CN110863256A - Preparation method of dry-jet wet-spun high-strength medium-modulus polyacrylonitrile-based carbon fiber precursor - Google Patents
Preparation method of dry-jet wet-spun high-strength medium-modulus polyacrylonitrile-based carbon fiber precursor Download PDFInfo
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- 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
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- 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
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- 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
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D10/00—Physical treatment of artificial filaments or the like during manufacture, i.e. during a continuous production process before the filaments have been collected
- D01D10/06—Washing or drying
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/04—Dry spinning methods
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/06—Wet spinning methods
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/12—Stretch-spinning methods
- D01D5/14—Stretch-spinning methods with flowing liquid or gaseous stretching media, e.g. solution-blowing
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- 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
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- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
- Y02P70/62—Manufacturing or production processes characterised by the final manufactured product related technologies for production or treatment of textile or flexible materials or products thereof, including footwear
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- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
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- General Chemical & Material Sciences (AREA)
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Abstract
The invention relates to a preparation method of dry-jet wet-spun high-strength medium-modulus polyacrylonitrile-based carbon fiber precursor, which is characterized by comprising the following steps of: taking acrylonitrile as a first monomer, adding a second monomer and a third monomer, and taking azobisisobutyronitrile as an initiator to prepare a spinning solution, wherein the solid content of the spinning solution is 19-23 wt%, the rotational viscosity is 80000-160000 cP, the weight average molecular weight is 22-30 ten thousand, the number average molecular weight is 8-12 ten thousand, the molecular weight distribution is 1.8-3.0, and the intrinsic viscosity is 2.0-2.5; and (3) performing high-power drawing on the spinning stock solution through an air layer, forming fibers in a front coagulating bath, and then performing winding after a second coagulating bath, water washing, hot water drafting, oiling, drying, steam drafting and drying and shaping to obtain the precursor. The filament number of the prepared finished protofilament is 0.75-0.90 dtex, the filament strength is 7.5-9.5 cN/dtex, the filament modulus is 95-130 cN/dtex, and the bulk density is 1.18-1.19 g/cm3. The carbon fiber obtained by carbonizing the precursor has the strength of more than or equal to 6370MPa, the modulus of more than or equal to 294GPa and the linear density of 440-490 g/km.
Description
Technical Field
The invention relates to a preparation method of precursor, in particular to a preparation method of dry-jet wet-spun high-strength medium-modulus polyacrylonitrile-based carbon fiber precursor.
Background
The polyacrylonitrile-based carbon fiber is called PAN-based fiber for short, and is widely applied to the fields of automobiles, spaceflight, buildings, sports, medical treatment and the like. The preparation method comprises the steps of copolymerizing acrylonitrile and other small amount of second and third monomers to generate copolymerized polyacrylonitrile resin, dissolving the resin by a solvent to form spinning solution with proper viscosity, spinning by a wet method, a dry method or a dry-wet method, and then washing, drawing, drying and heat setting to prepare the polyacrylonitrile fiber.
At present, the technology of the domestic T700S is mature, the T800S is in the development and production transition stage, but the performance indexes of the T700S and the T800S cannot well meet the requirements of national defense, military industry and aerospace.
Disclosure of Invention
The invention provides a preparation method of dry-jet wet-spun high-strength medium-modulus polyacrylonitrile-based carbon fiber precursor in order to overcome the defects of the prior art, and the carbon fiber prepared by carbonizing the precursor prepared by the method has the strength of more than or equal to 6370MPa, the modulus of more than or equal to 294GPa and the linear density of 440-490 g/km.
The beneficial effects produced by the invention comprise: a preparation method of dry-jet wet-spun high-strength medium-modulus polyacrylonitrile-based carbon fiber precursor comprises the steps of taking Acrylonitrile (AN) as a first monomer, adding a second monomer and/or a third monomer, and taking Azobisisobutyronitrile (AIBN) as AN initiator to prepare spinning stock solution, wherein the solid content of the spinning stock solution is 19-23 wt%, the rotational viscosity is 80000-160000 cP, the weight-average molecular weight is 22-30 ten thousand, the number-average molecular weight is 8-12 ten thousand, the molecular weight distribution is 1.8-3.0, and the intrinsic viscosity is 2.0-2.5;
and (3) performing high-power drawing on the spinning stock solution through an air layer, forming fibers in a front coagulating bath, and then performing winding after a second coagulating bath, water washing, hot water drafting, oiling, drying, steam drafting and drying and shaping to obtain the precursor. The rotational viscosity and the intrinsic viscosity are high molecular weight in nature, high-crystallinity and high-orientation protofilament can be obtained under the action of coagulating bath condition by higher molecular weight, and simultaneously, because the molecular weight distribution is narrower, the reduction of small molecules is beneficial to reducing the generation of monofilament breakage and broken filament.
Further, the second monomer comprises one of sodium methallyl sulfonate, sodium methallyl benzene sulfonate and itaconic acid, and the third monomer comprises one of methyl methacrylate, methyl acrylate and acrylamide.
Furthermore, the mass ratio of the second monomer to the third monomer is 0.3-3.5% based on the total amount of the first monomer, the second monomer and the third monomer. Namely AN: (second monomer + third monomer) =1- (0.3-3.5%): 0.3-3.5%, and the ratio is mass percent.
Further, the spinning solution enters the pre-coagulation bath under heat tracing of heat preservation water at the temperature of 30-65 ℃, the temperature of the pre-coagulation bath is 30-55 ℃, the concentration of dimethyl sulfoxide (DMSO) in the pre-coagulation bath is 60-78%, the height of an air layer is 2-8 mm, and the draft ratio of the air layer is 2.5-4.0; the temperature of the second coagulation bath is 40-70 ℃, the concentration of dimethyl sulfoxide in the second coagulation bath is 15-40%, and the draw ratio is 1.0-2.0. The high molecular weight stock solution is subjected to coagulation bath under the conditions of high temperature and concentration to obtain the protofilament with high orientation degree and crystallinity.
Further, the washing temperature is 50-80 ℃, the hot water drafting temperature is 80-99 ℃, and the drafting ratio is 2.0-4.0.
Further, a drying roller in the drying and shaping process is dried by using saturated steam, the steam pressure of the saturated steam is 1.5-10 bar, and the pressure adopts a stepped pressure gradient.
Furthermore, saturated steam is used as a medium in the steam drafting process, the steam pressure of the saturated steam is 3.0-6.0 bar, the temperature of the saturated steam is 135-160 ℃, the steam drafting ratio is 2.5-4.0, the crystallinity and the orientation degree of the drafted fibers are further improved, and finished product protofilaments are prepared.
The beneficial effects produced by the invention comprise: the filament number of the prepared finished protofilament is 0.75-0.90 dtex, the filament strength is 7.5-9.5 cN/dtex, the filament modulus is 95-130 cN/dtex, and the bulk density is 1.18-1.19 g/cm3. The strength of the carbon fiber obtained by carbonizing the precursor is more than or equal to 6370MPa, the modulus is more than or equal to 294GPa, and the linear density is 440-490 g/km, so that the performance requirement of the carbon fiber at the T1000S level is met, and the domestic market demand is met.
Detailed Description
The present invention is explained in further detail with reference to specific examples, but it should be understood that the scope of the present invention is not limited to the specific examples.
Example 1
The monomer of the ingredient is selected from acrylonitrile, methyl acrylate and sodium methallyl sulfonate.
The mass percentage of the ingredients is acrylonitrile: methyl acrylate: sodium propylene sulfonate =98:1:1, AIBN is used as an initiator, and a stock solution is prepared by polymerization, wherein the index is that the solid content is 20.5%, the rotational viscosity is 140000cP, the weight average molecular weight is 25 ten thousand, the number average molecular weight is 13 ten thousand, the molecular weight distribution is 1.9, and the intrinsic viscosity is 2.4.
The temperature of the spinning stock solution is 50 ℃, the height of an air layer is 8mm, the temperature of a front coagulation bath is 50 ℃, the concentration is 70%, the dry section drafting ratio is 3.5, the temperature of a second coagulation bath is 50 ℃, the concentration of DMSO of the second coagulation bath is 25%, the drafting ratio is 1.2, the tows enter water washing after passing through the front coagulation bath and the second coagulation bath, residual DMSO in the protofilament is removed through washing by water, the washing temperature is 60 ℃, the hot water drafting temperature is 92 ℃, the drafting ratio is 2.5, saturated steam is used for drying densification, the initial pressure is 1.5bar, the ending pressure is 10bar, and the stepped pressure gradient is set. The dried and densified precursor fibers enter the steamAnd (3) a steam drafting box, saturated steam is used, the steam drafting pressure is 5bar, the temperature is 152 ℃, the steam drafting ratio is 3.2, and the crystallinity and the orientation degree of the fiber are further improved to obtain the finished product protofilament. The finished protofilament is prepared, the filament number is 0.78dtex, the filament strength is 9.0cN/dtex, the filament modulus is 105cN/dtex, and the bulk density is 1.187g/cm3. The precursor is carbonized to prepare the carbon filament, the tensile strength of the multifilament is 6500MPa, the modulus is 298GPa, and the linear density is 458 g/km. The dry section draft ratio is also called air section or a condensing draft ratio, and both guide the linear speed of the godet roller/the spinneret plate spinning speed ratio, and the other draft ratios guide the linear speed ratios of the rear godet roller and the front godet roller.
Example 2
The mass percentage of the ingredients is acrylonitrile: methyl acrylate: itaconic acid =97:2.5:0.5, AIBN is used as an initiator, and a stock solution is prepared by polymerization, wherein the index is solid content of 22.0%, rotational viscosity of 110000cP, weight average molecular weight of 24 ten thousand, number average molecular weight of 9.6 ten thousand, molecular weight distribution of 2.5, and intrinsic viscosity of 2.2.
The temperature of the spinning solution tracing hot water is 45 ℃, the height of an air layer is 3mm, the temperature of a front coagulation bath is 48 ℃, the concentration is 76%, the dry section drafting ratio is 3.3, the secondary coagulation temperature is 65 ℃, and the DMSO concentration of a second coagulation bath is 32%. The drawing ratio is 1.1, the tows enter water washing after passing through a front coagulating bath and a second coagulating bath, residual DMSO in the protofilaments is removed through the washing of the water washing, the washing temperature is 65 ℃, the hot water drawing temperature is 98 ℃, the drawing ratio is 2.2, saturated steam is used for drying and densification, the initial pressure is 1.5bar, the ending pressure is 10bar, and the step-type pressure gradient is set. The dried and densified precursor filaments enter a steam drawing box, saturated steam is used, the steam drawing pressure is 4.8bar, the drawing ratio is 4.3, and the temperature is 150 ℃.
The finished protofilament is prepared, the filament number is 0.88dtex, the filament strength is 9.2cN/dtex, the filament modulus is 115cN/dtex, and the bulk density is 1.187g/cm3. The carbon filament is prepared by carbonizing the precursor, the tensile strength of the multifilament is 6800MPa, the modulus is 300GPa, and the linear density is 470 g/km.
Example 3
The mass percentage of the ingredients is acrylonitrile: itaconic acid =99.6:0.4, AIBN was used as an initiator, and a stock solution was obtained by polymerization, the index being a solid content of 21.5%, a rotational viscosity of 130000cP, a weight average molecular weight of 23 ten thousand, a number average molecular weight of 11.5 ten thousand, a molecular weight distribution of 2.0, and an intrinsic viscosity of 2.1.
The temperature of the spinning solution with hot water is 65 ℃, the height of an air layer is 5mm, the temperature of a front coagulation bath is 38 ℃, the concentration is 69.5%, the dry section drafting ratio is 3.45, the secondary coagulation temperature is 45 ℃, and the DMSO concentration of a second coagulation bath is 38%. The drawing ratio is 1.3, the tows enter water washing after passing through the front coagulating bath and the second coagulating bath, residual DMSO in the protofilaments is removed through the washing of the water washing, the water washing temperature is 68 ℃, the hot water drawing temperature is 97 ℃, the drawing ratio is 2.2, saturated steam is used for drying and densification, the initial pressure is 1.5bar, the ending pressure is 10bar, and the stepped pressure gradient is set. The steam draw pressure was 4.5bar, the temperature 148 ℃ and the draw ratio 3.45.
The finished protofilament is prepared, the filament number is 0.83dtex, the filament strength is 8.95cN/dtex, the filament modulus is 125cN/dtex, and the bulk density is 1.189g/cm3. The precursor is carbonized to prepare the carbon filament, the tensile strength of the multifilament is 7000MPa, the modulus is 297GPa, and the linear density is 465 g/km.
The above description is only a preferred embodiment of the present invention, and the present invention is not limited to the content of the embodiment. It will be apparent to those skilled in the art that various changes and modifications can be made within the technical scope of the present invention, and any changes and modifications made are within the protective scope of the present invention.
Claims (7)
1. A preparation method of dry-jet wet-spun high-strength medium-modulus polyacrylonitrile-based carbon fiber precursor is characterized by comprising the following steps: taking acrylonitrile as a first monomer, adding a second monomer and/or a third monomer, and taking azobisisobutyronitrile as an initiator to prepare a spinning solution, wherein the solid content of the spinning solution is 19-23 wt%, the rotational viscosity is 80000-160000 cP, the weight average molecular weight is 22-30 ten thousand, the number average molecular weight is 8-12 ten thousand, the molecular weight distribution is 1.8-3.0, and the intrinsic viscosity is 2.0-2.5;
and (3) performing high-power drawing on the spinning stock solution through an air layer, forming fibers in a front coagulating bath, and then performing winding after a second coagulating bath, water washing, hot water drafting, oiling, drying, steam drafting and drying and shaping to obtain the precursor.
2. The preparation method of the dry-jet wet-spun high-strength medium-modulus polyacrylonitrile-based carbon fiber precursor according to claim 1, which is characterized by comprising the following steps of: the second monomer comprises at least one of sodium methallyl sulfonate, sodium methallyl benzene sulfonate and itaconic acid, and the third monomer comprises at least one of methyl methacrylate, methyl acrylate and acrylamide.
3. The preparation method of the dry-jet wet-spun high-strength medium-modulus polyacrylonitrile-based carbon fiber precursor according to claim 1, which is characterized by comprising the following steps of: the mass ratio of the second monomer to the third monomer is 0.3-3.5% based on the total amount of the first monomer, the second monomer and the third monomer.
4. The preparation method of the dry-jet wet-spun high-strength medium-modulus polyacrylonitrile-based carbon fiber precursor according to claim 1, which is characterized by comprising the following steps of: the spinning stock solution enters the pre-coagulation bath under heat tracing of heat preservation water at the temperature of 30-65 ℃, the temperature of the pre-coagulation bath is 30-55 ℃, the concentration of dimethyl sulfoxide in the pre-coagulation bath is 60-78%, the height of an air layer is 2-8 mm, and the draft ratio of the air layer is 2.5-4.0; the temperature of the second coagulation bath is 40-70 ℃, the concentration of dimethyl sulfoxide in the second coagulation bath is 15-40%, and the draw ratio is 1.0-2.0.
5. The preparation method of the dry-jet wet-spun high-strength medium-modulus polyacrylonitrile-based carbon fiber precursor according to claim 1, which is characterized by comprising the following steps of: the washing temperature is 50-80 ℃, the hot water drafting temperature is 80-99 ℃, and the drafting ratio is 2.0-4.0.
6. The preparation method of the dry-jet wet-spun high-strength medium-modulus polyacrylonitrile-based carbon fiber precursor according to claim 1, which is characterized by comprising the following steps of: saturated steam is used for a drying roller in the drying and shaping process, the pressure is 1.5-10 bar, and the pressure adopts a step-type pressure gradient.
7. The preparation method of the dry-jet wet-spun high-strength medium-modulus polyacrylonitrile-based carbon fiber precursor according to claim 1, which is characterized by comprising the following steps of: saturated steam is used as a medium in the steam drafting process, the pressure is 3.0-6.0 bar, the temperature is 135-160 ℃, and the steam drafting ratio is 2.5-4.0.
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| CN114836841A (en) * | 2022-05-17 | 2022-08-02 | 中复神鹰碳纤维股份有限公司 | Method for directly preparing low-titer protofilament after dry-jet wet spinning and drying |
| CN115772719A (en) * | 2022-12-14 | 2023-03-10 | 江苏恒神股份有限公司 | Polyacrylonitrile-based carbon fiber and preparation method thereof |
| CN116065250A (en) * | 2021-10-29 | 2023-05-05 | 中国石油化工股份有限公司 | Polyacrylonitrile spinning solution and preparation method and application thereof |
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| CN113846386A (en) * | 2021-09-11 | 2021-12-28 | 中复神鹰碳纤维西宁有限公司 | Method for realizing synchronization of densification and orientation of carbon fiber precursor |
| CN116065250A (en) * | 2021-10-29 | 2023-05-05 | 中国石油化工股份有限公司 | Polyacrylonitrile spinning solution and preparation method and application thereof |
| CN114836841A (en) * | 2022-05-17 | 2022-08-02 | 中复神鹰碳纤维股份有限公司 | Method for directly preparing low-titer protofilament after dry-jet wet spinning and drying |
| CN115772719A (en) * | 2022-12-14 | 2023-03-10 | 江苏恒神股份有限公司 | Polyacrylonitrile-based carbon fiber and preparation method thereof |
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