CN118407142A - Method for improving dissolution performance of dry-method high-molecular-weight polyacrylonitrile spinning solution - Google Patents
Method for improving dissolution performance of dry-method high-molecular-weight polyacrylonitrile spinning solution Download PDFInfo
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- 229920002239 polyacrylonitrile Polymers 0.000 title claims abstract description 82
- 238000000034 method Methods 0.000 title claims abstract description 66
- 238000004090 dissolution Methods 0.000 title claims abstract description 54
- 238000009987 spinning Methods 0.000 title claims abstract description 36
- 230000008961 swelling Effects 0.000 claims abstract description 58
- 238000010438 heat treatment Methods 0.000 claims abstract description 52
- 238000003756 stirring Methods 0.000 claims abstract description 52
- 239000000843 powder Substances 0.000 claims abstract description 41
- 239000002904 solvent Substances 0.000 claims abstract description 34
- 239000007787 solid Substances 0.000 claims abstract description 10
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims abstract description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 7
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- 239000011550 stock solution Substances 0.000 abstract description 35
- 239000000243 solution Substances 0.000 abstract description 31
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- 238000005259 measurement Methods 0.000 abstract description 3
- 229920000642 polymer Polymers 0.000 description 13
- 238000005303 weighing Methods 0.000 description 9
- 238000011978 dissolution method Methods 0.000 description 8
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- 229920000049 Carbon (fiber) Polymers 0.000 description 5
- 239000004917 carbon fiber Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 5
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- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
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- 206010067484 Adverse reaction Diseases 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000011157 advanced composite material Substances 0.000 description 1
- 230000006838 adverse reaction Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 229920006125 amorphous polymer Polymers 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000010000 carbonizing Methods 0.000 description 1
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- 238000000578 dry spinning Methods 0.000 description 1
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- 229920006158 high molecular weight polymer Polymers 0.000 description 1
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- ANOBYBYXJXCGBS-UHFFFAOYSA-L stannous fluoride Chemical compound F[Sn]F ANOBYBYXJXCGBS-UHFFFAOYSA-L 0.000 description 1
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Abstract
A method for improving the solubility of a dry-method high molecular weight polyacrylonitrile spinning solution belongs to the technical field of polyacrylonitrile spinning solutions. The method comprises the following steps: uniformly stirring polyacrylonitrile powder in a dimethylacetamide solvent and dispersing the polyacrylonitrile powder in the solvent; swelling at room temperature; heating to 60-80deg.C for swelling; heating to 85-105deg.C for dissolution; the solution was subjected to viscosity measurement in a thermostat water bath at 80℃using the falling ball method. The method has the advantages of simple process and easy operation, improves the swelling degree of the stock solution and improves the uniformity of the spinning stock solution on the premise of ensuring higher solid content of the polyacrylonitrile spinning stock solution, thereby improving the product quality of the spun yarn.
Description
Technical Field
The invention belongs to the technical field of polyacrylonitrile spinning, and particularly relates to a method for improving the dissolution performance of a dry-method high-molecular-weight polyacrylonitrile spinning solution.
Background
The carbon fiber is an inorganic polymer fiber with carbon content higher than 95%, and the advanced composite material using the carbon fiber as a reinforcing material has a series of excellent performances such as high specific strength, high specific modulus, strong designability, high temperature resistance, corrosion resistance, fatigue resistance, small thermal expansion coefficient and the like. The excellent performance of the composite material can lead the composite material to be widely applied to the fields of aerospace, rail transit, vehicle manufacturing, weapon equipment, engineering machinery, wind energy, sports goods and the like.
The polyacrylonitrile-based fiber is the most promising precursor for producing high-performance carbon fiber, and is formed by spinning, pre-oxidizing and carbonizing polyacrylonitrile, and the carbon fiber prepared by using the polyacrylonitrile has excellent properties such as high tensile strength, high tensile modulus and the like. High-quality polyacrylonitrile precursor is a primary condition for preparing high-performance polyacrylonitrile carbon fiber, and high-quality spinning solution is a key factor for restricting the preparation of high-performance precursor. The rheological property and spinnability of the spinning solution are important reference factors for judging spinning, and the dissolution degree of the high polymer is closely related to the spinning quality.
High quality polyacrylonitrile precursors require higher polymerization degree and molecular weight, and increase the force between macromolecules, thereby obtaining higher tensile strength. However, because polyacrylonitrile belongs to a linear molecular chain polymer coexisting with crystalline and amorphous, in the dissolution process, solvent micromolecules penetrate into the interior of polyacrylonitrile molecular chains and the diffusion of the molecular chains to the solvent is more difficult than that of pure amorphous polymers, and the dry spinning process requires that the molecular weight and the solid content of polyacrylonitrile in the spinning solution are higher, so that the dissolution difficulty is further increased.
The addition of a certain amount of water is mentioned in the literature to aid in the dissolution of high molecular weight polyacrylonitrile, but the presence of water in the stock solution is detrimental to the progress of the swelling system and reduces the viscosity of the stock solution. There are also documents that suggest to reduce the concentration of the polymer in the stock solution, but when the concentration of the polymer is too low, the viscosity of the stock solution is also reduced, which causes insufficient volatilization of the solvent in the primary filaments, which is easy to form sticky filaments, and poor stability of fiber formation, which causes poor quality of fiber finished products.
Patent CN114457448a describes a method for improving the dissolution performance of dry high molecular weight polyacrylonitrile by adopting a method of mixing three solvents of dimethylacetamide, dimethylformamide and dimethyl sulfoxide, wherein the dimethylformamide has strong dissolution capability but high toxicity, and the mixed dissolution of double solvents adds a certain difficulty to the recovery of subsequent solvents.
Disclosure of Invention
In order to solve the technical problems in the background art, the invention provides the method for improving the dissolution performance of the dry-method high-molecular-weight polyacrylonitrile spinning solution, which has the advantages of simple process and easy operation, and improves the swelling degree of the solution and the uniformity of the spinning solution on the premise of ensuring the higher solid content of the polyacrylonitrile spinning solution, thereby improving the product quality of the spun yarn.
The technical scheme adopted for solving the technical problems is as follows: the method for improving the dissolution performance of the dry-method high molecular weight polyacrylonitrile spinning solution is characterized by comprising the following steps of:
1) Uniformly dispersing polyacrylonitrile powder in a dimethylacetamide solvent to prepare a polyacrylonitrile solution, wherein the viscosity average molecular weight of the polyacrylonitrile powder is 6-10 ten thousand, and the solid content of the obtained polyacrylonitrile solution is 26-30%;
2) Swelling the polyacrylonitrile solution for 1-6 hours at room temperature under the stirring condition, wherein the stirring rotating speed is 80-240 r/min;
3) Heating to 60-80 ℃, and continuing to carry out thermal swelling for 1-4 hours, wherein the stirring rotation speed is 150-300 r/min;
4) Heating to 85-105 ℃ to dissolve for 4-8 hours, and controlling the stirring rotation speed to 150-300 r/min.
The dissolution process of the polymer is difficult and slow due to the complex molecular shape and the structure in an aggregated state, and needs to undergo two stages of swelling and dissolution. Swelling is the process of gradually penetrating solvent molecules into the macromolecule from the outside to the inside under the action of the solvent to expand the volume of the polymer. Dissolution is the process by which macromolecules gradually diffuse into a solvent to form a uniform solution.
If the high molecular weight polymer does not swell sufficiently, i.e., dissolves, a high viscosity layer is formed at the polymer-solvent interface, which prevents diffusion of solvent molecules into the polymer, and affects the uniformity of the polymer solution.
According to the invention, the solvent molecules fully enter the polymer by adopting a method of stirring and swelling at room temperature, and the polymer stock solution reaches a uniform swelling state before heating and swelling-dissolution, so that the dissolution rate of the polymer stock solution is further improved, and a uniform and high-quality spinning stock solution is provided for subsequent products.
Preferably, the water content of the polyacrylonitrile powder in the step 1) of the above-mentioned dissolution method is less than 0.5%. The control of the water content of the polyacrylonitrile powder below 0.5% is not only beneficial to improving the dissolution efficiency and the product stability, but also can reduce the occurrence of adverse reactions.
Preferably, in the step 1) of the dissolution method, the viscosity average molecular weight of the polyacrylonitrile powder is 6.3-8.0 ten thousand, and the solid content of the obtained polyacrylonitrile solution is controlled to be 26-28%. The preferable viscosity average molecular weight of the polyacrylonitrile powder and the solid content of the obtained polyacrylonitrile solution are in the above range, which is more conducive to improving spinning performance, ensuring stable product quality, improving production efficiency and reducing rejection rate.
Preferably, in the step 2) of the dissolution method, the swelling time at room temperature is 3-5 h; the stirring speed is 100 r/min-140 r/min. The polyacrylonitrile molecules can fully expand and absorb the solvent under the preferable room-temperature swelling condition, so that the dissolution uniformity of the inside and the outside of the polyacrylonitrile molecules is ensured, and the difficulty of the subsequent thermal dissolution stage is reduced.
Preferably, the swelling temperature of the thermal swelling in step 3) of the above dissolution method is 60 ℃,70 ℃ or 80 ℃; the swelling time is 1h when the swelling temperature is 60 ℃; swelling time is 2h at the swelling temperature of 70 ℃; the swelling time is 1-2 h at the swelling temperature of 80 ℃. According to different swelling temperatures and different swelling times, the interaction between the polyacrylonitrile molecules and the solvent can be promoted, and the dissolution process is accelerated. The polyacrylonitrile can be dissolved more quickly and thoroughly by different swelling times at different temperatures.
Preferably, the temperature at the time of dissolution in the step 4) of the dissolution method is 90 ℃ to 95 ℃; the dissolution time is 5-7 h. The preferable dissolution process conditions can ensure that the polyacrylonitrile is completely dissolved in the solvent, avoid the occurrence of residues or agglomeration phenomenon, and ensure the uniformity and stability of the solution.
Preferably, in the step 3) of the dissolution method, the stirring rotation speed is 170 r/min-230 r/min during thermal swelling; the stirring rotating speed is 170 r/min-230 r/min during the dissolution in the step 4). In the thermal swelling and dissolution process, a more appropriate stirring speed can ensure uniform mixing of the solution and promote dissolution of the polymer.
Preferably, the temperature rising rate in the step 3) and the step 4) of the dissolution method is controlled to be 4.5 ℃/30 min-5.5 ℃/30min. The heating rate is controlled to reduce the thermal stress of the polyacrylonitrile in the heating process, and the slow heating rate is beneficial to the polyacrylonitrile molecules to absorb heat more uniformly, so that stress concentration caused by overlarge local temperature gradient is avoided, possible thermal stress damage is reduced, and meanwhile, the uniformity and quality stability of the product are improved.
Compared with the prior art, the method for improving the dissolution performance of the dry-method high-molecular-weight polyacrylonitrile spinning solution has the following working principle and beneficial effects: the method obviously improves the solubility of the dry-method high-molecular-weight polyacrylonitrile spinning solution by controlling the key parameters such as the dissolution temperature and time, the stirring rotation speed, the heating rate and the like in the optimization step. The dissolution temperature and time are accurately controlled to fully dissolve the polyacrylonitrile, so that the dissolution uniformity and stability are ensured; adjusting proper stirring rotation speed to promote intermolecular diffusion and dissolution speed, and improving dissolution efficiency and uniformity; and the control of the temperature rising rate can effectively reduce the thermal stress, improve the quality stability of the product, save energy and improve the operation safety and the production efficiency. The dissolution method can obviously improve the dissolution performance of the product and improve the production efficiency.
Detailed Description
The invention relates to a method for improving the dissolution performance of a dry-method high molecular weight polyacrylonitrile spinning solution, which specifically comprises the following steps:
1) Preparing a stock solution: and rapidly removing moisture from the polyacrylonitrile powder in a flash evaporation drying mode, drying until the moisture content of the powder is lower than 0.5%, crushing and sieving the powder by using a crusher, and then cooling the powder to room temperature in a dryer. Pouring the dimethylacetamide solvent into a stirring container, weighing polyacrylonitrile powder, slowly adding the polyacrylonitrile powder into the stirring container containing the dimethylacetamide solvent in batches, and pouring the mixture while stirring by using a glass rod until the polyacrylonitrile powder is uniformly dispersed in the solvent;
2) Swelling at room temperature: uniformly dispersed polyacrylonitrile solution is stirred and swelled for 1-6 hours at room temperature, and the rotating speed is 80-240 r/min until the polyacrylonitrile and the dimethylacetamide solvent are uniformly mixed to form pasty uniform solution;
3) Thermal swelling: heating the uniform solution to 60-80 ℃ and swelling for 1-4 hours, wherein the rotating speed is controlled to be 150-300 r/min until the stock solution swells to be colloid;
4) Dissolving: heating the colloidal swelling stock solution to 85-105 ℃ for dissolving for 4-8 hours, and controlling the rotating speed to 150-300 r/min until the colloidal swelling stock solution is dissolved into transparent solution;
5) Viscosity measurement: and (3) carrying out viscosity measurement on the transparent solution in a constant-temperature water bath kettle by using a falling ball method at the temperature of 80 ℃.
According to the above embodiment, the following is further described by way of specific examples:
Example 1
Weighing 120gDMAC g of polyacrylonitrile powder with the viscosity average molecular weight of 6.53 ten thousand, adding 43.27g of polyacrylonitrile powder, uniformly dispersing the powder into a solvent to prepare a 26.5% uniform stock solution, stirring and swelling at the room temperature, wherein the rotating speed is 120r/min, stirring for 3h, heating to 60 ℃ at the heating rate of 5.0 ℃/30min for swelling, stirring for 1h at the rotating speed of 200r/min, heating to 70 ℃ at the heating rate of 5.0 ℃/30min for stirring for 1h again, heating to 80 ℃ for continuous stirring for 1h, and finally dissolving for 5h at the temperature of 90 ℃, and measuring the viscosity of the polymerized stock solution by a falling ball method.
Example 2
Weighing 125gDMAC g, adding 46.23g of polyacrylonitrile powder with the viscosity average molecular weight of 6.58 ten thousand, uniformly dispersing the powder into a solvent to prepare 27.0% of uniform stock solution, stirring and swelling at the room temperature, wherein the rotating speed is 120r/min, stirring for 4h, heating to 70 ℃ at the heating rate of 5.0 ℃/30min for swelling, stirring for 2h at the rotating speed of 200r/min, heating to 80 ℃ at the heating rate of 5.0 ℃/30min for continuing stirring for 1h, and finally dissolving for 6h at the temperature of 90-100 ℃, and measuring the viscosity of the polymerized stock solution by a falling ball method.
Example 3
Weighing 125gDMAC g, adding 45.07g of polyacrylonitrile powder with the viscosity average molecular weight of 6.80 ten thousand, uniformly dispersing the powder into a solvent to prepare a 26.5% uniform stock solution, stirring and swelling at the room temperature, wherein the rotating speed is 120r/min, stirring for 5h, heating to 70 ℃ at the heating rate of 5.0 ℃/30min for swelling, stirring for 2h at the rotating speed of 200r/min, heating to 80 ℃ at the heating rate of 5.0 ℃/30min for continuing stirring for 1h, and finally dissolving for 6h at the temperature of 90-100 ℃, and measuring the viscosity of the polymerized stock solution by a falling ball method.
Example 4
130GDMAC g of polyacrylonitrile powder with the viscosity average molecular weight of 6.30 ten thousand is weighed, 50.55g of polyacrylonitrile powder with the viscosity average molecular weight is added, the powder is uniformly dispersed into a solvent to prepare a uniform stock solution with 28.0 percent, the mixture is stirred and swelled at the rotating speed of 120r/min at the room temperature, after stirring for 4 hours, the temperature is raised to 70 ℃ at the heating rate of 4.5 ℃/30min to swell, after stirring for 2 hours at the rotating speed of 180r/min, the temperature is raised to 80 ℃ at the heating rate of 4.5 ℃/30min to continue stirring for 2 hours, and finally, after dissolving for 6 hours at the temperature of 90-100 ℃, the viscosity of the polymerized stock solution is measured by a falling ball method.
Example 5
Weighing 125gDMAC g, adding 43.92g of polyacrylonitrile powder with the viscosity average molecular weight of 7.76 ten thousand, uniformly dispersing the powder into a solvent to prepare a 26.0% uniform stock solution, stirring and swelling at the room temperature, wherein the rotating speed is 120r/min, stirring for 4 hours, heating to 70 ℃ at the heating rate of 5.5 ℃/30min for swelling, stirring for 2 hours at the rotating speed of 200r/min, heating to 80 ℃ at the heating rate of 5.5 ℃/30min for continuous stirring for 2 hours, and finally dissolving for 6 hours at the temperature of 90-100 ℃, and measuring the viscosity of the polymerized stock solution by a falling ball method.
Example 6
Weighing 120gDMAC g of polyacrylonitrile powder with the viscosity average molecular weight of 6.53 ten thousand, adding 43.27g of polyacrylonitrile powder, uniformly dispersing the powder into a solvent to prepare a 26.5% uniform stock solution, stirring and swelling at the room temperature, wherein the rotating speed is 120r/min, stirring for 3h, heating to 60 ℃ at the heating rate of 10 ℃/30min for swelling, stirring for 1h at the rotating speed of 200r/min, heating to 70 ℃ at the heating rate of 10 ℃/30min for stirring for 1h, heating to 80 ℃ for continuous stirring for 1h, finally dissolving for 5h at the temperature of 90 ℃, and measuring the viscosity of the polymerized stock solution by a falling ball method.
Comparative example 1
Weighing 125gDMAC g, adding 46.23g of polyacrylonitrile powder with a viscosity average molecular weight of 6.56 ten thousand, uniformly dispersing the powder into a solvent to prepare 27.0% of uniform stock solution, heating to 60 ℃ to swell for 1h at a rotating speed of 160r/min, heating to 70 ℃ at a heating rate of 4.5 ℃/30 min-5.5 ℃/30min, stirring for 2h at a rotating speed of 200r/min, heating to 80 ℃ at a heating rate of 4.5 ℃/30 min-5.5 ℃/30min, continuously stirring for 1h, dissolving for 5h at a temperature of 90-100 ℃, and measuring the viscosity of the polymerized stock solution by a falling ball method.
Comparative example 2
Weighing 125gDMAC g, adding 45.07g of polyacrylonitrile powder with a viscosity average molecular weight of 6.83 ten thousand, uniformly dispersing the powder into a solvent to prepare 26.5% of uniform stock solution, heating to 70 ℃ at a heating rate of 4.5 ℃/30 min-5.5 ℃/30min, swelling for 2h at a rotating speed of 180r/min, heating to 80 ℃ at a heating rate of 4.5 ℃/30 min-5.5 ℃/30min, continuously stirring for 1h at a rotating speed of 200r/min, dissolving for 6h at a temperature of 90-100 ℃, and measuring the viscosity of the polymerized stock solution by a falling ball method.
Comparative example 3
Weighing 125gDMAC g, adding 43.92g of polyacrylonitrile powder with the viscosity average molecular weight of 7.76 ten thousand, uniformly dispersing the powder into a solvent to prepare 26.0% of uniform stock solution, heating to 70 ℃ at the heating rate of 4.5 ℃/30 min-5.5 ℃/30min, swelling for 2h at the rotating speed of 180r/min, heating to 80 ℃ at the heating rate of 4.5 ℃/30 min-5.5 ℃/30min, continuously stirring for 1h at the rotating speed of 200r/min, dissolving for 7h at the temperature of 90-100 ℃, and measuring the viscosity of the polymerized stock solution by a falling ball method.
Table 1 shows the spinnability and dissolution of the spinning dope prepared in the examples and comparative examples.
From the test results in the above table, it can be seen that:
comparing samples with the same molecular weight and the same solid content, increasing the room temperature stirring and swelling under the same dissolving process is beneficial to fully contacting the polyacrylonitrile powder with the solvent to form uniform stock solution, and reducing the viscosity fluctuation of the polyacrylonitrile spinning stock solution to prepare transparent stock solution.
Compared with the samples with the same molecular weight and solid content in examples 2,3 and 5, the dissolution process in comparative examples 1-3 does not adopt the method of the invention, and it can be seen that the raw liquid with high viscosity, serious pole climbing phenomenon, poor spinning continuity and poor raw liquid uniformity in the direct heating swelling dissolution process is caused because the integral polymer is not fully contacted with the solvent, and the heating causes non-uniform rates of raw liquid swelling and dissolution, thereby causing non-uniform raw liquid dissolution, discontinuous spinning due to high viscosity and easy gel generation.
Based on the above, the embodiment of the method for improving the dissolution performance of the dry-method high molecular weight polyacrylonitrile spinning solution according to the present invention is shown, and by the above description, related workers can completely make various changes and modifications without departing from the scope of the technical idea of the present invention. The technical scope of the present invention is not limited to the description, but must be determined according to the scope of claims.
Claims (8)
1. A method for improving the dissolution performance of a dry-method high molecular weight polyacrylonitrile spinning solution, which is characterized in that the dissolution step comprises the following steps:
1) Uniformly dispersing polyacrylonitrile powder in a dimethylacetamide solvent to prepare a polyacrylonitrile solution, wherein the viscosity average molecular weight of the polyacrylonitrile powder is 6-10 ten thousand, and the solid content of the obtained polyacrylonitrile solution is 26-30%;
2) Swelling the polyacrylonitrile solution for 1-6 hours at room temperature under the stirring condition, wherein the stirring rotating speed is 80-240 r/min;
3) Heating to 60-80 ℃, and continuing to carry out thermal swelling for 1-4 hours, wherein the stirring rotation speed is 150-300 r/min;
4) Heating to 85-105 ℃ to dissolve for 4-8 hours, and controlling the stirring rotation speed to 150-300 r/min.
2. The method for improving the dissolution property of a dry-process high molecular weight polyacrylonitrile spinning solution according to claim 1, wherein the method comprises the following steps: the water content of the polyacrylonitrile powder in the step 1) is lower than 0.5%.
3. The method for improving the dissolution property of a dry-process high molecular weight polyacrylonitrile spinning solution according to claim 1, wherein the method comprises the following steps: the viscosity average molecular weight of the polyacrylonitrile powder in the step 1) is 6.3-8.0 ten thousand, and the solid content of the obtained polyacrylonitrile solution is controlled to be 26-28%.
4. The method for improving the dissolution property of a dry-process high molecular weight polyacrylonitrile spinning solution according to claim 1, wherein the method comprises the following steps: the swelling time at room temperature in the step 2) is 3-5 h; the stirring speed is 100 r/min-140 r/min.
5. The method for improving the dissolution property of a dry-process high molecular weight polyacrylonitrile spinning solution according to claim 1, wherein the method comprises the following steps: the swelling temperature of the thermal swelling in step 3) is 60 ℃, 70 ℃ or 80 ℃; the swelling time is 1h when the swelling temperature is 60 ℃; swelling time is 2h at the swelling temperature of 70 ℃; the swelling time is 1-2 h at the swelling temperature of 80 ℃.
6. The method for improving the dissolution property of a dry-process high molecular weight polyacrylonitrile spinning solution according to claim 1, wherein the method comprises the following steps: the temperature during dissolution in the step 4) is 90-95 ℃; the dissolution time is 5-7 h.
7. The method for improving the dissolution property of a dry-process high molecular weight polyacrylonitrile spinning solution according to claim 1, wherein the method comprises the following steps: the stirring rotating speed is 170 r/min-230 r/min during the thermal swelling in the step 3); the stirring rotating speed is 170 r/min-230 r/min during the dissolution in the step 4).
8. The method for improving the dissolution property of a dry-process high molecular weight polyacrylonitrile spinning solution according to claim 1, wherein the method comprises the following steps: and controlling the temperature rising rate in the step 3) and the step 4) to be 4.5 ℃/30 min-5.5 ℃/30min.
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Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE10101627A1 (en) * | 2001-01-16 | 2002-08-01 | Cramer Weberei C | Textile fiber material with permanent phobing effect |
| JP2009221647A (en) * | 2008-02-22 | 2009-10-01 | Toray Ind Inc | Method for producing carbon fiber precursor fiber and carbon fiber |
| KR20120111473A (en) * | 2011-03-31 | 2012-10-10 | 코오롱인더스트리 주식회사 | Precursor fiber for carbon fiber and manufacturing method of it |
| US20150247025A1 (en) * | 2012-10-18 | 2015-09-03 | Toray Industries, Inc. | Carbon fiber-reinforced resin composition, method for manufacturing carbon fiber-reinforced resin composition, molding material, method for manufacturing molding material, and carbon fiber-reinforced resin molded article |
| US20160326672A1 (en) * | 2014-01-08 | 2016-11-10 | The University Of Tokyo | Pan-based carbon fiber and production method therefor |
| CN106917152A (en) * | 2017-02-26 | 2017-07-04 | 浙江峰赫纺织有限公司 | A kind of high water absorption acrylic fiber and preparation method thereof |
| CN117766742A (en) * | 2024-02-20 | 2024-03-26 | 华北电力大学 | Porous silicon-carbon composite material, preparation method thereof and application thereof in secondary battery |
| CN118272968A (en) * | 2024-05-17 | 2024-07-02 | 长盛(廊坊)科技有限公司 | Preparation method of ultra-high performance carbon fiber |
-
2024
- 2024-07-02 CN CN202410876831.9A patent/CN118407142B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE10101627A1 (en) * | 2001-01-16 | 2002-08-01 | Cramer Weberei C | Textile fiber material with permanent phobing effect |
| JP2009221647A (en) * | 2008-02-22 | 2009-10-01 | Toray Ind Inc | Method for producing carbon fiber precursor fiber and carbon fiber |
| KR20120111473A (en) * | 2011-03-31 | 2012-10-10 | 코오롱인더스트리 주식회사 | Precursor fiber for carbon fiber and manufacturing method of it |
| US20150247025A1 (en) * | 2012-10-18 | 2015-09-03 | Toray Industries, Inc. | Carbon fiber-reinforced resin composition, method for manufacturing carbon fiber-reinforced resin composition, molding material, method for manufacturing molding material, and carbon fiber-reinforced resin molded article |
| US20160326672A1 (en) * | 2014-01-08 | 2016-11-10 | The University Of Tokyo | Pan-based carbon fiber and production method therefor |
| CN106917152A (en) * | 2017-02-26 | 2017-07-04 | 浙江峰赫纺织有限公司 | A kind of high water absorption acrylic fiber and preparation method thereof |
| CN117766742A (en) * | 2024-02-20 | 2024-03-26 | 华北电力大学 | Porous silicon-carbon composite material, preparation method thereof and application thereof in secondary battery |
| CN118272968A (en) * | 2024-05-17 | 2024-07-02 | 长盛(廊坊)科技有限公司 | Preparation method of ultra-high performance carbon fiber |
Non-Patent Citations (1)
| Title |
|---|
| 陶煜;: "DMAC替代DMF溶剂在腈纶干法纺丝中的应用", 合成纤维工业, no. 05, 15 October 2016 (2016-10-15) * |
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