CN114517340B - Acrylic fiber structural body and preparation process thereof - Google Patents
Acrylic fiber structural body and preparation process thereof Download PDFInfo
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- CN114517340B CN114517340B CN202210112596.9A CN202210112596A CN114517340B CN 114517340 B CN114517340 B CN 114517340B CN 202210112596 A CN202210112596 A CN 202210112596A CN 114517340 B CN114517340 B CN 114517340B
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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
- D01F6/44—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds
- D01F6/54—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds of polymers of unsaturated nitriles
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
- C08F265/08—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of nitriles
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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
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
- D01F1/103—Agents inhibiting growth of microorganisms
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
- Y02P70/62—Manufacturing or production processes characterised by the final manufactured product related technologies for production or treatment of textile or flexible materials or products thereof, including footwear
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Abstract
The invention relates to a novel acrylic fiber structure body, in particular to a novel monomer-itaconic acid introduced into a system for producing functional acrylic fibers, which is structurally characterized in that a new monomer-itaconic acid is added into the original system for producing acrylic fibers (polyacrylonitrile) for copolymerization, and the acrylic fibers containing the itaconic acid have more excellent flexibility and strength after being subjected to a modified grafting process, so that the inherent performance of the original acrylic fibers can be further improved.
Description
Technical Field
The invention relates to a method for manufacturing acrylic fibers, belongs to the field of novel fiber manufacturing, and particularly relates to a novel acrylic fiber structure and a preparation process thereof.
Background
The traditional acrylic fiber is already on the market for decades in the textile fiber market, the production process is mature, but the limitation on the structure of the traditional acrylic fiber is always the target for improvement in the same industry of all countries in the world. Many manufacturers in the market began to study the effect of different monomers on polyacrylonitrile fibers.
CN105986328A discloses a preparation method of acrylic high Jiang Gong industrial yarn fiber, which comprises mixing 96-98.5 wt% of acrylonitrile, 1.0-3.0 wt% of methyl acrylate and 0.5-1.0 wt% of itaconic acid to adjust the concentration, adjusting the concentration to 20-30 wt%, and continuously carrying out aqueous phase suspension polymerization; the reacted polymer is terminated by chelation reaction, unreacted monomers are removed by steam stripping, then the salt and the moisture are removed by a washing filter, the powdery polymer obtained by drying after granulation forming is mixed and dissolved with DMAC, the spinning solution is prepared by spinning, double diffusion forming, washing, oiling, drying and curling, the draft multiple is 6-12 times, the spinning solution is shaped by 200-320 KPa shaping pressure, and the high-strength industrial acrylic fiber with the tensile strength of not less than 4.5cN/dtex, the heat resistance temperature of 110-130 ℃ and the elastic modulus of 45-75 cN/dtex is obtained after cutting.
CN108330563A relates to an acrylic fiber and a preparation method thereof. The acrylic fiber consists of a polymer A and a polymer B, wherein the content of the polymer B in the acrylic fiber is any content, preferably 0-30 wt%, more preferably 10-20 wt%; the polymer A is prepared from 92-94 wt% of acrylonitrile and 6-8 wt% of vinyl acetate; the polymer B is prepared from 88 to 99 weight percent of acrylonitrile, 0.8 to 8 weight percent of methyl acrylate and 0.2 to 4.8 weight percent of itaconic acid. The acrylic fiber of the invention not only has the excellent characteristics of rebound resilience, coverage, fluffiness and stiff feel of dry acrylic fiber, but also has the smoothness and better spinning performance of wet acrylic fiber.
Although the prior art has some technologies for adding itaconic acid monomers to polyacrylonitrile fibers, the prior art still has some defects, such as adding other complex monomers and complex reagents besides the itaconic acid monomers, adding itaconic acid structure modification mechanism is not deeply studied, and the properties of the obtained acrylic fibers are not ideal. Therefore, it is necessary to provide a simple and effective process for a novel acrylic fiber structure.
Disclosure of Invention
The invention aims to provide a novel process of a novel acrylic fiber structural body, and aims to solve the defects of the prior art that the research on itaconic acid monomers is blank and the performance of fiber products is insufficient.
The first aspect of the invention provides an advanced process for crosslinking and modifying conventional acrylic fibers into special acrylic fiber materials with multiple functions by the modification process of the invention, and particularly, after a new synthetic monomer itaconic acid is introduced, the performance of the produced flame-retardant acrylic fiber is more excellent, and the strength, the flexibility and the like are improved.
The inventors have found that although some of the prior art solutions exist using itaconic acid as a monomer and then spinning acrylic fibers, the improvement effect on the fibers is not significant. Since itaconic acid
Although the itaconic acid is an unsaturated monomer, the unsaturated double bond reaction activity is low, and the homopolymerization effect is poor, so when the itaconic acid is used as a monomer for acrylic fiber spinning, the crosslinking grafting reaction activity is poor, and some performances of the fiber obtained after process modification, such as flame retardant property and strength, are not ideal.
The invention provides that itaconic acid is modified by quaternary ammonium hydroxide to modify the activity of the itaconic acid, because the structure of the itaconic acid is reconstructed in the solution environment of the quaternary ammonium hydroxide and the itaconic acid is converted into other two types of methyl butene diacid with the same molecular formula but different structures. The conversion and existence of the multiple structures can improve the grafting cross probability among high molecular polymers in the fiber, thereby improving the crosslinking degree of subsequent reaction; the activity of itaconic acid is also stimulated by reconstitution. In addition, compared with the method of directly adding hydroxide basic exciting agent, the quaternary ammonium hydroxide, especially the quaternary ammonium hydroxide containing aliphatic unsaturated alkyl and/or aromatic hydrocarbon, has better biological activity on fibers and can also play roles in sterilizing, catalyzing and regulating crosslinking reaction.
The acrylic fiber obtained after spinning is obtained by modifying the composition and the structure of the acrylic fiber through the process, has better effective crosslinking degree than common fiber in the prior art, and shows better flame retardant property and strength than the prior fiber.
Specifically, the invention provides a preparation process of a novel acrylic fiber structural body, which comprises the following steps:
1) Preparation of spinning dope: preparing polyacrylonitrile colloid and itaconic acid accounting for 1-10% of the mass fraction of the polyacrylonitrile colloid for mixing to obtain spinning slurry;
2) Adding quaternary ammonium base: adding 1-10% of quaternary ammonium hydroxide in mass percent into the spinning slurry, and uniformly blending; wherein the content of the first and second substances, the quaternary ammonium base has a structural unit (I):
(I)
in the structural unit (I), R1 is C1-C20 straight chain or branched chain alkane, R2 is C2-C5 aliphatic unsaturated hydrocarbon, R3 is C1-C16 straight chain or branched chain alkane, and R4 is aromatic hydrocarbon;
3) Blending and spinning: swelling and standing at about room temperature, heating to 60-80 ℃, dissolving for 3 hours to form a uniform solution, and spinning after filtering and defoaming the solution;
4) Dewatering and cooling: placing the spun yarn in a closed container, heating to 120 ℃ for dehydration, preserving the heat for 1-2 hours after 2 hours, and then slowly reducing the temperature to 35-40 ℃ at a cooling rate of less than 1 ℃/6 minutes to obtain the required flame-retardant acrylic fiber semi-finished product;
5) Molding: and (3) placing the spinning fiber-forming semi-finished product in a closed container, preserving heat for 2-4 hours at the temperature of 90-100 ℃ to generate a crosslinking grafting reaction, slowly cooling to 35-40 ℃ under the condition of not more than 1 ℃/5 minutes, and discharging to obtain the flame-retardant acrylic fiber product.
In some preferred technical schemes, the spinning process comprises the following steps: spinning at 5-10m/min, washing the coagulated fiber with water, stretching, drying, setting and curling to obtain polyacrylonitrile fiber.
In some preferred embodiments, the R1 or R3 is selected from dodecyl, tetradecyl, or hexadecyl.
In some preferred embodiments, R4 is selected from phenyl.
In some preferred embodiments, the aliphatic unsaturated hydrocarbon is selected from aliphatic carboxylic acids containing unsaturated hydrocarbon groups, such as one of acrylic acid, methacrylic acid, maleic acid, and fumaric acid.
In some preferred technical schemes, in order to ensure the reaction to be complete, vacuum conditions are adopted or inert gas is filled for protection or 1-4% of antioxidant or ultraviolet-resistant absorbent is added in the preparation of spinning slurry.
In some preferred technical schemes, in order to improve the product performance, after the crosslinking grafting reaction is finished, an aldehyde compound containing hydroxyl or N group is adopted for post-finishing, the usage amount of the aldehyde compound is 1-3% of the mass fraction of the reaction liquid, and the temperature is 90-100 ℃.
The technical scheme of the invention has the following beneficial effects:
according to the invention, through modifying the itaconic acid monomer in the acrylic fiber spinning solution, after the unsaturated bond with limited activity is modified by quaternary ammonium hydroxide, the structure of the modified unsaturated bond can promote the subsequent polyacrylonitrile crosslinking grafting reaction, the effective crosslinking degree of the obtained spinning fiber can be enhanced, and the corresponding property can be enhanced.
Drawings
FIG. 1 is a Differential Scanning Calorimetry (DSC) curve of samples of example 1 of the present invention and comparative example 1.
Detailed Description
Reference will now be made in detail to embodiments of the present invention, examples of which are illustrated in the accompanying drawings, wherein like or similar reference numerals refer to the same or similar modules or modules having the same or similar functionality throughout. The embodiments described below with reference to the accompanying drawings are illustrative only for the purpose of explaining the present invention, and are not to be construed as limiting the present invention.
In the description herein, references to the description of "one embodiment," "another embodiment," etc., mean that a particular feature, structure, material, or characteristic described in connection with the embodiment is included in at least one embodiment of the invention. In this specification, the schematic representations of the terms used above are not necessarily intended to refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, various embodiments or examples and features of different embodiments or examples described in this specification can be combined and combined by one skilled in the art without contradiction.
The mass fraction of the itaconic acid monomer added in the invention is controlled to be 1-10% of that of polyacrylonitrile, and the itaconic acid monomer contains two double bonds and has the possibility of addition and polymerization reactions. White powdery crystals or colorless crystals at normal temperature, and has stable property during storage. The melting point of the itaconic acid is 167-168 ℃.
In the mixed system with proper quaternary ammonium hydroxide content, itaconic acid is structurally reconstructed.
The invention provides that in order to promote the improvement of an acrylic fiber structure, in the acrylic fiber process, the added quaternary ammonium hydroxide has a structural unit (I):
(I)
in the structural unit (I), R1 is C1-C20 straight chain or branched chain alkane, R2 is C2-C5 aliphatic unsaturated hydrocarbon, R3 is C1-C16 straight chain or branched chain alkane, and R4 is aromatic hydrocarbon.
The straight-chain or branched-chain alkane R1 or R3 can be selected from dodecyl, tetradecyl or hexadecyl; in some preferred embodiments, the aromatic hydrocarbon may be selected from phenyl, toluene, or xylene.
The aliphatic unsaturated hydrocarbon may be selected from aliphatic carboxylic acids containing an unsaturated hydrocarbon group, such as acrylic acid, methacrylic acid, maleic acid, fumaric acid, and the like.
The following sets forth a technical solution of a specific embodiment.
Example 1
Taking 600kg of colloid containing itaconic acid accounting for 4% of fiber-forming polyacrylonitrile by mass, adding 60kg of quaternary ammonium base accounting for 10% by mass, uniformly blending, standing, defoaming and spinning; in the quaternary ammonium base structural unit (I), R1 and R3 are dodecyl and tetradecyl respectively;
r2 is
And R4 is
Placing the spun yarn in a closed container, heating to 120 ℃ for dehydration, preserving the heat for 2 hours, then slowly reducing the temperature to 40 ℃ at a cooling rate of not more than 1 ℃/6 minutes to obtain the required flame-retardant acrylic fiber semi-finished product;
and (3) placing 300kg of the spinning fiber-forming semi-finished product in a closed container, preserving heat for 4 hours at the temperature of 98 ℃, slowly cooling to 40 ℃ under the condition of not more than 1 ℃/5 minutes, and discharging to obtain the flame-retardant acrylic fiber product.
Example 2
Taking 600kg of colloid containing itaconic acid accounting for 5% of fiber-forming polyacrylonitrile by mass, adding 30kg of quaternary ammonium base accounting for 5% of fiber-forming polyacrylonitrile by mass, uniformly blending, standing, defoaming and spinning; in the quaternary ammonium base structural unit (I), R1 and R3 are tetradecyl and hexadecyl respectively;
r2 is
And R4 is
Placing the spun yarn in a closed container, heating to 120 ℃ for dehydration, preserving the heat for 1 hour after 2 hours, and then slowly reducing the temperature to 35 ℃ at a cooling rate of not more than 1 ℃/6 minutes to obtain a required flame-retardant acrylic fiber semi-finished product;
and (3) placing 300kg of the spinning fiber-forming semi-finished product in a closed container, preserving heat for 4 hours at 95 ℃, slowly cooling to 40 ℃ under the condition of not more than 1 ℃/5 minutes, and discharging to obtain the flame-retardant acrylic fiber product.
Example 3
Taking 600kg of colloid containing itaconic acid accounting for 8% of fiber-forming polyacrylonitrile by mass, adding 60kg of quaternary ammonium base with the mass content of 10%, uniformly blending, standing, defoaming, and spinning; in the quaternary ammonium base structural unit (I), R1 and R3 are dodecyl and hexadecyl respectively;
r2 is
And R4 is
Placing the spun yarn in a closed container, heating to 120 ℃ for dehydration, preserving the heat for 2 hours, then slowly reducing the temperature to 40 ℃ at a cooling rate of not more than 1 ℃/6 minutes to obtain the required flame-retardant acrylic fiber semi-finished product;
taking 300kg of spinning fiber-forming semi-finished product, placing the semi-finished product in a closed container, preserving heat for 4 hours at the temperature of 98 ℃, slowly cooling to 30 ℃ under the condition that the temperature is not more than 1 ℃/5 minutes, and discharging to obtain the flame-retardant acrylic fiber product.
Example 4
Taking 600kg of colloid containing itaconic acid accounting for 9% of fiber-forming polyacrylonitrile by mass, adding 30kg of quaternary ammonium base with 5% of mass content, uniformly blending, standing, defoaming, and spinning; in the quaternary ammonium base structural unit (I), R1 and R3 are hexadecyl and dodecyl respectively;
r2 is
And R4 is
Placing the spun yarn in a closed container, heating to 120 ℃ for dehydration, preserving the heat for 2 hours, then slowly reducing the temperature to 40 ℃ at a cooling rate of not more than 1 ℃/6 minutes to obtain the required flame-retardant acrylic fiber semi-finished product;
and (3) placing 300kg of the spinning fiber-forming semi-finished product in a closed container, preserving heat for 4 hours at the temperature of 98 ℃, slowly cooling to 40 ℃ under the condition of not more than 1 ℃/5 minutes, and discharging to obtain the flame-retardant acrylic fiber product.
Example 5
Taking 600kg of colloid containing itaconic acid accounting for 5% of fiber-forming polyacrylonitrile by mass, adding 60kg of quaternary ammonium base with solid content of 10%, uniformly blending, standing, defoaming and spinning; in the quaternary ammonium base structural unit (I), R1 and R3 are hexadecyl and tetradecyl respectively;
r2 is
And R4 is
Putting the spun yarn into a closed container, heating to 120 ℃ for dehydration, preserving the heat for 1 hour after 2 hours, and then slowly reducing the temperature to 40 ℃ at the temperature reduction rate of not more than 1 ℃/6 minutes to obtain the required flame-retardant acrylic fiber finished product;
350kg of spinning fiber-forming semi-finished product is taken and placed in a closed container, heat preservation is carried out for 4 hours at the temperature of 98 ℃, then the temperature is slowly reduced to 35 ℃ under the condition of not more than 1 ℃/5 minutes, and discharging is carried out, thus obtaining the flame-retardant acrylic fiber product.
Comparative example 1
The parameters and flow were the same as in example 1, except that no quaternary ammonium base was added.
Comparative example 2
The parameters and flow are the same as in example 1, except that the quaternary ammonium hydroxide is added in an amount of 30%.
Thermal stability test
The results of the test for characterizing the thermal stability of the polymers using differential scanning calorimetry, DSC, are shown in figure 1: the solid line and the broken line are respectively embodiment 1 and DSC curve of the polymer fiber sample of comparative example 1. The test results show that the flame-retardant fiber sample obtained by the technical scheme of the invention has higher thermal decomposition temperature (thermal stability), while the polymer sample of the comparative example 1 has lower thermal stability than the sample of the example 1. Compared with the fiber obtained by the scheme in the prior art, the novel acrylic fiber structural body obtained by the process has higher flame retardant property and higher high temperature resistance. Can also work to maintain the specific properties of the fiber in certain high-temperature environments.
Physical mechanical Property test
The mechanical properties were tested using a fiber strength tester TB400C according to the International Standard "method for testing tensile Properties of chemical staple fibers" GB/T14337-2008. The fiber samples obtained in examples 1 to 5 of the present invention and comparative example 1 were subjected to the same mechanical property test, and the test results are shown in the following table. The mechanical property of the acrylic fiber obtained by the invention completely meets the strength requirement of fiber products in the market. In contrast, the polyacrylonitrile fiber product of comparative example 1 doped with only itaconic acid monomer is inferior in strength to the acrylic structure modified with quaternary ammonium hydroxide of the present invention; the embodiment of comparative example 2 has excessive quaternary ammonium hydroxide, which can promote the cracking of acrylic fiber or cause alkaline corrosion, thereby affecting the strength of the fiber.
TABLE 1
| Sample(s) | Breaking strength cN/dtex | Elongation at break% |
| Example 1 | 4.8 | 30 |
| Example 2 | 4.9 | 33 |
| Example 3 | 4.8 | 31 |
| Example 4 | 4.6 | 29 |
| Example 5 | 4.8 | 30 |
| Comparative example 1 | 4.1 | 25 |
| Comparative example 2 | 3.6 | 20 |
Although embodiments of the present invention have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting the present invention, and that variations, modifications, substitutions and alterations can be made to the above embodiments by those of ordinary skill in the art within the scope of the present invention.
Claims (7)
1. A preparation process of an acrylic fiber structure body comprises the following steps:
1) Preparation of spinning dope: preparing polyacrylonitrile colloid and itaconic acid accounting for 1-10% of the mass fraction of the polyacrylonitrile colloid for mixing to obtain spinning slurry;
2) Adding quaternary ammonium base: adding 1-10% of quaternary ammonium hydroxide in mass percent into the spinning slurry, and uniformly blending; wherein the quaternary ammonium base has a structural unit (I):
(I)
in the structural unit (I), R1 is C1-C20 straight chain or branched alkane, and R2 is
R3 is C1-C16 straight chain or branched chain alkane, and R4 is aromatic hydrocarbon;
3) Blending and spinning: swelling and standing at room temperature, heating to 60-80 ℃, dissolving for 3 hours to form a uniform solution, and spinning after filtering and defoaming the solution;
4) Dewatering and cooling: placing the spun yarn in a closed container, heating to 120 ℃ for dehydration, preserving the heat for 1-2 hours after 2 hours, and then slowly reducing the temperature to 35-40 ℃ at a cooling rate of less than 1 ℃/6 minutes to obtain the required flame-retardant acrylic fiber semi-finished product;
5) Molding: and (3) placing the spinning fiber-forming semi-finished product in a closed container, preserving heat for 2-4 hours at the temperature of 90-100 ℃ to generate a crosslinking grafting reaction, slowly cooling to 35-40 ℃ under the condition of not more than 1 ℃/5 minutes, and discharging to obtain the flame-retardant acrylic fiber product.
2. The process for producing an acrylic fiber structure according to claim 1, wherein the spinning process comprises: spinning at 5-10m/min, washing the coagulated fiber with water, stretching, drying, setting and curling to obtain polyacrylonitrile fiber.
3. The process for producing an acrylic fiber structure according to claim 1, wherein R1 or R3 is selected from the group consisting of dodecyl group, tetradecyl group and hexadecyl group.
4. The process for producing an acrylic fiber structure according to claim 1, wherein R4 is selected from the group consisting of phenyl, toluene and xylene.
5. The process for producing an acrylic fiber structure according to claim 1, wherein in order to achieve sufficient reaction, a vacuum condition is adopted or inert gas is introduced for protection or 1 to 4% of an antioxidant or ultraviolet absorber is added in preparation of the spinning dope.
6. The process for producing an acrylic fiber structure according to claim 1, wherein after the crosslinking graft reaction is completed, an aldehyde compound containing a hydroxyl group or an "N" group is used for post-finishing in an amount of 1 to 3% by mass of the reaction liquid at a temperature of 90 to 100 ℃.
7. An acrylic fiber structure obtained by the process for producing an acrylic fiber structure according to any one of claims 1 to 6.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3784512A (en) * | 1972-03-28 | 1974-01-08 | Monsanto Co | Color stabilized acid-dyeable acrylonitrile-containing fibers |
| US4170579A (en) * | 1976-11-24 | 1979-10-09 | Ppg Industries, Inc. | Coating compositions comprising aqueous dispersions of quaternary ammonium base group-containing polymers and a curing agent |
| US4859727A (en) * | 1986-08-22 | 1989-08-22 | Mitsubishi Rayon Company Ltd. | Antistatic thermoplastic resin composition |
| CN101864028A (en) * | 2010-05-28 | 2010-10-20 | 金发科技股份有限公司 | Preparation method of polyacrylonitrile spinning solution |
| CN108330563A (en) * | 2017-12-08 | 2018-07-27 | 吉林奇峰化纤股份有限公司 | A kind of acrylic fiber and preparation method thereof |
-
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3784512A (en) * | 1972-03-28 | 1974-01-08 | Monsanto Co | Color stabilized acid-dyeable acrylonitrile-containing fibers |
| US4170579A (en) * | 1976-11-24 | 1979-10-09 | Ppg Industries, Inc. | Coating compositions comprising aqueous dispersions of quaternary ammonium base group-containing polymers and a curing agent |
| US4859727A (en) * | 1986-08-22 | 1989-08-22 | Mitsubishi Rayon Company Ltd. | Antistatic thermoplastic resin composition |
| CN101864028A (en) * | 2010-05-28 | 2010-10-20 | 金发科技股份有限公司 | Preparation method of polyacrylonitrile spinning solution |
| CN108330563A (en) * | 2017-12-08 | 2018-07-27 | 吉林奇峰化纤股份有限公司 | A kind of acrylic fiber and preparation method thereof |
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