CN115584573B - T700-level wet-process large-tow carbon fiber as well as preparation method and application thereof - Google Patents

T700-level wet-process large-tow carbon fiber as well as preparation method and application thereof Download PDF

Info

Publication number
CN115584573B
CN115584573B CN202211227060.8A CN202211227060A CN115584573B CN 115584573 B CN115584573 B CN 115584573B CN 202211227060 A CN202211227060 A CN 202211227060A CN 115584573 B CN115584573 B CN 115584573B
Authority
CN
China
Prior art keywords
carbon fiber
preparing
tow carbon
fiber according
grade wet
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN202211227060.8A
Other languages
Chinese (zh)
Other versions
CN115584573A (en
Inventor
石金
殷伟涛
徐盼盼
钱鸿川
蔡涛
莫凎传
姜万峰
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Jiangsu Hengshen Co Ltd
Original Assignee
Jiangsu Hengshen Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Jiangsu Hengshen Co Ltd filed Critical Jiangsu Hengshen Co Ltd
Priority to CN202211227060.8A priority Critical patent/CN115584573B/en
Publication of CN115584573A publication Critical patent/CN115584573A/en
Application granted granted Critical
Publication of CN115584573B publication Critical patent/CN115584573B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

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

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Mechanical Engineering (AREA)
  • Inorganic Fibers (AREA)
  • Artificial Filaments (AREA)

Abstract

The application discloses a T700-level wet-process large-tow carbon fiber and a preparation method and application thereof, and relates to the technical field of polyacrylonitrile-based carbon fibers. The preparation method comprises the steps of adding a 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, performance indexes of products (such as spinning dope, precursor and carbon fiber) at each stage are limited, so that uniformity of the products is better, and meanwhile, the rotational viscosity of the spinning dope is reduced, so that the pressure of a wet spinning spinneret plate can be effectively reduced, and the spinning speed and the production efficiency are effectively improved in the spinning process. In addition, the application limits the hole number and the aperture of the spinneret plate, can obtain the T700 grade 50K big tow carbon fiber with the strength more than or equal to 4900MPa, the modulus more than or equal to 255GPa and the linear density more than or equal to 2800g/km, and fills the blank of the domestic 50K big tow product.

Description

T700-level wet-process large-tow carbon fiber as well as preparation method and application thereof
Technical Field
The invention relates to the technical field of polyacrylonitrile-based carbon fibers, in particular to a T700-level wet-process large-tow carbon fiber, and a preparation method and application thereof.
Background
Carbon fibers are classified into wet methods and dry spray wet methods according to a precursor preparation method; according to industry practice, the number of monofilaments is 1000 (1K) -50000 (50K) or less as small tows, 50000 or more (50K) as large tows, and the invention is wet 50K large tow carbon fibers.
The domestic Polyacrylonitrile (PAN) based carbon fiber belongs to a starting stage, and the product is mainly aimed at enterprises such as Toli, tobang, zhuoer Tek in the United states, SGL in Germany and the like. The small tows and the large tows are slightly different in application fields due to processing efficiency, cost and the like, wherein the small tows are mainly applied to aerospace, military industry, sports and leisure and the like, and in the wind power generation field, long-size wind power blade carbon fibers replace glass fibers, and the wind power generation field has the advantages of being low in cost, high in processing efficiency and the like along with national double-carbon indexes and policy call of green energy, and being rapidly applied to the wind power field.
However, the present large tow carbon fiber is in the development stage at present, and the invention is specially proposed in view of the fact.
Disclosure of Invention
The invention aims to provide a T700-level wet-process large-tow carbon fiber as well as a preparation method and application thereof.
The invention is realized in the following way:
In a first aspect, the invention provides a method for preparing a T700-grade wet-process large-tow carbon fiber, which comprises the following steps:
Adding at least one of a second monomer and a third monomer into acrylonitrile which is taken as a main polymerization monomer by taking dimethyl sulfoxide as a solvent, and adding a chain transfer agent into the acrylonitrile to carry out copolymerization reaction by taking azobisisobutyronitrile as an initiator to prepare spinning stock solution; the index of the spinning solution is 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;
The spinning solution is sprayed out by a spinneret plate, the spinneret plate is immersed in the first coagulating bath solution, and the spun spinning solution is instantaneously molded into nascent fibers; wherein the spinneret plate is a 50K spinneret plate, the number of holes is 50001-50010 holes, and the aperture is 0.05-0.08 mm;
The primary fiber is coiled after the second coagulating bath, washing, hot water drafting, oiling, drying densification, steam drafting, drying shaping and obtaining a precursor; the filament fineness of the precursor filaments is 1.15-1.5 dtex, the density of the precursor filaments 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 precursor is subjected to unreeling, oxidation furnace, low-temperature carbonization furnace, high-temperature carbonization furnace, water 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 elongation at break is 1.8-2.0%, 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 92% to 99%:1% -8%;
The second monomer comprises at least one of sodium methacrylate sulfonate, sodium methacrylate benzenesulfonate, itaconic acid and vinyl acetate;
preferably, the third monomer includes at least one of methyl methacrylate, methyl acrylate, and acrylamide;
Preferably, the chain transfer agent is added in an amount of 200 to 3000ppm based on the total mass of the polymerized monomers;
preferably, the chain transfer agent includes at least one of dithioesters, n-octanethiol, and isopropanol.
In an alternative embodiment, the spinneret has a hole spacing of 0.3 to 0.5mm and a spinneret hole aspect ratio of 2:1-3:1, a step of;
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 a dimethyl sulfoxide aqueous solution, the temperature is 30-65 ℃, and the concentration is 55% -70%;
Preferably, the pH of the first coagulation bath is adjusted to 7-10 using a regulator;
preferably, the regulator comprises at least one of sodium bicarbonate, ammonium bicarbonate and ammonia water;
In an alternative embodiment, the second coagulation bath is an aqueous dimethyl sulfoxide solution at a temperature of 55-70 ℃ and a concentration of 30% -40%;
Preferably, the draft of the as-spun fibers in the second coagulation bath is 1.2-1.8 times.
In an alternative embodiment, the water wash is 5-12 sections of water wash, the water wash temperature is 50-99 ℃, the draft ratio is 5-8 times, and the water flow and the nascent fiber are reversely operated during the water wash;
Preferably, saturated steam is used for drying densification, the pressure is 1.2-7bar, the pressure is arranged in a step-type manner, 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 in sequence; the step-type arrangement is as follows: the first roller set pressure is 1.2-3bar, the second roller set pressure is 2.5-4.5bar, the third roller set pressure is 4-5.5bar, and the fourth roller set pressure 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 oxidation oven has an initial temperature of 200-240 ℃ and a final temperature of 250-280 ℃,3-6 oxidation zones, and a pre-oxidized fiber density of 1.37-1.38g/cm 3;
the initial temperature of the low-temperature carbonization furnace is 380-450 ℃, and the end temperature is 720-800 ℃;
the initial temperature of the high-temperature carbonization furnace is 900-1000 ℃ and the end temperature is 1150-1350 ℃.
In an alternative embodiment, after the spinning dope is prepared, before detecting the index of the spinning dope, the method further comprises the steps of performing the deallocation and the deaeration on the spinning dope: the spinning solution flows into a filler in a single-removing and deaerating tower from top to bottom, dimethyl sulfoxide flows back from bottom to top, vacuum is pumped from the top of the tower, the pressure in the tower is 0-2KPa, the monomer content of the solution after single removing is 0-100ppm, and no bubbles are visible to naked eyes after deaerating.
In a second aspect, the present invention provides a T700 grade wet process large tow carbon fiber, which is prepared by the method for preparing a T700 grade wet process large tow carbon fiber according to any one of the previous embodiments.
In a third aspect, the invention provides an application of the T700-grade wet-process large-tow carbon fiber in preparing wind power blades.
The invention has the following beneficial effects:
According to the preparation method of the T700-level wet-process large-tow carbon fiber, provided by the application, 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 dope, precursor and carbon fiber) at each stage are limited, so that uniformity of the products is better, and meanwhile, the rotational viscosity of the spinning dope is reduced, so that the pressure of a wet spinning spinneret plate can be effectively reduced, and the spinning speed and the production efficiency are effectively improved in the spinning process. In addition, the application limits the hole number and the aperture of the spinneret plate, can obtain the T700 grade 50K big tow carbon fiber with the strength more than or equal to 4900MPa, the modulus more than or equal to 255GPa and the linear density more than or equal to 2800g/km, and fills the blank of the domestic 50K big tow product.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention more clear, the technical solutions of the embodiments of the present invention will be clearly and completely described below. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
The invention provides a preparation method of a T700-level wet-process large-tow carbon fiber, which comprises the following steps:
S1, preparing spinning solution.
At least one of a second monomer and a third monomer is added into acrylonitrile which is taken as a main polymerization monomer by taking dimethyl sulfoxide as a solvent, and azodiisobutyronitrile is taken as an initiator, and a chain transfer agent is added for copolymerization reaction to prepare spinning stock 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 chain transfer agent is added in an amount of 200 to 3000ppm based on the total mass of the polymerized monomers.
The second monomer comprises at least one of sodium methacrylate sulfonate, sodium methacrylate benzenesulfonate, 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 dithioesters, n-octanethiol, and isopropanol.
After the spinning solution is prepared, before the index of the spinning solution is detected, the method further comprises the steps of removing the monomer and defoaming the spinning solution: the spinning stock solution flows into the filler in the single degassing tower from top to bottom, dimethyl sulfoxide flows back from bottom to top, vacuum is pumped from the top of the tower, the pressure in the tower is 0-2KPa, the monomer content of the stock solution after single degassing is 0-100ppm, and no bubbles are visible to naked eyes after degassing.
The spinning dope has the following indexes: 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 second monomer and/or third monomer is added in the reaction process, and the introduction of new groups improves the processability of the stock solution. Meanwhile, the chain transfer agent is added, so that the generation of macromolecular chains in the reaction process is effectively reduced, and the processability of the stock solution is further improved. 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 a nascent fiber.
The spinning solution is sprayed out by a spinneret plate, the spinneret plate is immersed in the first coagulating bath, and the spun spinning solution is instantaneously molded into nascent fibers.
Before the spinning solution is sprayed out from the spinneret plate, the spinning process 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 is 40-60cc/r, the number of gears is 2 or 3, the number of teeth is 18-30, and the precision of the filter is 2-5 mu m.
Wherein the spinneret plate is a 50K spinneret plate, the number of holes is 50001-50010 holes, and the aperture is 0.05-0.08 mm; the hole spacing of the spinneret plate is 0.3-0.5mm, and the length-diameter ratio of the spinneret holes is 2:1-3:1, a step of; 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 or planar plate of tantalum material. The ratio (negative draft) of the spinning speed of the spinneret to the speed of the first guide roller 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 solution to 7-10 by using an adjusting agent; the regulator comprises at least one of sodium bicarbonate, ammonium bicarbonate and ammonia water. By limiting the temperature, concentration and pH of the first coagulation bath liquid, the application can effectively adjust the crystallinity and orientation degree of the precursor and obtain excellent subsequent processing performance.
S3, preparing a precursor.
And (3) winding the nascent fiber after the second coagulating bath, washing, hot water drafting, oiling, drying densification, steam drafting, drying and shaping to obtain the precursor.
The second coagulating bath liquid is dimethyl sulfoxide water solution, the temperature is 55-70 ℃, and the concentration is 30% -40%; the draft of the nascent fiber in the second coagulation bath is 1.2-1.8 times.
The washing is 5-12 sections of washing, the washing temperature is 50-99 ℃, the draft ratio is 5-8 times, the water flow and the nascent fiber are operated reversely during the washing, specifically, the water flow is from back to front, the tows are operated reversely from front to back, each section of the 5-12 sections of washing is provided with a washing tank, and the front and back groups of traction rollers carry out traction.
Drafting 5-7 times in hot water.
The oil is at least one of Wake EZ002202, bamboo JHX-506 and pine JH-88 or a mixture of more than two of them, when the oil is a mixture, the Wake EZ002202, bamboo JHX-506 and pine JH-88 are compounded according to a certain proportion, the compounding proportion can be adjusted according to the actual situation, and the oil application 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, the pressure of different roller groups is limited, so that the roller group pressure 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 group, a second roller group, a third roller group and a fourth roller group in sequence; the stepwise arrangement may be, for example, as follows: the first roller set pressure is 1.2-3bar, the second roller set pressure is 2.5-4.5bar, the third roller set pressure is 4-5.5bar, and the fourth roller set pressure is 5-7bar.
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.
The filament fineness of the precursor filaments is 1.15-1.5 dtex, the density of the precursor filaments 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.
S4, preparing carbon fibers.
The obtained precursor is subjected to unreeling, oxidation furnace, low-temperature carbonization furnace, high-temperature carbonization furnace, water washing, surface treatment, sizing and drying to obtain the carbon fiber.
The initial temperature in the oxidation furnace is 200-240 ℃, the end temperature is 250-280 ℃,3-6 oxidation areas are provided, and the density of the pre-oxidized fiber body is 1.37-1.38g/cm 3; the initial temperature of the low-temperature carbonization furnace is 380-450 ℃ and the end temperature is 720-800 ℃; the initial temperature of the high-temperature carbonization furnace is 900-1000 ℃ and the end temperature is 1150-1350 ℃. The subsequent water washing, surface treatment, sizing, drying and the like are conventional techniques.
The T700-level wet-process large-tow carbon fiber prepared by the preparation method of the T700-level wet-process large-tow carbon fiber has the tensile strength of 4900-5100 MPa, the tensile modulus of 255-270 GPa, the elongation at break of 1.8-2.0%, the linear density of 2800-3700 g/km and the bulk density of 1.75-1.83 g/cm 3, fills the blank of the domestic 50K large-tow product, and can be widely applied to the preparation of wind power blades.
The features and capabilities of the present invention are described in further detail below in connection with the examples.
Example 1
The embodiment provides a T700-level wet-process large-tow carbon fiber, and the preparation method comprises the following steps:
(1) Taking dimethyl sulfoxide as a solvent, adding acrylonitrile and vinyl acetate with the mass percentage of 97:3, taking AIBN as an initiator, taking isopropanol as a chain transfer agent, taking 1000ppm of the chain transfer agent as the mass of a polymerized monomer, polymerizing for 21 hours at 65 ℃ to prepare a spinning solution, flowing the spinning solution into a filler in a single degassing tower from top to bottom, countercurrent dimethyl sulfoxide from bottom to top, vacuumizing from the top of the tower, wherein the pressure in the tower is 0.5KPa, the monomer content of the solution after single degassing is 20ppm, and no bubbles are visible to naked eyes after the degassing. The spinning dope has the following indexes: the index was 20.5wt% solids, 38000cP rotational viscosity, 20 ten thousand weight average molecular weight, 8 ten thousand number average molecular weight, 2.5 molecular weight distribution, and 1.9 intrinsic viscosity.
(2) The spinning solution is extruded by a metering pump, then enters a spinneret plate through a filter to be sprayed out, the spinneret plate is immersed into the first coagulating bath liquid, and the spun fiber is formed into the nascent fiber instantly. Wherein, the temperature of the stock solution for spinning is 50 ℃, the capacity of a metering pump is 50cc/r, the number of gears is 2, the number of teeth is 25, the filter is a metal sintering felt disc filter, the filtering precision is 2 mu m, the spinneret plate is a tantalum plane spinneret plate, the number of holes is 50005 holes, the aperture is 0.065mm, and the length-diameter ratio is 2:1, the spinneret plate surface diameter is 120mm, the hole spacing is 0.04mm, and 16 subareas. The first coagulation bath was an aqueous DMSO solution at 50 ℃, 68% strength, and the pH of the coagulation bath was adjusted to 8.5 using sodium bicarbonate, setting the negative draft of the coagulation bath to 0.7.
(3) And (3) winding the nascent fiber after the second coagulating bath, washing, hot water drafting, oiling, drying densification, steam drafting, drying and shaping to obtain the precursor. Wherein the second coagulation bath is DMSO aqueous solution, the second coagulation temperature is 60 ℃, the concentration is 36%, and the draft multiple is 1.35 times. The water washing is 8 sections of water washing, the water washing temperature is 60 ℃, 80 ℃, 90 ℃,93 ℃,97 ℃ and hot water drafting multiple is 6 times, amino silicone oil is used for oiling, oil A (Wake EZ 002202) and oil B (bamboo JHX-506) are used for compounding, the oil A/oil B=90/10, and the oiling rate is 1.8%. The number of the rollers used for drying densification is 20, the steam pressure is 1.2bar at the beginning and 5bar at the end, the steam pressure is arranged in a step 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, saturated steam of 2.6bar is used for a steam draft box, and the draft ratio is 1.8 times. The filament number of the finished product precursor is 1.23dtex, the density of the precursor 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) The finished product precursor is oxidized by a fuming furnace, the oxidation initial temperature is 200 ℃, the termination temperature is 250 ℃, the density of the pre-oxidized precursor is 1.375g/cm 3 in 4 oxidation areas. Carbonizing in a low temperature carbonization furnace with an initial temperature of 390 ℃ and a final temperature of 780 ℃ after the oxidation is finished, carbonizing in a high temperature carbonization furnace with an initial temperature of 930 ℃ and a final temperature of 1200 ℃. And carrying out conventional water washing, surface treatment, sizing, drying and the like to obtain the finished product 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%, the linear density is 3080g/km, and the bulk density is 1.82g/cm 3.
Example 2
The embodiment provides a T700-level wet-process large-tow carbon fiber, and the preparation method comprises the following steps:
(1) Taking dimethyl sulfoxide as a solvent, adding acrylonitrile, methyl methacrylate and sodium acrylate with the mass percentage of 96:3:1, taking azodiisobutyronitrile as an initiator, taking n-octyl mercaptan as a chain transfer agent, taking 2200ppm of the chain transfer agent as the mass of a polymerized monomer, and polymerizing for 21 hours at 65 ℃ to obtain a spinning solution, wherein the spinning solution flows into a filler in a single degassing tower from top to bottom, the dimethyl sulfoxide flows back from bottom to top, vacuum is pumped from the top of the tower, the pressure in the tower is 1kpa absolute, the monomer content of the stock solution after single degassing is 100ppm, and no bubbles are visible after the single degassing. The spinning dope has the following indexes: 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 to be sprayed out, the spinneret plate is immersed into the first coagulating bath liquid, and the spun fiber is formed into the nascent fiber instantly. The temperature of the 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 teeth; 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 spinneret plate surface diameter is 100mm, the hole spacing is 0.03mm, and 24 subareas. The first coagulation bath was DMSO aqueous solution at 42 ℃, 65% strength, and the pH of the coagulation bath was adjusted to 9.5 using ammonia water, setting the coagulation bath negative draft to 0.8.
(3) And (3) winding the nascent fiber after the second coagulating bath, washing, hot water drafting, oiling, drying densification, steam drafting, drying and shaping to obtain the precursor. Wherein the second coagulation bath is DMSO aqueous solution, the temperature is 55 ℃, the concentration is 33%, and the draft multiple is 1.6 times. The water washing is 10 sections of water washing, the water washing temperature is 60 ℃, 80 ℃, 90 ℃, 93 ℃, 95 ℃, 97 ℃ and hot water drafting multiple is 5 times, amino silicone oil is used for oiling, oil A (Wake EZ 002202) and oil C (Songben JH-88) are used for compounding, the oil A/oil C=60/40, and the oiling rate is 1.4%. The number of the rollers used for drying densification is 28, the steam pressure is initially 1.2bar, the termination pressure is 6bar, and the steam pressure is arranged in a stepped manner, wherein 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, the steam drafting box uses 4bar saturated steam, and the drafting ratio is 2.2 times. The filament number of the finished product precursor is 1.18dtex, the density of the precursor 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) The finished product precursor is oxidized by a fuming furnace, the oxidation initial temperature is 240 ℃, the oxidation end temperature is 270 ℃, the density of the pre-oxidized precursor is 1.378g/cm 3 in 6 oxidation areas. Carbonizing in a low temperature carbonization furnace with an initial temperature of 420 ℃ and a final temperature of 800 ℃ after the oxidation is finished, carbonizing in a high temperature carbonization furnace with an initial temperature of 920 ℃ and a final temperature of 1300 ℃. And carrying out conventional water washing, surface treatment, sizing, drying and the like to obtain the finished product 50K carbon fiber, wherein the tensile strength of the 50K carbon fiber is 4995MPa, the tensile modulus is 263GPa, the elongation at break is 1.9%, the linear density is 2950g/km, and the bulk density is 1.8g/cm 3.
Example 3
The embodiment provides a T700-level wet-process 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 94:2:4, taking AIBN as an initiator, taking dithioester as a chain transfer agent, taking 500ppm of the chain transfer agent as the mass of a polymerized monomer, polymerizing for 21 hours at 65 ℃ to prepare a spinning solution, flowing the spinning solution into a filler in a single degassing tower from top to bottom, countercurrent dimethyl sulfoxide from bottom to top, vacuumizing from the top of the tower, wherein the pressure in the tower is 2kpa absolute, the monomer content of the solution is 30ppm, no bubbles are visible to naked eyes, the indexes are 22wt% of solid content, 35000cP of rotational viscosity, 20 ten thousand of weight average molecular weight, 10.5 ten thousand of number average molecular weight, 1.9 of molecular weight distribution and 1.95 of intrinsic viscosity.
(2) The spinning solution is extruded by a metering pump, then enters a spinneret plate through a filter to be sprayed out, the spinneret plate is immersed into the first coagulating bath liquid, and the spun fiber is formed into the nascent fiber instantly. 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 teeth; 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 spinneret plate surface diameter is 130mm, the hole spacing is 0.035mm, and 16 subareas. The first coagulation bath was DMSO aqueous solution at 35 ℃, concentration 55%, and the pH of the coagulation bath was adjusted to 9.8 using ammonium bicarbonate, setting the negative draft of the coagulation bath to 0.7.
(3) And (3) winding the nascent fiber after the second coagulating bath, washing, hot water drafting, oiling, drying densification, steam drafting, drying and shaping to obtain the precursor. Wherein the second coagulation bath is DMSO aqueous solution, the second coagulation temperature is 65 ℃, the concentration is 35%, and the draft multiple is 1.5 times. The water washing is 6 sections of water washing, the water washing temperature is 60 ℃, 90 ℃, 93 ℃, 97 ℃, hot water drafting multiple is 7 times, amino silicone oil is used for oiling, oil A (Wake EZ 002202), oil B (Zhuben JHX-506) and oil C (Songben JH-88) are compounded, the oil A/oil B/oil C=70/10/20, and the oiling rate is 1.8%. The number of the rollers used for drying densification is 20, the steam pressure is 3bar initially, the steam pressure is 7bar, the steam pressure is arranged in a step mode, wherein the pressure of the first roller set is 3bar, the pressure of the second roller set is 4.5bar, the pressure of the third roller set is 5.5bar, the pressure of the fourth roller set is 7bar, 3bar saturated steam is used for a steam drafting box, and the drafting ratio is 1.9 times. The filament number of the finished product precursor is 1.4dtex, the density of the precursor 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 precursor is oxidized by a fuming furnace, the oxidation initial temperature is 228 ℃, the oxidation end temperature is 260 ℃,3 oxidation areas are provided, and the density of the pre-oxidized precursor is 1.372g/cm 3. Carbonizing in a low temperature carbonization furnace with an initial temperature of 445 ℃ and a final temperature of 780 ℃ after the oxidation is finished, carbonizing in a high temperature carbonization furnace with an initial temperature of 1000 ℃ and a final temperature of 1330 ℃. And carrying out conventional water washing, surface treatment, sizing, drying and the like to obtain the finished product 50K carbon fiber, wherein the tensile strength of the 50K carbon fiber is 5150MPa, the tensile modulus of the 50K carbon fiber is 253GPa, the elongation at break is 2.0%, the linear density is 3500g/km, and the bulk density is 1.79g/cm 3.
Comparative example 1
This comparative example is substantially identical to example 1, except that: the chain transfer agent in example 1 was omitted.
At this time, the index of the spinning dope is: the index was 20.5wt% of solids, 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 fineness of the precursor yarn is 1.22dtex, the density of the precursor yarn 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; the finally obtained carbon fiber has tensile strength of 4305MPa, tensile modulus of 225GPa, elongation at break of 1.91%, linear density of 3050g/km and bulk density of 1.79g/cm 3.
From the above detection indexes, it can be seen that omitting the chain transfer agent results in the generation of macromolecular chains in the reaction process, the rotational viscosity, the weight average molecular weight and the intrinsic viscosity of the spinning dope are all increased, the processability of the dope is reduced, and further, the strength, the modulus and the bulk density of the monofilaments are all remarkably reduced, and the tensile strength, the tensile modulus, the linear density and the bulk density of the final product are all remarkably lower than those of example 1.
Comparative example 2
This comparative example is substantially identical to example 1, except that: the spinneret plate 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 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; the finally obtained carbon fiber has tensile strength of 5298MPa, tensile modulus of 263GPa, elongation at break of 2.0%, linear density of 0.06g/km and bulk density of 1.82g/cm 3.
As can be seen from comparative examples 1 and 2, the carbon fiber prepared by reducing the number of pores is a small tow, and the raw silk thread density and the linear density of the final product are remarkably reduced, which does not meet the production index of the large tow of the present application.
Comparative example 3
This comparative example is substantially identical to example 1, except that: the first coagulation bath and the second coagulation bath in example 1 were modified from DMSO aqueous solutions to glycerol solutions.
At this time, the filament fineness of the filaments was 1.21dtex, the filament 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; the finally obtained carbon fiber has tensile strength of 5019MPa, tensile modulus of 236GPa, elongation at break of 2.0%, linear density of 3022g/km and bulk density of 1.81g/cm 3.
As can be seen from comparative examples 1 and 3, the change of the coagulation bath resulted in a decrease in the strength of the monofilaments, particularly a significant decrease in the modulus of the monofilaments, from the modulus of 104cN/dtex of the monofilaments of example 1 to 92cN/dtex, glycerol was an inorganic solution, the hydrophilicity of the stock solution and the coagulation bath increased, resulting in an increase in double diffusion of the stock solution during the coagulation bath forming, formation of large-size grains, a decrease in the modulus of the precursors, and a decrease in the final modulus due to the large-size grains being unfavorable for rearrangement of the carbon layer during carbonization.
Comparative example 4
This comparative example is substantially identical to example 1, except that: the filter of example 1 was modified to a candle-type nonwoven fabric filter cartridge.
At this time, the filament fineness of the filaments was 1.23dtex, the filament 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; the finally obtained carbon fiber has tensile strength of 4472MPa, tensile modulus of 235GPa, elongation at break of 1.9%, linear density of 3005g/km and bulk density of 1.81g/cm 3.
As can be seen from comparative examples 1 and 4, the candle-type nonwoven filter element has a lower filtration effect than the filter, resulting in a slightly lower monofilament strength and monofilament modulus than in example 1, and the resulting carbon fiber has a slightly lower performance than in example 1.
Comparative example 5
This comparative example is substantially identical to example 1, except that: the dry densification and steam draw conditions in example 1 were modified as: the number of the rollers used for drying densification is 20, the steam pressure is 3bar at the beginning and 3bar at the end, no step arrangement is carried out, 2.6bar saturated steam is used for the steam drafting box, and the drafting ratio is 1.8 times.
At this time, the filament fineness of the filaments was 1.22dtex, the filament 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; the finally obtained carbon fiber has tensile strength of 4662MPa, tensile modulus of 223GPa, elongation at break of 2.1%, linear density of 3060g/km and bulk density of 1.79g/cm 3.
As can be seen from comparative examples 1 and 3, the stepwise arrangement was not performed and the draft ratio was increased, resulting in that both the properties of the precursor and the properties of the finally obtained carbon fiber were lower than those of example 1, and in particular, the linear density of the finally obtained carbon fiber was changed from 3080g/km of example 1 to 3060g/km of comparative example 5, because the surface of the filament bundle and the filament bundle contained a large amount of moisture after the water washing, the filament bundle was in a fluffy turntable at this time, the crystallinity was lower, and when the drying was not provided with a gradient, the fluffy filament bundle was continuously baked at a high temperature, resulting in the skin being hard even pre-oxidized, but the internal moisture was not yet dried, the pores were more, and at this time the crystalline size of the outer skin of the filament bundle was larger, but the crystallinity was low, the internal moisture was not dried, the crystalline size was too small, and the high-power stretching at the later stage was unfavorable, the high-orientation degree and the proper crystalline size of the filament was not obtained, and the strength and modulus of the final carbon fiber were reduced.
In summary, according to the preparation method of the T700-level 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 dope, precursor and carbon fiber) at each stage are limited, so that uniformity of the products is better, and meanwhile, the rotational viscosity of the spinning dope is reduced, so that the pressure of a wet spinning spinneret plate can be effectively reduced, and the spinning speed and the production efficiency are effectively improved in the spinning process. In addition, the application limits the hole number and the hole diameter of the spinneret plate, can obtain the T700-grade large-tow carbon fiber with the strength more than or equal to 4900MPa, the modulus more than or equal to 255GPa and the linear density more than or equal to 2800g/km, and fills the blank of the domestic 50K large-tow product.
The above description is only of the preferred embodiments of the present invention and is not intended to limit the present invention, but various modifications and variations can be made to the present invention by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (21)

1. The preparation method of the T700-grade wet-process large-tow carbon fiber is characterized by comprising the following steps of:
Adding at least one of a second monomer and a third monomer into acrylonitrile serving as a main polymerization monomer by taking dimethyl sulfoxide as a solvent, wherein the mass percent of the acrylonitrile and the mass percent of the sum of the second monomer and the third monomer are 92% -97%:3% -8%; taking azodiisobutyronitrile as an initiator, adding a chain transfer agent, and carrying out copolymerization reaction to obtain spinning solution; the index of the spinning solution is as follows: the solid content is 18 to 23 weight percent, the rotational viscosity is 32000 to 42000cP, 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 by a spinneret plate, the spinneret plate is immersed in the first coagulating bath solution, and the spun spinning solution is instantaneously molded into nascent fibers; the spinning solution is extruded by a metering pump, and then enters the spinneret plate by a filter, wherein the capacity of the metering pump is 40-60cc/r, the number of gears is 2 or 3, the number of teeth is 18-30, the filter is a metal sintered felt, and the precision is 2-5 mu m; 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 primary fiber is coiled after the second coagulating bath, washing, hot water drafting, oiling, drying densification, steam drafting, drying shaping and obtaining a precursor; the filament fineness of the precursor is 1.15-1.5 dtex, the density of the precursor 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 precursor is subjected to unreeling, oxidation furnace, low-temperature carbonization furnace, high-temperature carbonization furnace, water 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 elongation at break is 1.8-2.0%, 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 a T700 grade wet large tow carbon fiber according to claim 1, wherein the second monomer comprises at least one of sodium methallyl sulfonate, sodium methallyl benzenesulfonate, itaconic acid and vinyl acetate.
3. The method for preparing a T700 grade wet large tow carbon fiber according to claim 1, wherein the third monomer comprises at least one of methyl methacrylate, methyl acrylate and acrylamide.
4. The method for producing a T700 grade wet process large tow carbon fiber according to claim 1, wherein the chain transfer agent is added in an amount of 200 to 3000ppm based on the total mass of the polymerized monomers.
5. The method for preparing a T700 grade wet large tow carbon fiber according to claim 1, wherein the chain transfer agent comprises at least one of dithioesters, n-octanethiol and isopropyl alcohol.
6. The method for preparing the T700 grade wet large tow carbon fiber according to claim 1, wherein the hole spacing of the spinneret plate is 0.3-0.5mm, and the aspect ratio of the spinneret holes is 2:1-3:1.
7. The method for preparing the T700-grade wet-process large-tow carbon fiber according to claim 1, wherein the surface diameter of the spinneret plate is 95-135mm, and the spinneret plate is divided into 6-24 areas.
8. The method for preparing the T700 grade wet large tow carbon fiber according to claim 1, wherein the spinneret plate is a spherical or planar plate of tantalum material.
9. The method for preparing the T700 grade wet large-strand carbon fiber according to claim 1, wherein the first coagulating bath liquid is a dimethyl sulfoxide aqueous solution, the temperature is 30-65 ℃, and the concentration is 55% -70%.
10. The method for preparing T700 grade wet large tow carbon fiber according to claim 1, wherein the pH of the first coagulation bath is adjusted to 7-10 using an adjusting agent.
11. The method for preparing a T700 grade wet large tow carbon fiber according to claim 10, wherein the regulator comprises at least one of sodium bicarbonate, ammonium bicarbonate and ammonia water.
12. The method for preparing the T700 grade wet large-strand carbon fiber according to claim 1, wherein the second coagulating bath liquid is a dimethyl sulfoxide aqueous solution, the temperature is 55-70 ℃, and the concentration is 30% -40%.
13. The method for producing a T700 grade wet large tow carbon fiber according to claim 1, wherein the draft of the nascent fiber in the second coagulation bath is 1.2 to 1.8 times.
14. The method for producing a T700 grade wet large tow carbon fiber according to claim 1, wherein the water washing is 5-12 stage water washing, the water washing temperature is 50-99 ℃, the draft ratio is 5-8 times, and the water flow and the nascent fiber are operated in reverse direction during the water washing.
15. The method for preparing the T700 grade wet large tow carbon fiber according to claim 1, wherein saturated steam is used for drying densification, the pressure is 1.2-7bar, the pressure is arranged in a step mode, and the number of drying rollers is 16-32.
16. The method for preparing the T700 grade wet-process large tow carbon fiber according to claim 15, wherein the drying rolls are divided into four groups, namely a first roll group, a second roll group, a third roll group and a fourth roll group in sequence; the step-type arrangement is as follows: the first roller set pressure is 1.2-3bar, the second roller set pressure is 2.5-4.5bar, the third roller set pressure is 4-5.5bar, and the fourth roller set pressure is 5-7bar.
17. The method for preparing the T700 grade wet large tow carbon fiber according to claim 1, wherein 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.
18. The method for preparing the T700 grade wet large tow carbon fiber according to claim 1, wherein the initial temperature in the oxidation furnace is 200-240 ℃, the end temperature is 250-280 ℃,3-6 oxidation areas are provided, and the density of the pre-oxidized fiber body is 1.37-1.38g/cm 3;
the initial temperature of the low-temperature carbonization furnace is 380-450 ℃, and the end temperature is 720-800 ℃;
the initial temperature of the high-temperature carbonization furnace is 900-1000 ℃ and the end temperature is 1150-1350 ℃.
19. The method for preparing the T700 grade wet-process large-tow carbon fiber according to claim 1, wherein after preparing the spinning dope, before detecting the index of the spinning dope, further comprising the steps of performing the desingulation and the deaeration of the spinning dope: the spinning solution flows into a filler in a single-removing and deaerating tower from top to bottom, dimethyl sulfoxide flows back from bottom to top, vacuum is pumped from the top of the tower, the pressure in the tower is 0-2KPa, the monomer content of the solution after single removing is 0-100ppm, and no bubbles are visible to naked eyes after deaerating.
20. A T700 grade wet-process large tow carbon fiber prepared by the method of any one of claims 1 to 19.
21. The use of the T700 grade wet large tow carbon fiber of claim 20 in the preparation of wind blades.
CN202211227060.8A 2022-10-09 2022-10-09 T700-level wet-process large-tow carbon fiber as well as preparation method and application thereof Active CN115584573B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202211227060.8A CN115584573B (en) 2022-10-09 2022-10-09 T700-level wet-process large-tow carbon fiber as well as preparation method and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202211227060.8A CN115584573B (en) 2022-10-09 2022-10-09 T700-level wet-process large-tow carbon fiber as well as preparation method and application thereof

Publications (2)

Publication Number Publication Date
CN115584573A CN115584573A (en) 2023-01-10
CN115584573B true CN115584573B (en) 2024-05-28

Family

ID=84780800

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202211227060.8A Active CN115584573B (en) 2022-10-09 2022-10-09 T700-level wet-process large-tow carbon fiber as well as preparation method and application thereof

Country Status (1)

Country Link
CN (1) CN115584573B (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115233320B (en) * 2022-08-04 2024-01-09 青岛大学 Preparation method of high-conductivity special-shaped composite fiber

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101316956A (en) * 2005-12-13 2008-12-03 东丽株式会社 Carbon fiber, process for production of polyacrylonitrile-base precursor fiber for carbon fiber production, and process for production of carbon fiber
JP2010235794A (en) * 2009-03-31 2010-10-21 Toray Ind Inc Manufacturing methods of polyacrylonitrile polymer solution, carbon fiber precursor fiber, and carbon fiber
CN103249880A (en) * 2010-11-30 2013-08-14 东丽株式会社 Polyacrylonitrile fiber manufacturing method and carbon fiber manufacturing method
CN104562265A (en) * 2013-10-28 2015-04-29 中国石油化工股份有限公司 Preparation method of polyacrylonitrile-based carbon fiber precursor
CN106012111A (en) * 2016-07-21 2016-10-12 中国石油大学(北京) Preparation method of carbon fiber precursor
CN106906527A (en) * 2017-04-28 2017-06-30 山西钢科碳材料有限公司 A kind of big the tow many pressurization of spinning position polyacrylonitrile fiber steam drafting system and methods
CN112410891A (en) * 2019-08-20 2021-02-26 蒙特美艾意技术有限责任公司 Method for optimizing the preparation of a spinning solution for acrylic fiber precursors for the production of carbon fibers, and related carbon fibers
CN113072658A (en) * 2021-04-02 2021-07-06 长春工业大学 High-solid-content low-viscosity polyacrylonitrile turbid liquid, preparation method and application thereof, and preparation method of polyacrylonitrile-based carbon fiber
CN114457444A (en) * 2020-11-10 2022-05-10 中国石油化工股份有限公司 Preparation method of high-strength polyacrylonitrile fiber

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101316956A (en) * 2005-12-13 2008-12-03 东丽株式会社 Carbon fiber, process for production of polyacrylonitrile-base precursor fiber for carbon fiber production, and process for production of carbon fiber
JP2010235794A (en) * 2009-03-31 2010-10-21 Toray Ind Inc Manufacturing methods of polyacrylonitrile polymer solution, carbon fiber precursor fiber, and carbon fiber
CN103249880A (en) * 2010-11-30 2013-08-14 东丽株式会社 Polyacrylonitrile fiber manufacturing method and carbon fiber manufacturing method
CN104562265A (en) * 2013-10-28 2015-04-29 中国石油化工股份有限公司 Preparation method of polyacrylonitrile-based carbon fiber precursor
CN106012111A (en) * 2016-07-21 2016-10-12 中国石油大学(北京) Preparation method of carbon fiber precursor
CN106906527A (en) * 2017-04-28 2017-06-30 山西钢科碳材料有限公司 A kind of big the tow many pressurization of spinning position polyacrylonitrile fiber steam drafting system and methods
CN112410891A (en) * 2019-08-20 2021-02-26 蒙特美艾意技术有限责任公司 Method for optimizing the preparation of a spinning solution for acrylic fiber precursors for the production of carbon fibers, and related carbon fibers
CN114457444A (en) * 2020-11-10 2022-05-10 中国石油化工股份有限公司 Preparation method of high-strength polyacrylonitrile fiber
CN113072658A (en) * 2021-04-02 2021-07-06 长春工业大学 High-solid-content low-viscosity polyacrylonitrile turbid liquid, preparation method and application thereof, and preparation method of polyacrylonitrile-based carbon fiber

Also Published As

Publication number Publication date
CN115584573A (en) 2023-01-10

Similar Documents

Publication Publication Date Title
CN101724922B (en) Method for preparing high-strength polyacrylonitrile-based precursor for carbon fiber
CN102146595B (en) Method for preparing polyacrylonitrile carbon fiber protofilament by dry and wet methods
CN101768791B (en) Polyacrylonitrile-based hollow carbon fiber precursor preparation method
CN104562265B (en) The preparation method of polyacrylonitrile base carbon fiber precursors
CN102517671B (en) Method for preparing carbon fiber precursor by two-step process of aqueous suspension and solution polymerization
CN101161880A (en) Method for preparing polyacrylonitrile-based carbon fiber precursor fiber
CN110863256B (en) Preparation method of dry-jet wet-spun high-strength medium-modulus polyacrylonitrile-based carbon fiber precursor
CN109023594B (en) Polyacrylonitrile carbon fiber with ultrahigh strength and medium-high modulus property and preparation method thereof
CN111139554B (en) High-permeability polyacrylonitrile-based carbon fiber and preparation method thereof
CN115584573B (en) T700-level wet-process large-tow carbon fiber as well as preparation method and application thereof
CN110331470A (en) Band shape polyacrylonitrile carbon fiber and preparation method thereof
CN112226851B (en) Preparation method of polyacrylonitrile-based carbon fiber
CN103614800B (en) A kind of preparation method of binary polyacrylonitrile base carbon fiber precursors
CN115772719A (en) Polyacrylonitrile-based carbon fiber and preparation method thereof
CN108330563B (en) Acrylic fiber and preparation method thereof
CN111304768B (en) High-crystallinity polyacrylonitrile nascent fiber and preparation method thereof
JP5504678B2 (en) Polyacrylonitrile polymer solution, carbon fiber precursor fiber, and method for producing carbon fiber
CN111088532B (en) Method for manufacturing high-performance polyacrylonitrile carbon fiber precursor
CN115074868B (en) Preparation method of pre-oxidized fiber and pre-oxidized fiber
CN115506050B (en) Preparation method of 48k carbon fiber precursor, 48k carbon fiber precursor and 48k carbon fiber
CN112226829B (en) Preparation method of high-strength polyacrylonitrile precursor
CN111085088B (en) Polyacrylonitrile fiber for gas filtration and preparation method and application thereof
CN114606602B (en) Preparation method of 25k carbon fiber and carbon fiber
CN115506049B (en) Preparation method of 24-50k carbon fiber precursor, carbon fiber precursor and carbon fiber
CN111088535B (en) Oiling method of low-silicon polyacrylonitrile protofilament

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant