CN116084034A - Solidification forming method for improving homogenization and crystallinity of polyacrylonitrile nascent fiber - Google Patents

Solidification forming method for improving homogenization and crystallinity of polyacrylonitrile nascent fiber Download PDF

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CN116084034A
CN116084034A CN202310073393.8A CN202310073393A CN116084034A CN 116084034 A CN116084034 A CN 116084034A CN 202310073393 A CN202310073393 A CN 202310073393A CN 116084034 A CN116084034 A CN 116084034A
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polyacrylonitrile
crystallinity
molding method
coagulating bath
primary
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朱波
冯建顺
朱安平
孙永连
律建国
乔琨
赵圣尧
高学平
袁晓敏
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Shandong University
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Shandong University
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    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/28—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D01F6/38—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds comprising unsaturated nitriles as the major constituent
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
    • Y02P70/62—Manufacturing or production processes characterised by the final manufactured product related technologies for production or treatment of textile or flexible materials or products thereof, including footwear

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Artificial Filaments (AREA)

Abstract

The invention discloses a solidification forming method for improving homogenization and crystallinity of polyacrylonitrile nascent fibers, which comprises the following steps: the polyacrylonitrile stock solution obtained by copolymerizing acrylonitrile and comonomer is sprayed into a coagulating bath and is drawn to obtain nascent fibers; the coagulating bath comprises coagulating agent and solvent, wherein the coagulating agent is diethylene glycol, and the solvent is selected from dimethyl sulfoxide, dimethylformamide, dimethylacetamide, acetone, naSCN water solution or ZnCl 2 The mass percentage of the coagulant in the aqueous solution and the coagulating bath is 20-80%; the comonomer is selected from itaconic acid, sodium acrylate, sodium methacrylate, methyl acrylate, methyl methacrylate, methacrylic acid or acrylamide.

Description

Solidification forming method for improving homogenization and crystallinity of polyacrylonitrile nascent fiber
Technical Field
The invention belongs to the technical field of high-performance carbon fiber precursor preparation, and particularly relates to a solidification forming method for improving homogenization and crystallinity of polyacrylonitrile nascent fibers, which is used for preparing a high-performance carbon fiber PAN precursor.
Background
The statements herein merely provide background information related to the present disclosure and may not necessarily constitute prior art.
The carbon fiber has the advantages of high specific strength, high specific modulus, heat conduction, heat resistance, self lubrication and the like. As an indispensable material, carbon fiber is widely used in the fields of automobiles, aerospace, biological medicine, renewable energy sources, building materials, and the like.
In the wet spinning process, polyacrylonitrile trickles enter the coagulating bath through the spinneret holes, then the solvent in the stock solution diffuses into the coagulating bath due to concentration difference and the coagulating agent diffuses into the stock solution in the coagulating bath, and finally the stock solution trickles reach critical concentration to separate out nascent fibers. This process determines the degree of homogeneity of the nascent fiber. The faster the double diffusion speed is, the stronger the acting force of the coagulant and the polyacrylonitrile is, the more easily a compact structure is formed in the primary fiber cortex, the resistance of the coagulant to diffusion into the primary fiber is increased, the loose structure of the primary fiber is caused, the severe structure of the sheath core is caused, and the structure is inherited to the carbon fiber. Further, the stronger the coagulant acts on the polyacrylonitrile chain, the greater the binding of the polyacrylonitrile chain, and therefore, the free movement of the arrangement is not possible to participate in the crystallization, and the crystallinity of the nascent fiber eventually becomes low.
At present, the common technology uses water as a coagulant, but because the polarity of the water is strong, the polyacrylonitrile chains are strongly bound, and the severe phase separation is caused, the primary fibers are easy to generate holes and have uneven texture. The action degree of water and polyacrylonitrile chains in the coagulating bath is relieved by increasing the concentration of the solvent, and insufficient diffusion power is caused, so that the nascent fibers are swelled and adhered, and the whole structure is loose. In addition, increasing the solvent to coagulation bath ratio tends to increase the production cost in consideration of the price of the solvent in the coagulation bath.
Disclosure of Invention
Aiming at the defects existing in the prior art, the invention aims to provide a solidification forming method for improving the homogenization and crystallinity of polyacrylonitrile nascent fibers, which can effectively slow down double diffusion and reduce the consumption of solvents, thereby obtaining high-performance polyacrylonitrile precursor and carbon fibers. In the wet spinning process, the coagulating agent is reasonably selected, and the strong phase separation caused by double diffusion can be slowed down and the crystallinity of the nascent fiber is improved by reducing the consumption of the solvent, so that the precursor with high mechanical strength and homogeneity can be prepared.
In order to achieve the above object, the present invention is realized by the following technical scheme:
a solidification molding method for improving homogenization and crystallinity of polyacrylonitrile nascent fiber comprises the following steps:
the polyacrylonitrile stock solution obtained by copolymerizing acrylonitrile and comonomer is sprayed into a coagulating bath and is drawn to obtain nascent fibers;
the coagulating bath comprises coagulating agent and solvent, wherein the coagulating agent is diethylene glycol, and the solvent is selected from dimethyl sulfoxide, dimethylformamide, dimethylacetamide, acetone, naSCN water solution or ZnCl 2 The mass percentage of the coagulant in the aqueous solution and the coagulating bath is 20-80%;
the above solvents are solvents for producing polyacrylonitrile precursor, and the solvents in the coagulation bath should be matched with the solvents.
The comonomer is selected from itaconic acid, sodium acrylate, sodium methacrylate, methyl acrylate, methyl methacrylate, methacrylic acid or acrylamide.
The comonomer has the advantage of larger space volume, so that the action between polyacrylonitrile molecular chains can be reduced, thereby improving the elasticity of the polyacrylonitrile fiber. In addition, the comonomer can improve the cyclization degree of the polyacrylonitrile fiber, so that the fiber is more compact.
In the coagulation bath, the solvent in the polyacrylonitrile stock solution trickle diffuses into the coagulation bath, the coagulant in the coagulation bath diffuses into the stock solution trickle, and when double diffusion reaches equilibrium, the stock solution trickle reaches a critical concentration and is separated out.
In some embodiments, the temperature of the coagulation bath is 20-70 ℃. With this setting temperature a uniform setting of the fibers can be obtained.
In some embodiments, the comonomer is itaconic acid. The itaconic acid has active reaction property, and is favorable for the cyclization process of the polyacrylonitrile precursor during pre-oxidation.
In some embodiments, the solvent of the coagulation bath is dimethyl sulfoxide. Dimethyl sulfoxide has low toxicity.
In some embodiments, the linear velocity of the polyacrylonitrile stock solution sprayed after spinning is 5-50m/min.
In some embodiments, the draft ratio is-10% to-100%.
The beneficial effects achieved by one or more embodiments of the present invention described above are as follows:
according to the invention, the coagulant water in the traditional coagulation bath is replaced by diethylene glycol, so that the effect between the coagulant and polyacrylonitrile chain molecules is reduced, and the polyacrylonitrile molecular chains can be freely piled up to a large extent to participate in crystallization, thereby improving the crystallinity of the nascent fiber. Meanwhile, the weak acting force of the coagulant and the polyacrylonitrile chain weakens the phase separation degree, inhibits the formation of a compact cortex structure, reduces the diffusion resistance of the coagulant in trickle, ensures that the obtained nascent fiber has a structure from inside to outside, improves the skin-core structure, and improves the mechanical property of the polyacrylonitrile precursor.
In the coagulating bath, diethylene glycol enters the stock solution trickle from the coagulating bath through double diffusion, and the precipitation speed of polyacrylonitrile is regulated. The ternary phase diagram of polyacrylonitrile-di-solvent-diethylene glycol has a larger metastable region than the usual coagulation baths with water as coagulant. Since diethylene glycol is less polar than water, the diethylene glycol/polyacrylonitrile interaction parameter is less than the water/polyacrylonitrile interaction parameter.
Therefore, compared with water used as a coagulant, the diethylene glycol has smaller constraint on a polyacrylonitrile chain, on one hand, the rapid solidification and precipitation on the surface of the stock solution trickle are slowed down, the coagulant is facilitated to diffuse into the stock solution trickle, and the formation of homogeneous nascent fibers is facilitated; on the other hand, the diethylene glycol has relatively weak action with the polyacrylonitrile molecular chain, so that the entanglement among the polyacrylonitrile molecules is small, and the ordered movement of the molecular chain is facilitated to participate in the crystal growth.
When the mass percentage of the diglycol in the coagulating bath is 20-80%, the homogenization degree of the fiber can be better improved, and meanwhile, the loose of the integral structure of the fiber caused by insufficient double diffusion power is avoided.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the invention.
FIG. 1 is a schematic illustration of wet spinning for preparing high homogeneity and high crystallinity as-spun fibers in accordance with an embodiment of the present invention.
Wherein, 1, a spinneret; 2. coagulation bath; 3. a nascent fiber; 4. a guide wire disc.
Detailed Description
It should be noted that the following detailed description is illustrative and is intended to provide further explanation of the invention. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.
The invention is further illustrated below with reference to examples.
Example 1
A solidification molding method for improving homogenization and crystallinity of polyacrylonitrile nascent fiber comprises the following preparation steps:
the polyacrylonitrile copolymer is obtained by adopting a solution polymerization mode. Acrylonitrile and itaconic acid are used as comonomers, dimethyl sulfoxide is used as a solvent, azodiisobutyronitrile is used as an initiator to carry out free radical polymerization reaction at 60 ℃, and finally the acrylonitrile-itaconic acid binary copolymer is obtained, wherein the proportion of the comonomers is 99:1. And (5) performing single removal and deaeration for 12 hours to perform wet spinning.
The linear velocity of the polymer of the spinneret orifice is 20m/min, the coagulating bath adopts a mixed solution of dimethyl sulfoxide and diethylene glycol (the mass ratio is 3:7), the drafting of the coagulating bath is-25%, the residence time of the nascent fiber in the coagulating bath is 7s, and the temperature of the coagulating bath is kept at 30 ℃.
And washing the nascent fiber with water, drafting and drying to obtain the polyacrylonitrile precursor. The tensile strength of the obtained filaments was 6.4cN/Dtex. Cutting and grinding the dried nascent fiber into powder, analyzing the powder by adopting a D/max-rc type X-ray diffraction diffractometer, testing the powder, wherein the scanning area is 5-50 degrees, the scanning speed is 4 degrees/min, calculating the crystallinity C by adopting a Hinrich en method, and calculating the formula C=Ac/Ac+aa, wherein Ac is the area of a diffraction peak of a crystal region at 2 theta (approximately 17 degrees), aa is the area of a diffraction peak of an amorphous region, and calculating to obtain the crystallinity of 42.31 percent.
Example 2
The polyacrylonitrile copolymer is obtained by adopting a solution polymerization mode. The acrylonitrile-itaconic acid binary copolymer is finally obtained by free radical polymerization reaction of acrylonitrile and itaconic acid as comonomers, dimethyl sulfoxide as solvent and azodiisobutyronitrile as initiator at 60 ℃, the proportion of the comonomers is 99:1, and the polymerization process is as in example 1.
The rotational speed of the metering pump was adjusted, the linear polymer velocity of the spinneret orifice was 25m/min, the remaining process parameters and steps were the same as in example 1, the tensile strength of the precursor was calculated to be 7.3cN/Dtex, and the crystallinity of the as-spun fiber was calculated to be 47.85%.
Example 3
The polyacrylonitrile copolymer is obtained by adopting a solution polymerization mode. The acrylonitrile-itaconic acid binary copolymer is finally obtained by free radical polymerization reaction of acrylonitrile and itaconic acid as comonomers, dimethyl sulfoxide as solvent and azodiisobutyronitrile as initiator at 60 ℃, the proportion of the comonomers is 99:1, and the polymerization process is as in example 1.
The rotational speed of the metering pump was adjusted, the linear polymer velocity of the polymeric spinneret orifice was 30m/min, the remaining process parameters and steps were the same as in example 1, the tensile strength of the precursor was calculated to be 6.9cN/Dtex, and the crystallinity of the as-spun fiber was calculated to be 46.35%.
Example 4
The polyacrylonitrile copolymer is obtained by adopting a solution polymerization mode. The acrylonitrile-itaconic acid binary copolymer is finally obtained by free radical polymerization reaction of acrylonitrile and itaconic acid as comonomers, dimethyl sulfoxide as solvent and azodiisobutyronitrile as initiator at 60 ℃, the proportion of the comonomers is 99:1, and the polymerization process is as in example 1.
The coagulation bath was prepared by using a mixed solution of dimethyl sulfoxide and diethylene glycol (mass ratio was adjusted to 3.5:6.5), and the other process parameters and steps were the same as in example 2, and the tensile strength of the filaments was calculated to be 6.6cN/Dtex, and the crystallinity of the as-spun fibers was calculated to be 43.72%.
Example 5
The polyacrylonitrile copolymer is obtained by adopting a solution polymerization mode. The acrylonitrile-itaconic acid binary copolymer is finally obtained by free radical polymerization reaction of acrylonitrile and itaconic acid as comonomers, dimethyl sulfoxide as solvent and azodiisobutyronitrile as initiator at 60 ℃, the proportion of the comonomers is 99:1, and the polymerization process is as in example 1.
The coagulation bath was prepared by using a mixed solution of dimethyl sulfoxide and diethylene glycol (mass ratio was adjusted to 2:8), and the other process parameters and steps were the same as in example 2, and the tensile strength of the precursor was calculated to be 6.1cN/Dtex, and the crystallinity of the as-spun fiber was calculated to be 44.34%.
Example 6
The polyacrylonitrile copolymer is obtained by adopting a solution polymerization mode. The acrylonitrile-itaconic acid binary copolymer is finally obtained by free radical polymerization reaction of acrylonitrile and itaconic acid as comonomers, dimethyl sulfoxide as solvent and azodiisobutyronitrile as initiator at 60 ℃, the proportion of the comonomers is 99:1, and the polymerization process is as in example 1.
The coagulation bath quality was as in example 4, and the coagulation bath temperature was adjusted to 40 ℃. The remaining process parameters were as in example 2, calculated to give a tensile strength of the precursor of 5.6cN/Dtex and a crystallinity of the as-spun fiber of 40.04%.
Example 7
The polyacrylonitrile copolymer is obtained by adopting a solution polymerization mode. The acrylonitrile-itaconic acid binary copolymer is finally obtained by free radical polymerization reaction of acrylonitrile and itaconic acid as comonomers, dimethyl sulfoxide as solvent and azodiisobutyronitrile as initiator at 60 ℃, the proportion of the comonomers is 99:1, and the polymerization process is as in example 1.
The coagulation bath temperature and mass were as in example 4, and the coagulation bath draft ratio was adjusted to-60%. The remaining process parameters and steps are as in example 2. The tensile strength of the precursor was calculated to be 5.5cN/Dtex, and the crystallinity of the as-spun fiber was calculated to be 39.01%.
Comparative example 1
The polyacrylonitrile copolymer is obtained by adopting a solution polymerization mode. The acrylonitrile-itaconic acid binary copolymer is finally obtained by free radical polymerization reaction of acrylonitrile and itaconic acid as comonomers, dimethyl sulfoxide as solvent and azodiisobutyronitrile as initiator at 60 ℃, the proportion of the comonomers is 99:1, and the polymerization process is as in example 1.
The coagulation bath was prepared by using a mixed solution of dimethyl sulfoxide and water (mass ratio: 3:7), and the other process parameters and steps were the same as in example 1, and the tensile strength of the precursor was calculated to be 5.3cN/Dtex, and the crystallinity of the as-spun fiber was calculated to be 35.51%.
Comparative example 2
The polyacrylonitrile copolymer is obtained by adopting a solution polymerization mode. The acrylonitrile-itaconic acid binary copolymer is finally obtained by free radical polymerization reaction of acrylonitrile and itaconic acid as comonomers, dimethyl sulfoxide as solvent and azodiisobutyronitrile as initiator at 60 ℃, the proportion of the comonomers is 99:1, and the polymerization process is as in example 1. The coagulation bath was prepared by using a mixed solution of dimethyl sulfoxide and water (mass ratio was adjusted to 3:7), and the other process parameters and steps were the same as in example 2, and the tensile strength of the precursor was calculated to be 6.2cN/Dtex, and the crystallinity of the as-spun fiber was calculated to be 36.52%.
Comparative example 3
The polyacrylonitrile copolymer is obtained by adopting a solution polymerization mode. The acrylonitrile-itaconic acid binary copolymer is finally obtained by free radical polymerization reaction of acrylonitrile and itaconic acid as comonomers, dimethyl sulfoxide as solvent and azodiisobutyronitrile as initiator at 60 ℃, the proportion of the comonomers is 99:1, and the polymerization process is as in example 1. The coagulation bath was a mixed solution of dimethyl sulfoxide and water (mass ratio 3:7), and the rest of the process parameters were as in example 3. The tensile strength of the precursor was calculated to be 5.5cN/Dtex, and the crystallinity of the as-spun fiber was calculated to be 31.65%.
Comparative example 4
The polyacrylonitrile copolymer is obtained by adopting a solution polymerization mode. The acrylonitrile-itaconic acid binary copolymer is finally obtained by free radical polymerization reaction of acrylonitrile and itaconic acid as comonomers, dimethyl sulfoxide as solvent and azodiisobutyronitrile as initiator at 60 ℃, the proportion of the comonomers is 99:1, and the polymerization process is as in example 1. The coagulation bath was a mixed solution of dimethyl sulfoxide and water (mass ratio 3.5:6.5), and the rest of the process parameters were as in example 4. The tensile strength of the precursor was calculated to be 5.8cN/Dtex, and the crystallinity of the as-spun fiber was calculated to be 40.31%.
Comparative example 5
The polyacrylonitrile copolymer is obtained by adopting a solution polymerization mode. The acrylonitrile-itaconic acid binary copolymer is finally obtained by free radical polymerization reaction of acrylonitrile and itaconic acid as comonomers, dimethyl sulfoxide as solvent and azodiisobutyronitrile as initiator at 60 ℃, the proportion of the comonomers is 99:1, and the polymerization process is as in example 1. The coagulation bath was a mixed solution of dimethyl sulfoxide and water (mass ratio of 2:8), and the rest of the process parameters were as in example 5. The tensile strength of the precursor was calculated to be 5.1cN/Dtex, and the crystallinity of the as-spun fiber was calculated to be 41.48%.
Table 1 shows the tensile strength of the polyacrylonitrile precursor and the crystallinity of the as-spun fiber obtained in the examples and comparative examples
Figure BDA0004065462720000101
The above description is only of the preferred embodiments of the present invention and is not intended to limit the present invention, but various modifications and variations can be made to the present invention by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (10)

1. A solidification molding method for improving homogenization and crystallinity of polyacrylonitrile nascent fiber is characterized in that: the method comprises the following steps:
the polyacrylonitrile stock solution obtained by copolymerizing acrylonitrile and comonomer is sprayed into a coagulating bath and is drawn to obtain nascent fibers;
the coagulating bath comprises coagulating agent and solvent, wherein the coagulating agent is diethylene glycol, and the solvent is selected from dimethyl sulfoxide, dimethylformamide, dimethylacetamide, acetone, naSCN water solution or ZnCl 2 The mass percentage of the coagulant in the aqueous solution and the coagulating bath is 20-80%;
the comonomer is selected from itaconic acid, sodium acrylate, sodium methacrylate, methyl acrylate, methyl methacrylate, methacrylic acid or acrylamide.
2. The solidification molding method for improving homogenization and crystallinity of a primary polyacrylonitrile fiber according to claim 1, wherein: the temperature of the coagulating bath is 20-70 ℃.
3. The solidification molding method for improving homogenization and crystallinity of a primary polyacrylonitrile fiber according to claim 2, wherein: the temperature of the coagulating bath is 30-60 ℃.
4. The solidification molding method for improving homogenization and crystallinity of a primary polyacrylonitrile fiber according to claim 1, wherein: the comonomer is itaconic acid.
5. The solidification molding method for improving homogenization and crystallinity of a primary polyacrylonitrile fiber according to claim 1, wherein: the solvent of the coagulating bath is dimethyl sulfoxide.
6. The solidification molding method for improving homogenization and crystallinity of a primary polyacrylonitrile fiber according to claim 1, wherein: the linear velocity of the sprayed polyacrylonitrile stock solution after spinning is 5-50m/min.
7. The solidification molding method for improving homogenization and crystallinity of a primary polyacrylonitrile fiber according to claim 6, wherein: the linear velocity of the sprayed polyacrylonitrile stock solution after spinning is 15-40m/min.
8. The solidification molding method for improving homogenization and crystallinity of a primary polyacrylonitrile fiber according to claim 1, wherein: the draft ratio is-10% to-100%.
9. The solidification molding method for improving homogenization and crystallinity of a primary polyacrylonitrile fiber according to claim 1, wherein: in the coagulating bath, the mass percentage of the coagulating agent is 30-70%.
10. The solidification molding method for improving homogenization and crystallinity of a primary polyacrylonitrile fiber according to claim 9, wherein: in the coagulating bath, the mass percentage of the coagulating agent is 30% -60%.
CN202310073393.8A 2023-01-17 2023-01-17 Solidification forming method for improving homogenization and crystallinity of polyacrylonitrile nascent fiber Pending CN116084034A (en)

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GB2007240A (en) * 1977-10-27 1979-05-16 Snia Viscosa Acrylic Filaments
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CN101486400A (en) * 2007-12-14 2009-07-22 日东电工株式会社 Patch package structure
CN102733009A (en) * 2012-06-26 2012-10-17 北京化工大学 High strength polyacrylonitrile-base carbon fibers having structured surface grooves, and preparation method thereof

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2007240A (en) * 1977-10-27 1979-05-16 Snia Viscosa Acrylic Filaments
US4902452A (en) * 1986-07-28 1990-02-20 Mitsubishi Rayon Co., Ltd. Process for producing an acrylic fiber having high fiber characteristics
CN101486400A (en) * 2007-12-14 2009-07-22 日东电工株式会社 Patch package structure
CN102733009A (en) * 2012-06-26 2012-10-17 北京化工大学 High strength polyacrylonitrile-base carbon fibers having structured surface grooves, and preparation method thereof

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Title
王菊生等: "染整工艺原理", 31 January 2001, 中国纺织出版社, pages: 237 *
薛金秋: "化纤机械", 30 September 1999, 中国纺织出版社, pages: 120 *

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