CN111088543B - Method for manufacturing high-performance wet-spun polyacrylonitrile carbon fiber precursor - Google Patents

Method for manufacturing high-performance wet-spun polyacrylonitrile carbon fiber precursor Download PDF

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CN111088543B
CN111088543B CN201811235289.XA CN201811235289A CN111088543B CN 111088543 B CN111088543 B CN 111088543B CN 201811235289 A CN201811235289 A CN 201811235289A CN 111088543 B CN111088543 B CN 111088543B
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carbon fiber
drafting
fiber
polyacrylonitrile
temperature
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CN111088543A (en
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李磊
沈志刚
张静
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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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
    • D01F6/02—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D01F6/18—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds from polymers of unsaturated nitriles, e.g. polyacrylonitrile, polyvinylidene cyanide
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D10/00—Physical treatment of artificial filaments or the like during manufacture, i.e. during a continuous production process before the filaments have been collected
    • D01D10/06—Washing or drying
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/06—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
    • 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
    • D01F9/225—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 from stabilised polyacrylonitriles

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Mechanical Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Toxicology (AREA)
  • Inorganic Fibers (AREA)
  • Artificial Filaments (AREA)

Abstract

The invention relates to a manufacturing method of polyacrylonitrile carbon fiber precursor, which mainly solves the problems of easy generation of broken filaments and poor mechanical properties of carbon fiber in the preoxidation process in the prior art. The invention adopts a manufacturing method of polyacrylonitrile carbon fiber precursor, adopts wet spinning, and comprises the steps of steam drafting, wherein each fiber bears tension of at least 1mN in the steam drafting process, and the tension borne by the fiber is less than or equal to 10% of the breaking strength of the fiber, so that the problem is better solved, and the method can be used in industrial production of the polyacrylonitrile carbon fiber precursor.

Description

Method for manufacturing high-performance wet-spun polyacrylonitrile carbon fiber precursor
Technical Field
The invention relates to a manufacturing method of high-performance polyacrylonitrile carbon fiber precursor, in particular to a method for preparing the polyacrylonitrile carbon fiber precursor by wet spinning with dimethyl sulfoxide as a solvent.
Background
The carbon fiber is an inorganic fiber with carbon content of 90% or more, has a series of advantages of light weight, high specific strength, high specific modulus, high temperature resistance, corrosion resistance, wear resistance, fatigue resistance and the like, and is excellent in performance of a composite material prepared by a composite process of the carbon fiber and various matrixes, and widely applied to the fields of automobile weight reduction, wind power generation blades, sports and leisure articles and the like.
The precursor for preparing the carbon fiber comprises three raw material systems of polyacrylonitrile base, viscose base, asphalt base and the like. The polyacrylonitrile-based carbon fiber has the advantages of simple preparation process, excellent carbon fiber performance and the like, and is rapidly developed, and the yield is maximum.
The preparation process of the polyacrylonitrile-based carbon fiber comprises the preparation of carbon fiber precursor and the oxidization carbonization treatment of the precursor. Carbon fiber precursors are key to preparing carbon fibers, high-quality carbon fiber precursors are the basis for preparing high-performance carbon fibers, and how to prepare high-quality carbon fiber precursors has been the key point and difficulty in the preparation process of carbon fibers. The preparation process of the carbon fiber precursor can be classified into wet spinning and dry-jet wet spinning according to the spinning process. The wet spinning has the advantages of easy control of the process, less residual quantity of the fiber solvent, good combination property of the prepared carbon fiber and the composite material, and the like, and is one of the important methods for preparing the carbon fiber precursor.
The solvent system for preparing the polyacrylonitrile-based carbon fiber precursor through wet spinning is various, and the industrial production of sodium thiocyanate system, dimethyl sulfoxide system, dimethylacetamide and the like is realized at present, wherein the preparation of the polyacrylonitrile-based carbon fiber precursor by taking dimethyl sulfoxide as a solvent has the characteristics of low toxicity, high solubility of a polyacrylonitrile copolymer in the solvent and the like, and is an important method for preparing the polyacrylonitrile-based carbon fiber precursor through wet spinning.
Steam drafting is an important step in the process of preparing polyacrylonitrile-based carbon fiber precursor by wet spinning. Patent JP1983214526A, JP2004076208A discloses a preparation method of polyacrylonitrile-based carbon fiber precursor, adopts a wet spinning method, and only discloses the tension of nascent fiber, and does not disclose the tension suitable for the fiber in the steam drafting process. The fiber prepared by wet spinning has a surface structure which is obviously different from that of dry-jet wet spinning before steam drafting, has an obvious groove structure, so that the specific surface area of the fiber is obviously larger than that of the dry-jet wet spinning fiber, and steam inevitably impacts tows in the steam drafting process, so that obvious friction occurs between tows, more filaments are generated in the subsequent pre-oxidation process more easily, and finally the mechanical property of the carbon fiber is deteriorated. Meanwhile, the wet spinning is used for preparing an obvious groove structure of the fiber, so that stress concentration points are easily generated in the fiber during the drawing process, and the tension control in the drawing process is more important than that in the dry-jet wet spinning process.
In view of this, the present invention has been made.
Disclosure of Invention
The invention mainly solves the technical problems that in the prior art, the polyacrylonitrile fiber is used as a carbon fiber precursor to prepare the carbon fiber, and the preoxidation process is easy to generate hairline and the mechanical property of the carbon fiber is poor. The method for manufacturing the polyacrylonitrile carbon fiber precursor solves the problem well, and has the characteristics of less broken filaments and good mechanical properties of carbon fibers in the pre-oxidation process.
In order to solve the technical problems, the invention adopts the following technical scheme: a manufacturing method of polyacrylonitrile carbon fiber precursor adopts wet spinning, and comprises the steps of steam drafting, wherein each fiber bears tension of at least 1mN in the steam drafting process, and the tension borne by the fiber is less than or equal to 10% of the breaking strength of the fiber.
In the above technical solution, each fiber is subjected to a tension of at least 2mN during the steam drafting process.
According to the technical scheme, the manufacturing method further comprises the steps of wet solidification molding, multi-stage solidification drafting, water washing, hot water drafting, primary oiling, drying densification, steam drafting, secondary oiling, secondary drying and filament collecting of the polyacrylonitrile spinning solution, and the polyacrylonitrile carbon fiber precursor is obtained.
In the technical scheme, the solid content of polyacrylonitrile in the polyacrylonitrile spinning solution is 17-22%, and the intrinsic viscosity of the solution is 1.7-2.5dL/g.
In the technical scheme, the multi-stage solidification draft is multi-stage draft with the temperature of 20-70 ℃ and the draft ratio of 1-2 during the preparation of the precursor.
In the technical scheme, the hot water drafting temperature is 80-95 ℃ during the preparation of the precursor.
In the technical scheme, the water washing adopts a plurality of water washing processes with the temperature of 60-90 ℃ during the preparation of the precursor, and no drafting is applied during the water washing process.
In the technical scheme, the temperature of the first oiling agent is 30-50 ℃ during the preparation of the precursor.
In the technical scheme, the drying densification temperature of the precursor is 90-150 ℃ and the draft ratio is 0.9-1.0.
In the technical scheme, the secondary drying temperature is 90-150 ℃ during the preparation of the precursor.
In the above technical solution, a further preferred solution is: the solid content of polyacrylonitrile in the polyacrylonitrile spinning solution is 19-21%, and the intrinsic viscosity of the polyacrylonitrile spinning solution is 1.7-2.4; the method is characterized in that each fiber bears tension less than 2.15mN in the steam drafting process, and the tension borne by the fiber is less than or equal to 8% of the breaking strength of the fiber; the drying densification temperature is 100-140 ℃.
In the above technical scheme, other aspects of the polyacrylonitrile-based precursor are not particularly limited, the polyacrylonitrile-based precursor can be prepared from a polyacrylonitrile spinning solution commonly used in the field through a spinning process commonly used in the field, the polyacrylonitrile spinning solution and the spinning process are not particularly limited, and compared with the preparation of the polyacrylonitrile fiber in the prior art, the mechanical properties of the fiber can be improved; for example, but not limiting to, the polyacrylonitrile comonomer is a vinyl-containing monomer, and the comonomer is preferably one or more of acrylic acid esters, vinyl esters, acrylamide, sulfonate and ammonium salts.
According to the invention, the tension born by each fiber in the saturated steam drafting process is controlled in the wet spinning process, so that the too small tension is avoided, the friction of the fiber when being subjected to steam impact is reduced, the electrostatic effect is reduced, and the phenomenon of yarn breakage of the fiber due to static electricity is relieved; meanwhile, the broken filaments generated by stress concentration caused by a groove structure on the surface of wet spinning are reduced, and finally, broken filaments in the pre-oxidation process are reduced and the performance of carbon fibers is improved.
The tension value born by each fiber in the saturated steam drafting process is obtained by dividing the tension of the tows between the front and rear drafting rollers of the steam drafting machine which is additionally driven by a handheld tension meter by the number of the tows. The fineness of the fiber is obtained by cutting a filament bundle with the length of 20cm from the outlet of a steam drafting box on line through a length fixing device, then placing the fiber and the length fixing device together in an oven for drying so as to avoid the change of the fiber length of the fiber in the drying process, and finally dividing the weight (in g) of the dried fiber by the total length (in 1 ten thousand meters) of the fiber. The breaking strength of the fibers was measured using GB/T14337-2008.
By adopting the technical scheme of the invention, 15 filaments in the fiber bundle at the last outlet of the pre-oxidation furnace are counted by the online camera within 100 hours, the tensile strength of the prepared carbon fiber can reach 5.6GPa, the modulus can reach 298GPa, and a better technical effect is obtained.
The invention is further illustrated by the following examples.
Detailed Description
[ example 1 ]
1. Solidifying and drawing: the method comprises the steps of preparing a primary fiber by wet spinning, wherein the intrinsic viscosity of the used stock solution is 1.75dL/g, the solid content of the spinning stock solution is 22%, accurately metering the spinning stock solution by a metering pump, filtering again, spinning, and carrying out two-stage solidification drafting with the solidification temperature of 25 ℃ and the concentration of 50% by the number of spinning holes of 12000, wherein the drafting ratio is 1.0 and 1.05 respectively, so as to obtain the solidified fiber.
2. Hot water drafting: the 3-grade hot water drafting is adopted, the drafting temperatures are respectively 90, 98 and 99 ℃, and the drafting ratios are respectively 1.8, 2.0 and 2.4.
3. Washing with water and oiling for the first time: the water washing temperature is 60 ℃, the draft ratio is 1.0, and the oiling temperature is 45 ℃.
4. Drying and densification: and (3) carrying out drying densification on the fiber obtained in the step (3), wherein the drying densification temperature is in a step heating mode, the 1 st drying densification temperature is 88 ℃, and the 2 nd drying densification temperature is 145 ℃.
5. Steam drafting: and (3) adopting saturated steam drafting, wherein the tension born by each fiber in the control process is 1mN, and the tension born by the fiber is 6% of the breaking strength of the fiber.
6. Secondary oiling, secondary drying and filament collection: performing secondary oiling treatment on the fiber obtained in the step 5, and performing secondary drying at 120 ℃; and then the silk is collected to obtain the polyacrylonitrile precursor.
7. Pre-oxidation treatment: and (3) pre-oxidizing the precursor obtained in the step (6) at 180-260 ℃ to obtain a pre-oxidized total draft ratio of 1.3 times.
8. Carbonizing: carbonizing the preoxidized yarn obtained in the step 7 at a low temperature of 300-750 ℃ with a draft ratio of 1.1 times; followed by high temperature carbonization at 800-1500 c with a draft ratio of 0.98.
9. Surface treatment and sizing: the carbon fiber obtained in the step 8 is subjected to surface treatment at a current intensity of 10 coulombs per g weight, and then subjected to sizing treatment, and dried at 120 ℃ to obtain the carbon fiber.
The number of filaments in the fiber bundle at the last outlet of the pre-oxidation furnace is 15 in 100 hours through statistics of an online camera, the tensile strength of the carbon fiber is 5.2GPa, and the modulus is 294GPa.
[ example 2 ]
1. Solidifying and drawing: the method comprises the steps of preparing a primary fiber by wet spinning, wherein the intrinsic viscosity of the used stock solution is 1.75dL/g, the solid content of the spinning stock solution is 22%, accurately metering the spinning stock solution by a metering pump, filtering again, spinning, and carrying out two-stage solidification drafting with the solidification temperature of 25 ℃ and the concentration of 50% by the number of spinning holes of 12000, wherein the drafting ratio is 1.0 and 1.05 respectively, so as to obtain the solidified fiber.
2. Hot water drafting: the 3-grade hot water drafting is adopted, the drafting temperatures are respectively 90, 98 and 99 ℃, and the drafting ratios are respectively 1.8, 2.0 and 2.4.
3. Washing with water and oiling for the first time: the water washing temperature is 60 ℃, the draft ratio is 1.0, and the oiling temperature is 45 ℃.
4. Drying and densification: and (3) carrying out drying densification on the fiber obtained in the step (3), wherein the drying densification temperature is in a step heating mode, the 1 st drying densification temperature is 88 ℃, and the 2 nd drying densification temperature is 145 ℃.
5. Steam drafting: and (3) adopting saturated steam drafting, wherein the tension born by each fiber in the control process is 2mN, and the tension born by the fiber is 5.7% of the breaking strength of the fiber.
6. Secondary oiling, secondary drying and filament collection: performing secondary oiling treatment on the fiber obtained in the step 5, and performing secondary drying at 120 ℃; and then the silk is collected to obtain the polyacrylonitrile precursor.
7. Pre-oxidation treatment: and (3) pre-oxidizing the precursor obtained in the step (6) at 180-260 ℃ to obtain a pre-oxidized total draft ratio of 1.3 times.
8. Carbonizing: carbonizing the preoxidized yarn obtained in the step 7 at a low temperature of 300-750 ℃ with a draft ratio of 1.1 times; followed by high temperature carbonization at 800-1500 c with a draft ratio of 0.98.
9. Surface treatment and sizing: the carbon fiber obtained in the step 8 is subjected to surface treatment at a current intensity of 10 coulombs per g weight, and then subjected to sizing treatment, and dried at 120 ℃ to obtain the carbon fiber.
The number of filaments in the fiber bundle at the last outlet of the pre-oxidation furnace is 25 within 100 hours through statistics of an online camera, the tensile strength of the carbon fiber is 5.5GPa, and the modulus is 294GPa.
[ example 3 ]
1. Solidifying and drawing: the method comprises the steps of preparing a primary fiber by wet spinning, wherein the intrinsic viscosity of the used stock solution is 1.75dL/g, the solid content of the spinning stock solution is 22%, accurately metering the spinning stock solution by a metering pump, filtering again, spinning, and carrying out two-stage solidification drafting with the solidification temperature of 25 ℃ and the concentration of 50% by the number of spinning holes of 12000, wherein the drafting ratio is 1.0 and 1.05 respectively, so as to obtain the solidified fiber.
2. Hot water drafting: the 3-grade hot water drafting is adopted, the drafting temperatures are respectively 90, 98 and 99 ℃, and the drafting ratios are respectively 1.8, 2.0 and 2.4.
3. Washing with water and oiling for the first time: the water washing temperature is 60 ℃, the draft ratio is 1.0, and the oiling temperature is 45 ℃.
4. Drying and densification: and (3) carrying out drying densification on the fiber obtained in the step (3), wherein the drying densification temperature is in a step heating mode, the 1 st drying densification temperature is 88 ℃, and the 2 nd drying densification temperature is 145 ℃.
5. Steam drafting: and (3) adopting saturated steam drafting, wherein the tension born by each fiber in the control process is 2.2mN, and the tension born by the fiber is 10% of the breaking strength of the fiber.
6. Secondary oiling, secondary drying and filament collection: performing secondary oiling treatment on the fiber obtained in the step 5, and performing secondary drying at 120 ℃; and then the silk is collected to obtain the polyacrylonitrile precursor.
7. Pre-oxidation treatment: and (3) pre-oxidizing the precursor obtained in the step (6) at 180-260 ℃ to obtain a pre-oxidized total draft ratio of 1.3 times.
8. Carbonizing: carbonizing the preoxidized yarn obtained in the step 7 at a low temperature of 300-750 ℃ with a draft ratio of 1.1 times; followed by high temperature carbonization at 800-1500 c with a draft ratio of 0.98.
9. Surface treatment and sizing: the carbon fiber obtained in the step 8 is subjected to surface treatment at a current intensity of 10 coulombs per g weight, and then subjected to sizing treatment, and dried at 120 ℃ to obtain the carbon fiber.
The number of filaments in the fiber bundle at the last outlet of the preoxidation furnace is 28 in 100 hours by counting through an online camera, the tensile strength of the carbon fiber is 5.2GPa, and the modulus is 294GPa.
[ example 4 ]
1. Solidifying and drawing: the method comprises the steps of preparing a primary fiber by wet spinning, wherein the intrinsic viscosity of the used stock solution is 1.75dL/g, the solid content of the spinning stock solution is 22%, accurately metering the spinning stock solution by a metering pump, filtering again, spinning, and carrying out two-stage solidification drafting with the solidification temperature of 25 ℃ and the concentration of 50% by the number of spinning holes of 12000, wherein the drafting ratio is 1.0 and 1.05 respectively, so as to obtain the solidified fiber.
2. Hot water drafting: the 3-grade hot water drafting is adopted, the drafting temperatures are respectively 90, 98 and 99 ℃, and the drafting ratios are respectively 1.8, 2.0 and 2.4.
3. Washing with water and oiling for the first time: the water washing temperature is 60 ℃, the draft ratio is 1.0, and the oiling temperature is 45 ℃.
4. Drying and densification: and (3) carrying out drying densification on the fiber obtained in the step (3), wherein the drying densification temperature is in a step heating mode, the 1 st drying densification temperature is 88 ℃, and the 2 nd drying densification temperature is 145 ℃.
5. Steam drafting: and (3) adopting saturated steam drafting, wherein the tension born by each fiber in the control process is 2.1mN, and the tension born by the fiber is 9% of the breaking strength of the fiber.
6. Secondary oiling, secondary drying and filament collection: performing secondary oiling treatment on the fiber obtained in the step 5, and performing secondary drying at 120 ℃; and then the silk is collected to obtain the polyacrylonitrile precursor.
7. Pre-oxidation treatment: and (3) pre-oxidizing the precursor obtained in the step (6) at 180-260 ℃ to obtain a pre-oxidized total draft ratio of 1.3 times.
8. Carbonizing: carbonizing the preoxidized yarn obtained in the step 7 at a low temperature of 300-750 ℃ with a draft ratio of 1.1 times; followed by high temperature carbonization at 800-1500 c with a draft ratio of 0.98.
9. Surface treatment and sizing: the carbon fiber obtained in the step 8 is subjected to surface treatment at a current intensity of 10 coulombs per g weight, and then subjected to sizing treatment, and dried at 120 ℃ to obtain the carbon fiber.
The number of filaments in the fiber bundle at the last outlet of the preoxidation furnace is 28 in 100 hours by counting through an online camera, the tensile strength of the carbon fiber is 5.6GPa, and the modulus is 298GPa.
[ example 5 ]
1. Solidifying and drawing: the method comprises the steps of preparing a primary fiber by wet spinning, wherein the intrinsic viscosity of the used stock solution is 1.75dL/g, the solid content of the spinning stock solution is 22%, accurately metering the spinning stock solution by a metering pump, filtering again, spinning, and carrying out two-stage solidification drafting with the solidification temperature of 25 ℃ and the concentration of 50% by the number of spinning holes of 12000, wherein the drafting ratio is 1.0 and 1.05 respectively, so as to obtain the solidified fiber.
2. Hot water drafting: the 3-grade hot water drafting is adopted, the drafting temperatures are respectively 90, 98 and 99 ℃, and the drafting ratios are respectively 1.8, 2.0 and 2.4.
3. Washing with water and oiling for the first time: the water washing temperature is 60 ℃, the draft ratio is 1.0, and the oiling temperature is 45 ℃.
4. Drying and densification: and (3) carrying out drying densification on the fiber obtained in the step (3), wherein the drying densification temperature is in a step heating mode, the 1 st drying densification temperature is 88 ℃, and the 2 nd drying densification temperature is 145 ℃.
5. Steam drafting: and (3) adopting saturated steam drafting, wherein the tension born by each fiber in the control process is 1.5mN, and the tension born by the fiber is 10% of the breaking strength of the fiber.
6. Secondary oiling, secondary drying and filament collection: performing secondary oiling treatment on the fiber obtained in the step 5, and performing secondary drying at 120 ℃; and then the silk is collected to obtain the polyacrylonitrile precursor.
7. Pre-oxidation treatment: and (3) pre-oxidizing the precursor obtained in the step (6) at 180-260 ℃ to obtain a pre-oxidized total draft ratio of 1.3 times.
8. Carbonizing: carbonizing the preoxidized yarn obtained in the step 7 at a low temperature of 300-750 ℃ with a draft ratio of 1.1 times; followed by high temperature carbonization at 800-1500 c with a draft ratio of 0.98.
9. Surface treatment and sizing: the carbon fiber obtained in the step 8 is subjected to surface treatment at a current intensity of 10 coulombs per g weight, and then subjected to sizing treatment, and dried at 120 ℃ to obtain the carbon fiber.
The number of filaments in the fiber bundle at the last outlet of the pre-oxidation furnace is 30 in 100 hours through statistics of an online camera, the tensile strength of the carbon fiber is 5.4GPa, and the modulus is 287GPa.
[ comparative example 1 ]
1. Solidifying and drawing: the method comprises the steps of preparing a primary fiber by wet spinning, wherein the intrinsic viscosity of the used stock solution is 1.75dL/g, the solid content of the spinning stock solution is 22%, accurately metering the spinning stock solution by a metering pump, filtering again, spinning, and carrying out two-stage solidification drafting with the solidification temperature of 25 ℃ and the concentration of 50% by the number of spinning holes of 12000, wherein the drafting ratio is 1.0 and 1.05 respectively, so as to obtain the solidified fiber.
2. Hot water drafting: the 3-grade hot water drafting is adopted, the drafting temperatures are respectively 90, 98 and 99 ℃, and the drafting ratios are respectively 1.8, 2.0 and 2.4.
3. Washing with water and oiling for the first time: the water washing temperature is 60 ℃, the draft ratio is 1.0, and the oiling temperature is 45 ℃.
4. Drying and densification: and (3) carrying out drying densification on the fiber obtained in the step (3), wherein the drying densification temperature is in a step heating mode, the 1 st drying densification temperature is 88 ℃, and the 2 nd drying densification temperature is 145 ℃.
5. Steam drafting: and (3) adopting saturated steam drafting, wherein the tension born by each fiber in the control process is 0.5mN, and the tension born by the fiber is 5% of the breaking strength of the fiber.
6. Secondary oiling, secondary drying and filament collection: performing secondary oiling treatment on the fiber obtained in the step 5, and performing secondary drying at 120 ℃; and then the silk is collected to obtain the polyacrylonitrile precursor.
7. Pre-oxidation treatment: and (3) pre-oxidizing the precursor obtained in the step (6) at 180-260 ℃ to obtain a pre-oxidized total draft ratio of 1.3 times.
8. Carbonizing: carbonizing the preoxidized yarn obtained in the step 7 at a low temperature of 300-750 ℃ with a draft ratio of 1.1 times; followed by high temperature carbonization at 800-1500 c with a draft ratio of 0.98.
9. Surface treatment and sizing: the carbon fiber obtained in the step 8 is subjected to surface treatment at a current intensity of 10 coulombs per g weight, and then subjected to sizing treatment, and dried at 120 ℃ to obtain the carbon fiber.
The number of filaments in the fiber bundle at the last outlet of the preoxidation furnace is 10 within 100 hours through statistics of an online camera, the tensile strength of the carbon fiber is 4.8GPa, and the modulus is 285GPa.
[ comparative example 2 ]
1. Solidifying and drawing: the method comprises the steps of preparing a primary fiber by wet spinning, wherein the intrinsic viscosity of the used stock solution is 1.75dL/g, the solid content of the spinning stock solution is 22%, accurately metering the spinning stock solution by a metering pump, filtering again, spinning, and carrying out two-stage solidification drafting with the solidification temperature of 25 ℃ and the concentration of 50% by the number of spinning holes of 12000, wherein the drafting ratio is 1.0 and 1.05 respectively, so as to obtain the solidified fiber.
2. Hot water drafting: the 3-grade hot water drafting is adopted, the drafting temperatures are respectively 90, 98 and 99 ℃, and the drafting ratios are respectively 1.8, 2.0 and 2.4.
3. Washing with water and oiling for the first time: the water washing temperature is 60 ℃, the draft ratio is 1.0, and the oiling temperature is 45 ℃.
4. Drying and densification: and (3) carrying out drying densification on the fiber obtained in the step (3), wherein the drying densification temperature is in a step heating mode, the 1 st drying densification temperature is 88 ℃, and the 2 nd drying densification temperature is 145 ℃.
5. Steam drafting: and (3) adopting saturated steam drafting, wherein the tension born by each fiber in the control process is 2mN, and the tension born by the fiber is 15% of the breaking strength of the fiber.
6. Secondary oiling, secondary drying and filament collection: performing secondary oiling treatment on the fiber obtained in the step 5, and performing secondary drying at 120 ℃; and then the silk is collected to obtain the polyacrylonitrile precursor.
7. Pre-oxidation treatment: and (3) pre-oxidizing the precursor obtained in the step (6) at 180-260 ℃ to obtain a pre-oxidized total draft ratio of 1.3 times.
8. Carbonizing: carbonizing the preoxidized yarn obtained in the step 7 at a low temperature of 300-750 ℃ with a draft ratio of 1.1 times; followed by high temperature carbonization at 800-1500 c with a draft ratio of 0.98.
9. Surface treatment and sizing: the carbon fiber obtained in the step 8 is subjected to surface treatment at a current intensity of 10 coulombs per g weight, and then subjected to sizing treatment, and dried at 120 ℃ to obtain the carbon fiber.
The number of filaments in the fiber bundle at the last outlet of the pre-oxidation furnace is 50 in 100 hours by counting through an online camera, and the tensile strength of the carbon fiber is 4.7GPa and the modulus is 283GPa.

Claims (9)

1. The manufacturing method of the polyacrylonitrile carbon fiber precursor adopts wet spinning, and the manufacturing method further comprises the steps of wet coagulation forming, multi-stage coagulation drafting, water washing, hot water drafting, primary oiling, drying densification, steam drafting, secondary oiling, secondary drying and filament collecting of the polyacrylonitrile carbon fiber precursor to obtain the polyacrylonitrile carbon fiber precursor; wherein, the tension born by each fiber in the steam drafting process is at least 1mN and less than 2.15mN, and the tension born by the fiber is less than or equal to 10% of the breaking strength of the fiber;
the intrinsic viscosity of the polyacrylonitrile spinning solution is 1.7-2.5dL/g;
the draft ratio of the multistage solidification draft is 1-2;
the draft ratio of the dry densification is 0.9-1.0.
2. The method of claim 1, wherein each fiber is subjected to a tension of at least 2mN and less than 2.15mN during steam drawing.
3. The method for producing a polyacrylonitrile carbon fiber precursor according to claim 1, wherein the polyacrylonitrile spinning solution has a polyacrylonitrile solid content of 17 to 22%.
4. The method for producing polyacrylonitrile carbon fiber precursor according to claim 1, wherein the multistage coagulation drawing is carried out at a temperature of 20 to 70 o C, multi-channel drafting.
5. According to claim 1The method for manufacturing the polyacrylonitrile carbon fiber precursor is characterized in that the hot water draft is at a temperature of 80-95 DEG C o C。
6. The method for producing polyacrylonitrile carbon fiber precursor according to claim 1, wherein the water washing is carried out at a temperature of 60 to 90 o C, multi-channel water washing, wherein no drafting is applied in the water washing process.
7. The method for producing polyacrylonitrile carbon fiber precursor according to claim 1, wherein the first oiling agent has a temperature of 30 to 50℃in one oiling o C。
8. The method for producing polyacrylonitrile carbon fiber precursor according to claim 1, wherein the dry densification temperature is 90 to 150 o C。
9. The method for producing polyacrylonitrile carbon fiber precursor according to claim 1, wherein the secondary drying temperature is 90 to 150 o C。
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