CN111893592B - Polyacrylonitrile fiber, preparation method thereof and polyacrylonitrile-based carbon fiber - Google Patents

Polyacrylonitrile fiber, preparation method thereof and polyacrylonitrile-based carbon fiber Download PDF

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CN111893592B
CN111893592B CN202010646196.7A CN202010646196A CN111893592B CN 111893592 B CN111893592 B CN 111893592B CN 202010646196 A CN202010646196 A CN 202010646196A CN 111893592 B CN111893592 B CN 111893592B
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polyacrylonitrile
fiber
spinning
polyacrylonitrile fiber
spinneret
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CN111893592A (en
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马跃文
郝俊杰
常春报
刘纳新
赵日杰
韩笑笑
李艳
杨晗
景延军
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Shanxi Gangke Carbon Materials Co Ltd
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Shanxi Gangke Carbon Materials Co Ltd
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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
    • D01D1/00—Treatment of filament-forming or like material
    • D01D1/10—Filtering or de-aerating the spinning solution or melt
    • D01D1/106—Filtering
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D4/00—Spinnerette packs; Cleaning thereof
    • D01D4/02—Spinnerettes
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/06—Wet spinning methods
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • 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
    • 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
    • D01D7/00—Collecting the newly-spun products
    • 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)
  • 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)
  • Artificial Filaments (AREA)

Abstract

The invention relates to a polyacrylonitrile fiber and a preparation method thereof, and a polyacrylonitrile-based carbon fiber, which mainly adopts the technical scheme that: a preparation method of polyacrylonitrile fiber comprises the following steps: the spinning solution is metered by a metering device and then forms spinning trickle through a spinneret plate, the spinning trickle forms nascent fiber after solidification forming treatment, and the nascent fiber is subjected to post-treatment to obtain polyacrylonitrile fiber; wherein, in the spinning step, the following conditions are satisfied: v1= V2= pi × R 2 Xvxnλ; wherein V1 is the metering volume cc/min of the spinning solution; v2 is the volume cc/min of the spinning solution sprayed by the spinneret plate; r is the radius mm of a spinneret orifice; v is the extrusion speed m/min of the spinning solution; n is the number of spinneret orifices on the spinneret plate; λ is a coefficient factor, and λ is 0.33-0.50. The invention can realize the preparation of polyacrylonitrile fiber and polyacrylonitrile-based carbon fiber with fine diameter by adopting a spinneret plate with conventional aperture and conventional drafting multiple.

Description

Polyacrylonitrile fiber, preparation method thereof and polyacrylonitrile-based carbon fiber
Technical Field
The invention relates to the technical field of fibers, in particular to polyacrylonitrile fibers, a preparation method thereof and polyacrylonitrile-based carbon fibers.
Background
The polyacrylonitrile-based carbon fiber has the advantages of high tensile strength, high tensile modulus, low density, ablation resistance, corrosion resistance and the like, and is widely applied to the tip technical fields of aerospace, aviation, ocean, building reinforcement, hydrogen storage cylinders and the like. The mechanical properties of carbon fibers are related to surface defects of the fibers, fiber diameters, and the like. The smaller the monofilament diameter of the carbon fiber is, the smaller the defect size is, and the higher the section uniformity is, which is advantageous for improving the tensile strength of the carbon fiber. The larger the monofilament diameter of the carbon fiber is, the less the improvement of mechanical properties such as strength and modulus is. Thus, the difference in the diameter of the carbon fibers is one of the main differences of different grades of carbon fibers.
In recent years, polyacrylonitrile-based carbon fibers generally have a diameter of 5 to 8 μm. Wherein the diameters of the T300 and T700 grade carbon fibers are about 7 μm, and the diameters of the T800 and T1000 grade carbon fibers are about 5 μm. The diameter of the protofilament can be calculated according to the fiber volume shrinkage rule in the carbonization process as follows: the monofilament diameter for producing the T300 and T700 carbon fiber precursor is about 11 to 12 μm; the monofilament diameter for producing the T800 and T1000 carbon fiber precursor is about 8 to 10 mu m. And polyacrylonitrile fiber protofilament with monofilament diameter less than 8 μm is rarely reported in research and practical application.
In the prior art, the diameter of protofilaments is thinned mainly by technical means such as matching small-aperture silk spraying plates, high-power multistage drafting and the like; however, the technical means has high requirements on production equipment of the protofilament, so that the production equipment is complex and high in cost, and the improvement of the production efficiency is not facilitated.
Disclosure of Invention
In view of this, the present invention provides a polyacrylonitrile fiber, a preparation method thereof, and a polyacrylonitrile-based carbon fiber, and mainly aims at: the polyacrylonitrile fiber with a fine diameter can be prepared by adopting a spinneret plate with a conventional aperture and a conventional drafting multiple.
In order to achieve the purpose, the invention mainly provides the following technical scheme:
in one aspect, an embodiment of the present invention provides a method for preparing polyacrylonitrile fiber, wherein the method includes the following steps:
spinning: the spinning solution is metered by a metering device and then forms spinning trickle through a spinneret plate;
solidification and forming: the spinning trickle forms as-spun fibers after solidification forming treatment;
and (3) post-treatment: carrying out post-treatment on the nascent fiber to obtain polyacrylonitrile fiber;
wherein, in the spinning step, the following conditions are satisfied:
V1=V2=π×R 2 ×v×N×λ；
wherein V1 is the metering volume cc/min of the spinning solution; v2 is the volume cc/min of the spinning solution sprayed by the spinneret plate; r is the radius mm of a spinneret orifice; v is the extrusion speed m/min of the spinning solution; n is the number of spinneret orifices on the spinneret plate; λ is a coefficient factor, and λ is 0.33-0.50.
Preferably, the metering device is a metering pump; and/or
The metering volume of the spinning solution is determined by the specification of the metering device and the rotating speed of the metering device, and is as follows: v1= Q × n; wherein V1 is a metering volume cc/min of the spinning solution, Q is a specification cc/r of the metering device, and n is a rotation speed r/min of the metering device.
Preferably, the preparation method of the polyacrylonitrile fiber adopts a wet spinning process; preferably, the extrusion speed of the spinning solution is 15-25m/min; preferably, the spinneret orifices are circular spinneret orifices, and the diameter of each spinneret orifice is 0.055-0.065mm; preferably, the number of spinneret holes on the spinneret plate is 3K-24K.
Preferably, the spinneret plate is provided with a plurality of layers of first filter screens so as to filter the spinning solution and increase the spinning pressure of the spinneret plate; preferably, the first filter screen is made of metal; preferably, the mesh number of the metal filter screen is 500-2000 meshes.
Preferably, in the preparation process of the polyacrylonitrile fiber, the total drafting multiple applied to the fiber is 5-7 times; preferably, the post-processing step comprises: washing the nascent fiber with water, drying and densifying, drafting, winding and collecting to obtain polyacrylonitrile fiber; preferably, the winding speed is 75 to 130m/min.
Preferably, the preparation method of the polyacrylonitrile fiber adopts a dry-jet wet spinning process; preferably, the extrusion speed of the spinning solution is 10.0-12.5m/min; preferably, the spinneret orifices are circular spinneret orifices, and the diameters of the spinneret orifices are 0.09-0.15mm; preferably, the number of spinneret orifices on the spinneret plate is 1K-6K.
Preferably, the spinneret plate is provided with a plurality of second filter screens for filtering the spinning solution and increasing the spinning pressure of the spinneret plate; preferably, the second filter screen is a metal filter screen and/or a polymer material filter screen; further preferably, the mesh number of the metal filter screen is 500-2000 meshes; preferably, the precision of the high polymer material filter screen is 0.1-0.5 μm.
Preferably, in the preparation process of the polyacrylonitrile fiber, the total drafting multiple applied to the fiber is 20-35 times; preferably, the post-processing step comprises: washing the nascent fiber with water, drying and densifying, drafting, winding and collecting to obtain polyacrylonitrile fiber; preferably, the winding speed is 240-400m/min.
In another aspect, embodiments of the present invention provide a polyacrylonitrile fiber, wherein the diameter of the polyacrylonitrile fiber is 5.3 to 7.8 μm; preferably, the polyacrylonitrile fiber is prepared by the preparation method of any one of the polyacrylonitrile fibers; preferably, if the preparation method of the polyacrylonitrile fiber adopts a dry-jet wet spinning process, the monofilament breaking strength of the polyacrylonitrile fiber is 5.9-7.5cN/dtex, and the elongation at break is 8.4-9.8%; preferably, if the preparation method of the polyacrylonitrile fiber adopts a wet spinning process, the monofilament breaking strength of the polyacrylonitrile fiber is 4.8-6.5cN/dtex, and the elongation at break is 10.1-12.8%.
In another aspect, an embodiment of the present invention provides a polyacrylonitrile-based carbon fiber, where a diameter of the polyacrylonitrile-based carbon fiber is 3.2 to 4.8 μm; preferably, the polyacrylonitrile-based carbon fiber is made of the polyacrylonitrile fiber.
Compared with the prior art, the polyacrylonitrile fiber and the preparation method thereof, and the polyacrylonitrile-based carbon fiber have at least the following beneficial effects:
the preparation method of the polyacrylonitrile fiber provided by the embodiment of the invention enables the spinning solution to meet the following conditions during spinning: the measured volume (cc/min) = measuring pump specification (cc/r) × rotating speed (r/min) = polyacrylonitrile solution volume (cc/min) = pi × (spinneret hole radius mm) sprayed by a spinneret plate of polyacrylonitrile solution 2 The x extrusion speed (m/min) x the number of spinneret holes x a coefficient factor lambda, wherein the coefficient factor lambda is 0.33-0.50; the volume of the spinning solution sprayed out of each spinneret orifice is substantially reduced, so that the fluid swelling effect (namely, the Barless effect) when the spinning solution leaves the spinneret orifices is weakened, and the polyacrylonitrile fiber with the small diameter is prepared by matching with a proper drawing ratio. The filament diameter of the polyacrylonitrile fiber made by the above method is 5.3-7.8 μm, and the diameter of the polyacrylonitrile-based carbon fiber made from the polyacrylonitrile fiber is 3.2-4.8 μm. Therefore, the preparation method of the polyacrylonitrile fiber provided by the embodiment of the invention can realize the preparation of the polyacrylonitrile fiber with the fine diameter under the conditions of the aperture size of the conventional spinneret plate and the conventional drafting multiple, has simple operation and equipment, and is beneficial to reducing the production cost of the polyacrylonitrile fiber with the fine diameter and the polyacrylonitrile-based carbon fiber.
The foregoing description is only an overview of the technical solutions of the present invention, and in order to make the technical solutions of the present invention more clearly understood and to implement them in accordance with the contents of the description, the following detailed description is given with reference to the preferred embodiments of the present invention and the accompanying drawings.
Drawings
FIG. 1 is an electron microscope image of the axial structure of polyacrylonitrile fiber prepared in example 1;
FIG. 2 is an electron microscope image of the axial structure of the polyacrylonitrile carbon fiber prepared in example 2;
FIG. 3 is an electron microscope image of the axial structure of the polyacrylonitrile fiber prepared in comparative example 1.
Detailed Description
To further illustrate the technical means and effects of the present invention adopted to achieve the predetermined objects, the following detailed description of the embodiments, structures, characteristics and effects according to the present invention will be made with reference to the accompanying drawings and preferred embodiments. In the following description, different "one embodiment" or "an embodiment" refers to not necessarily the same embodiment. Furthermore, the particular features, structures, or characteristics may be combined in any suitable manner in one or more embodiments.
On one hand, the embodiment of the invention provides a preparation method of polyacrylonitrile fiber, and the main purpose is to prepare polyacrylonitrile fiber with a fine diameter (the monofilament diameter of the polyacrylonitrile fiber is 5.3-7.8 μm) by adopting a spinneret plate with a conventional pore diameter and a conventional drafting multiple. Which comprises the following steps:
1) Spinning: the spinning solution is metered by a metering pump and then forms spinning trickle through a spinneret plate.
2) Solidification and forming: and forming the nascent fiber after the spinning trickle is subjected to solidification forming treatment.
3) And (3) post-treatment: and (3) performing post-treatment (such as water washing, drying densification, drafting and other processes) on the nascent fiber, and curling and collecting to obtain the polyacrylonitrile fiber.
Wherein, the spinning step satisfies the following conditions:
V1=Q×n=V2=π×R 2 ×v×N×λ；
wherein V1 is the measured volume of the spinning solution and the unit is cc/min; q is the specification of a metering pump, and the unit is cc/r; n is the rotating speed of the metering pump, and the unit is r/min; v2 is the volume V2 of the spinning solution sprayed by a spinneret plate, and the unit is cc/min; r is the radius of the spinneret orifice and the unit is mm; v is the extrusion speed in m/min; n is the number of spinneret orifices on the spinneret plate; λ is coefficient factor, λ is 0.33-0.50.
Wherein, in this step: under the condition that the metering volume of the spinning solution passing through the metering pump is certain, the volume of the spinning solution sprayed out from a single spinneret orifice is reduced by increasing the number of the spinneret orifices, when polyacrylonitrile fluid (spinning trickle) leaves the spinneret orifices, the expansion effect (Bales effect) of the fluid is weakened by the energy stored by contraction of the streamline, the diameter of nascent fiber is reduced, and polyacrylonitrile fiber and polyacrylonitrile-based carbon fiber with fine diameters are further obtained.
The invention mainly improves the spinning step in the preparation process of the polyacrylonitrile fiber, the improved part has convenient operation and simple equipment, and the preparation of the polyacrylonitrile precursor with fine diameter can be realized by adopting a spinneret plate with conventional aperture size and conventional drawing, thereby being beneficial to reducing the production cost of the polyacrylonitrile fiber and the polyacrylonitrile-based carbon fiber.
The spinning solution of the present application is preferably a polyacrylonitrile solution (here, polyacrylonitrile in the polyacrylonitrile solution may be a homopolymer or a copolymer), and preferably, the polyacrylonitrile solution has a viscosity of 60 to 120Pa · s and a weight average molecular weight in a range of 14.6 to 16.8 ten thousand.
In addition, the preparation method of the polyacrylonitrile fiber can adopt a wet spinning process (spinning thin flow directly enters a coagulating bath for coagulation forming) or a dry spraying wet spinning process (spinning thin flow enters the coagulating bath through a dry section air layer for coagulation forming).
Wherein, if a wet spinning process is adopted: in the spinning process, the extrusion speed of the spinning solution is 15-25m/min; the spinneret orifices are circular spinneret orifices, and the diameter of each spinneret orifice is 0.055-0.065mm; the number of spinneret holes on the spinneret plate is 3K-24K. Preferably, the spinneret is provided with a plurality of (preferably 1 to 3) first screens to filter the spinning solution and increase the spinning pressure of the spinneret; the first filter screen is made of metal; the mesh number of the first filter screen is 500-2000 meshes (on one hand, the filter screen can filter and remove impurities and gel of the spinning solution, on the other hand, after the volume of the spinning solution discharged from each spinneret orifice on the spinneret plate is reduced, the spinning pressure of the spinneret plate is reduced, and after the filter screen is added, the spinning pressure can be improved, so that the spinning solution is mixed and distributed more uniformly). Preferably, the total draft ratio is 5 to 7 times during the preparation of the polyacrylonitrile fiber. Preferably, the speed of winding is 75-130m/min.
Wherein, if a dry-jet wet spinning process is adopted: in the spinning process, the extrusion speed of the spinning solution is 10.0-12.5m/min; the spinneret orifice is a circular spinneret orifice, and the diameter of the spinneret orifice is 0.09-0.15mm; the number of spinneret orifices on the spinneret plate is 1K-6K. Preferably, the spinneret is provided with a plurality of (preferably 1 to 3) second screens to filter the spinning solution and increase the spinning pressure of the spinneret; the second filter screens are metal filter screens (the number of the metal filter screens is 500-2000 meshes) and/or polymer material filter membranes (PP or PA, the precision is 0.1-0.5 mu m), namely, when a plurality of second filter screens are provided, the metal filter screens can be completely adopted, or the polymer material filter membranes can be completely adopted, or one part of the metal filter screens are adopted, and one part of the polymer material filter membranes are adopted (here, the filter screens can filter and remove impurities and gel of the spinning solution on one hand, and on the other hand, after the volume of the spinning solution discharged from each spinneret orifice on the spinneret plate is reduced, the spinning pressure of the spinneret plate is reduced, and the spinning pressure can be improved after the filter screens are added, so that the spinning solution is mixed and distributed more uniformly). Preferably, the total draft ratio during the preparation of the polyacrylonitrile fiber is 20-35 times. Preferably, the winding speed is 240-400m/min.
In addition, the polyacrylonitrile fiber prepared by the method is subjected to pre-oxidation, low-temperature carbonization and high-temperature carbonization treatment to obtain the polyacrylonitrile-based carbon fiber. Wherein the pre-oxidation treatment is carried out in air atmosphere, the temperature range is 200-260 ℃, the retention time is 50-80min, and preferably 60min; the low-temperature carbonization treatment is carried out in the nitrogen atmosphere, and the temperature range is 300-800 ℃; the high-temperature carbonization treatment is carried out in a nitrogen atmosphere, and the temperature range is 1100-1400 ℃.
The following are further illustrated by specific experimental examples:
example 1
The preparation of polyacrylonitrile fiber and polyacrylonitrile-based carbon fiber in this embodiment includes the following specific steps:
the polyacrylonitrile solution (spinning solution) with the viscosity of 66 Pa.s and the weight-average molecular weight of 14.93 ten thousand is metered by a metering pump and then passes through a 3K spinneret with the diameter of 0.060 mm, and the formed spinning trickle directly enters a coagulating bath to be coagulated and formed into nascent fiber. Wherein the specification of the metering pump is 3cc/r, the rotating speed of the metering pump is 15.0796 r/min, the metering volume of the spinning solution is 45.2389 cc/min, the extrusion speed of the spinning solution is 16 m/min, and the coefficient factor lambda is 1/3=0.3333. In addition, 1 layer of metal filter screen is arranged in front of the spinneret plate, the mesh number of the metal filter screen is 1800 meshes, and the spinning pressure of the spinneret plate is 0.90 +/-0.03 MPa.
And (3) washing the nascent fiber by adopting a flowing water bath at the temperature of 60 ℃ to remove residual solvent in the nascent fiber, wherein the retention time of washing is 2min. Drying densification treatment is carried out on the fiber by adopting 10-grade electric heating hot rollers (wherein the temperature gradient of drying densification is 100 ℃, 105 ℃, 110 ℃, 115 ℃, 125 ℃ and 130 ℃, and the drying time of each grade is 8 s); then drafting the fiber in boiling water at 90 ℃ and saturated water vapor at 0.16MPa respectively, and winding and collecting the polyacrylonitrile fiber. Wherein the total draft applied to the fiber was 5.2 times and the winding speed was 83.20m/min.
The obtained polyacrylonitrile fiber had a filament diameter of 6.63 μm, a filament breaking strength of 5.71 cN/dtex, and an elongation at break of 10.44%.
And carrying out preoxidation, low-temperature carbonization and high-temperature carbonization treatment on the obtained polyacrylonitrile fiber to obtain the polyacrylonitrile carbon fiber. Wherein the pre-oxidation treatment is carried out in air atmosphere, the pre-oxidation starting temperature is 210 ℃, the termination temperature is 260 ℃, the temperature difference between adjacent temperature gradients is 10 ℃, and the retention time is 60min; the low-temperature carbonization treatment is carried out in nitrogen atmosphere, and the temperature of each temperature zone is 350 ℃, 450 ℃, 570 ℃, 650 ℃, 730 ℃ and 800 ℃; the high-temperature carbonization treatment is carried out in a nitrogen atmosphere, and the temperature of each temperature zone is 1100 ℃, 1250 ℃ and 1320 ℃.
The obtained polyacrylonitrile-based carbon fiber had a monofilament diameter of 3.96 μm, a tensile strength of 3.78 GPa, and a tensile modulus of 240 GPa.
Example 2
The preparation method of the polyacrylonitrile fiber and the polyacrylonitrile-based carbon fiber comprises the following specific steps:
the polyacrylonitrile solution (spinning solution) with the viscosity of 90 Pa.s and the weight-average molecular weight range of 16.11 ten thousand is metered by a metering pump and then passes through a 6K spinneret plate with the diameter of 0.065mm, and the formed spinning trickle directly enters a coagulating bath to be coagulated and formed into nascent fiber. Wherein the specification of the metering pump is 8cc/r, the rotating speed of the metering pump is 22.8134 r/min, the metering volume of the spinning solution is 182.5069 cc/min, the extrusion speed of the spinning solution is 22m/min, and the coefficient factor lambda is 5/12=0.41666. In addition, 1 layer of metal filter screen is arranged in front of the spinneret plate, the mesh number of the metal filter screen is 1500 meshes, and the spinning pressure of the spinneret plate is 1.53 +/-0.03 MPa.
Washing the nascent fiber by adopting a flowing water bath at 60 ℃ to remove residual solvent in the nascent fiber, wherein the retention time of washing is 1.5min; drying densification treatment of the fiber with 10-stage electric heating hot roller (wherein the gradient of drying densification is 100 deg.C, 105 deg.C, 110 deg.C, 115 deg.C, 125 deg.C, 130 deg.C; and each stage drying time is 6 s); then drafting the fiber in boiling water at 90 ℃ and saturated water vapor at 0.26MPa respectively, and winding and collecting to obtain the polyacrylonitrile fiber. Wherein the total draft multiple is 5.63 times, and the crimp speed is 123.86m/min.
Wherein, the filament diameter of the obtained polyacrylonitrile fiber is 7.64 μm, the filament breaking strength is 5.98 cN/dtex, and the elongation at break is 11.22%.
And carrying out preoxidation, low-temperature carbonization and high-temperature carbonization treatment on the obtained polyacrylonitrile fiber to obtain the polyacrylonitrile carbon fiber. Wherein the pre-oxidation treatment is carried out in air atmosphere, the pre-oxidation starting temperature is 210 ℃, the termination temperature is 260 ℃, the temperature difference between adjacent temperature gradients is 10 ℃, and the retention time is 65min; the low-temperature carbonization treatment is carried out in nitrogen atmosphere, and the temperature of each temperature zone is 350 ℃, 430 ℃, 550 ℃, 630 ℃, 710 ℃ and 780 ℃; the high-temperature carbonization treatment is carried out in a nitrogen atmosphere, and the temperature of each temperature zone is 1200 ℃, 1250 ℃ and 1330 ℃.
The obtained polyacrylonitrile-based carbon fiber had a monofilament diameter of 4.43 μm, a tensile strength of 5.25 GPa, and a tensile modulus of 250 GPa.
Example 3
The preparation method of the polyacrylonitrile fiber and the polyacrylonitrile-based carbon fiber comprises the following specific steps:
the polyacrylonitrile solution (spinning solution) with the viscosity of 90 Pa.s and the weight-average molecular weight range of 16.11 ten thousand is metered by a metering pump and then passes through a 12K spinneret plate with the diameter of 0.055 mm, and the formed spinning trickle directly enters a coagulating bath to be coagulated and formed into nascent fiber. Wherein the specification of the metering pump is 8cc/r, the rotating speed of the metering pump is 26.7281 r/min, the metering volume of the spinning solution is 213.8246 cc/min, the extrusion speed of the spinning solution is 15 m/min, and the coefficient factor lambda is 0.50. In addition, 2 layers of metal filter screens are arranged in front of the spinneret plate, the mesh number of the first layer of metal filter screen is 1000 meshes, the mesh number of the second layer of metal filter screen is 500 meshes, and the spinning pressure of the spinneret plate is 1.28 +/-0.04 MPa.
Washing the nascent fiber by adopting a flowing water bath at 60 ℃ to remove the residual solvent in the nascent fiber, wherein the retention time of the washing is 1.8min; drying densification treatment is carried out on the fiber by adopting 10-grade electric heating hot rollers (wherein the gradient of the drying densification is 100 ℃, 105 ℃, 110 ℃, 115 ℃, 125 ℃ and 130 ℃, and the drying time of each grade is 7.2 s); then drafting the fiber in boiling water at 90 ℃ and saturated water vapor at 0.29MPa respectively, and winding and collecting to obtain the polyacrylonitrile fiber. Wherein the total draft multiple is 6.1 times, and the crimp speed is 91.50m/min.
Wherein, the diameter of the obtained polyacrylonitrile fiber monofilament is 6.75 μm, the monofilament breaking strength is 5.63 cN/dtex, and the elongation at break is 12.34%.
And carrying out preoxidation, low-temperature carbonization and high-temperature carbonization treatment on the polyacrylonitrile fiber to obtain the polyacrylonitrile carbon fiber. Wherein the pre-oxidation treatment is carried out in an air atmosphere, the pre-oxidation starting temperature is 210 ℃, the pre-oxidation ending temperature is 260 ℃, the temperature difference between adjacent temperature gradients is 10 ℃, and the retention time is 60min; the low-temperature carbonization treatment is carried out in nitrogen atmosphere, and the temperature of each temperature zone is 350 ℃, 450 ℃, 550 ℃, 650 ℃, 700 ℃ and 760 ℃; the high-temperature carbonization treatment is carried out in a nitrogen atmosphere, and the temperature of each temperature zone is 1200 ℃, 1300 ℃ and 1380 ℃.
The obtained polyacrylonitrile-based carbon fiber had a filament diameter of 3.84 μm, a tensile strength of 5.73 GPa, and a tensile modulus of 301GPa.
Example 4
The preparation method of the polyacrylonitrile fiber and the polyacrylonitrile-based carbon fiber comprises the following specific steps:
the polyacrylonitrile solution (spinning solution) with the viscosity of 90 Pa.s and the weight-average molecular weight range of 16.11 ten thousand is metered by a metering pump and then passes through a 3K spinneret plate with the diameter of 0.12 mm, and the formed spinning trickle enters a coagulating bath through an air layer at a dry section to be coagulated and formed into nascent fiber. Wherein the specification of the metering pump is 5 cc/r, the rotating speed of the metering pump is 27.1434 r/min, the metering volume of the spinning solution is 135.7168 cc/min, the extrusion speed of the spinning solution is 12 m/min, and the coefficient factor lambda is 1/3=0.333. In addition, 1 layer of metal filter screen and 1 layer of high molecular PP filter screen are arranged in front of the spinneret plate, the mesh number of the metal filter screen is 500 meshes, the precision of the high molecular PP filter screen is 0.5 mu m, and the spinning pressure of the spinneret plate is 1.41 +/-0.03 MPa.
Washing the nascent fiber by adopting a flowing water bath at the temperature of 55 ℃ to remove residual solvent in the nascent fiber, wherein the retention time of water washing is 1min; drying densification treatment of the fiber by 10-grade electric heating hot roller (wherein the gradient of drying densification is 100 deg.C, 110 deg.C, 120 deg.C, 130 deg.C, 140 deg.C, and drying time of each grade is 1.6 s); then drafting the fiber in hot water at 70 ℃ and saturated water vapor at 0.32MPa respectively, and winding and collecting to obtain the polyacrylonitrile fiber. Wherein the total drawing multiple is 22 times, and the curling speed is 264m/min.
The obtained polyacrylonitrile fiber had a monofilament diameter of 6.29 μm, a monofilament breaking strength of 6.46 cN/dtex, and an elongation at break of 9.26%.
And carrying out preoxidation, low-temperature carbonization and high-temperature carbonization treatment on the obtained polyacrylonitrile fiber to obtain the polyacrylonitrile carbon fiber. Wherein the pre-oxidation treatment is carried out in an air atmosphere, the pre-oxidation starting temperature is 210 ℃, the pre-oxidation ending temperature is 260 ℃, the temperature difference between adjacent temperature gradients is 10 ℃, and the retention time is 65min; the low-temperature carbonization treatment is carried out in nitrogen atmosphere, and the temperature of each temperature zone is 350 ℃, 430 ℃, 550 ℃, 630 ℃, 740 ℃ and 800 ℃; the high-temperature carbonization treatment is carried out in a nitrogen atmosphere, and the temperature of each temperature zone is 1200 ℃, 1260 ℃ and 1330 ℃.
The obtained polyacrylonitrile-based carbon fiber has a monofilament diameter of 3.95 μm, a tensile strength of 5.28 GPa, and a tensile modulus of 250 GPa.
Example 5
The preparation of polyacrylonitrile fiber and polyacrylonitrile-based carbon fiber in this embodiment includes the following specific steps:
the polyacrylonitrile solution (spinning solution) with the viscosity of 90 Pa.s and the weight-average molecular weight range of 16.11 ten thousand is metered by a metering pump and then passes through a 4K spinneret plate with the diameter of 0.12 mm, and the formed spinning trickle enters a coagulating bath through an air layer at a dry section to be coagulated and formed into nascent fiber. Wherein the specification of the metering pump is 10cc/r, the rotating speed of the metering pump is 22.6195 r/min, the metering volume of the spinning solution is 226.1947 cc/min, the extrusion speed of the spinning solution is 10 m/min, and the coefficient factor lambda is 0.5. In addition, 1 layer of metal filter screen and 1 layer of high molecular PP filter screen are arranged in front of the spinneret plate, the mesh number of the metal filter screen is 500 meshes, the precision of the high molecular PP filter screen is 0.5 mu m, and the spinning pressure of the spinneret plate is 1.76 +/-0.03 MPa.
Washing the nascent fiber by adopting a flowing water bath at the temperature of 55 ℃ to remove residual solvent in the nascent fiber, wherein the retention time of water washing is 1min; drying densification treatment of the fiber by 10-grade electric heating hot roller (wherein the gradient of drying densification is 100 deg.C, 110 deg.C, 120 deg.C, 130 deg.C, 140 deg.C, and drying time of each grade is 1.6 s); then drafting the fiber in hot water at 70 ℃ and saturated water vapor at 0.36MPa respectively, and winding and collecting to obtain the polyacrylonitrile fiber. Wherein the total draft multiple is 32.64 times, and the crimp speed is 326.4m/min.
The obtained polyacrylonitrile fiber had a monofilament diameter of 6.42 μm, a monofilament breaking strength of 7.20 cN/dtex, and an elongation at break of 8.79%.
And carrying out preoxidation, low-temperature carbonization and high-temperature carbonization treatment on the obtained polyacrylonitrile fiber to obtain the polyacrylonitrile carbon fiber. Wherein the pre-oxidation treatment is carried out in air atmosphere, the pre-oxidation starting temperature is 210 ℃, the termination temperature is 260 ℃, the temperature difference between adjacent temperature gradients is 10 ℃, and the retention time is 60min; the low-temperature carbonization treatment is carried out in nitrogen atmosphere, and the temperature of each temperature zone is 350 ℃, 450 ℃, 550 ℃, 650 ℃, 710 ℃ and 780 ℃; the high-temperature carbonization treatment is carried out in a nitrogen atmosphere, and the temperature of each temperature zone is 1200 ℃, 1300 ℃ and 1380 ℃.
The obtained polyacrylonitrile-based carbon fiber had a monofilament diameter of 3.85 μm, a tensile strength of 5.66 GPa, and a tensile modulus of 298 GPa.
Comparative example 1
Comparative example 1 polyacrylonitrile fiber and polyacrylonitrile-based carbon fiber were prepared, the specific steps are as follows:
the polyacrylonitrile solution (spinning solution) with the viscosity of 66 Pa.s and the weight average molecular weight range of 14.93 ten thousand is metered by a metering pump and then passes through a 1K spinneret with the diameter of 0.060 mm, and the formed spinning trickle directly enters a coagulating bath to be coagulated and formed into nascent fiber. Wherein the specification of the metering pump is 3cc/r, the rotating speed of the metering pump is 15.0796 r/min, the metering volume of the spinning solution is 45.2389 cc/min, the extrusion speed of the spinning solution is 16 m/min, and the coefficient factor lambda is 1. In addition, 1 layer of metal filter screen is arranged in front of the spinneret plate, the mesh number of the metal filter screen is 1800 meshes, and the spinning pressure of the spinneret plate is 1.15 +/-0.04 MPa.
Washing the nascent fiber by adopting a flowing water bath at 60 ℃ to remove the residual solvent in the nascent fiber, wherein the retention time of the washing is 2min; drying densification treatment of the fiber by 8-stage electric heating hot roller under the condition (wherein the temperature gradient of the drying densification is 100 ℃, 105 ℃, 110 ℃, 115 ℃, 120 ℃, 125 ℃, and the drying time of each stage is 8 s); then drafting the fiber in boiling water at 90 ℃ and saturated water vapor at 0.16MPa respectively, and winding and collecting to obtain the polyacrylonitrile fiber. Wherein the total draft ratio is 5.2, and the crimp speed is 83.20m/min.
The obtained polyacrylonitrile fiber had a filament diameter of 12.16 μm, a filament breaking strength of 5.87 cN/dtex, and an elongation at break of 11.28%.
And carrying out preoxidation, low-temperature carbonization and high-temperature carbonization treatment on the obtained polyacrylonitrile fiber to obtain the polyacrylonitrile carbon fiber. Wherein the pre-oxidation treatment is carried out in air atmosphere, the pre-oxidation starting temperature is 210 ℃, the termination temperature is 260 ℃, the temperature difference between adjacent temperature gradients is 10 ℃, and the retention time is 60min; the low-temperature carbonization treatment is carried out in nitrogen atmosphere, and the temperature of each temperature zone is 350 ℃, 450 ℃, 570 ℃, 650 ℃, 730 ℃ and 800 ℃; the high-temperature carbonization treatment is carried out in a nitrogen atmosphere, and the temperature of each temperature zone is 1100 ℃, 1250 ℃ and 1320 ℃.
The obtained polyacrylonitrile-based carbon fiber had a filament diameter of 6.86 μm, a tensile strength of 3.83GPa and a tensile modulus of 235GPa.
Comparative example 2
The preparation method of the polyacrylonitrile fiber and the polyacrylonitrile-based carbon fiber comprises the following specific steps:
the polyacrylonitrile solution (spinning solution) with the viscosity of 90 Pa.s and the weight-average molecular weight range of 16.11 ten thousand is metered by a metering pump and then passes through a 1K spinneret plate with the diameter of 0.12 mm, and the formed spinning trickle enters a coagulating bath through an air layer at a dry section to be coagulated and formed into nascent fiber. Wherein the specification of the metering pump is 5 cc/r, the rotating speed of the metering pump is 27.1434 r/min, the metering volume of the spinning solution is 135.7168 cc/min, the extrusion speed of the spinning solution is 12 m/min, and the coefficient factor lambda is 1. In addition, 1 layer of metal filter screen and 1 layer of high molecular PP filter screen are arranged in front of the spinneret plate, the mesh number of the metal filter screen is 500 meshes, the precision of the high molecular PP filter screen is 0.5 mu m, and the spinning pressure of the spinneret plate is 1.63 +/-0.03 MPa.
Washing the nascent fiber by adopting a flowing water bath at 55 ℃ to remove residual solvent in the nascent fiber, wherein the retention time of washing is 1min; drying densification treatment is carried out on the fiber by adopting 10-grade electric heating hot rollers (wherein the gradient of the drying densification is 100 ℃, 110 ℃, 120 ℃, 130 ℃, 140 ℃ and 140 ℃, and the drying time of each grade is 1.6 s); then drafting the fiber in hot water at 70 ℃ and saturated water vapor at 0.32MPa respectively, and winding and collecting the polyacrylonitrile fiber. Wherein the total drawing multiple is 22 times, and the curling speed is 264m/min.
Wherein, the filament diameter of the obtained polyacrylonitrile fiber is 10.89 μm, the filament breaking strength is 6.96 cN/dtex, and the elongation at break is 8.68%.
And carrying out preoxidation, low-temperature carbonization and high-temperature carbonization treatment on the polyacrylonitrile fiber to obtain the polyacrylonitrile carbon fiber. Wherein the pre-oxidation treatment is carried out in air atmosphere, the pre-oxidation starting temperature is 210 ℃, the termination temperature is 260 ℃, the temperature difference between adjacent temperature gradients is 10 ℃, and the retention time is 65min; the low-temperature carbonization treatment is carried out in nitrogen atmosphere, and the temperature of each temperature zone is 350 ℃, 430 ℃, 550 ℃, 630 ℃, 710 ℃ and 780 ℃; the high-temperature carbonization treatment is carried out in a nitrogen atmosphere, and the temperature of each temperature zone is 1200 ℃, 1250 ℃ and 1330 ℃.
The obtained polyacrylonitrile-based carbon fiber had a monofilament diameter of 6.88 μm, a tensile strength of 5.35 GPa, and a tensile modulus of 250 GPa.
From the above-described characterization data (monofilament diameter data) of the polyacrylonitrile fibers and the polyacrylonitrile-based carbon fibers prepared in examples 1 to 5 and comparative examples 1 to 2, and fig. 1, 2 and 3, it is apparent that: the preparation method of polyacrylonitrile provided by the embodiment of the invention can be used for preparing polyacrylonitrile fibers with fine diameters, and then the polyacrylonitrile fibers can be used for preparing polyacrylonitrile-based carbon fibers with fine diameters.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention in any way, and any simple modification, equivalent change and modification made to the above embodiment according to the technical spirit of the present invention are still within the scope of the technical solution of the present invention.

Claims (16)

1. A preparation method of polyacrylonitrile fiber is characterized by comprising the following steps:
spinning: the spinning solution is metered by a metering device and then forms spinning trickle through a spinneret plate;
solidification and forming: the spinning trickle forms as-spun fibers after solidification forming treatment;
and (3) post-treatment: carrying out post-treatment on the nascent fiber to obtain polyacrylonitrile fiber;
wherein, in the spinning step, the following conditions are satisfied:
V1=V2=π×R 2 ×v×N×λ；
wherein V1 is the metering volume cc/min of the spinning solution; v2 is the volume cc/min of the spinning solution sprayed by the spinneret plate; r is the radius mm of a spinneret orifice; v is the extrusion speed m/min of the spinning solution; n is the number of spinneret orifices on the spinneret plate; λ is a coefficient factor, and λ is 0.33-0.50;
wherein, the preparation method of the polyacrylonitrile fiber adopts a wet spinning process; wherein the extrusion speed of the spinning solution is 15-25m/min; the spinneret orifices are circular spinneret orifices, and the diameters of the spinneret orifices are 0.055-0.065mm; the number of spinneret orifices on the spinneret plate is 3K-24K; the spinneret plate is provided with a plurality of layers of first filter screens so as to filter spinning liquid and improve the spinning pressure of the spinneret plate; in the preparation process of the polyacrylonitrile fiber, the total drafting multiple applied to the fiber is 5 to 7 times.
2. The method for producing polyacrylonitrile fiber according to claim 1,
the metering device is a metering pump; and/or
The metering volume of the spinning solution is related to the specification of the metering device and the rotating speed of the metering device, and the metering volume is as follows: v1= Q × n; wherein V1 is a metering volume cc/min of the spinning solution, Q is a specification cc/r of the metering device, and n is a rotation speed r/min of the metering device.
3. The method for producing polyacrylonitrile fiber according to claim 1, characterized in that,
the first filter screen is a metal filter screen.
4. The method for producing polyacrylonitrile fiber according to claim 3, characterized in that,
the mesh number of the metal filter screen is 500-2000 meshes.
5. The method for producing polyacrylonitrile fiber according to claim 1,
the post-processing step comprises: and washing the nascent fiber with water, drying and densifying, drafting, winding and collecting to obtain the polyacrylonitrile fiber.
6. The method for producing polyacrylonitrile fiber according to claim 5,
the winding speed is 75-130m/min.
7. The preparation method of the polyacrylonitrile fiber is characterized by comprising the following steps:
spinning: the spinning solution is metered by a metering device and then forms spinning trickle through a spinneret plate;
solidification and forming: the spinning trickle is subjected to solidification forming treatment to form nascent fiber;
and (3) post-treatment: carrying out post-treatment on the nascent fiber to obtain polyacrylonitrile fiber;
wherein, in the spinning step, the following conditions are satisfied:
V1=V2=π×R 2 ×v×N×λ；
wherein V1 is the metering volume cc/min of the spinning solution; v2 is the volume cc/min of the spinning solution sprayed by the spinneret plate; r is the radius mm of a spinneret orifice; v is the extrusion speed m/min of the spinning solution; n is the number of spinneret orifices on the spinneret plate; λ is a coefficient factor, and λ is 0.33-0.50;
the preparation method of the polyacrylonitrile fiber adopts a dry-jet wet spinning process;
the extrusion speed of the spinning solution is 10.0-12.5m/min; the spinneret orifices are circular spinneret orifices, and the diameters of the spinneret orifices are 0.09-0.15mm; the number of spinneret orifices on the spinneret plate is 1K-6K; the spinneret plate is provided with a plurality of layers of second filter screens so as to filter the spinning solution and improve the spinning pressure of the spinneret plate; in the preparation process of the polyacrylonitrile fiber, the total drafting multiple applied to the fiber is 20-35 times.
8. The method for producing polyacrylonitrile fiber according to claim 7,
the metering device is a metering pump; and/or
The metering volume of the spinning solution is related to the specification of the metering device and the rotating speed of the metering device, and the metering volume is as follows: v1= Q × n; wherein V1 is a metering volume cc/min of the spinning solution, Q is a specification cc/r of the metering device, and n is a rotation speed r/min of the metering device.
9. The method for producing polyacrylonitrile fiber according to claim 7,
the second filter screen is a metal filter screen and/or a polymer material filter screen.
10. The method for producing polyacrylonitrile fiber according to claim 9, characterized in that,
the mesh number of the metal filter screen is 500-2000 meshes.
11. The method for producing polyacrylonitrile fiber according to claim 9,
the precision of the high polymer material filter screen is 0.1-0.5 μm.
12. The method for producing polyacrylonitrile fiber according to claim 7,
the post-processing step comprises: and washing the nascent fiber with water, drying and densifying, drafting, winding and collecting to obtain the polyacrylonitrile fiber.
13. The method for producing polyacrylonitrile fiber according to claim 12,
the winding speed is 240-400m/min.
14. Polyacrylonitrile fiber, characterized in that the monofilament diameter of the polyacrylonitrile fiber is 5.3-7.8 μm; wherein the polyacrylonitrile fiber is prepared by the preparation method of the polyacrylonitrile fiber according to any one of claims 1 to 6; the single-filament breaking strength of the polyacrylonitrile fiber is 4.8-6.5cN/dtex, and the elongation at break is 10.1-12.8%.
15. Polyacrylonitrile fiber, characterized in that the monofilament diameter of the polyacrylonitrile fiber is 5.3-7.8 μm; wherein, the polyacrylonitrile fiber is prepared by the preparation method of the polyacrylonitrile fiber according to any one of claims 7 to 13; the single-filament breaking strength of the polyacrylonitrile fiber is 5.9-7.5cN/dtex, and the elongation at break is 8.4-9.8%.
16. Polyacrylonitrile-based carbon fiber, characterized in that, the monofilament diameter of the polyacrylonitrile-based carbon fiber is 3.2-4.8 μm;
wherein the polyacrylonitrile-based carbon fiber is made of the polyacrylonitrile fiber of claim 14 or 15.
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