CN117987937A - Preparation method and application of polyacrylonitrile spinning solution and preparation device thereof - Google Patents
Preparation method and application of polyacrylonitrile spinning solution and preparation device thereof Download PDFInfo
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- CN117987937A CN117987937A CN202211325533.8A CN202211325533A CN117987937A CN 117987937 A CN117987937 A CN 117987937A CN 202211325533 A CN202211325533 A CN 202211325533A CN 117987937 A CN117987937 A CN 117987937A
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- 238000009987 spinning Methods 0.000 title claims abstract description 116
- 229920002239 polyacrylonitrile Polymers 0.000 title claims abstract description 77
- 238000002360 preparation method Methods 0.000 title claims abstract description 42
- 239000011550 stock solution Substances 0.000 claims abstract description 73
- 239000000243 solution Substances 0.000 claims abstract description 67
- 238000002156 mixing Methods 0.000 claims abstract description 53
- 230000008961 swelling Effects 0.000 claims abstract description 25
- 239000000843 powder Substances 0.000 claims abstract description 24
- 239000002904 solvent Substances 0.000 claims abstract description 23
- 239000007787 solid Substances 0.000 claims abstract description 17
- 239000000203 mixture Substances 0.000 claims abstract description 7
- 238000003756 stirring Methods 0.000 claims description 78
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical group CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 30
- 239000000835 fiber Substances 0.000 claims description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- 238000000578 dry spinning Methods 0.000 claims description 18
- 238000000227 grinding Methods 0.000 claims description 18
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 17
- 229910052757 nitrogen Inorganic materials 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 9
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 8
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 8
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 8
- 229910021529 ammonia Inorganic materials 0.000 claims description 4
- 229910052786 argon Inorganic materials 0.000 claims description 4
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 4
- 239000001569 carbon dioxide Substances 0.000 claims description 4
- 238000004090 dissolution Methods 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- 238000007670 refining Methods 0.000 claims description 2
- 229920002972 Acrylic fiber Polymers 0.000 abstract description 5
- KUKFKAPJCRZILJ-UHFFFAOYSA-N prop-2-enenitrile;prop-2-enoic acid Chemical compound C=CC#N.OC(=O)C=C KUKFKAPJCRZILJ-UHFFFAOYSA-N 0.000 description 12
- 229920001577 copolymer Polymers 0.000 description 11
- 239000011261 inert gas Substances 0.000 description 11
- 238000006116 polymerization reaction Methods 0.000 description 9
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 7
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 5
- 229920006350 polyacrylonitrile resin Polymers 0.000 description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- VGTPCRGMBIAPIM-UHFFFAOYSA-M sodium thiocyanate Chemical compound [Na+].[S-]C#N VGTPCRGMBIAPIM-UHFFFAOYSA-M 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 229920000049 Carbon (fiber) Polymers 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000004917 carbon fiber Substances 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 235000011837 pasties Nutrition 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- IMBKASBLAKCLEM-UHFFFAOYSA-L ferrous ammonium sulfate (anhydrous) Chemical compound [NH4+].[NH4+].[Fe+2].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O IMBKASBLAKCLEM-UHFFFAOYSA-L 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000001891 gel spinning Methods 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- -1 polypropylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 238000012673 precipitation polymerization Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000004537 pulping Methods 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- WBHQBSYUUJJSRZ-UHFFFAOYSA-M sodium bisulfate Chemical compound [Na+].OS([O-])(=O)=O WBHQBSYUUJJSRZ-UHFFFAOYSA-M 0.000 description 1
- 229910000342 sodium bisulfate Inorganic materials 0.000 description 1
- MNCGMVDMOKPCSQ-UHFFFAOYSA-M sodium;2-phenylethenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C=CC1=CC=CC=C1 MNCGMVDMOKPCSQ-UHFFFAOYSA-M 0.000 description 1
Classifications
-
- 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
- D01D5/04—Dry 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
- D01D1/00—Treatment of filament-forming or like material
- D01D1/02—Preparation of spinning solutions
-
- 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
Landscapes
- 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 belongs to the technical field of acrylic fiber spinning, and particularly relates to a preparation method and application of a polyacrylonitrile spinning solution and a preparation device thereof. The preparation method of the polyacrylonitrile spinning solution comprises the following steps: after the temperature of the solvent rises, the solvent and the polyacrylonitrile powder synchronously enter a mixing device to be swelled; and (3) after mixing and swelling, the mixture enters a stock solution mixing tank, and is stirred and dissolved to prepare spinning stock solution. The invention provides a preparation method of a polyacrylonitrile spinning solution, which can reduce uneven mixing in the preparation process of the solution and improve the high solid content of the product quality and the working efficiency; the invention also provides a device thereof.
Description
Technical Field
The invention belongs to the technical field of acrylic fiber spinning, and particularly relates to a preparation method and application of a polyacrylonitrile spinning solution and a preparation device thereof.
Background
The dry polyacrylonitrile powder for dry acrylic fiber spinning is prepared by polymerization reaction with acrylonitrile, methyl acrylate and sodium styrene sulfonate as comonomer. The dry spinning process of polyacrylonitrile is to dissolve the dry polyacrylonitrile powder obtained after polymerization in organic solvent Dimethylformamide (DMF) or Dimethylacetamide (DMAC) to form spinning solution with solid content of 30-33%, and to convey the spinning solution to spinning channel and to eliminate solvent with hot nitrogen to form primary polyacrylonitrile filament. The dry spinning forming process is mild, the internal structure of the fiber is uniform, so that the dry spinning fiber has good physical and mechanical properties and dyeing properties, and the spinning section strength is good.
When a large number of hydrophilic groups such as-OH, -NH 3, -COOH and-CONH are introduced into the molecular chain of the polyacrylonitrile fiber, the moisture absorption and release performances are obviously improved, so that the hydrophilic groups are introduced into the polyacrylonitrile fiber to well play a role in temperature and humidity adjustment. The polyacrylonitrile fiber can also be used as an ion exchange fiber to further develop a new functional material with certain characteristics. However, the introduction of the hydrophilic group can cause the solubility of polyacrylonitrile in the dry acrylic solvent to be poor, when the novel polyacrylonitrile product of acrylonitrile-acrylic acid with the hydrophilic group is introduced, the phenomenon of white core is often generated in the preparation process of industrial dry spinning dope, the outer surface of the clustered white core is swelled, the powder in the inside is wrapped, the solvent is prevented from diffusing into the inside, the powder in the inside cannot be swelled and dissolved, and the change of solution viscosity is uncontrollable, so that the phenomena of yarn doubling or yarn breakage and the like occur in the spinning process.
CN102400234a discloses a preparation method of polyacrylonitrile-based carbon fiber precursor spinning solution, wherein the spinning solution is a solution formed by dissolving powdery polyacrylonitrile resin in solvent NaSCN aqueous solution, and the preparation process comprises the following steps: mixing polyacrylonitrile resin with NaSCN water solution, controlling the content of the polyacrylonitrile resin in the mixture to be 15-25wt%, and maintaining the mixture material for dispersion and pulping to enable the polyacrylonitrile resin to be uniformly dispersed in the NaSCN water solution to form a pasty mixture; and (3) further adding NaSCN aqueous solution into the obtained pasty mixture, controlling the content of the polypropylene resin in the mixture to be 8-14 wt%, stirring and homogenizing until the polyacrylonitrile resin is completely dissolved, thus obtaining spinning solution.
CN109321994A discloses a dry-wet spinning solution of polyacrylonitrile-based carbon fiber and a preparation method thereof, wherein dimethyl sulfoxide is used as a reaction medium, azo compounds are used as an initiator, acrylonitrile is used as a1 st monomer, itaconic acid or a derivative thereof is used as a2 nd monomer, acrylic acid or a derivative thereof is used as a3 rd monomer for copolymerization reaction, and ammonia water is added to adjust the pH value of the polymerization solution to 8-9 when the intrinsic viscosity of a copolymerization product is 1.6-5 dL/g; then the residual acrylonitrile mass concentration is less than 0.1 percent after the removal, the viscosity is modulated: adjusting the dynamic viscosity of the polymer liquid to 120-600 Pa.s, and defoaming to obtain the final product.
CN112142888a discloses a polyacrylonitrile spinning solution and a preparation method thereof, wherein a polyacrylonitrile oligomer and a polyacrylonitrile copolymer are subjected to solution blending to obtain the polyacrylonitrile spinning solution; wherein the solution blending step comprises: carrying out solution blending on the polyacrylonitrile oligomer and the polyacrylonitrile copolymer to obtain a mixed solution; defoaming the mixed solution to obtain a polyacrylonitrile spinning solution; wherein, in the mixed solution, the mass fraction of the polyacrylonitrile oligomer is 0.05-0.2%.
Disclosure of Invention
The technical problem to be solved by the invention is to overcome the defects in the prior art, and provide the preparation method of the polyacrylonitrile spinning solution, which can reduce uneven mixing in the preparation process of the solution and improve the high solid content of the product quality and the working efficiency; the invention also provides a device thereof.
The preparation method of the polyacrylonitrile spinning solution comprises the following steps:
(1) After the temperature of the solvent rises, the solvent and the polyacrylonitrile powder synchronously enter a mixing device to be swelled;
(2) Mixing and swelling, and then entering a stock solution mixing tank, stirring and dissolving to prepare spinning stock solution;
application: and (3) after the filtering and refining treatment of the spinning solution, performing dry spinning in a spinning channel through a metering pump and a spinneret plate to obtain the nascent fiber.
The solvent is N, N-dimethylacetamide, and the mass ratio of the N, N-dimethylacetamide to polyacrylonitrile is (69-75): (25-31).
The temperature of the N, N-dimethylacetamide is raised to 65-85 ℃, preferably 75-79 ℃.
The solid content of the spinning solution in the step (2) is 26-30%.
The stirring speed of the step (2) is 30 to 80 rpm, preferably 40 to 70 rpm, more preferably 50 to 60 rpm, and the dissolution time is 4 to 16 hours, preferably 6 to 13 hours, more preferably 8 to 10 hours.
The channel atmosphere in application is one or more of nitrogen, ammonia, carbon dioxide, argon and the like, preferably nitrogen; the channel temperature is 150-300 ℃, the channel draft multiple is 2-10, and the residence time is 1-30 s.
The mixing device in the step (1) is a Mark mixer.
The prepared polyacrylonitrile spinning solution has acrylonitrile content of 90-100% and acrylic acid mass content of 0-10%. Wherein the rotational viscosity of the polyacrylonitrile powder is 50000-80000 mPa.s, and the number average molecular weight is 2-4 ten thousand.
The preparation device of the polyacrylonitrile spinning solution comprises a solution mixing tank, wherein the solution mixing tank comprises a shell and a preparation cavity, and the shell is provided with a solution inlet, a solution outlet and a cylinder cover; a stirring assembly is arranged in the stock solution mixing tank and comprises a stirring rod, and a stirring paddle and a grinding plate are connected to the stirring rod; the outer layer of the shell is provided with a jacket, and the jacket is provided with a jacket inlet, a jacket water outlet and a jacket outlet; a thermometer is arranged on the jacket water outlet.
The stirring paddle adopts a hoop to be fixedly connected with the stirring rod through a bolt.
The grinding plate is anchor-type, and is fixed with the stirring rod by adopting a hoop through bolts.
The stirring paddles are downward-pressing inclined blade paddles, and the stirring rod is connected with an upper group of stirring paddles, a middle group of stirring paddles and a lower group of stirring paddles which are arranged in a cross manner; the lower parts of the upper stirring paddles and the middle stirring paddles are provided with grinding plates, and the lower parts and the side edges of the stirring paddles are of a zigzag structure; the grinding plate is of an inverted saw-tooth structure and can be overlapped with the stirring paddle up and down, namely, the grinding plate is arranged right below the stirring paddle and has a gap smaller than 1mm with the stirring paddle, and the grinding plate is fixed with the inner wall of the stock solution mixing tank and does not rotate along with the stirring rod. The stirring paddle is fastened on the stirring rod by a hoop and is fixed by a bolt. The grinding plate is fastened on the stirring rod by a hoop and is fixed by a bolt.
Specifically, the preparation method of the polyacrylonitrile spinning solution comprises the following steps:
(1) The solvent N, N-dimethylacetamide is heated to 65-85 ℃ and then enters a Mark mixer together with polyacrylonitrile powder for swelling; the mass ratio of the N, N-dimethylacetamide to the polyacrylonitrile is (69-75): (25-31);
(2) Introducing inert gas into a stock solution mixing tank after mixing and swelling, evacuating and deoxidizing, stirring and dissolving for 4-16 hours at 30-80 rpm to prepare spinning stock solution with solid content of 26-30%, rotational viscosity of 50000-80000 mPa.s and water content of 0.1-0.4wt%;
(3) After the spinning solution is filtered and refined, dry spinning is carried out in a spinning channel through a metering pump and a spinneret plate to obtain nascent fibers; the channel atmosphere is any one or more of nitrogen, ammonia, carbon dioxide, argon and the like, the channel temperature is 150-300 ℃, the channel draft multiple is 2-10, and the residence time is 1-30 s.
Compared with the prior art, the invention has the following beneficial effects:
(1) The polyacrylonitrile spinning solution with high carboxylic acid content is prepared by adopting the preparation method of the polyacrylonitrile spinning solution, and proper polyacrylonitrile fibers can be prepared by a dry spinning process;
(2) By adopting the preparation device of the polyacrylonitrile spinning solution, the polyacrylonitrile powder has good solubility, the phenomenon of white core can not occur, the phenomena of broken ends or doubling in the spinning process are greatly reduced, and the production efficiency is improved.
Drawings
FIG. 1 is a schematic diagram of a preparation device of an acrylonitrile-acrylic acid binary copolymer spinning solution;
FIG. 2 is a schematic view of a stirring assembly of the stock solution mixing tank of the present invention;
In the figure: 1. a stock solution mixing tank; 2. a stock solution inlet; 3. a stirring assembly; 4. a housing; 5. stirring paddles; 6. a jacket water outlet; 7. a jacket; 8. a jacket inlet; 9. a stock solution outlet; 10. a jacket outlet; 11. a grinding plate; 12. a stirring rod; 13. preparing a cavity; 14. a cylinder cover; 15. a thermometer.
Detailed Description
The technical scheme of the present invention is further described by examples and comparative examples, but the scope of the present invention is not limited by the examples.
Preparation of polyacrylonitrile powder:
Adding a comonomer into a polymerization kettle according to the proportion of acrylonitrile=95 and acrylic acid=5 in parts by weight, simultaneously adding the initiator potassium persulfate, sodium bisulfate, ferrous ammonium sulfate, desalted water and sulfur dioxide which are required by the reaction into the polymerization kettle together, controlling the polymerization temperature to 60 ℃, controlling the pH value of a polymerization reaction system to be 3.0, and carrying out aqueous phase precipitation polymerization reaction;
After the polymerization reaction, EDTA is added to terminate the reaction, the material obtained by the polymerization is filtered, washed and dried to obtain a dried polymer with the water content of 0.3%, the number average molecular weight of the obtained polymer is 3.2 ten thousand, the molecular weight distribution is 3.0, and the polyacrylonitrile powder is obtained after the material is crushed into fine powder.
As shown in fig. 1, the preparation device of the polyacrylonitrile spinning solution comprises a solution mixing tank 1, wherein the solution mixing tank 1 comprises a shell 4 and a preparation cavity 13, and the shell 4 is provided with a solution inlet 2, a solution outlet 9 and a cylinder cover 14; the inside of the stock solution mixing tank 1 is provided with a stirring assembly 3, the stirring assembly 3 comprises a stirring rod 12, and the stirring rod 12 is connected with a stirring paddle 5 and a grinding plate 11; the outer layer of the shell 4 is provided with a jacket 7, and the jacket 7 is provided with a jacket inlet 8, a jacket water outlet 6 and a jacket outlet 10; a thermometer 15 is arranged on the jacket water outlet 6.
The stirring paddle 5 is fixedly connected with the stirring rod 12 through bolts by adopting a hoop.
The grinding plate 11 is anchor-type and is fastened to the stirring rod 12 by bolts using a collar.
The stirring paddles are downward-pressing inclined blade paddles, and the stirring rod is connected with an upper group of stirring paddles, a middle group of stirring paddles and a lower group of stirring paddles which are arranged in a cross manner; the lower parts of the upper stirring paddles and the middle stirring paddles are provided with grinding plates, and the lower parts and the side edges of the stirring paddles are of a zigzag structure; the grinding plate is of an inverted saw-tooth structure and can be overlapped with the stirring paddle up and down, namely, the grinding plate is arranged right below the stirring paddle and has a gap smaller than 1mm with the stirring paddle, and the grinding plate is fixed with the inner wall of the stock solution mixing tank and does not rotate along with the stirring rod. The stirring paddle is fastened on the stirring rod by a hoop and is fixed by a bolt. The grinding plate is fastened on the stirring rod by a hoop and is fixed by a bolt.
Example 1
The preparation method of the acrylonitrile-acrylic acid binary copolymer spinning stock solution comprises the following steps:
(1) The solvent N, N-dimethylacetamide and polyacrylonitrile powder synchronously enter a Mark mixer for swelling after the temperature is increased to 80 ℃; the mass ratio of the N, N-dimethylacetamide to the polyacrylonitrile is 69:31;
(2) Introducing inert gas into a stock solution mixing tank after mixing and swelling, evacuating and deoxidizing, stirring and dissolving for 8 hours at 30 revolutions per minute to prepare spinning stock solution with the solid content of 28%, wherein the rotational viscosity of the spinning stock solution is 66000mpa.s, and the water content in the spinning stock solution is 0.2%;
Application: after the spinning solution is filtered and refined, dry spinning is carried out in a spinning channel through a metering pump and a spinneret plate to obtain nascent fibers; the channel atmosphere is nitrogen, the channel temperature is 240 ℃, the channel draft multiple is 6, and the residence time is 20s.
Example 2
The preparation method of the acrylonitrile-acrylic acid binary copolymer spinning stock solution comprises the following steps:
(1) The solvent N, N-dimethylacetamide and polyacrylonitrile powder synchronously enter a Mark mixer for swelling after the temperature is raised to 70 ℃; the mass ratio of the N, N-dimethylacetamide to the polyacrylonitrile is 70:30;
(2) Introducing inert gas into a stock solution mixing tank after mixing and swelling, evacuating and deoxidizing, stirring and dissolving for 8 hours at 40 revolutions per minute to prepare spinning stock solution with the solid content of 28%, wherein the rotational viscosity of the spinning stock solution is 66000mpa.s, and the water content in the spinning stock solution is 0.2%;
Application: after the spinning solution is filtered and refined, dry spinning is carried out in a spinning channel through a metering pump and a spinneret plate to obtain nascent fibers; the channel atmosphere is nitrogen, the channel temperature is 300 ℃, the channel draft multiple is 4, and the residence time is 25s.
Example 3
The preparation method of the acrylonitrile-acrylic acid binary copolymer spinning stock solution comprises the following steps:
(1) The solvent N, N-dimethylacetamide and polyacrylonitrile powder synchronously enter a Mark mixer for swelling after the temperature is raised to 65 ℃; the mass ratio of the N, N-dimethylacetamide to the polyacrylonitrile is 75:25;
(2) Introducing inert gas into a stock solution mixing tank after mixing and swelling, evacuating and deoxidizing, stirring and dissolving for 8 hours at 50 revolutions per minute to prepare a spinning stock solution with the solid content of 30%, wherein the rotational viscosity of the spinning stock solution is 66000mpa.s, and the water content in the spinning stock solution is 0.2%;
Application: after the spinning solution is filtered and refined, dry spinning is carried out in a spinning channel through a metering pump and a spinneret plate to obtain nascent fibers; the channel atmosphere is nitrogen, the channel temperature is 150 ℃, the channel draft multiple is 10, and the residence time is 10s.
Example 4
The preparation method of the acrylonitrile-acrylic acid binary copolymer spinning stock solution comprises the following steps:
(1) The solvent N, N-dimethylacetamide and polyacrylonitrile powder synchronously enter a Mark mixer for swelling after the temperature is raised to 85 ℃; the mass ratio of the N, N-dimethylacetamide to the polyacrylonitrile is 69:31;
(2) Introducing inert gas into a stock solution mixing tank after mixing and swelling, evacuating and deoxidizing, stirring and dissolving for 8 hours at 60 revolutions per minute to prepare a spinning stock solution with the solid content of 26%, wherein the rotational viscosity of the spinning stock solution is 66000mpa.s, and the water content in the spinning stock solution is 0.2%;
Application: after the spinning solution is filtered and refined, dry spinning is carried out in a spinning channel through a metering pump and a spinneret plate to obtain nascent fibers; the channel atmosphere is nitrogen, the channel temperature is 200 ℃, the channel draft multiple is 6, and the residence time is 10s.
Example 5
The preparation method of the acrylonitrile-acrylic acid binary copolymer spinning stock solution comprises the following steps:
(1) The solvent N, N-dimethylacetamide and polyacrylonitrile powder synchronously enter a Mark mixer for swelling after the temperature is increased to 80 ℃; the mass ratio of the N, N-dimethylacetamide to the polyacrylonitrile is 69:31;
(2) Introducing inert gas into a stock solution mixing tank after mixing and swelling, evacuating and deoxidizing, stirring and dissolving for 8 hours at 70 revolutions per minute to prepare spinning stock solution with the solid content of 28%, wherein the rotational viscosity of the spinning stock solution is 66000mpa.s, and the water content in the spinning stock solution is 0.2%;
Application: after the spinning solution is filtered and refined, dry spinning is carried out in a spinning channel through a metering pump and a spinneret plate to obtain nascent fibers; the channel atmosphere is nitrogen, the channel temperature is 240 ℃, the channel draft multiple is 2, and the residence time is 30s.
Example 6
The preparation method of the acrylonitrile-acrylic acid binary copolymer spinning stock solution comprises the following steps:
(1) The solvent N, N-dimethylacetamide and polyacrylonitrile powder synchronously enter a Mark mixer for swelling after the temperature is increased to 80 ℃; the mass ratio of the N, N-dimethylacetamide to the polyacrylonitrile is 69:31;
(2) Mixing and swelling, then, entering a stock solution mixing tank, introducing inert gas, evacuating and deoxidizing, stirring and dissolving for 8 hours at 80 revolutions per minute to prepare spinning stock solution with the solid content of 28%, wherein the rotational viscosity of the spinning stock solution is 80000mpa.s, and the water content in the spinning stock solution is 0.1%;
Application: after the spinning solution is filtered and refined, dry spinning is carried out in a spinning channel through a metering pump and a spinneret plate to obtain nascent fibers; the channel atmosphere is nitrogen, the channel temperature is 240 ℃, the channel draft multiple is 6, and the residence time is 5s.
Example 7
The preparation method of the acrylonitrile-acrylic acid binary copolymer spinning stock solution comprises the following steps:
(1) The solvent N, N-dimethylacetamide and polyacrylonitrile powder synchronously enter a Mark mixer for swelling after the temperature is increased to 80 ℃; the mass ratio of the N, N-dimethylacetamide to the polyacrylonitrile is 69:31;
(2) Introducing inert gas into a stock solution mixing tank after mixing and swelling, evacuating and deoxidizing, stirring and dissolving for 6 hours at 50 revolutions per minute to prepare a spinning stock solution with solid content of 30%, wherein the rotational viscosity of the spinning stock solution is 50000mpa.s, and the water content of the spinning stock solution is 0.4%;
Application: after the spinning solution is filtered and refined, dry spinning is carried out in a spinning channel through a metering pump and a spinneret plate to obtain nascent fibers; the atmosphere of the channel is ammonia, the channel temperature is 240 ℃, the channel draft multiple is 6, and the residence time is 20s.
Example 8
The preparation method of the acrylonitrile-acrylic acid binary copolymer spinning stock solution comprises the following steps:
(1) The solvent N, N-dimethylacetamide and polyacrylonitrile powder synchronously enter a Mark mixer for swelling after the temperature is increased to 80 ℃; the mass ratio of the N, N-dimethylacetamide to the polyacrylonitrile is 69:31;
(2) Introducing inert gas into a stock solution mixing tank after mixing and swelling, evacuating and deoxidizing, stirring and dissolving for 7 hours at 50 revolutions per minute to prepare spinning stock solution with the solid content of 28%, wherein the rotational viscosity of the spinning stock solution is 66000mpa.s, and the water content in the spinning stock solution is 0.2%;
Application: after the spinning solution is filtered and refined, dry spinning is carried out in a spinning channel through a metering pump and a spinneret plate to obtain nascent fibers; the channel atmosphere is carbon dioxide, the channel temperature is 240 ℃, the channel draft multiple is 6, and the residence time is 20s.
Example 9
The preparation method of the acrylonitrile-acrylic acid binary copolymer spinning stock solution comprises the following steps:
(1) The solvent N, N-dimethylacetamide and polyacrylonitrile powder synchronously enter a Mark mixer for swelling after the temperature is increased to 80 ℃; the mass ratio of the N, N-dimethylacetamide to the polyacrylonitrile is 69:31;
(2) Introducing inert gas into a stock solution mixing tank after mixing and swelling, evacuating and deoxidizing, stirring and dissolving for 9 hours at 50 revolutions per minute to prepare spinning stock solution with the solid content of 28%, wherein the rotational viscosity of the spinning stock solution is 66000mpa.s, and the water content in the spinning stock solution is 0.2%;
application: after the spinning solution is filtered and refined, dry spinning is carried out in a spinning channel through a metering pump and a spinneret plate to obtain nascent fibers; the channel atmosphere is argon, the channel temperature is 240 ℃, the channel draft multiple is 6, and the residence time is 20s.
Example 10
The preparation method of the acrylonitrile-acrylic acid binary copolymer spinning stock solution comprises the following steps:
(1) The solvent N, N-dimethylacetamide and polyacrylonitrile powder synchronously enter a Mark mixer for swelling after the temperature is increased to 80 ℃; the mass ratio of the N, N-dimethylacetamide to the polyacrylonitrile is 69:31;
(2) Introducing inert gas into a stock solution mixing tank after mixing and swelling, evacuating and deoxidizing, stirring and dissolving for 10 hours at 50 revolutions per minute to prepare spinning stock solution with the solid content of 28%, wherein the rotational viscosity of the spinning stock solution is 66000mpa.s, and the water content in the spinning stock solution is 0.2%;
Application: after the spinning solution is filtered and refined, dry spinning is carried out in a spinning channel through a metering pump and a spinneret plate to obtain nascent fibers; the channel atmosphere is nitrogen, the channel temperature is 240 ℃, the channel draft multiple is 6, and the residence time is 20s.
Comparative example 1
A dope was prepared as in example 3, except that the dope mixing tank stirring assembly was a beveled blade non-serrated stirring paddle and stirring rod.
Comparative example 2
A dope was prepared as in example 3, except that the dope mixing tank stirring blade was a bevel blade zigzag stirring blade and a stirring rod, and there was no grinding plate.
Performance testing
The testing method comprises the following steps: in the production line, when the quality of the stock solution changes, yarn breakage occurs in the spinning process, acrylic fibers are broken, plates are required to be replaced, and the number of sleeves required to be replaced for producing 100 tons of acrylic fibers is used as a standard for evaluating the yarn breakage phenomenon or viscosity stability of the stock solution. The more broken filaments or the higher the viscosity, the more plate changes are required.
The pressure is the pressure at the nozzle of the spinning step in the spinning process, and when the nozzle pressure is too high, the powder is not sufficiently dissolved to block the nozzle in a solid form, so that the nozzle pressure is increased. The test results are shown in Table 1.
Table 1 test results
The primary fibers prepared in the above examples and comparative examples, i.e., dry PAN long fibers, were examined, and the examination results are shown in table 2.
TABLE 2 results of as-spun fiber detection Performance
Of course, the foregoing is merely preferred embodiments of the present invention and is not to be construed as limiting the scope of the embodiments of the present invention. The present invention is not limited to the above examples, and those skilled in the art will appreciate that the present invention is capable of equally varying and improving within the spirit and scope of the present invention.
Claims (10)
1. A preparation method of polyacrylonitrile spinning solution is characterized in that: the method comprises the following steps:
(1) After the temperature of the solvent rises, the solvent and the polyacrylonitrile powder synchronously enter a mixing device to be swelled;
(2) And (3) after mixing and swelling, the mixture enters a stock solution mixing tank, and is stirred and dissolved to prepare spinning stock solution.
2. The method for preparing the polyacrylonitrile spinning solution according to claim 1, wherein: the solvent is N, N-dimethylacetamide, and the mass ratio of the N, N-dimethylacetamide to polyacrylonitrile is (69-75): (25-31).
3. The method for preparing the polyacrylonitrile spinning solution according to claim 2, wherein: the temperature of the dimethylacetamide is raised to 65-85 ℃.
4. The method for preparing the polyacrylonitrile spinning solution according to claim 1, wherein: the solid content of the spinning solution in the step (2) is 26-30%.
5. The method for preparing the polyacrylonitrile spinning solution according to claim 4, wherein: the stirring speed of the step (2) is 30-80 rpm, and the dissolution time is 4-16 hours.
6. Use of the polyacrylonitrile spinning solution prepared by the preparation method according to any one of claims 1 to 5, characterized in that: and (3) after the filtering and refining treatment of the spinning solution, performing dry spinning in a spinning channel through a metering pump and a spinneret plate to obtain the nascent fiber.
7. The use of the polyacrylonitrile spinning solution prepared by the preparation method according to claim 6, which is characterized in that: the channel atmosphere is one or more of nitrogen, ammonia, carbon dioxide and argon, the channel temperature is 150-300 ℃, the channel draft multiple is 2-10, and the residence time is 1-30 s.
8. An apparatus for use in the process for producing a polyacrylonitrile spinning solution according to any one of claims 1 to 5, characterized in that: the device comprises a stock solution mixing tank (1), wherein the stock solution mixing tank (1) comprises a shell (4) and a preparation cavity (13), and the shell (4) is provided with a stock solution inlet (2), a stock solution outlet (9) and a cylinder cover (14); a stirring assembly (3) is arranged in the stock solution mixing tank (1), the stirring assembly (3) comprises a stirring rod (12), and a stirring paddle (5) and a grinding plate (11) are connected to the stirring rod (12); the outer layer of the shell (4) is provided with a jacket (7), and the jacket (7) is provided with a jacket inlet (8), a jacket water outlet (6) and a jacket outlet (10); a thermometer (15) is arranged on the jacket water outlet (6).
9. The apparatus for preparing the polyacrylonitrile spinning solution according to claim 8, wherein: the stirring paddle (5) is fixedly connected with the stirring rod (12) through a bolt by adopting a hoop.
10. The apparatus for preparing the polyacrylonitrile spinning solution according to claim 8, wherein: the grinding plate (11) is anchor-type and is fixed with the stirring rod (12) through bolts by adopting hoops.
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