CN115584573A - T700-grade wet large-tow carbon fiber and preparation method and application thereof - Google Patents
T700-grade wet large-tow carbon fiber and preparation method and application thereof Download PDFInfo
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- 229920000049 Carbon (fiber) Polymers 0.000 title claims abstract description 62
- 239000004917 carbon fiber Substances 0.000 title claims abstract description 62
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 49
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 239000000243 solution Substances 0.000 claims abstract description 59
- 238000009987 spinning Methods 0.000 claims abstract description 57
- 238000000034 method Methods 0.000 claims abstract description 21
- 239000012986 chain transfer agent Substances 0.000 claims abstract description 19
- 239000011550 stock solution Substances 0.000 claims abstract description 19
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 7
- 238000004519 manufacturing process Methods 0.000 claims abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 48
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 42
- 238000005406 washing Methods 0.000 claims description 37
- 230000015271 coagulation Effects 0.000 claims description 33
- 238000005345 coagulation Methods 0.000 claims description 33
- 239000000178 monomer Substances 0.000 claims description 33
- 238000001035 drying Methods 0.000 claims description 29
- 238000003763 carbonization Methods 0.000 claims description 22
- 239000000835 fiber Substances 0.000 claims description 20
- 239000007788 liquid Substances 0.000 claims description 15
- 230000003647 oxidation Effects 0.000 claims description 15
- 238000007254 oxidation reaction Methods 0.000 claims description 15
- 238000000280 densification Methods 0.000 claims description 12
- 230000001112 coagulating effect Effects 0.000 claims description 10
- 229920006395 saturated elastomer Polymers 0.000 claims description 10
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 9
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 9
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 8
- 239000007864 aqueous solution Substances 0.000 claims description 7
- 238000004513 sizing Methods 0.000 claims description 7
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 6
- 238000009826 distribution Methods 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- 238000004381 surface treatment Methods 0.000 claims description 6
- 229910052715 tantalum Inorganic materials 0.000 claims description 6
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 5
- 239000003999 initiator Substances 0.000 claims description 5
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 claims description 4
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 4
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 4
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 4
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 4
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 4
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 4
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 4
- 239000001099 ammonium carbonate Substances 0.000 claims description 4
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 claims description 4
- KZCOBXFFBQJQHH-UHFFFAOYSA-N octane-1-thiol Chemical compound CCCCCCCCS KZCOBXFFBQJQHH-UHFFFAOYSA-N 0.000 claims description 4
- 238000007493 shaping process Methods 0.000 claims description 4
- MXTNFIYGTWARIN-UHFFFAOYSA-N 2-methylprop-2-enylbenzene Chemical compound CC(=C)CC1=CC=CC=C1 MXTNFIYGTWARIN-UHFFFAOYSA-N 0.000 claims description 3
- 239000012988 Dithioester Substances 0.000 claims description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 3
- 229940077388 benzenesulfonate Drugs 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 230000003750 conditioning effect Effects 0.000 claims description 3
- 238000007334 copolymerization reaction Methods 0.000 claims description 3
- 125000005022 dithioester group Chemical group 0.000 claims description 3
- 239000000463 material Substances 0.000 claims description 3
- 230000008569 process Effects 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- 239000011734 sodium Substances 0.000 claims description 3
- SZHIIIPPJJXYRY-UHFFFAOYSA-M sodium;2-methylprop-2-ene-1-sulfonate Chemical compound [Na+].CC(=C)CS([O-])(=O)=O SZHIIIPPJJXYRY-UHFFFAOYSA-M 0.000 claims description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 2
- 238000001514 detection method Methods 0.000 claims description 2
- 239000002243 precursor Substances 0.000 abstract description 8
- 238000006243 chemical reaction Methods 0.000 abstract description 6
- 229920002239 polyacrylonitrile Polymers 0.000 abstract description 4
- 238000002166 wet spinning Methods 0.000 abstract description 4
- 230000000052 comparative effect Effects 0.000 description 15
- 239000008041 oiling agent Substances 0.000 description 14
- 239000000047 product Substances 0.000 description 12
- 238000010000 carbonizing Methods 0.000 description 10
- 239000000203 mixture Substances 0.000 description 7
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 6
- PGXWDLGWMQIXDT-UHFFFAOYSA-N methylsulfinylmethane;hydrate Chemical compound O.CS(C)=O PGXWDLGWMQIXDT-UHFFFAOYSA-N 0.000 description 5
- 230000001590 oxidative effect Effects 0.000 description 5
- 235000017166 Bambusa arundinacea Nutrition 0.000 description 4
- 235000017491 Bambusa tulda Nutrition 0.000 description 4
- 241001330002 Bambuseae Species 0.000 description 4
- 235000015334 Phyllostachys viridis Nutrition 0.000 description 4
- 229920013822 aminosilicone Polymers 0.000 description 4
- 239000011425 bamboo Substances 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 238000012545 processing Methods 0.000 description 3
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000004745 nonwoven fabric Substances 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- OZAIFHULBGXAKX-VAWYXSNFSA-N AIBN Substances N#CC(C)(C)\N=N\C(C)(C)C#N OZAIFHULBGXAKX-VAWYXSNFSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 235000008331 Pinus X rigitaeda Nutrition 0.000 description 1
- 235000011613 Pinus brutia Nutrition 0.000 description 1
- 241000018646 Pinus brutia Species 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000005192 partition Methods 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 230000008707 rearrangement Effects 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- -1 sodium propylene sulfonate Chemical compound 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000010913 used oil Substances 0.000 description 1
Classifications
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
- D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
- D01F9/12—Carbon filaments; Apparatus specially adapted for the manufacture thereof
- D01F9/14—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments
- D01F9/20—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products
- D01F9/21—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products from macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D01F9/22—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products from macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds from polyacrylonitriles
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/42—Nitriles
- C08F220/44—Acrylonitrile
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/42—Nitriles
- C08F220/44—Acrylonitrile
- C08F220/46—Acrylonitrile with carboxylic acids, sulfonic acids or salts thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/42—Nitriles
- C08F220/44—Acrylonitrile
- C08F220/48—Acrylonitrile with nitrogen-containing monomers
-
- 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
- D01D4/00—Spinnerette packs; Cleaning thereof
- D01D4/02—Spinnerettes
-
- 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
- D01F6/28—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D01F6/38—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds comprising unsaturated nitriles as the major constituent
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/70—Wind energy
- Y02E10/72—Wind turbines with rotation axis in wind direction
Abstract
The invention discloses a T700-grade wet-process large-tow carbon fiber, a preparation method and application thereof, and relates to the technical field of polyacrylonitrile-based carbon fibers. The preparation method comprises the step of adding the chain transfer agent in the polymerization process, so that the generation of macromolecular chains in the reaction process is effectively reduced, and the processability of the stock solution is further improved. Meanwhile, the performance indexes of products (such as spinning solution, precursor and carbon fiber) in each stage are limited, so that the uniformity of the products is better, meanwhile, the rotary viscosity of the spinning solution is reduced, the pressure of a wet spinning spinneret plate can be effectively reduced, the spinning speed is effectively increased and the production efficiency is improved in the spinning process. In addition, the number and the aperture of the holes of the spinneret plate are limited, T700 grade 50K large-tow carbon fibers with the strength of more than or equal to 4900MPa, the modulus of more than or equal to 255GPa and the linear density of more than or equal to 2800g/km can be obtained, and the blank of domestic 50K large-tow products is filled.
Description
Technical Field
The invention relates to the technical field of polyacrylonitrile-based carbon fibers, in particular to T700-grade wet large-tow carbon fibers and a preparation method and application thereof.
Background
The carbon fiber is divided into a wet method and a dry spraying wet method according to a precursor preparation method; according to the conventional practice in the industry, the number of the monofilaments is 1000 (1K) -50000 or less (50K) and is small tows, 50000 or more (50K) is large tows, and the invention is wet-process 50K large tow carbon fiber.
Domestic Polyacrylonitrile (PAN) -based carbon fiber is still in the beginning stage, and the product is mainly applied to enterprises such as standard Japanese Dongli, toho and American Tuoltike and Germany SGL. The small tows and the large tows are slightly different in application field due to reasons such as processing efficiency and cost, wherein the main application field of the small tows is aerospace, military industry, sports leisure and the like, and in the field of wind power generation, long-size wind power blade carbon fibers replace glass fibers, and along with the policy call of national double-carbon indexes and green energy, the wind power industry develops rapidly, 50K is low in cost, and the processing efficiency is high.
However, the invention is specially provided in view of the fact that domestic large-tow carbon fibers are in the development stage at present.
Disclosure of Invention
The invention aims to provide a T700-grade wet large-tow carbon fiber and a preparation method and application thereof.
The invention is realized by the following steps:
in a first aspect, the invention provides a preparation method of a T700-grade wet large-tow carbon fiber, which comprises the following steps:
taking dimethyl sulfoxide as a solvent, adding at least one of a second monomer and a third monomer into acrylonitrile which is used as a main polymerization monomer, taking azobisisobutyronitrile as an initiator, and adding a chain transfer agent to perform copolymerization reaction to obtain a spinning solution; the indexes of the spinning solution are as follows: the solid content is 18 to 23 weight percent, the rotational viscosity is 32000 to 45000cP, the weight average molecular weight is 18 to 23 ten thousand, the number average molecular weight is 6 to 9 ten thousand, the molecular weight distribution is 1.4 to 3.0, and the intrinsic viscosity is 1.7 to 2.1;
the spinning solution is sprayed out from a spinneret plate, the spinneret plate is immersed in the first coagulating bath solution, and the spinning solution is sprayed out and instantly formed into nascent fiber; wherein the spinneret plate is a 50K spinneret plate, the number of holes is 50001-50010, and the aperture is 0.05-0.08 mm;
the nascent fiber is rolled after being subjected to second coagulation bath liquid, water washing, hot water drafting, oiling, drying densification, steam drafting and drying shaping to obtain protofilament; the filament number of the protofilament is 1.15 to 1.5dtex, the linear density of the protofilament is 5.7 to 7.5g/m, the filament strength is 6.5 to 8.0cN/dtex, the filament modulus is 90 to 130cN/dtex, and the bulk density is 1.17 to 1.19g/cm 3 ；
The obtained protofilament is processed by uncoiling, oxidizing, low-temperature carbonizing, high-temperature carbonizing, washing, surface treatment, sizing and drying to obtain carbon fiber; the tensile strength of the carbon fiber is 4900-5100 MPa, the tensile modulus is 255-270 GPa, the breaking elongation is 1.8-2.0 percent, the linear density is 2800-3700 g/km, and the bulk density is 1.75-1.83 g/cm 3 。
In an alternative embodiment, the mass percent of acrylonitrile and the mass percent of the sum of the second monomer and the third monomer is from 92% to 99%:1% -8%;
the second monomer comprises at least one of sodium methallyl sulfonate, sodium methallyl benzene sulfonate, itaconic acid and vinyl acetate;
preferably, the third monomer comprises at least one of methyl methacrylate, methyl acrylate and acrylamide;
preferably, the chain transfer agent is added in an amount of 200-3000ppm based on the total mass of the polymerized monomers;
preferably, the chain transfer agent comprises at least one of a dithioester, n-octylmercaptan, and isopropanol.
In an alternative embodiment, the spinneret has a hole pitch of 0.3 to 0.5mm and a spinneret hole aspect ratio of 2:1-3:1;
preferably, the surface diameter of the spinneret plate is 95-135mm, and the spinneret plate is divided into 6-24 areas;
preferably, the spinneret plate is a spherical or planar plate of tantalum material.
In an alternative embodiment, the first coagulation bath liquid is an aqueous solution of dimethyl sulfoxide at a temperature of 30-65 ℃ and a concentration of 55% -70%;
preferably, the pH value of the first coagulation bath liquid is adjusted to 7-10 by using a regulator;
preferably, the conditioning agent comprises at least one of sodium bicarbonate, ammonium bicarbonate and ammonia;
in an alternative embodiment, the second coagulation bath solution is an aqueous solution of dimethyl sulfoxide at a temperature of 55-70 ℃ and a concentration of 30% -40%;
preferably, the draft ratio of the nascent fiber in the second coagulation bath liquid is 1.2 to 1.8 times.
In an optional embodiment, the water washing is 5-12 sections of water washing, the water washing temperature is 50-99 ℃, the drafting ratio is 5-8 times, and the water flow and the nascent fiber run in reverse directions during the water washing;
preferably, the dry densification uses saturated steam, the pressure is 1.2-7bar, the pressure is arranged in a step mode, and the number of drying rollers is 16-32;
preferably, the drying rollers are divided into four groups, namely a first roller group, a second roller group, a third roller group and a fourth roller group; the stepped arrangement is that: the pressure of the first roller set is 1.2-3bar, the pressure of the second roller set is 2.5-4.5bar, the pressure of the third roller set is 4-5.5bar, and the pressure of the fourth roller set is 5-7bar;
preferably, the steam drafting box uses saturated steam, the pressure is 1.5-4 bar, the corresponding temperature is 120-144 ℃, and the steam drafting ratio is 1.3-2.0.
In an alternative embodiment, the initial temperature in the oxidation furnace is 200-240 ℃, the final temperature is 250-280 ℃, the number of oxidation zones is 3-6, and the density of the pre-oxidized filaments is 1.37-1.38g/cm 3 ；
The starting temperature of the low-temperature carbonization furnace is 380-450 ℃, and the ending temperature is 720-800 ℃;
the starting temperature of the high-temperature carbonization furnace is 900-1000 ℃, and the ending temperature is 1150-1350 ℃.
In an alternative embodiment, after preparing the spinning solution, before detecting the index of the spinning solution, the method further comprises the following steps: the spinning stock solution flows into a demonomerization and deaeration tower from top to bottom, dimethyl sulfoxide flows back from bottom to top, the tower top is vacuumized, the pressure in the tower is 0-2KPa absolute pressure, the stock solution monomer content after demonomerization is 0-100ppm, and no bubbles can be seen by naked eyes after deaeration.
In a second aspect, the invention provides a T700 grade wet large tow carbon fiber, which is prepared by the method for preparing the T700 grade wet large tow carbon fiber according to any one of the previous embodiments.
In a third aspect, the invention provides application of the T700-grade large wet-process tow carbon fiber in preparation of wind power blades according to the previous embodiments.
The invention has the following beneficial effects:
according to the preparation method of the T700-grade wet-process large-tow carbon fiber, the chain transfer agent is added in the polymerization process, so that the generation of macromolecular chains in the reaction process is effectively reduced, and the processability of the stock solution is further improved. Meanwhile, performance indexes of products (such as spinning solution, precursor and carbon fibers) in each stage are limited, so that the uniformity of the products is better, meanwhile, the rotary viscosity of the spinning solution is reduced, the pressure of a wet spinning spinneret plate can be effectively reduced, the spinning speed is effectively increased, and the production efficiency is improved in the spinning process. In addition, the number and the aperture of the holes of the spinneret plate are limited, T700-grade 50K large-tow carbon fibers with the strength of more than or equal to 4900MPa, the modulus of more than or equal to 255GPa and the linear density of more than or equal to 2800g/km can be obtained, and the blank of products of 50K large tows in China is filled.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are conventional products which are not indicated by manufacturers and are commercially available.
The invention provides a preparation method of T700-grade wet large-tow carbon fibers, which comprises the following steps:
s1, preparing a spinning solution.
Taking dimethyl sulfoxide as a solvent, adding at least one of a second monomer and a third monomer into acrylonitrile which is used as a main polymerization monomer, taking azobisisobutyronitrile as an initiator, and adding a chain transfer agent to perform copolymerization reaction to obtain a spinning solution.
The mass percent of the acrylonitrile and the mass percent of the sum of the second monomer and the third monomer are 92-99%: 1% -8%; the adding amount of the chain transfer agent is 200-3000ppm of the total mass of the polymerized monomers.
The second monomer comprises at least one of sodium methallyl sulfonate, sodium methallyl benzene sulfonate, itaconic acid and vinyl acetate; the third monomer comprises at least one of methyl methacrylate, methyl acrylate and acrylamide; the chain transfer agent includes at least one of a dithioester, n-octylmercaptan and isopropanol.
After preparing the spinning solution, before detecting the index of the spinning solution, the method also comprises the following steps: the spinning stock solution flows into a demonomerization and deaeration tower from top to bottom and is filled with filler, dimethyl sulfoxide flows back from bottom to top, the tower top is vacuumized, the pressure in the tower is 0-2KPa absolute pressure, the monomer content of the stock solution after demonomerization is 0-100ppm, and no bubbles can be seen by naked eyes after deaeration.
The indexes of the spinning solution are as follows: the solid content is 18-23 wt%, the rotational viscosity is 32000-45000 cP, the weight average molecular weight is 18-23 ten thousand, the number average molecular weight is 6-9 ten thousand, the molecular weight distribution is 1.4-3.0, and the intrinsic viscosity is 1.7-2.1.
In the application, a certain amount of the second monomer and/or the third monomer is added in the reaction process, and the introduction of a new group improves the processability of the stock solution. Meanwhile, the addition of the chain transfer agent effectively reduces the generation of macromolecular chains in the reaction process and further improves the processability of the stock solution. The reduction of the rotational viscosity of the stock solution can effectively reduce the pressure of a wet spinning spinneret plate, and effectively improve the spinning speed and the production efficiency in the spinning process.
S2, preparing the nascent fiber.
The spinning solution is sprayed out from a spinneret plate, the spinneret plate is immersed in the first coagulating bath liquid, and the spinning solution is sprayed out and instantly formed into nascent fibers.
The spinning solution is heated to 45-65 ℃ before being sprayed out of a spinneret plate, the spinning process in the application is wet forming, the spinning solution is extruded by a metering pump and then enters the spinneret plate through a filter, the capacity of the metering pump in the application is 40-60cc/r, the number of gears is 2 or 3, the number of teeth is 18-30, the filter is in a metal sintered felt type, and the precision is 2-5 mu m.
Wherein the spinneret plate is a 50K spinneret plate, the number of holes is 50001-50010, and the aperture is 0.05-0.08 mm; the hole pitch of the spinneret plate is 0.3-0.5mm, the length-diameter ratio of the spinneret hole is 2:1-3:1; the surface diameter of the spinneret plate is 95-135mm, and the spinneret plate is divided into 6-24 areas; the spinneret plate is a spherical surface or a plane plate made of tantalum material. The ratio of the spinning speed of the spinneret plate to the speed of the first guide roller (negative draft) is 0.5-0.9.
The first coagulating bath liquid is dimethyl sulfoxide water solution, the temperature is 30-65 ℃, and the concentration is 55-70%; adjusting the pH value of the first coagulating bath liquid to 7-10 by using a regulator; the conditioning agent comprises at least one of sodium bicarbonate, ammonium bicarbonate and ammonia water. The temperature, the concentration and the pH value of the first coagulation bath liquid are limited, so that the crystallinity and the orientation degree of the protofilament can be effectively adjusted, and excellent subsequent processing performance is obtained.
And S3, preparing protofilaments.
And (3) the nascent fiber is rolled after being subjected to second coagulation bath solution, water washing, hot water drafting, oiling, drying densification, steam drafting and drying setting to obtain the protofilament.
The second coagulating bath liquid is dimethyl sulfoxide water solution, the temperature is 55-70 ℃, and the concentration is 30-40%; the draft ratio of the nascent fiber in the second coagulation bath liquid is 1.2-1.8 times.
The water washing is 5-12 sections of water washing, the water washing temperature is 50-99 ℃, the drafting ratio is 5-8 times, the water flow and the nascent fiber run in reverse directions during the water washing, specifically, the water washing water flow runs from back to front, the tow runs from front to back, the water flow and the nascent fiber run in reverse directions, each section in the 5-12 sections of water washing is provided with a water washing tank, and the front and the rear groups of traction rollers carry out traction.
Drawing with hot water for 5-7 times.
The oiling is carried out by using amino silicone oil, the used oil is at least one or a mixture of more than two of Wake EZ002202, bamboo JHX-506 and loose JH-88, when the oil is the mixture, the Wake EZ002202, the bamboo JHX-506 and the loose JH-88 are compounded according to a certain proportion, the compounding proportion can be adjusted according to actual conditions, and the oiling rate is 1.2-2%.
Saturated steam is used for drying densification, the pressure is 1.2-7bar, the pressure is in a step-type arrangement, and the pressure of the roller sets is limited, so that the pressure of the roller sets is increased in a step-type manner, in the application, the number of drying rollers is 16-32, the drying rollers are divided into four groups, namely a first roller set, a second roller set, a third roller set and a fourth roller set; the stepped arrangement may for example be arranged as: the pressure of the first roll group is 1.2-3bar, the pressure of the second roll group is 2.5-4.5bar, the pressure of the third roll group is 4-5.5bar, and the pressure of the fourth roll group is 5-7bar.
Saturated steam is used in the steam drafting box, the pressure is 1.5-4 bar, the corresponding temperature is 120-144 ℃, and the steam drafting ratio is 1.3-2.0.
The filament number of the protofilament is 1.15 to 1.5dtex, the linear density of the protofilament is 5.7 to 7.5g/m, the filament strength is 6.5 to 8.0cN/dtex, the filament modulus is 90 to 130cN/dtex, and the bulk density is 1.17 to 1.19g/cm 3 。
And S4, preparing the carbon fiber.
The obtained protofilament is processed by uncoiling, oxidizing, low-temperature carbonizing, high-temperature carbonizing, washing, surface treating, sizing and drying to obtain the carbon fiber.
The initial temperature in the oxidation furnace is 200-240 ℃, the termination temperature is 250-280 ℃, the pre-oxidized filament density is 1.37-1.38g/cm and the number of oxidation zones is 3-6 3 (ii) a The initial temperature of the low-temperature carbonization furnace is 380-450 ℃, and the termination temperature is 720-800 ℃; the starting temperature of the high-temperature carbonization furnace is 900-1000 ℃, and the ending temperature is 1150-1350 ℃. The subsequent water washing, surface treatment, sizing, drying and the like are conventional techniques.
The T700-grade wet large tow carbon fiber prepared by the preparation method of the T700-grade wet large tow carbon fiber has the tensile strength of 4900-5100 MPa, the tensile modulus of 255-270 GPa, the breaking elongation of 1.8-2.0 percent, the linear density of 2800-3700 g/km and the bulk density of 1.75-1.83 g/cm 3 The method fills the blank of domestic 50K large tow products, and can be widely applied to the preparation of wind power blades.
The features and properties of the present invention are described in further detail below with reference to examples.
Example 1
The embodiment provides a T700-grade wet large-tow carbon fiber, and the preparation method comprises the following steps:
(1) Taking dimethyl sulfoxide as a solvent, adding 97 mass percent of acrylonitrile and vinyl acetate, taking AIBN as an initiator, taking isopropanol as a chain transfer agent, wherein the chain transfer agent accounts for 1000ppm of the mass of a polymerization monomer, polymerizing at 65 ℃ for 21 hours to prepare a spinning dope, allowing the spinning dope to flow into a de-mono-defoaming tower from top to bottom, performing countercurrent flow on the dimethyl sulfoxide from bottom to top, vacuumizing from the top of the tower, wherein the pressure in the tower is 0.5KPa (absolute pressure), the monomer content of the dope after the de-mono-defoaming is 20ppm, and no bubbles can be seen by naked eyes after the defoaming. The indexes of the spinning solution are as follows: the index is a solid content of 20.5wt%, a rotational viscosity of 38000cP, a weight average molecular weight of 20 ten thousand, a number average molecular weight of 8 ten thousand, a molecular weight distribution of 2.5, and an intrinsic viscosity of 1.9.
(2) The spinning solution is extruded by a metering pump, then enters a spinneret plate through a filter and is sprayed out, the spinneret plate is immersed in the first coagulating bath solution, and the spinning solution is sprayed out and instantly formed into nascent fiber. Wherein, the temperature of spinning stock solution is 50 ℃, the capacity of a metering pump is 50cc/r, the number of gears is 2, the number of teeth is 25, the used filter is a metal sintered felt disc filter, the filtering precision is 2 mu m, the spinneret plate is a tantalum plate plane spinneret plate, the number of holes is 50005 holes, the aperture is 0.065mm, and the length-diameter ratio is 2:1, the surface diameter of a spinneret plate is 120mm, the hole spacing is 0.04mm, and 16 subareas are arranged. The first coagulation bath was DMSO water solution at 50 ℃, concentration 68%, pH of the coagulation bath was adjusted to 8.5 with sodium bicarbonate, and the coagulation bath negative draft was set to 0.7.
(3) And (3) the nascent fiber is coiled after being subjected to second coagulation bath liquid, water washing, hot water drafting, oiling, drying densification, steam drafting, drying and shaping to obtain the protofilament. Wherein the second coagulation bath is a DMSO aqueous solution, the second coagulation temperature is 60 ℃, the concentration is 36 percent, and the drawing multiple is 1.35 times. The water washing is 8-stage water washing, the water washing temperature is 60 ℃, 80 ℃, 90 ℃, 93 ℃, 97 ℃ and 97 ℃, the hot water drafting multiple is 6 times, amino silicone oil is used for oiling, an oiling agent A (Wake EZ 002202) and an oiling agent B (bamboo JHX-506) are compounded, the oiling agent A/oiling agent B =90/10, and the oiling rate is 1.8%. The number of rollers used for dry densification is 20, the steam pressure is 1.2bar at the beginning, the ending pressure is 5bar, the steam pressure is set in a stepped mode, wherein the pressure of the first roller set is 1.2bar, the pressure of the second roller set is 2.5bar, the pressure of the third roller set is 4bar, the pressure of the fourth roller set is 5bar, 2.6bar saturated steam is used in a steam drawing box, and the drawing ratio is 1.8 times. The filament number of the finished protofilament is 1.23dtex, the linear density of the protofilament is 6.15g/m, the filament strength is 7.2cN/dtex, the filament modulus is 104cN/dtex, and the bulk density is 1.175g/cm 3 。
(4) Oxidizing the finished protofilament in fuming furnace at 200 deg.C and 250 deg.C, 4 oxidation zones, and pre-oxidizing to obtain dense protofilamentThe degree is 1.375g/cm 3 . Carbonizing the mixture by a low-temperature carbonization furnace after the oxidation is finished, wherein the starting temperature of the low-temperature carbonization furnace is 390 ℃, the ending temperature is 780 ℃, and carbonizing the mixture by a high-temperature carbonization furnace, wherein the starting temperature of the high-temperature carbonization furnace is 930 ℃, and the ending temperature of the high-temperature carbonization furnace is 1200 ℃. Then, conventional water washing, surface treatment, sizing, drying and the like are carried out to obtain the finished product of the 50K carbon fiber, wherein the tensile strength of the 50K carbon fiber is 4950MPa, the tensile modulus is 258GPa, the elongation at break is 1.9 percent, the linear density is 3080g/km, and the bulk density is 1.82g/cm 3 。
Example 2
The embodiment provides a T700-grade wet large-tow carbon fiber, and the preparation method comprises the following steps:
(1) Taking dimethyl sulfoxide as a solvent, adding 96 mass percent of acrylonitrile, methyl methacrylate and sodium propylene sulfonate into the mixture, taking azobisisobutyronitrile as an initiator, taking n-octyl mercaptan as a chain transfer agent, wherein the chain transfer agent accounts for 2200ppm of the mass of a polymerized monomer, polymerizing for 21 hours at 65 ℃ to obtain a spinning stock solution, allowing the spinning stock solution to flow into a de-monomerization defoaming tower from top to bottom to fill, allowing the dimethyl sulfoxide to flow in a counter-current manner from bottom to top, vacuumizing from the top of the tower, keeping the pressure in the tower at 1kpa absolute, keeping the monomer content of the stock solution after de-monomerization at 100ppm, and ensuring that no bubbles are visible to naked eyes after defoaming. The indexes of the spinning solution are as follows: the solid content was 19.3% by weight, the rotational viscosity was 42000cP, the weight-average molecular weight was 21 ten thousand, the number-average molecular weight was 12 ten thousand, the molecular weight distribution was 1.75, and the intrinsic viscosity was 2.0.
(2) The spinning solution is extruded by a metering pump, then enters a spinneret plate through a filter and is sprayed out, the spinneret plate is immersed in the first coagulating bath solution, and the spinning solution is sprayed out and instantly formed into nascent fiber. The temperature of spinning stock solution is 58 ℃, the capacity of a metering pump is 55cc/r, the number of gears is 3, and the number of teeth is 18; the filter is a metal sintered felt disc filter, and the filtering precision is 5 mu m; the spinneret plate is a tantalum plane spinneret plate, the number of holes is 50008 holes, the aperture is 0.06mm, and the length-diameter ratio is 3:1, the surface diameter of the spinneret plate is 100mm, the hole spacing is 0.03mm, and 24 partitions are arranged. The first coagulation bath was DMSO water solution at 42 ℃, 65% concentration, the pH of the coagulation bath was adjusted to 9.5 with ammonia, and the coagulation bath negative draft was set to 0.8.
(3) The nascent fiber passes through a second coagulating bathLiquid washing, hot water drafting, oiling, drying densification, steam drafting, drying and shaping, and then rolling to obtain the precursor. Wherein the second coagulation bath is DMSO aqueous solution, the temperature is 55 ℃, the concentration is 33%, and the drawing multiple is 1.6 times. The water washing is 10-stage water washing, the water washing temperature is 60 ℃, 80 ℃, 90 ℃, 93 ℃, 95 ℃, 97 ℃ and the hot water drafting multiple is 5 times, amino silicone oil is used for oiling, an oiling agent A (Wake EZ 002202) and an oiling agent C (Songben JH-88) are compounded, the oiling agent A/oiling agent C =60/40, and the oiling rate is 1.4%. The number of rollers used for drying and densifying is 28, the steam pressure is 1.2bar at the beginning, the termination pressure is 6bar, the steam pressure is set in a stepped mode, the pressure of the first roller set is 1.2bar, the pressure of the second roller set is 3bar, the pressure of the third roller set is 4.5bar, the pressure of the fourth roller set is 6bar, saturated steam of 4bar is used in a steam drawing box, and the drawing ratio is 2.2 times. The filament number of the finished protofilament is 1.18dtex, the linear density of the protofilament is 5.9g/m, the filament strength is 7.8cN/dtex, the filament modulus is 125cN/dtex, and the bulk density is 1.18g/cm 3 。
(4) Oxidizing the finished protofilament by a fuming furnace, wherein the oxidation starting temperature is 240 ℃, the termination temperature is 270 ℃,6 oxidation zones are provided, and the pre-oxidized protofilament density is 1.378g/cm 3 . Carbonizing the mixture by a low-temperature carbonization furnace after the oxidation is finished, wherein the starting temperature of the low-temperature carbonization furnace is 420 ℃, the ending temperature of the low-temperature carbonization furnace is 800 ℃, and then carbonizing the mixture by a high-temperature carbonization furnace, the starting temperature of the high-temperature carbonization furnace is 920 ℃, and the ending temperature of the high-temperature carbonization furnace is 1300 ℃. Then, the 50K carbon fiber is prepared by conventional water washing, surface treatment, sizing, drying and the like, the tensile strength of the 50K carbon fiber is 4995MPa, the tensile modulus is 263GPa, the elongation at break is 1.9 percent, the linear density is 2950g/km and the bulk density is 1.8g/cm 3 。
Example 3
The embodiment provides a T700-grade wet large-tow carbon fiber, and the preparation method comprises the following steps:
(1) Taking dimethyl sulfoxide as a solvent, adding acrylonitrile, itaconic acid and acrylamide with the mass percentage of 94.
(2) The spinning solution is extruded by a metering pump, then enters a spinneret plate through a filter and is sprayed out, the spinneret plate is immersed in the first coagulating bath solution, and the spinning solution is sprayed out and instantly formed into nascent fiber. Wherein the temperature of the spinning solution is 62 ℃, the capacity of a metering pump is 60cc/r, the number of gears is 3, and the number of teeth is 30; the filter is a metal sintered felt disc filter, and the filtering precision is 4 mu m; the spinneret plate is a tantalum spherical spinneret plate, the number of holes is 50010, the aperture is 0.075mm, and the length-diameter ratio is 2:1, the surface diameter of a spinneret plate is 130mm, the hole spacing is 0.035mm, and 16 subareas are arranged. The first coagulation bath was DMSO water solution at 35 ℃, concentration 55%, pH of the coagulation bath was adjusted to 9.8 with ammonium bicarbonate, and the coagulation bath negative draft was set to 0.7.
(3) And (3) the nascent fiber is rolled after being subjected to second coagulation bath solution, water washing, hot water drafting, oiling, drying densification, steam drafting and drying setting to obtain the protofilament. Wherein the second coagulation bath is a DMSO aqueous solution, the second coagulation temperature is 65 ℃, the concentration is 35%, and the drawing multiple is 1.5 times. The water washing is 6-stage water washing, the water washing temperature is 60 ℃, 90 ℃, 93 ℃, 97 ℃ and 97 ℃, the hot water drafting multiple is 7 times, amino silicone oil is used for oiling, oiling agent A (watt-gram EZ 002202), oiling agent B (bamboo JHX-506) and oiling agent C (pine JH-88) are compounded, the oiling agent A/oiling agent B/oiling agent C =70/10/20, and the oiling rate is 1.8%. The number of rollers used for drying and densifying is 20, the steam pressure is 3bar at the beginning, the termination pressure is 7bar, the steam pressure is set in a stepped mode, the pressure of a first roller set is 3bar, the pressure of a second roller set is 4.5bar, the pressure of a third roller set is 5.5bar, the pressure of a fourth roller set is 7bar, 3bar saturated steam is used in a steam drawing box, and the drawing ratio is 1.9 times. The filament number of the finished protofilament is 1.4dtex, the linear density of the protofilament is 7g/m, the filament strength is 6.5cN/dtex, the filament modulus is 130cN/dtex, and the bulk density is 1.18g/cm 3 。
(4) The finished product protofilament is oxidized by a fuming furnace, the oxidation starting temperature is 228 ℃, and the end isThe temperature is stopped at 260 ℃,3 oxidation zones are formed, and the pre-oxidized filament density is 1.372g/cm 3 . Carbonizing in a low-temperature carbonization furnace at the initial temperature of 445 ℃ and the final temperature of 780 ℃ after the oxidation is finished, and carbonizing in a high-temperature carbonization furnace at the initial temperature of 1000 ℃ and the final temperature of 1330 ℃. Then, conventional water washing, surface treatment, sizing, drying and the like are carried out to obtain the finished product of 50K carbon fiber, wherein the tensile strength of the 50K carbon fiber is 5150MPa, the tensile modulus is 253GPa, the breaking elongation is 2.0 percent, the linear density is 3500g/km, and the bulk density is 1.79g/cm 3 。
Comparative example 1
This comparative example is essentially the same as example 1, except that: the chain transfer agent in example 1 was omitted.
At this time, the indices of the spinning dope are: the index is a solid content of 20.5% by weight, a rotational viscosity of 38200cP, a weight average molecular weight of 21 ten thousand, a number average molecular weight of 6.1 ten thousand, a molecular weight distribution of 3.5, and an intrinsic viscosity of 2.0. The filament number of the protofilament is 1.22dtex, the linear density of the protofilament is 6.15g/m, the filament strength is 6.1cN/dtex, the filament modulus is 88cN/dtex, and the bulk density is 1.17g/cm 3 (ii) a The finally obtained carbon fiber has the tensile strength of 4305MPa, the tensile modulus of 225GPa, the breaking elongation of 1.91 percent, the linear density of 3050g/km and the bulk density of 1.79g/cm 3 。
According to the detection indexes, the omission of a chain transfer agent causes the generation of macromolecular chains in the reaction process, the rotational viscosity, the weight average molecular weight and the intrinsic viscosity of the spinning solution are increased, the processability of the solution is reduced, the strength, the modulus and the bulk density of the monofilament are further remarkably reduced, and the tensile strength, the tensile modulus, the linear density and the bulk density of the final product are remarkably lower than those of the example 1.
Comparative example 2
This comparative example is essentially the same as example 1, except that: the spinneret in example 1 was changed to have a hole number of 1000 and a hole diameter of 0.055mm.
At this time, the filament fineness of the filaments was 1.23dtex, the filament linear density was 0.13g/m, the filament strength was 7.9cN/dtex, the filament modulus was 112cN/dtex, and the bulk density was 1.18g/cm 3 (ii) a The tensile strength of the finally obtained carbon fiber is 5298MPa, and the tensile modulus is 263GPa, elongation at break of 2.0%, linear density of 0.06g/km and bulk density of 1.82g/cm 3 。
It can be seen from comparison between example 1 and comparative example 2 that the carbon fiber prepared after the number of holes is reduced is a small tow, and the linear density of the precursor and the linear density of the final product are significantly reduced, which does not meet the production index of the large tow of the present application.
Comparative example 3
This comparative example is essentially the same as example 1, except that: the first and second coagulation baths in example 1 were modified from aqueous DMSO solutions to glycerol solutions.
At this time, the filament fineness of the filaments was 1.21dtex, the filament linear density was 6.05g/m, the filament strength was 6.34cN/dtex, the filament modulus was 92cN/dtex, and the bulk density was 1.175g/cm 3 (ii) a The finally obtained carbon fiber has the tensile strength of 5019MPa, the tensile modulus of 236GPa, the elongation at break of 2.0 percent, the linear density of 3022g/km and the bulk density of 1.81g/cm 3 。
Comparing example 1 and comparative example 3, it can be seen that the change of the coagulation bath solution can cause the reduction of the strength of the monofilaments, especially the modulus of the monofilaments is obviously reduced, the modulus of the monofilaments is reduced to 92cN/dtex from 104cN/dtex of example 1, glycerol is an inorganic solution, the hydrophilicity of the stock solution and the coagulation bath solution is increased, the double diffusion of the stock solution is accelerated during the formation of the coagulation bath, large-size grains are formed, the modulus of the protofilament is reduced, and the large-size grains are not beneficial to the rearrangement of the carbon layer in the carbonization process, so that the final modulus is reduced.
Comparative example 4
This comparative example is essentially the same as example 1, except that: the filter in example 1 was modified to a candle-type nonwoven fabric filter element.
At this time, the filament fineness of the filaments was 1.23dtex, the filament linear density was 5.9g/m, the filament strength was 6.7cN/dtex, the filament modulus was 101cN/dtex, and the bulk density was 1.175g/cm 3 (ii) a The finally obtained carbon fiber has the tensile strength of 4472MPa, the tensile modulus of 235GPa, the elongation at break of 1.9 percent, the linear density of 3005g/km and the bulk density of 1.81g/cm 3 。
As can be seen by comparing example 1 and comparative example 4, the filtration effect of the candle-type non-woven fabric filter element is lower than that of the filter, resulting in slightly lower monofilament strength and monofilament modulus than example 1, and the properties of the finally obtained carbon fiber are also slightly lower than example 1.
Comparative example 5
This comparative example is essentially the same as example 1, except that: the dry densification and steam draw conditions in example 1 were modified to: the dry densification was carried out using 20 rolls, a steam pressure of 3bar at the start and 3bar at the end, without a step-wise setting, with a steam draw box using 2.6bar saturated steam and a draw ratio of 1.8.
At this time, the filament fineness of the filaments was 1.22dtex, the filament linear density was 6.12g/m, the filament strength was 6.96cN/dtex, the filament modulus was 102cN/dtex, and the bulk density was 1.168g/cm 3 (ii) a The finally obtained carbon fiber has the tensile strength of 4662MPa, the tensile modulus of 223GPa, the elongation at break of 2.1 percent, the linear density of 3060g/km and the bulk density of 1.79g/cm 3 。
It can be seen from comparison between example 1 and comparative example 3 that the step arrangement is not performed, and the draft ratio is increased, which results in that the performance of the precursor and the performance of the finally obtained carbon fiber are lower than those of example 1, and in particular, the linear density of the finally obtained carbon fiber is changed from 3080g/km of example 1 to 3060g/km of comparative example 5, because the tow surface and the tow contain a large amount of moisture after being washed, the tow is at a fluffy turntable at the moment, the crystallinity is low, when the drying is not provided with a gradient, the fluffy tow is continuously baked at high temperature, the skin is hard and even preoxidation is caused, but the internal moisture is still not dried, the holes are more, at the moment, the crystallization size of the outer skin of the tow is larger, but the crystallinity is low, the internal moisture is not dried, the grain size is too small, high-magnification stretching at the later stage is not facilitated, the higher orientation degree and the proper grain size and high crystallinity precursor cannot be obtained, and finally the strength and modulus of the carbon fiber are reduced.
In summary, the chain transfer agent is added in the polymerization process, so that the generation of macromolecular chains in the reaction process is effectively reduced, and the processability of the stock solution is further improved. Meanwhile, the performance indexes of products (such as spinning solution, precursor and carbon fiber) in each stage are limited, so that the uniformity of the products is better, meanwhile, the rotary viscosity of the spinning solution is reduced, the pressure of a wet spinning spinneret plate can be effectively reduced, the spinning speed is effectively increased and the production efficiency is improved in the spinning process. In addition, the number and the aperture of the holes of the spinneret plate are limited, T700-grade large-tow carbon fibers with the strength of more than or equal to 4900MPa, the modulus of more than or equal to 255GPa and the linear density of more than or equal to 2800g/km can be obtained, and the blank of domestic 50K large-tow products is filled.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A preparation method of T700-grade wet large-tow carbon fibers is characterized by comprising the following steps:
taking dimethyl sulfoxide as a solvent, adding at least one of a second monomer and a third monomer into acrylonitrile which is used as a main polymerization monomer, taking azobisisobutyronitrile as an initiator, and adding a chain transfer agent to perform copolymerization reaction to obtain a spinning solution; the indexes of the spinning solution are as follows: the solid content is 18 to 23 weight percent, the rotational viscosity is 32000 to 45000cP, the weight average molecular weight is 18 to 23 ten thousand, the number average molecular weight is 6 to 9 ten thousand, the molecular weight distribution is 1.4 to 3.0, and the intrinsic viscosity is 1.7 to 2.1;
the spinning solution is sprayed out from a spinneret plate, the spinneret plate is immersed in the first coagulating bath solution, and the spinning solution is sprayed out and instantly formed into nascent fiber; wherein the spinneret plate is a 50K spinneret plate, the number of holes is 50001-50010, and the aperture is 0.05-0.08 mm;
the nascent fiber is rolled after being subjected to second coagulation bath liquid, water washing, hot water drafting, oiling, drying densification, steam drafting and drying shaping to obtain protofilament; the filament number of the protofilament is 1.15-1.5 dtex, the linear density of the protofilament is 5.7-7.5g/m, the filament strength is 6.5-8.0 cN/dtex, the filament modulus is 90-130 cN/dtex, and the bulk density is 1.17-1.19 g/cm 3 ；
The obtained raw silk is uncoiled and oxidizedPreparing carbon fibers by using a furnace, a low-temperature carbonization furnace, a high-temperature carbonization furnace, washing, surface treatment, sizing and drying; the tensile strength of the carbon fiber is 4900-5100 MPa, the tensile modulus is 255-270 GPa, the breaking elongation is 1.8-2.0 percent, the linear density is 2800-3700 g/km, and the bulk density is 1.75-1.83 g/cm 3 。
2. The method for preparing T700 grade wet large-tow carbon fibers according to claim 1, wherein the mass percent of the acrylonitrile and the sum of the second monomer and the third monomer is 92-99%: 1% -8%;
the second monomer comprises at least one of sodium methallyl sulfonate, sodium methallyl benzene sulfonate, itaconic acid and vinyl acetate;
preferably, the third monomer comprises at least one of methyl methacrylate, methyl acrylate, and acrylamide;
preferably, the chain transfer agent is added in an amount of 200-3000ppm based on the total mass of the polymerized monomers;
preferably, the chain transfer agent comprises at least one of a dithioester, n-octylmercaptan, and isopropanol.
3. The method for preparing large tow carbon fiber by the T700 wet process according to claim 1, wherein the distance between holes of the spinneret plate is 0.3-0.5mm, the length-diameter ratio of the spinneret hole is 2:1-3:1;
preferably, the surface diameter of the spinneret plate is 95-135mm, and the spinneret plate is divided into 6-24 areas;
preferably, the spinneret plate is a spherical or planar plate made of tantalum material.
4. The method for preparing the T700-grade wet large-tow carbon fiber according to claim 1, wherein the first coagulation bath solution is an aqueous solution of dimethyl sulfoxide, the temperature is 30-65 ℃, and the concentration is 55-70%;
preferably, the pH value of the first coagulation bath liquid is adjusted to 7-10 by using a regulator;
preferably, the conditioning agent comprises at least one of sodium bicarbonate, ammonium bicarbonate and aqueous ammonia.
5. The method for preparing the T700-grade large-tow wet carbon fiber according to claim 1, wherein the second coagulation bath liquid is an aqueous solution of dimethyl sulfoxide, the temperature is 55-70 ℃, and the concentration is 30% -40%;
preferably, the drawing ratio of the nascent fiber in the second coagulation bath liquid is 1.2 to 1.8 times.
6. The preparation method of the T700 grade wet large-tow carbon fiber according to claim 1, wherein the water washing is 5-12 stages of water washing, the water washing temperature is 50-99 ℃, the drafting ratio is 5-8 times, and the water flow and the nascent fiber run in reverse directions during the water washing;
preferably, the dry densification uses saturated steam, the pressure is 1.2-7bar, the pressure is arranged in a step mode, and the number of drying rollers is 16-32;
preferably, the drying rollers are divided into four groups, namely a first roller group, a second roller group, a third roller group and a fourth roller group; the stepped arrangement is as follows: the pressure of the first roller set is 1.2-3bar, the pressure of the second roller set is 2.5-4.5bar, the pressure of the third roller set is 4-5.5bar, and the pressure of the fourth roller set is 5-7bar;
preferably, the steam drafting box uses saturated steam, the pressure is 1.5-4 bar, the corresponding temperature is 120-144 ℃, and the steam drafting ratio is 1.3-2.0.
7. The method for preparing the T700-grade large-tow carbon fiber by the wet process according to claim 1, wherein the initial temperature in the oxidation furnace is 200-240 ℃, the termination temperature is 250-280 ℃, the oxidation zones are 3-6, and the pre-oxidation filament density is 1.37-1.38g/cm 3 ；
The starting temperature of the low-temperature carbonization furnace is 380-450 ℃, and the ending temperature is 720-800 ℃;
the starting temperature of the high-temperature carbonization furnace is 900-1000 ℃, and the ending temperature is 1150-1350 ℃.
8. The method for preparing the T700-grade large-tow wet carbon fiber according to claim 1, wherein after the preparation of the spinning solution, before the detection of the index of the spinning solution, the method further comprises the following steps of: the spinning stock solution flows into a demonomerization and deaeration tower from top to bottom, dimethyl sulfoxide flows back from bottom to top, the tower top is vacuumized, the pressure in the tower is 0-2KPa absolute pressure, the stock solution monomer content after demonomerization is 0-100ppm, and no bubbles can be seen by naked eyes after deaeration.
9. A T700 grade large wet tow carbon fiber, prepared by the method of preparing a T700 grade large wet tow carbon fiber according to any one of claims 1 to 8.
10. Use of the T700 grade wet large tow carbon fiber of claim 9 in the manufacture of wind blades.
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