liquid;
2) polyvinyl alcohol of 1 weight portion is dissolved in to the water of 20 weight portions, obtains poly-vinyl alcohol solution;
3) graphene oxide dispersion liquid step 1) being obtained joins step 2) in the poly-vinyl alcohol solution that obtains, add while stirring, add rear continuation to stir completely 0.1 hour, add 1 weight portion hydrazine, centrifugal, concentrated, proceed in device for spinning, from diameter, be that 5 μ m spinnerets, continuously and smoothly extrudes, enter after stopping 1S moulding in acetone and collect on roller bearing, obtain the vinal that continuous Graphene strengthens.
Through above step, the diameter of the vinal obtaining is 3～5 μ m, and graphene film is along the axially-aligned of fiber.The vinal TENSILE STRENGTH that the Graphene of preparation strengthens is 200～500MPa, and elongation at break is 1%～10%.
Embodiment 2
1) the graphene oxide raw material of 1 weight portion is dissolved in to the DMF of 5000 weight portions, in the ultra sonic bath of 50Hz, processes 1 hour, obtain graphene oxide dispersion liquid;
2) polystyrene of 1000 weight portions is dissolved in to the DMF of 4000000 weight portions, obtains polystyrene solution;
3) graphene oxide dispersion liquid step 1) being obtained joins step 2) in the polystyrene solution that obtains, add while stirring, add rear continuation to stir completely 48 hours, add phenylhydrazine, revolve to steam and process, concentrated, proceed in device for spinning, from diameter, be that 1000 μ m spinnerets, continuously and smoothly extrudes, enter after stopping 100h moulding in calcium chloride water and collect on roller bearing, obtain the styroflex that continuous Graphene strengthens.
Through above step, the diameter of the styroflex obtaining is 500～800 μ m, and graphene film is along the axially-aligned of fiber.The styroflex TENSILE STRENGTH that the Graphene of preparation strengthens is 50～100MPa, and elongation at break is 1%～5%.
Embodiment 3
1) the graphene oxide raw material of 1 weight portion is dissolved in to the ethylene glycol of 1000 weight portions, in the ultra sonic bath of 40Hz, processes 0.5 hour, obtain graphene oxide dispersion liquid;
2) polyethylene glycol of 20 weight portions is dissolved in to the ethylene glycol of 1000000 weight portions, obtains polyglycol solution;
3) graphene oxide dispersion liquid step 1) being obtained joins step 2) in the polyglycol solution that obtains, add while stirring, add rear continuation to stir completely 24 hours, add methyl hydrazine, centrifugal or revolve and steam to process, concentrated, proceed in device for spinning, from diameter, be that 50 μ m spinnerets, continuously and smoothly extrudes, enter after stopping 30S moulding in ethyl acetate and collect on roller bearing, obtain the polyethylene glycol fiber that continuous Graphene strengthens.
Through above step, the diameter of the polyethylene glycol fiber obtaining is 30～45 μ m, and graphene film is along the axially-aligned of fiber.The polyethylene glycol tensile strength of fiber that the Graphene of preparation strengthens is 150～200MPa, and elongation at break is 5%～10%.
Embodiment 4
1) the graphene oxide raw material of 1 weight portion is dissolved in to the DMA of 3000 weight portions, in the ultra sonic bath of 30Hz, processes 40 minutes, obtain graphene oxide dispersion liquid;
2) Carboxymethyl Cellulose of 10 weight portions is dissolved in to the DMA of 200000 weight portions, obtains Carboxymethyl Cellulose solution;
3) graphene oxide dispersion liquid step 1) being obtained joins step 2) in the Carboxymethyl Cellulose solution that obtains, add while stirring, add rear continuation to stir completely 2 hours, add hydroiodic acid, centrifugal, concentrated, proceed in device for spinning, from diameter, be that 10 μ m spinnerets, continuously and smoothly extrudes, enter after stopping moulding in 1 minute in sodium hydrate aqueous solution and collect on roller bearing, obtain the Carboxymethyl Cellulose fiber that continuous Graphene strengthens.
Through above step, the diameter of the Carboxymethyl Cellulose fiber obtaining is 5～9 μ m, and graphene film is along the axially-aligned of fiber.The Carboxymethyl Cellulose tensile strength of fiber that the Graphene of preparation strengthens is 80～120MPa, and elongation at break is 50%～100%.
Embodiment 5
1) the graphene oxide raw material of 1 weight portion is dissolved in to the ethanol of 4000 weight portions, in the ultra sonic bath of 40Hz, processes 15 minutes, obtain graphene oxide dispersion liquid;
2) polyacrylic acid of 50 weight portions is dissolved in to the ethanol of 3000000 weight portions, obtains polyacrylic acid solution;
3) graphene oxide dispersion liquid step 1) being obtained joins step 2) in the polyacrylic acid solution that obtains, add while stirring, add rear continuation to stir completely 10 hours, add hydroiodic acid, centrifugal or revolve and steam to process, concentrated, proceed in device for spinning, from diameter, be that 100 μ m spinnerets, continuously and smoothly extrudes, enter after stopping 1h moulding in oxolane and collect on roller bearing, obtain the polyacrylic fibre that continuous Graphene strengthens.
Through above step, the diameter of the polyacrylic fibre obtaining is 50～80 μ m, and graphene film is along the axially-aligned of fiber.The polyacrylic fibre TENSILE STRENGTH that the Graphene of preparation strengthens is 50～100MPa, and elongation at break is 30%～50%.
Embodiment 6
1) the graphene oxide raw material of 1 weight portion is dissolved in to (volume ratio is 1:1) in the water of 100 weight portions and the mixed solution of DMF, in the ultra sonic bath of 20Hz, processes 45 minutes, obtain graphene oxide dispersion liquid;
2) poly-N-isopropyl acrylamide of 500 weight portions is dissolved in to (volume ratio is 1:1) in the water of 3000000 weight portions and the mixed solution of DMF, obtains poly-N-isopropyl acrylamide solution;
3) graphene oxide dispersion liquid step 1) being obtained joins step 2) in the poly-N-isopropyl acrylamide solution that obtains, add while stirring, add rear continuation to stir completely 0.1～48 hour, add NaOH, centrifugal or revolve and steam to process, concentrated, proceed in device for spinning, from diameter, be that 200 μ m spinnerets, continuously and smoothly extrudes, enter after stopping 0.5h moulding in the mixed liquor (volume ratio is 1:1) of oxolane and ethyl acetate and collect on roller bearing, obtain the poly-N-isopropyl acrylamide fiber that continuous Graphene strengthens.
Through above step, the diameter of the poly-N-isopropyl acrylamide fiber obtaining is 100～180 μ m, and graphene film is along the axially-aligned of fiber.The poly-N-isopropyl acrylamide tensile strength of fiber that the Graphene of preparation strengthens is 50～150MPa, and elongation at break is 10%～40%.
Claims (5)
1. a preparation method for the polymer fiber that the high-intensity Graphene of conduction strengthens, is characterized in that comprising the following steps:
1) the graphene oxide raw material of 1 weight portion is dissolved in to the solvent of 50～5000 weight portions, in the ultra sonic bath of 1～50Hz, processes 0.1～1 hour, obtain graphene oxide dispersion liquid;
2) by the polymer dissolution of 1～1000 weight portion in the solvent of 20～4000000 weight portions, obtain polymer solution;
3) graphene oxide dispersion liquid step 1) being obtained joins step 2) in the polymer solution that obtains, add while stirring, add rear continuation to stir completely 0.1～48 hour, add 1 weight portion reductant, centrifugal or revolve and steam to process, concentrated, proceed in device for spinning, from diameter, be that 5～1000 μ m spinnerets, continuously and smoothly extrudes, enter after stopping 1s～100h moulding in solidification liquid and collect on roller bearing, obtain the polymer fiber that continuous Graphene strengthens.
2. the preparation method of the polymer fiber that the high-intensity Graphene of a kind of conduction according to claim 1 strengthens, it is characterized in that described solvent is water, N, one or more of dinethylformamide, DMA, 1-METHYLPYRROLIDONE, methyl alcohol, ethanol, isopropyl alcohol, n-butanol or ethylene glycol mix and form.
3. the preparation method of the polymer fiber that the high-intensity Graphene of a kind of conduction according to claim 1 strengthens, is characterized in that described polymer is one or more mixing compositions in polyvinyl alcohol, polyethylene glycol, Carboxymethyl Cellulose, polyacrylic acid, poly hydroxy ethyl acrylate, poly-N-isopropyl acrylamide, polyamide, polyacrylamide or polystyrene.
4. the preparation method of the polymer fiber that the high-intensity Graphene of a kind of conduction according to claim 1 strengthens, is characterized in that described reductant is hydrazine, methyl hydrazine, phenylhydrazine, NaOH, KOH, ammoniacal liquor or hydroiodic acid.
5. the preparation method of the polymer fiber that the high-intensity Graphene of a kind of conduction according to claim 1 strengthens, is characterized in that described solidification liquid is one or more mixing compositions of calcium chloride water, sodium hydrate aqueous solution, aqueous sodium persulfate solution, calcium chloride water, sodium nitrate aqueous solution, calcium nitrate aqueous solution, sodium phosphate aqueous solution, aqueous ammonium chloride solution, ammoniacal liquor, acetone, methyl alcohol, oxolane or ethyl acetate.
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| CN103710790A (en) * | 2013-12-30 | 2014-04-09 | 厦门翔鹭化纤股份有限公司 | Antistatic, antibacterial and graphene-reinforced composite polyester fiber and preparation method thereof |
| CN104328533A (en) * | 2014-11-10 | 2015-02-04 | 沙嫣 | Preparation method of high-strength and high-modulus polyvinyl alcohol-graphene nano composite fibers |
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