CN104695040A - Preparation method of high-strength polyacrylonitrile nano-composite fiber - Google Patents
Preparation method of high-strength polyacrylonitrile nano-composite fiber Download PDFInfo
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- CN104695040A CN104695040A CN201510067794.8A CN201510067794A CN104695040A CN 104695040 A CN104695040 A CN 104695040A CN 201510067794 A CN201510067794 A CN 201510067794A CN 104695040 A CN104695040 A CN 104695040A
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- 239000000835 fiber Substances 0.000 title claims abstract description 72
- 229920002239 polyacrylonitrile Polymers 0.000 title claims abstract description 67
- 238000002360 preparation method Methods 0.000 title claims abstract description 33
- 239000002114 nanocomposite Substances 0.000 title claims abstract description 27
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 56
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 43
- 239000000243 solution Substances 0.000 claims abstract description 25
- 238000009987 spinning Methods 0.000 claims abstract description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000003960 organic solvent Substances 0.000 claims abstract description 15
- 230000001112 coagulating effect Effects 0.000 claims abstract description 10
- 239000011259 mixed solution Substances 0.000 claims abstract description 8
- 238000001035 drying Methods 0.000 claims abstract description 7
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229920001577 copolymer Polymers 0.000 claims abstract description 5
- 238000009998 heat setting Methods 0.000 claims abstract description 5
- 239000002253 acid Substances 0.000 claims abstract description 4
- 229920001519 homopolymer Polymers 0.000 claims abstract description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 46
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 21
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 21
- 238000000605 extraction Methods 0.000 claims description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000000178 monomer Substances 0.000 claims description 5
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 4
- 230000005611 electricity Effects 0.000 claims description 4
- 230000004048 modification Effects 0.000 claims description 4
- 238000012986 modification Methods 0.000 claims description 4
- 239000006185 dispersion Substances 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- -1 nitric acid ethylidene ester Chemical class 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims description 2
- WFKAJVHLWXSISD-UHFFFAOYSA-N isobutyramide Chemical compound CC(C)C(N)=O WFKAJVHLWXSISD-UHFFFAOYSA-N 0.000 claims description 2
- 239000011148 porous material Substances 0.000 claims 1
- 238000001914 filtration Methods 0.000 abstract description 6
- 238000004519 manufacturing process Methods 0.000 abstract description 6
- 238000005516 engineering process Methods 0.000 abstract description 4
- 239000000203 mixture Substances 0.000 abstract description 3
- 229910017053 inorganic salt Inorganic materials 0.000 abstract 1
- 238000002156 mixing Methods 0.000 abstract 1
- 238000005507 spraying Methods 0.000 abstract 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 14
- 239000004917 carbon fiber Substances 0.000 description 14
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 14
- 238000000034 method Methods 0.000 description 8
- 239000012046 mixed solvent Substances 0.000 description 8
- 239000002243 precursor Substances 0.000 description 8
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 7
- 239000013078 crystal Substances 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 229910052799 carbon Inorganic materials 0.000 description 5
- 238000012681 fiber drawing Methods 0.000 description 5
- 239000003292 glue Substances 0.000 description 5
- 229910002804 graphite Inorganic materials 0.000 description 5
- 239000010439 graphite Substances 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 230000008901 benefit Effects 0.000 description 4
- 238000003763 carbonization Methods 0.000 description 4
- 238000001891 gel spinning Methods 0.000 description 4
- 230000007547 defect Effects 0.000 description 3
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 2
- JHUFGBSGINLPOW-UHFFFAOYSA-N 3-chloro-4-(trifluoromethoxy)benzoyl cyanide Chemical compound FC(F)(F)OC1=CC=C(C(=O)C#N)C=C1Cl JHUFGBSGINLPOW-UHFFFAOYSA-N 0.000 description 2
- JPAOMENBKRZQDR-UHFFFAOYSA-N CC=CC.[Na] Chemical compound CC=CC.[Na] JPAOMENBKRZQDR-UHFFFAOYSA-N 0.000 description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 229910003460 diamond Inorganic materials 0.000 description 2
- 239000010432 diamond Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000001939 inductive effect Effects 0.000 description 2
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 2
- 238000010791 quenching Methods 0.000 description 2
- 230000000171 quenching effect Effects 0.000 description 2
- MZSDGDXXBZSFTG-UHFFFAOYSA-M sodium;benzenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C1=CC=CC=C1 MZSDGDXXBZSFTG-UHFFFAOYSA-M 0.000 description 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- 229940117958 vinyl acetate Drugs 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- XMWRBQBLMFGWIX-UHFFFAOYSA-N C60 fullerene Chemical compound C12=C3C(C4=C56)=C7C8=C5C5=C9C%10=C6C6=C4C1=C1C4=C6C6=C%10C%10=C9C9=C%11C5=C8C5=C8C7=C3C3=C7C2=C1C1=C2C4=C6C4=C%10C6=C9C9=C%11C5=C5C8=C3C3=C7C1=C1C2=C4C6=C2C9=C5C3=C12 XMWRBQBLMFGWIX-UHFFFAOYSA-N 0.000 description 1
- 230000005355 Hall effect Effects 0.000 description 1
- 241000446313 Lamella Species 0.000 description 1
- 229920000297 Rayon Polymers 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- RHZUVFJBSILHOK-UHFFFAOYSA-N anthracen-1-ylmethanolate Chemical compound C1=CC=C2C=C3C(C[O-])=CC=CC3=CC2=C1 RHZUVFJBSILHOK-UHFFFAOYSA-N 0.000 description 1
- 239000003830 anthracite Substances 0.000 description 1
- 210000001130 astrocyte Anatomy 0.000 description 1
- 230000003796 beauty Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000008280 blood Substances 0.000 description 1
- 210000004369 blood Anatomy 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 229910021387 carbon allotrope Inorganic materials 0.000 description 1
- 238000010000 carbonizing Methods 0.000 description 1
- 210000004027 cell Anatomy 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000005485 electric heating Methods 0.000 description 1
- 230000005307 ferromagnetism Effects 0.000 description 1
- 229940085805 fiberall Drugs 0.000 description 1
- 210000002950 fibroblast Anatomy 0.000 description 1
- 230000005669 field effect Effects 0.000 description 1
- 229910003472 fullerene Inorganic materials 0.000 description 1
- 238000005087 graphitization Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- JFHJOMSTWVDDHW-UHFFFAOYSA-N methyl prop-2-enoate;prop-2-enenitrile Chemical compound C=CC#N.COC(=O)C=C JFHJOMSTWVDDHW-UHFFFAOYSA-N 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000002964 rayon Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- VGTPCRGMBIAPIM-UHFFFAOYSA-M sodium thiocyanate Chemical compound [Na+].[S-]C#N VGTPCRGMBIAPIM-UHFFFAOYSA-M 0.000 description 1
- 238000002166 wet spinning Methods 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
Classifications
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D1/00—Treatment of filament-forming or like material
- D01D1/02—Preparation of spinning solutions
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/06—Wet spinning methods
-
- 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
- D01F6/44—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds
- D01F6/54—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds of polymers of unsaturated nitriles
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D1/00—Treatment of filament-forming or like material
- D01D1/10—Filtering or de-aerating the spinning solution or melt
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D10/00—Physical treatment of artificial filaments or the like during manufacture, i.e. during a continuous production process before the filaments have been collected
- D01D10/02—Heat treatment
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D10/00—Physical treatment of artificial filaments or the like during manufacture, i.e. during a continuous production process before the filaments have been collected
- D01D10/06—Washing or drying
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/12—Stretch-spinning methods
-
- 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
Landscapes
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Mechanical Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Artificial Filaments (AREA)
- Inorganic Fibers (AREA)
Abstract
The invention discloses a preparation method of high-strength polyacrylonitrile nano-composite fiber. The preparation method comprises the following steps: 1, feeding graphene into an organic solvent or a mixed solution of the organic solvent and water, evenly dispersing, feeding homopolymer or copolymer of acrylonitrile, and dissolving at the temperature of 30-120 DEG C to obtain a spinning solution; or directly mixing the homopolymer or copolymer of acrylonitrile with graphene, and then dispersing the mixture into concentrated acid or a water solution of inorganic salt to obtain the spinning solution; 2, filtering the spinning solution at the temperature of 20-80 DEG C, defoaming, and spraying the deformed spinning solution into a coagulating bath with the temperature of -40 to 5 DEG C by a spinneret plate to form nascent fiber; 3, extracting the nascent fiber, drying, and carrying thermal stretch and heat setting to obtain the high-strength polyacrylonitrile nano-composite fiber. The preparation method is simple in production technology, high in product performance and easy in realization of industrial mass production.
Description
Technical field
The present invention relates to a kind of preparation method of high-strength polyacrylonitrile nano-composite fiber.
Background technology
Carbon is extensively present in occurring in nature, is one of basic element forming living organism.Graphene as a kind of carbonaceous new material, by one deck intensive, be wrapped in carbon atom in honeycomb crystal lattice with sp
2the monoatomic layer composition that hydridization is formed by connecting, it is the elementary cell forming other carbon allotropes, it can be folded into the fullerene of zero dimension, be curled into the CNT of one dimension, be stacked to three-dimensional graphite and diamond, there is the mechanical property of fabulous crystallinity and electricity quality and excellence, Graphene intensity is high, performance can match in excellence or beauty with diamond, actual measurement tensile strength and elastic modelling quantity are respectively 125GPa and 1.1T Pa, graphene platelet only has an atomic layers thick (0.335nm), be only hair 200,000/, it is the hardest the thinnest material known in the world at present.In addition, Graphene has much other character in electricity and magnetic etc., as room-temperature quantum, Hall effect, bipolarity field effect, ferromagnetism, superconductivity and high electron mobility, become rapidly the hot research problem of material, chemistry, physics and engineering field.Especially the specific area of its super large and the mechanical performance of excellence, be widely used among novel high-strength composite.
Carbon fiber refers to that carbon content is greater than 90%, the crystallite meta anthracite material usually obtained after high temperature cabonization and graphitization processing by organic fiber, and its micro molecule similar Delanium is random graphits structure.Carbon fiber has the combination property of the excellences such as axial specific strength is high, specific modulus is high, endurance creep, good stability, electric heating good conductor, X-ray transparent is good, density is little, thermal coefficient of expansion is little, and is widely used in the fields such as Aero-Space, automobile, building and physical culture.Carbon fiber carries out compound usually used as structure enhancement mode material and other matrix material, and composition composite, directly can be used as structural element in fields such as Aero-Space, sports equipment, building, haulage vehicle, machineries.
The precursor preparing high-performance carbon fibre mainly contains polyacrylonitrile (PAN) base fiber, rayon fiber and pitch-based fiber three major types.Wherein PAN fiber has high molecularly oriented, higher fusing point and higher carbon fiber productive rate, heat-treat PAN fiber when low temperature, can form a kind of Heat stability is good, height-oriented molecular structure.This heat endurance structure also can not be subject to heavy damage when carrying out carbonization treatment, can obtain the best carbon fiber of combination property.These advantages of PAN fiber make it become the current most important and the most rising precursor manufacturing carbon fiber.The structures shape performance of material, the structure of carbon fiber is developed through pre-oxidation and carbonisation by precursor structure, and therefore, the performance quality key of carbon fiber is the quality of precursor (in precursor the axial orientation of PAN molecule and defect).
Domestic production polyacrylonitrile fibril for carbon fiber all adopts wet spinning process, it is that production technology is simple that the method prepares the maximum advantage of carbon fibre precursor, the carbon fiber cost produced is low, gained PAN molecular defect is less, exothermic peak temperature in preoxidation process is lower, but hot-stretch multiple is little in spinning, the degree of orientation of PAN molecule is not high.In preoxidation process, because molecular thermalmotion can produce disorientation, make the degree of orientation of the class graphite flake layer of end product carbon fiber poor, TENSILE STRENGTH and the modulus of carbon fiber are low.
Summary of the invention
For above-mentioned technological deficiency, the object of this invention is to provide a kind of preparation method of high-strength polyacrylonitrile nano-composite fiber, specifically a kind of production technology is simple, the preparation method of high-strength polyacrylonitrile nano-composite fiber that cost is low.
The present invention utilizes the specific area of Graphene super large and excellent mechanical performance, prepares the Graphene/PAN fiber of high-strength and high-modulus by the method for gel spinning.Gel spinning is the polyacrylonitrile utilizing relative molecular mass high, through being dissolved into half weak solution, entanglement between macromolecular chain significantly reduces, after spinning, quenching makes the solution state of twining between this macromolecular chain be remained in the gel precursor of preparation, by super times hot-stretch, improve fibre crystallinity and the degree of orientation, the sheet crystal orientation extended chain in folded chain is transformed, thus obtains super high-strength high-modulus fibre.When super drawing, macromolecular chain in finished fiber not only can be made to present the extended configuration of regular arrangement, graphene film also can be allowed to become to align, improve the performance of fiber further.The Graphene of lamella rigid structure can guide the arrangement of fiber Middle molecule chain in fiber fibroblast and drawing process, improves its degree of crystallinity.Secondly Graphene carries out orientation under the effect of drawing-off, can carry out orientations by inducing fibrous strand along Graphene synusia direction; Will there is physical constriction when heat treatment in fiber, its degree of orientation also will decline thereupon, and now Graphene can the disorientation of Inhibitory molecules chain by the motion of restriction molecule chain, thus improves the degree of orientation of fiber.The structure of the last pre-oxidized fibers when carbonizing is by the Structure Transformation to class graphite, at this moment the effect that the Graphene of monolithic layer graphite-structure can play template guides the transformation of fibre structure to be melted into wherein simultaneously but can not cause structurally does not mate the defect brought, the carbonization structure that final promotion processbearing astrocyte is more perfect, and as crystal around independently anatomical connectivity, be conducive to the performance improving carbon fiber.
The object of the invention is to be achieved through the following technical solutions:
The invention provides a kind of preparation method of high-strength polyacrylonitrile nano-composite fiber, described preparation method comprises the following steps:
Step one, in the mixed solution of organic solvent or organic solvent and water, add Graphene, be uniformly dispersed, then add polyacrylonitrile, dissolve under 30 ~ 120 DEG C of conditions, obtain spinning solution;
Or polyacrylonitrile and Graphene are directly dissolved, be scattered in the aqueous solution of concentrated acid or inorganic salts, obtain spinning solution;
Step 2, by described spinning solution under 20 ~ 80 DEG C of conditions, filter, after deaeration, be ejected into through spinnerets in the coagulating bath of-40 ~ 5 DEG C, form as-spun fibre;
Step 3, described as-spun fibre, through extraction, drying, hot-stretch, HEAT SETTING, obtain described high-strength polyacrylonitrile nano-composite fiber.
Preferably, in step one, described dispersion specifically refers to high-speed stirred or ultrasonic disperse; The time of described high-speed stirred or ultrasonic disperse is 1 ~ 6h; The speed of described high-speed stirred is 3000 ~ 10000 revs/min.
Preferably, in step one, the weight ratio 98:2 ~ 70:30 of organic solvent and water in described mixed solution,
Preferably, in step one, described organic solvent comprises the one of nitric acid ethylidene ester, ethylene carbonate, dimethyl sulfoxide (DMSO), dimethyl formamide, dimethylacetylamide.
Preferably, in step one, described concentrated acid is the red fuming nitric acid (RFNA) that mass concentration is greater than 65%; Described inorganic salts comprise the one in rhodanate, zinc chloride or lithium bromide.
Preferably, in step one, described Graphene comprises graphene oxide, modification or the Graphene of modification, the one of electricity stripping Graphene.
Preferably, in step one, described polyacrylonitrile comprises the homopolymers of acrylonitrile or the copolymer of acrylonitrile and other monomers; The viscosity average molecular weigh scope of described polyacrylonitrile is 5 ~ 150,000; Other monomers described comprise methyl acrylate, methyl methacrylate, vinylacetate, sodium allylsulfonate, itaconic acid, methylpropene sodium sulfonate or metering system benzene sulfonic acid sodium salt.
Preferably, in step one, in described spinning solution, the percentage by weight of polyacrylonitrile is 15 ~ 30%, and the percentage by weight of described Graphene is 0.05 ~ 20%.
Preferably, in step 2, described deaeration mode comprises vacuum defoamation or normal pressure standing and defoaming; Described the hole diameter of spinneret scope is 0.06 ~ 0.25mm.
Preferably, in step 2, described coagulating bath is the mixed solution of organic solvent and water, and described organic solvent comprises dimethyl sulfoxide (DMSO) (DMSO) or dimethyl formamide (DMF); Volume range 50:50 ~ the 80:20 of organic solvent and water in described mixed solution.
Preferably, in step 3, the extractant in described extraction comprises methyl alcohol or ethanol; The temperature of extraction is-20 ~ 60 DEG C, and the time is 2 ~ 60min.
Preferably, in step 3, the temperature of described drying is 60 ~ 120 DEG C; The dry time is 2 ~ 24h; The temperature of hot-stretch is 120 ~ 240 DEG C, and the multiple of hot-stretch is 4 ~ 40 times, and the time of HEAT SETTING is 0.5 ~ 15min.
The present invention compared with prior art has the following advantages:
1, the intrinsic non-polar carbon chains of the polyacrylonitrile itrile group and molecular skeleton that contain polarity can be used as the dispersant of graphite weak solution, makes graphene uniform be dispersed in mixed solvent;
2, by the specific area of Graphene super large and the mechanical performance of excellence, high-strength Graphene/PAN fiber is prepared by the method for gel spinning; Gel spinning is the polyacrylonitrile utilizing relative molecular mass high, through being dissolved into half weak solution, entanglement between macromolecular chain significantly reduces, after spinning, quenching makes the solution state of twining between this macromolecular chain be remained in the gel precursor of preparation, by super times hot-stretch, improve fibre crystallinity and the degree of orientation, the sheet crystal orientation extended chain in folded chain is transformed, thus obtains super high-strength high-modulus fibre; When super drawing, macromolecular chain in finished fiber not only can be made to present the extended configuration of regular arrangement, graphene film also can be allowed to become to align, improve the performance of fiber further; Simultaneously, add the graphene molecules of rigidity, be conducive to the disorientation that restriction PAN molecule causes due to warm-up movement, in carbonisation, Graphene can be dissolved in the crystal structure of fiber, the class graphite flake crystal of inductive formation high orientation, and as crystal around independently anatomical connectivity, be conducive to the performance improving carbon fiber.
Accompanying drawing explanation
By reading the detailed description done non-limiting example with reference to the following drawings, other features, objects and advantages of the present invention will become more obvious:
Fig. 1 is polyacrylonitrile fibre outward appearance photo;
Fig. 2 is SEM figure (electron scanning micrograph) in polyacrylonitrile fibre cross section.
Detailed description of the invention
Below in conjunction with specific embodiment, the present invention is described in detail.Following examples will contribute to those skilled in the art and understand the present invention further, but not limit the present invention in any form.It should be pointed out that to those skilled in the art, without departing from the inventive concept of the premise, some distortion and improvement can also be made.These all belong to protection scope of the present invention.
embodiment 1
The present embodiment provides a kind of preparation method of high-strength polyacrylonitrile nano-composite fiber, and described preparation method comprises the following steps:
Graphene oxide is joined containing dimethyl sulfoxide (DMSO) (DMSO): water=95: in the mixed solvent of 5, after ultrasonic disperse 1h.By molecular weight be 8.8 ten thousand polyacrylonitrile join in mixed solvent, stirring and dissolving 2h at 50 DEG C.The percetage by weight of graphene oxide is 0.3%, and the percetage by weight of polyacrylonitrile is 30%;
Normal pressure deaeration 8 hours, deaeration temperature 30 DEG C, obtained spinning solution temperature 30 DEG C, by filtering, the spinnerets of via hole diameter 0.10mm enters into the coagulating bath of 60/40 (V/V) DMSO/ water of-10 DEG C, forms the as-spun fibre of frozen glue state;
Make gel spun fiber drawing extraction removing dimethyl sulfoxide (DMSO) in-20 DEG C of methanol bath; Extraction time is 60min, drying 4 hours in 80 DEG C of baking ovens; Then, shape 0.5 minute through 120 DEG C of hot-stretchs, draw ratio is 13 times.
The TENSILE STRENGTH of the polyacrylonitrile fibre that the present embodiment obtains is 7.2cN/dtex, and Young's modulus is 26cN/dtex, specifically sees Fig. 1,2.Fig. 1 is that the present invention prepares graphene nano composite fibre photomacrograph, and the smooth crin of fiber surface is even.Fig. 2 is graphene nano composite fibre cross sectional Scanning Electron microphotograph, find out that fibrous inner structure compact, Graphene are evenly distributed in polyacrylonitrile matrix from cross section, two-phase interface combines firmly, the generation of the skin-core structure caused because being separated when there is not usual Material cladding and cohesion.
embodiment 2
The present embodiment provides a kind of preparation method of high-strength polyacrylonitrile nano-composite fiber, and described preparation method comprises the following steps:
Electrochemical stripping Graphene is joined containing dimethyl formamide: water=70: in the mixed solvent of 30, after ultrasonic disperse 2h.By molecular weight be 50,000 polyacrylonitrile join in mixed solvent, stirring and dissolving 2h at 80 DEG C; The percetage by weight of graphene oxide is 0.05%, and the percetage by weight of polyacrylonitrile is 15%;
Normal pressure deaeration 6 hours, deaeration temperature 50 C, obtained spinning solution temperature 50 C, by filtering, the spinnerets of via hole diameter 0.25mm enters into the coagulating bath of 60/40 (V/V) dimethyl formamide/water of-40 DEG C, forms the as-spun fibre of frozen glue state;
Make gel spun fiber drawing extraction removing dimethyl sulfoxide (DMSO) in 60 DEG C of methanol bath; Extraction time is 60min, dry in 100 DEG C of baking ovens; Then, shape 5 minutes through 200 DEG C of hot-stretchs, draw ratio is 4 times.
The TENSILE STRENGTH 7.8cN/dtex of the polyacrylonitrile fibre that the present embodiment obtains, Young's modulus 28N/dtex.
embodiment 3
The present embodiment provides a kind of preparation method of high-strength polyacrylonitrile nano-composite fiber, and described preparation method comprises the following steps:
Amino modified graphene oxide is joined in the solution of sodium sulfocyanate, after ultrasonic disperse 4h; By molecular weight be 120,000 polyacrylonitrile join in mixed solvent, stirring and dissolving 2h at 80 DEG C; The percetage by weight of modified graphene is 10%, and the percetage by weight of polyacrylonitrile is 25%;
Normal pressure deaeration 8 hours, deaeration temperature 80 DEG C, obtained spinning solution temperature 80 DEG C; By filtering, the spinnerets of via hole diameter 0.06mm enters into 60/40 (V/V) distilled water coagulating bath of-5 DEG C, forms the as-spun fibre of frozen glue state;
Gel spun fiber drawing extraction in 30 DEG C of methanol bath is made to remove desolventizing; Extraction time is 60min, dry in 120 DEG C of baking ovens; Then, shape 15 minutes through 240 DEG C of hot-stretchs, draw ratio is 9 times.
The TENSILE STRENGTH of the polyacrylonitrile fibre that the present embodiment obtains is 7.9cN/dtex, and Young's modulus is 31cN/dtex.
embodiment 4
The present embodiment provides a kind of preparation method of high-strength polyacrylonitrile nano-composite fiber, and described preparation method comprises the following steps:
Silane coupler modified graphene oxide is joined in red fuming nitric acid (RFNA), after ultrasonic disperse 6h; By molecular weight be 150,000 polyacrylonitrile join in red fuming nitric acid (RFNA), stirring and dissolving 1h at 40 DEG C.The percetage by weight of modified graphene is 20%, and the percetage by weight of polyacrylonitrile is 25%;
Normal pressure deaeration 8 hours, deaeration temperature 40 DEG C, obtained spinning solution temperature 40 DEG C, by filtering, the spinnerets of via hole diameter 0.20mm enters into the coagulating bath of 60/40 (V/V) ethanol of-40 DEG C, forms the as-spun fibre of frozen glue state;
Make gel spun fiber drawing extraction removing nitric acid in 20 DEG C of methanol bath; Extraction time is 160min, dry in 120 DEG C of baking ovens; Then, shape 5 minutes through 130 DEG C of hot-stretchs, draw ratio is 30 times.
The TENSILE STRENGTH of the polyacrylonitrile fibre that the present embodiment obtains is 8.9cN/dtex, and Young's modulus is 36cN/dtex.
embodiment 5
The present embodiment provides a kind of preparation method of high-strength polyacrylonitrile nano-composite fiber, and described preparation method comprises the following steps:
Graphene oxide is joined containing dimethyl sulfoxide (DMSO) (DMSO): water=95: in the mixed solvent of 5, after high-speed stirred (3000 revs/min) dispersion 1h.Be that the copolymer of the acrylonitrile methyl-acrylate of 7.5 ten thousand joins in mixed solvent by mean molecule quantity, stirring and dissolving 2h at 50 DEG C.The percetage by weight of graphene oxide is 0.5%, and the percetage by weight of polyacrylonitrile is 20%;
Normal pressure deaeration 8 hours, deaeration temperature 30 DEG C, obtained spinning solution temperature 30 DEG C, by filtering, the spinnerets of via hole diameter 0.10mm enters into the coagulating bath of 60/40 (V/V) DMSO/ water of 5 DEG C, forms the as-spun fibre of frozen glue state;
Make gel spun fiber drawing extraction removing dimethyl sulfoxide (DMSO) in-30 DEG C of methanol bath; Extraction time is 160min, drying 4 hours in 80 DEG C of baking ovens; Then, shape 3 minutes through 120 DEG C of hot-stretchs, draw ratio is 10 times.
The TENSILE STRENGTH of the polyacrylonitrile fibre that the present embodiment obtains is 7.5cN/dtex, and Young's modulus is 28cN/dtex.
In implementation process of the present invention, the speed of high-speed stirred all can realize the present invention between 3000 ~ 10000 revs/min, and the polymer monomers of polyacrylonitrile is methyl methacrylate, vinylacetate, sodium allylsulfonate, itaconic acid, methylpropene sodium sulfonate or metering system benzene sulfonic acid sodium salt all can realize the present invention.
Above specific embodiments of the invention are described.It is to be appreciated that the present invention is not limited to above-mentioned particular implementation, those skilled in the art can make various distortion or amendment within the scope of the claims, and this does not affect flesh and blood of the present invention.
Claims (10)
1. a preparation method for high-strength polyacrylonitrile nano-composite fiber, is characterized in that, described preparation method comprises the following steps:
Step one, in the mixed solution of organic solvent or organic solvent and water, add Graphene, be uniformly dispersed, then add polyacrylonitrile, dissolve under 30 ~ 120 DEG C of conditions, obtain spinning solution;
Or polyacrylonitrile and Graphene are directly dissolved and are scattered in the aqueous solution of concentrated acid or inorganic salts, obtain spinning solution;
Step 2, by described spinning solution under 20 ~ 80 DEG C of conditions, filter, after deaeration, be ejected into through spinnerets in the coagulating bath of-40 ~ 5 DEG C, form as-spun fibre;
Step 3, described as-spun fibre, through extraction, drying, hot-stretch, HEAT SETTING, obtain described high-strength polyacrylonitrile nano-composite fiber.
2. the preparation method of high-strength polyacrylonitrile nano-composite fiber according to claim 1, is characterized in that, in step one, described dispersion specifically refers to high-speed stirred or ultrasonic disperse; The time of described high-speed stirred or ultrasonic disperse is 1 ~ 6h; The speed of described high-speed stirred is specially 3000 ~ 10000 revs/min.
3. the preparation method of high-strength polyacrylonitrile nano-composite fiber according to claim 1, is characterized in that, in step one, and the weight ratio 98:2 ~ 70:30 of organic solvent and water in described mixed solution.
4. the preparation method of the high-strength polyacrylonitrile nano-composite fiber according to claim 1 or 3, it is characterized in that, in step one, described organic solvent comprises the one of nitric acid ethylidene ester, ethylene carbonate, dimethyl sulfoxide (DMSO), dimethyl formamide, dimethylacetylamide.
5. the preparation method of high-strength polyacrylonitrile nano-composite fiber according to claim 1, is characterized in that, in step one, described Graphene comprises graphene oxide, modification or the Graphene of modification, the one of electricity stripping Graphene; Described polyacrylonitrile comprises the homopolymers of acrylonitrile or the copolymer of acrylonitrile and other monomers; Other monomers described comprise methyl acrylate.
6. the preparation method of high-strength polyacrylonitrile nano-composite fiber according to claim 1, is characterized in that, in step one, in described spinning solution, the percentage by weight of polyacrylonitrile is 15 ~ 30%, and the percentage by weight of described Graphene is 0.05 ~ 20%.
7. the preparation method of high-strength polyacrylonitrile nano-composite fiber according to claim 1, is characterized in that, in step 2, described deaeration mode comprises vacuum defoamation or normal pressure standing and defoaming;
The pore diameter range of described spinnerets is 0.06 ~ 0.25mm.
8. the preparation method of high-strength polyacrylonitrile nano-composite fiber according to claim 1, is characterized in that, in step 2, described coagulating bath is the mixed solution of organic solvent and water; Described organic solvent comprises dimethyl sulfoxide (DMSO) or dimethyl formamide.
9. the preparation method of high-strength polyacrylonitrile nano-composite fiber according to claim 1, is characterized in that, in step 3, the extractant in described extraction comprises methyl alcohol or ethanol; The temperature of extraction is-20 ~ 60 DEG C, and the time is 2 ~ 60min.
10. the preparation method of high-strength polyacrylonitrile nano-composite fiber according to claim 1, is characterized in that, in step 3, the temperature of described drying is 60 ~ 120 DEG C, and the dry time is 2 ~ 24h;
The temperature of described hot-stretch is 120 ~ 240 DEG C, and the multiple of hot-stretch is 4 ~ 40 times;
The time of described HEAT SETTING is 0.5 ~ 15min.
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