CN111088531B - Method for manufacturing wet spinning polyacrylonitrile carbon fiber precursor - Google Patents

Method for manufacturing wet spinning polyacrylonitrile carbon fiber precursor Download PDF

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CN111088531B
CN111088531B CN201811235031.XA CN201811235031A CN111088531B CN 111088531 B CN111088531 B CN 111088531B CN 201811235031 A CN201811235031 A CN 201811235031A CN 111088531 B CN111088531 B CN 111088531B
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carbon fiber
fiber
drafting
temperature
hot water
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CN111088531A (en
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李磊
沈志刚
王贺团
赵微微
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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
    • 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
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D10/00—Physical treatment of artificial filaments or the like during manufacture, i.e. during a continuous production process before the filaments have been collected
    • D01D10/06—Washing or drying
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/12—Stretch-spinning methods
    • D01D5/14—Stretch-spinning methods with flowing liquid or gaseous stretching media, e.g. solution-blowing
    • 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
    • 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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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Toxicology (AREA)
  • Inorganic Fibers (AREA)

Abstract

The invention relates to a manufacturing method of polyacrylonitrile carbon fiber precursor, which mainly solves the problems that precursor is easy to generate broken filaments and the mechanical property of carbon fiber is poor in the prior art. The invention adopts a manufacturing method of polyacrylonitrile carbon fiber precursor, adopts wet spinning, and comprises the step of hot water drafting, wherein the hot water drafting comprises at least three stages, the tension born by each fiber in the first stage hot water drafting process is at least 3mN, and the tension born by the fiber is less than or equal to 12% of the breaking strength of the fiber, thereby better solving the problem and being applicable to the industrial production of polyacrylonitrile fiber.

Description

Method for manufacturing wet spinning polyacrylonitrile carbon fiber precursor
Technical Field
The invention relates to a method for manufacturing polyacrylonitrile carbon fiber precursor by wet spinning, in particular to a method for preparing the polyacrylonitrile carbon fiber precursor by high-performance wet spinning.
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, is a composite material prepared by the carbon fiber and various matrixes through a composite process, has excellent performance, and is widely applied to the fields of light weight of automobiles, 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 is rapidly developed due to the advantages of simple preparation process, excellent carbon fiber performance and the like, and the yield is the largest.
The preparation process of the polyacrylonitrile-based carbon fiber comprises the preparation of carbon fiber precursors and the oxidation and carbonization treatment of the precursors. The carbon fiber precursor is the key for preparing the carbon fiber, the high-quality carbon fiber precursor is the basis for preparing the high-performance carbon fiber, and how to prepare the high-quality carbon fiber precursor is always the key and difficult point of the carbon fiber preparation process. The preparation process of the carbon fiber precursor can be divided into wet spinning and wet spinning according to the difference of the spinning process. The wet spinning method has the advantages of easily controlled process, less residual quantity of fiber solvent, good bonding performance of the prepared carbon fiber and the composite material and the like, and is one of important methods for preparing carbon fiber precursors.
Various solvent systems can be used for preparing the polyacrylonitrile-based carbon fiber precursor by wet spinning, and currently, a sodium thiocyanate system, a dimethyl sulfoxide system, dimethylacetamide and the like are used for industrial production, wherein the polyacrylonitrile-based carbon fiber precursor prepared by using dimethyl sulfoxide as a solvent has the characteristics of low toxicity, high solubility of polyacrylonitrile copolymer in the solvent and the like, and is an important method for preparing the polyacrylonitrile-based carbon fiber precursor by wet spinning.
Hot water drafting is an important step in the process of preparing the polyacrylonitrile-based carbon fiber precursor by wet spinning, has obvious influence on the orientation degree, the regularity and the fiber crystallinity of the molecular chain of the polyacrylonitrile-based carbon fiber precursor, and finally influences the performance of a carbon fiber product. Patents JP1983214526A and JP2004076208A disclose a method for preparing polyacrylonitrile-based carbon fiber precursor, and a wet spinning method is adopted, and the patents only disclose the tension of nascent fiber, but do not disclose the drawing stage number during hot water drawing, and more disclose the proper tension of the most important first-stage hot water drawing process. The carbon fiber precursor prepared by wet spinning has a groove structure formed in the primary fiber forming process, so that the stress of the primary fiber is more concentrated in the hot water drafting process, and the fluffing of the fiber is easy to occur; improper hot water drawing can ultimately lead to a reduction in the performance of the carbon fibers.
In view of the above, the present invention is particularly proposed.
Disclosure of Invention
The invention mainly solves the technical problems that precursor fibers are easy to generate broken filaments and the mechanical property of carbon fibers is poor in the process of preparing the carbon fibers by using the wet spinning polyacrylonitrile fibers as carbon fiber precursors in the prior art. The method for manufacturing the polyacrylonitrile carbon fiber precursor better solves the problem and has the characteristics of less precursor broken filaments and good mechanical property of the carbon fiber in the spinning process.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows: a manufacturing method of polyacrylonitrile carbon fiber precursor adopts wet spinning, and comprises the step of hot water drafting, wherein the hot water drafting at least comprises three stages, the tension born by each fiber in the first stage of hot water drafting is at least 3mN, and the tension born by the fiber is less than or equal to 12% of the breaking strength of the fiber.
In the technical scheme, the hot water drafting is less than or equal to five levels, and the tension born by each fiber in the first-level hot water drafting process is at least 4 mN.
In the technical scheme, the manufacturing method further comprises the steps of performing wet solidification molding, multistage solidification drafting, washing, hot water drafting, primary oiling, drying densification, steam drafting, secondary oiling, secondary drying and filament collection on the polyacrylonitrile spinning solution to obtain the polyacrylonitrile carbon fiber precursor.
In the technical scheme, the intrinsic viscosity of the polyacrylonitrile stock solution is 1.7-2.5 dL/g.
In the technical scheme, the multi-stage solidification drafting is multi-channel drafting at the temperature of 20-70 ℃ during the preparation of the precursor fiber, and the drafting ratio is 1-2.
In the technical scheme, hot water drafting is carried out at the temperature of 80-95 ℃ during the preparation of the precursor.
In the technical scheme, the water washing during the preparation of the protofilament adopts multiple times of water washing at the temperature of 60-90 ℃, and drafting is not applied in the water washing process.
In the technical scheme, the drying densification temperature during the preparation of the precursor is 90-150 ℃, and the draw ratio is 0.9-1.0.
In the technical scheme, the secondary drafting during the preparation of the precursor adopts steam drafting, the steam pressure is 0.2-0.5MPa, and the drafting ratio is 1-5.
In the technical scheme, the secondary drying temperature is 90-150 ℃ during the preparation of the protofilament.
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; in the hot water drafting process, the tension born by each fiber in the first-stage hot water drafting process is at least 4.5mN, and the tension born by the fiber is less than or equal to 10% of the breaking strength of the fiber; the drying densification temperature is 100-140 ℃; the steam pressure is 0.2-0.4MPa, and the draft ratio is 2-4.
In the 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 by a spinning process commonly used in the field, and the polyacrylonitrile spinning solution and the spinning process are not particularly limited, so that the mechanical property of the fiber can be improved compared with the polyacrylonitrile fiber prepared by the prior art; for example, but not limited to, the polyacrylonitrile comonomer is a vinyl-containing monomer, and the comonomer is preferably one or more of acrylates, vinyl esters, acrylamides, sulfonates, and ammonium salts.
According to the invention, five-level or below hot water drafting is adopted, so that the most important minimum tension directly born by the first-level hot water drafting fiber in the drafting process is controlled, and the reduction of the mechanical property of the carbon fiber caused by insufficient fiber orientation is avoided. Meanwhile, the maximum value of the tension of the fiber is controlled, and stress concentration caused by surface grooves in the fiber drafting process is avoided, so that broken filaments are easily generated in the hot water drafting and subsequent drafting processes, and the subsequent fiber cannot bear drafting of higher multiple.
The tension value borne by each fiber in the first-stage hot water drafting process is obtained by measuring the tension of the tows in the first-stage hot water drafting bath which is kept walking by a handheld tension meter and dividing the tension by the number of the tows. The fiber fineness is obtained by intercepting the tows 30cm in front of the last drawing roller of the first-stage hot water drawing bath on line through a fixed length device, then putting the fibers and the fixed length device into an oven for drying together to avoid the change of the fiber length caused by the drying process of the fibers, and finally dividing the dried fiber weight (unit is g) by the total fiber length (unit is 1 ten thousand meters). The breaking strength of the fibers was measured using GB/T14337-2008.
By adopting the technical scheme of the invention, the number of the broken filaments in the prepared precursor is counted to be 24 minimum in length per 10000 m of precursor through the online camera, the tensile strength of the prepared carbon fiber can reach 5.7GPa, the modulus can reach 299GPa, and a better technical effect is achieved.
The invention is further illustrated by the following examples.
Detailed Description
[ example 1 ]
1. Solidification and drawing: wet spinning is adopted for preparing nascent fiber, the intrinsic viscosity of the used stock solution is 1.75dL/g, the solid content of the spinning stock solution is 22%, the spinning stock solution is precisely metered by a metering pump and filtered again, wet spinning is adopted, the aperture of a spinneret plate is 60 mu m, the number of spinneret holes is 12000, the solidification temperature is 25 ℃, the concentration is 50%, two-stage solidification drafting is carried out subsequently, and the drafting ratio is 1.0 and 1.05 respectively, so that the solidified fiber is obtained.
2. Hot water drafting: and 4-level hot water drafting is adopted, the fiber tension is controlled to be 3mN in the first-level hot water drafting process, the fiber fineness is 5.2dtex, and the tension born by the fiber is 12% of the breaking strength of the fiber.
3. Washing and oiling: the water washing temperature is 60 ℃, the drafting ratio is 1.0, and the oiling temperature is 35 ℃.
4. And (3) drying and densifying: and (3) drying and densifying the fiber obtained in the step (3), wherein the drying and densifying temperature is in a stepped temperature rise mode, the drying and densifying temperature of the 1 st step is 88 ℃, and the drying and densifying temperature of the 2 nd step is 145 ℃.
5. Steam drafting, secondary oiling, secondary drying and filament collecting: 3.5 times of drafting is carried out on the fiber obtained in the step 4 in steam of 0.35 MPa; secondary drying at 120 ℃ after secondary oiling; and then collecting the filaments to obtain the polyacrylonitrile protofilament.
6. Pre-oxidation treatment: and (3) carrying out pre-oxidation on the protofilament obtained in the step (5) at the temperature of 180-260 ℃, wherein the total draft ratio of the pre-oxidation is 1.2 times.
7. Carbonizing treatment: carrying out low-temperature carbonization on the pre-oxidized fiber obtained in the step 6 at the temperature of 300-750 ℃, wherein the drawing ratio is 1.1 times; followed by high temperature carbonization at 800-.
8. Surface treatment and sizing: the carbon fiber obtained in step 7 was subjected to surface treatment at a current intensity of 10 coulombs per g weight, followed by sizing treatment and drying at 120 ℃ to obtain a carbon fiber.
The number of broken filaments in each 10000-meter-long protofilament is counted to be 25 through an online camera, the tensile strength of the carbon fiber is 5.6GPa, and the modulus is 294 GPa.
[ example 2 ]
1. Solidification and drawing: wet spinning is adopted for preparing nascent fiber, the intrinsic viscosity of the used stock solution is 1.75dL/g, the solid content of the spinning stock solution is 22%, the spinning stock solution is precisely metered by a metering pump and filtered again, wet spinning is adopted, the aperture of a spinneret plate is 60 mu m, the number of spinneret holes is 12000, the solidification temperature is 25 ℃, the concentration is 50%, two-stage solidification drafting is carried out subsequently, and the drafting ratio is 1.0 and 1.05 respectively, so that the solidified fiber is obtained.
2. Hot water drafting: 4-level hot water drafting is adopted, the fiber tension in the first-level hot water drafting process is controlled to be 4mN, the fiber fineness is 5.2dtex, and the tension born by the fiber is 12% of the breaking strength of the fiber.
3. Washing and oiling: the water washing temperature is 60 ℃, the drafting ratio is 1.0, and the oiling temperature is 35 ℃.
4. And (3) drying and densifying: and (3) drying and densifying the fiber obtained in the step (3), wherein the drying and densifying temperature is in a stepped temperature rise mode, the drying and densifying temperature of the 1 st step is 88 ℃, and the drying and densifying temperature of the 2 nd step is 145 ℃.
5. Steam drafting, secondary oiling, secondary drying and filament collecting: 3.5 times of drafting is carried out on the fiber obtained in the step 4 in steam of 0.35 MPa; secondary drying at 120 ℃ after secondary oiling; and then collecting the filaments to obtain the polyacrylonitrile protofilament.
6. Pre-oxidation treatment: and (3) carrying out pre-oxidation on the protofilament obtained in the step (5) at the temperature of 180-260 ℃, wherein the total draft ratio of the pre-oxidation is 1.2 times.
7. Carbonizing treatment: carrying out low-temperature carbonization on the pre-oxidized fiber obtained in the step 6 at the temperature of 300-750 ℃, wherein the drawing ratio is 1.1 times; followed by high temperature carbonization at 800-.
8. Surface treatment and sizing: the carbon fiber obtained in step 7 was subjected to surface treatment at a current intensity of 10 coulombs per g weight, followed by sizing treatment and drying at 120 ℃ to obtain a carbon fiber.
The number of broken filaments in each 10000-meter-long protofilament is counted to be 28 through an online camera, the tensile strength of the carbon fiber is 5.65GPa, and the modulus is 296 GPa.
[ example 3 ]
1. Solidification and drawing: wet spinning is adopted for preparing nascent fiber, the intrinsic viscosity of the used stock solution is 1.75dL/g, the solid content of the spinning stock solution is 22%, the spinning stock solution is precisely metered by a metering pump and filtered again, wet spinning is adopted, the aperture of a spinneret plate is 60 mu m, the number of spinneret holes is 12000, the solidification temperature is 25 ℃, the concentration is 50%, two-stage solidification drafting is carried out subsequently, and the drafting ratio is 1.0 and 1.05 respectively, so that the solidified fiber is obtained.
2. Hot water drafting: 3-level hot water drafting is adopted, the fiber tension in the first-level hot water drafting process is controlled to be 4.5mN, the fiber fineness is 5.2dtex, and the tension born by the fiber is 10% of the breaking strength of the fiber.
3. Washing and oiling: the water washing temperature is 60 ℃, the drafting ratio is 1.0, and the oiling temperature is 35 ℃.
4. And (3) drying and densifying: and (3) drying and densifying the fiber obtained in the step (3), wherein the drying and densifying temperature is in a stepped temperature rise mode, the drying and densifying temperature of the 1 st step is 88 ℃, and the drying and densifying temperature of the 2 nd step is 145 ℃.
5. Steam drafting, secondary oiling, secondary drying and filament collecting: 3.5 times of drafting is carried out on the fiber obtained in the step 4 in steam of 0.35 MPa; secondary drying at 120 ℃ after secondary oiling; and then collecting the filaments to obtain the polyacrylonitrile protofilament.
6. Pre-oxidation treatment: and (3) carrying out pre-oxidation on the protofilament obtained in the step (5) at the temperature of 180-260 ℃, wherein the total draft ratio of the pre-oxidation is 1.2 times.
7. Carbonizing treatment: carrying out low-temperature carbonization on the pre-oxidized fiber obtained in the step 6 at the temperature of 300-750 ℃, wherein the drawing ratio is 1.1 times; followed by high temperature carbonization at 800-.
8. Surface treatment and sizing: the carbon fiber obtained in step 7 was subjected to surface treatment at a current intensity of 10 coulombs per g weight, followed by sizing treatment and drying at 120 ℃ to obtain a carbon fiber.
The number of broken filaments in each 10000 meters of precursor is counted by an online camera to be 29, the tensile strength of the carbon fiber is 5.7GPa, and the modulus is 299 GPa.
[ example 4 ]
1. Solidification and drawing: wet spinning is adopted for preparing nascent fiber, the intrinsic viscosity of the used stock solution is 1.75dL/g, the solid content of the spinning stock solution is 22%, the spinning stock solution is precisely metered by a metering pump and filtered again, wet spinning is adopted, the aperture of a spinneret plate is 60 mu m, the number of spinneret holes is 12000, the solidification temperature is 25 ℃, the concentration is 50%, two-stage solidification drafting is carried out subsequently, and the drafting ratio is 1.0 and 1.05 respectively, so that the solidified fiber is obtained.
2. Hot water drafting: 5-level hot water drafting is adopted, the fiber tension in the first-level hot water drafting process is controlled to be 6mN, the fiber fineness is 5.2dtex, and the tension born by the fiber is 12% of the breaking strength of the fiber.
3. Washing and oiling: the water washing temperature is 60 ℃, the drafting ratio is 1.0, and the oiling temperature is 35 ℃.
4. And (3) drying and densifying: and (3) drying and densifying the fiber obtained in the step (3), wherein the drying and densifying temperature is in a stepped temperature rise mode, the drying and densifying temperature of the 1 st step is 88 ℃, and the drying and densifying temperature of the 2 nd step is 145 ℃.
5. Steam drafting, secondary oiling, secondary drying and filament collecting: 3.5 times of drafting is carried out on the fiber obtained in the step 4 in steam of 0.35 MPa; secondary drying at 120 ℃ after secondary oiling; and then collecting the filaments to obtain the polyacrylonitrile protofilament.
6. Pre-oxidation treatment: and (3) carrying out pre-oxidation on the protofilament obtained in the step (5) at the temperature of 180-260 ℃, wherein the total draft ratio of the pre-oxidation is 1.2 times.
7. Carbonizing treatment: carrying out low-temperature carbonization on the pre-oxidized fiber obtained in the step 6 at the temperature of 300-750 ℃, wherein the drawing ratio is 1.1 times; followed by high temperature carbonization at 800-.
8. Surface treatment and sizing: the carbon fiber obtained in step 7 was subjected to surface treatment at a current intensity of 10 coulombs per g weight, followed by sizing treatment and drying at 120 ℃ to obtain a carbon fiber.
The number of broken filaments in each 10000 meters of precursor is counted by an online camera to be 35, the tensile strength of the carbon fiber is 5.5GPa, and the modulus is 294 GPa.
[ example 5 ]
1. Solidification and drawing: wet spinning is adopted for preparing nascent fiber, the intrinsic viscosity of the used stock solution is 1.75dL/g, the solid content of the spinning stock solution is 22%, the spinning stock solution is precisely metered by a metering pump and filtered again, wet spinning is adopted, the aperture of a spinneret plate is 60 mu m, the number of spinneret holes is 12000, the solidification temperature is 25 ℃, the concentration is 50%, two-stage solidification drafting is carried out subsequently, and the drafting ratio is 1.0 and 1.05 respectively, so that the solidified fiber is obtained.
2. Hot water drafting: and 6-level hot water drafting is adopted, the fiber tension is controlled to be 3mN in the first-level hot water drafting process, the fiber fineness is 5.2dtex, and the tension born by the fiber is 9% of the breaking strength of the fiber.
3. Washing and oiling: the water washing temperature is 60 ℃, the drafting ratio is 1.0, and the oiling temperature is 35 ℃.
4. And (3) drying and densifying: and (3) drying and densifying the fiber obtained in the step (3), wherein the drying and densifying temperature is in a stepped temperature rise mode, the drying and densifying temperature of the 1 st step is 88 ℃, and the drying and densifying temperature of the 2 nd step is 145 ℃.
5. Steam drafting, secondary oiling, secondary drying and filament collecting: 3.5 times of drafting is carried out on the fiber obtained in the step 4 in steam of 0.35 MPa; secondary drying at 120 ℃ after secondary oiling; and then collecting the filaments to obtain the polyacrylonitrile protofilament.
6. Pre-oxidation treatment: and (3) carrying out pre-oxidation on the protofilament obtained in the step (5) at the temperature of 180-260 ℃, wherein the total draft ratio of the pre-oxidation is 1.2 times.
7. Carbonizing treatment: carrying out low-temperature carbonization on the pre-oxidized fiber obtained in the step 6 at the temperature of 300-750 ℃, wherein the drawing ratio is 1.1 times; followed by high temperature carbonization at 800-.
8. Surface treatment and sizing: the carbon fiber obtained in step 7 was subjected to surface treatment at a current intensity of 10 coulombs per g weight, followed by sizing treatment and drying at 120 ℃ to obtain a carbon fiber.
The number of broken filaments in each 10000 meters of precursor is counted by an online camera to be 24, the tensile strength of the carbon fiber is 5.2GPa, and the modulus is 294 GPa.
[ COMPARATIVE EXAMPLE 1 ]
1. Solidification and drawing: wet spinning is adopted for preparing nascent fiber, the intrinsic viscosity of the used stock solution is 1.75dL/g, the solid content of the spinning stock solution is 22%, the spinning stock solution is precisely metered by a metering pump and filtered again, wet spinning is adopted, the aperture of a spinneret plate is 60 mu m, the number of spinneret holes is 12000, the solidification temperature is 25 ℃, the concentration is 50%, two-stage solidification drafting is carried out subsequently, and the drafting ratio is 1.0 and 1.05 respectively, so that the solidified fiber is obtained.
2. Hot water drafting: 3-level hot water drafting is adopted, the fiber tension in the first-level hot water drafting process is controlled to be 2mN, the fiber titer is 5.2dtex, and the tension born by the fiber is 8% of the breaking strength of the fiber.
3. Washing and oiling: the water washing temperature is 60 ℃, the drafting ratio is 1.0, and the oiling temperature is 35 ℃.
4. And (3) drying and densifying: and (3) drying and densifying the fiber obtained in the step (3), wherein the drying and densifying temperature is in a stepped temperature rise mode, the drying and densifying temperature of the 1 st step is 88 ℃, and the drying and densifying temperature of the 2 nd step is 145 ℃.
5. Steam drafting, secondary oiling, secondary drying and filament collecting: 3.5 times of drafting is carried out on the fiber obtained in the step 4 in steam of 0.35 MPa; secondary drying at 120 ℃ after secondary oiling; and then collecting the filaments to obtain the polyacrylonitrile protofilament.
6. Pre-oxidation treatment: and (3) carrying out pre-oxidation on the protofilament obtained in the step (5) at the temperature of 180-260 ℃, wherein the total draft ratio of the pre-oxidation is 1.2 times.
7. Carbonizing treatment: carrying out low-temperature carbonization on the pre-oxidized fiber obtained in the step 6 at the temperature of 300-750 ℃, wherein the drawing ratio is 1.1 times; followed by high temperature carbonization at 800-.
8. Surface treatment and sizing: the carbon fiber obtained in step 7 was subjected to surface treatment at a current intensity of 10 coulombs per g weight, followed by sizing treatment and drying at 120 ℃ to obtain a carbon fiber.
The number of broken filaments in each 10000-meter-long protofilament is counted to be 20 through an online camera, the tensile strength of the carbon fiber is 5.2GPa, and the modulus is 294 GPa.
[ COMPARATIVE EXAMPLE 2 ]
1. Solidification and drawing: wet spinning is adopted for preparing nascent fiber, the intrinsic viscosity of the used stock solution is 1.75dL/g, the solid content of the spinning stock solution is 22%, the spinning stock solution is precisely metered by a metering pump and filtered again, wet spinning is adopted, the aperture of a spinneret plate is 60 mu m, the number of spinneret holes is 12000, the solidification temperature is 25 ℃, the concentration is 50%, two-stage solidification drafting is carried out subsequently, and the drafting ratio is 1.0 and 1.05 respectively, so that the solidified fiber is obtained.
2. Hot water drafting: and 4-level hot water drafting is adopted, the tension of the drafting fiber in the first-level hot water drafting process is controlled to be 7.8mN, the fiber fineness is 5.2dtex, and the tension born by the fiber is 15% of the breaking strength of the fiber.
3. Washing and oiling: the water washing temperature is 60 ℃, the drafting ratio is 1.0, and the oiling temperature is 35 ℃.
4. And (3) drying and densifying: and (3) drying and densifying the fiber obtained in the step (3), wherein the drying and densifying temperature is in a stepped temperature rise mode, the drying and densifying temperature of the 1 st step is 88 ℃, and the drying and densifying temperature of the 2 nd step is 145 ℃.
5. Steam drafting, secondary oiling, secondary drying and filament collecting: 3.5 times of drafting is carried out on the fiber obtained in the step 4 in steam of 0.35 MPa; secondary drying at 120 ℃ after secondary oiling; and then collecting the filaments to obtain the polyacrylonitrile protofilament.
6. Pre-oxidation treatment: and (3) carrying out pre-oxidation on the protofilament obtained in the step (5) at the temperature of 180-260 ℃, wherein the total draft ratio of the pre-oxidation is 1.2 times.
7. Carbonizing treatment: carrying out low-temperature carbonization on the pre-oxidized fiber obtained in the step 6 at the temperature of 300-750 ℃, wherein the drawing ratio is 1.1 times; followed by high temperature carbonization at 800-.
8. Surface treatment and sizing: the carbon fiber obtained in step 7 was subjected to surface treatment at a current intensity of 10 coulombs per g weight, followed by sizing treatment and drying at 120 ℃ to obtain a carbon fiber.
The number of broken filaments in each 10000 meters of precursor is counted by an online camera to be 50, the tensile strength of the carbon fiber is 4.7GPa, and the modulus is 275 GPa.
[ COMPARATIVE EXAMPLE 3 ]
1. Solidification and drawing: wet spinning is adopted for preparing nascent fiber, the intrinsic viscosity of the used stock solution is 1.75dL/g, the solid content of the spinning stock solution is 22%, the spinning stock solution is precisely metered by a metering pump and filtered again, wet spinning is adopted, the aperture of a spinneret plate is 60 mu m, the number of spinneret holes is 12000, the solidification temperature is 25 ℃, the concentration is 50%, two-stage solidification drafting is carried out subsequently, and the drafting ratio is 1.0 and 1.05 respectively, so that the solidified fiber is obtained.
2. Hot water drafting: and 4-level hot water drafting is adopted, the fiber tension is controlled to be 3mN in the first-level hot water drafting process, the fiber fineness is 5.2dtex, and the tension born by the fiber is 15% of the breaking strength of the fiber.
3. Washing and oiling: the water washing temperature is 60 ℃, the drafting ratio is 1.0, and the oiling temperature is 35 ℃.
4. And (3) drying and densifying: and (3) drying and densifying the fiber obtained in the step (3), wherein the drying and densifying temperature is in a stepped temperature rise mode, the drying and densifying temperature of the 1 st step is 88 ℃, and the drying and densifying temperature of the 2 nd step is 145 ℃.
5. Steam drafting, secondary oiling, secondary drying and filament collecting: 3.5 times of drafting is carried out on the fiber obtained in the step 4 in steam of 0.35 MPa; secondary drying at 120 ℃ after secondary oiling; and then collecting the filaments to obtain the polyacrylonitrile protofilament.
6. Pre-oxidation treatment: and (3) carrying out pre-oxidation on the protofilament obtained in the step (5) at the temperature of 180-260 ℃, wherein the total draft ratio of the pre-oxidation is 1.2 times.
7. Carbonizing treatment: carrying out low-temperature carbonization on the pre-oxidized fiber obtained in the step 6 at the temperature of 300-750 ℃, wherein the drawing ratio is 1.1 times; followed by high temperature carbonization at 800-.
8. Surface treatment and sizing: the carbon fiber obtained in step 7 was subjected to surface treatment at a current intensity of 10 coulombs per g weight, followed by sizing treatment and drying at 120 ℃ to obtain a carbon fiber.
The number of broken filaments in each 10000-meter-long protofilament is counted to be 48 through an online camera, the tensile strength of the carbon fiber is 4.8GPa, and the modulus is 278 GPa.

Claims (9)

1. A manufacturing method of polyacrylonitrile carbon fiber precursor adopts wet spinning, and comprises the step of hot water drafting, wherein the hot water drafting at least comprises three stages, the hot water drafting is less than or equal to five stages, the tension born by each fiber in the first stage hot water drafting process is at least 4mN, and the tension born by each fiber is less than or equal to 12% of the breaking strength of each fiber.
2. The manufacturing method of the polyacrylonitrile carbon fiber precursor according to claim 1, further comprising the steps of performing wet solidification molding, multi-stage solidification drawing, water washing, hot water drawing, primary oiling, drying densification, steam drawing, secondary oiling, secondary drying and filament collection on the polyacrylonitrile spinning solution to obtain the polyacrylonitrile carbon fiber precursor.
3. The method for manufacturing polyacrylonitrile carbon fiber precursor according to claim 2, characterized in that the intrinsic viscosity of the polyacrylonitrile spinning solution is 1.7-2.5 dL/g.
4. The method for manufacturing polyacrylonitrile carbon fiber precursor according to claim 2, characterized in that the multistage coagulation drawing is at a temperature of 20-70 degoC, multi-pass drawing, wherein the drawing ratio is 1-2.
5. The method for manufacturing polyacrylonitrile carbon fiber precursor according to claim 2, characterized in that the temperature of hot water drawing is 80-95 ℃.
6. The method for manufacturing polyacrylonitrile carbon fiber precursor according to claim 2, characterized in that the temperature adopted for washing with water is 60-90 ℃oC, multiple washing steps are carried out, and no drafting is applied in the washing process.
7. The method for manufacturing polyacrylonitrile carbon fiber precursor according to claim 2, characterized in that the temperature of drying densification is 90-150%oC, the draw ratio is 0.9-1.0.
8. The method for producing polyacrylonitrile carbon fiber precursor according to claim 2, characterized in that the steam pressure of the steam draft is 0.2 to 0.5MPa, and the draft ratio is 1 to 5.
9. The method for manufacturing polyacrylonitrile carbon fiber precursor according to claim 2, characterized in that the temperature of the secondary drying is 90-150 ℃.
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