CN101736411A - Method for preparing polyacrylonitrile spinning solution for carbon fiber - Google Patents
Method for preparing polyacrylonitrile spinning solution for carbon fiber Download PDFInfo
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- CN101736411A CN101736411A CN200810227312A CN200810227312A CN101736411A CN 101736411 A CN101736411 A CN 101736411A CN 200810227312 A CN200810227312 A CN 200810227312A CN 200810227312 A CN200810227312 A CN 200810227312A CN 101736411 A CN101736411 A CN 101736411A
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- polyacrylonitrile
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- spinning solution
- carbon fiber
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Abstract
The invention relates to a method for preparing spinning solution, in particular to a method for preparing polyacrylonitrile spinning solution for carbon fiber. The method prepares the polyacrylonitrile spinning solution for carbon fiber by a two-step method. When polyacrylonitrile is dissolved, dilute solubilizer low in boiling point is added to a conventional dissolution system so as to help the dispersion and dissolution of polymers, and homogeneous polyacrylonitrile solution with low viscosity can be obtained. The low-viscosity polyacrylonitrile solution can be easily conveyed and filtered. After the low-viscosity polyacrylonitrile solution is filtered and then subjected to devolatilization under reduced pressure, as the added dilute solubilizer can be removed from the solution due to low boiling point, the solid content of the solution is improved, and the volatilization of the low-boiling-point dilute solubilizer also helps to remove bubbles in the solution. The homogeneous polyacrylonitrile spinning solution with high concentration can be finally obtained.
Description
Technical field
The present invention relates to a kind of preparation method of spinning dope, relate in particular to a kind of preparation method of polyacrylonitrile spinning solution for carbon fiber.
Technical background
Carbon fiber and composite thereof are a kind of important structure materials of high technology content, have series of advantages such as high specific strength, high ratio modulus, light weight, high temperature resistant, corrosion-resistant, endurance and thermal coefficient of expansion be little, be widely used in fields such as space flight and aviation, strategic arms, automobile, traffic, the energy, building and sports goods.Along with the continuous development of Chinese national economy and war industry, growing to the demand of carbon fiber, the quality requirement to carbon fiber also improves constantly simultaneously.As everyone knows, polyacrylonitrile fibril is the basis of preparation high-performance carbon fibre, the final performance of carbon fiber depends on the quality of precursor to a great extent, if there are defective in various degree in the molecular structure of polyacrylonitrile fibril and aggregated structure, will develop and entails carbon fiber.
Prepare high-quality precursor and depend on technology of preparing.In preparation process, the selection of comonomer, polymer molecular weight and distribution, spinning process, coagulation forming condition, fiber densification degree, stretching ratio, oiling process etc. all are influence factors.In order to improve former yarn quality, a lot of scholars' research emphasis is the modification of precursor or lays particular emphasis on process route and copolymer composition aspect.But China's precursor is of low quality more is because some basic problems known and that must solve are also unresolved.Polymer concentration is wherein more crucial in the raising spinning solution.
Generally speaking, improve the polymer concentration of spinning solution, the physical and mechanical properties of fiber all can be improved.
During wet spinning, because solvent and the double diffusion of coagulating agent and being separated of spinning solution take place in becoming fine process, the structure of as-spun fibre is the gel network of being separated, being run through mutually by hole.Along with the concentration of polyacrylonitrile spinning solution, the increase of solid content, double diffusion becomes evenly slowly, the fiber that forms solidifies that epidermal area is soft, yielding, good penetrability, cortex also shrinks thereupon when the fibrous inside sandwich layer shrinks owing to desolventizing and solidifying, thereby avoided the formation of macroscopic-void, so porosity reduces gradually, density increases.Finally can make the as-spun fibre cross section trend towards circle, external and internal compositions becomes evenly, and intensity increases, and elongation at break raises.Therefore, the spinning solution of preparation high concentration helps obtaining the high polyacrylonitrile fibril of quality.
And problem is, when using two step method to prepare polyacrylonitrile spinning solution, if obtain the high concentration spinning solution, need to add more polymer powder, this can make and the difficulty that polyacrylonitrile dissolving becomes be easy to occur the uneven phenomenon of dissolving, the reunion of luming easily of some polyacrylonitrile powders, therefore need dissolution time and stir speed (S.S.) more of a specified duration, make energy consumption increase; Polymer concentration greatly also can make polymer solution viscosity increase, and must improve the former liquid systems discharge pressure of polyacrylonitrile, along with the raising of pressure, can cause gel to pass filter cloth, enter spinnerets, cause spinneret orifice to stop up, make the spinning leakage, product quality and spinning production continuity are impacted; Along with the raising of filter pressure, it is frequent also to cause filter cloth to change.
Therefore, will guarantee the needs of spinning and press filteration system aborning, just have to reduce former fluid solid content, be generally 15wt%～20wt%, the fiber compactness that make this moment is low, can not improve the degree of orientation of fiber even stretch.
Summary of the invention
The purpose of this invention is to provide a kind of higher concentration that obtains, can solve simultaneously the preparation method of the polyacrylonitrile spinning solution for carbon fiber of dissolving that high concentration brings and filtration difficulty again.
The present invention adopts two step method to prepare polyacrylonitrile spinning solution for carbon fiber.When polyacrylonitrile dissolves, in traditional dissolution system, add a kind of lower boiling dilution solubilizer, its adding helps the dispersion and the dissolving of polymer, can make even low viscous polyacrylonitrile solution.Low viscous polyacrylonitrile solution just can be carried and filter easily.Low viscous polyacrylonitrile solution vacuumizes the decompression devolatilization after filtering again, because the dilution solubilizer boiling point that adds is low, just can remove from solution, and the solid content of solution is improved; The volatilization of lower boiling dilution solubilizer simultaneously also helps removing of bubble in the solution.Finally can obtain the polyacrylonitrile spinning solution of the high concentration of homogeneous.Use the spinning solution of high concentration, the polyacrylonitrile fibril quality that makes obviously improves.
The preparation method of polyacrylonitrile spinning solution for carbon fiber of the present invention may further comprise the steps:
(1) with the polypropylene dedicated nitrile polymer powder of carbon fiber, the organic solvent of traditional higher and lower boiling dilution solubilizer join in the dissolution kettle according to certain ratio;
Wherein, polyacrylonitrile polymer powder: organic solvent: the mass ratio of dilution solubilizer is 10～60: 35～85: 5～35;
(2) dissolution kettle of heating steps (1), in the stir speed (S.S.) of 10～100rpm, under 20 ℃～100 ℃ the temperature, dissolution time is 0.5～10 hour, and the polyacrylonitrile polymer powder is fully dissolved, and obtains low viscous polymer solution;
(3) the low viscous polymer solution that step (2) is obtained is transported to filter, filters the polyacrylonitrile polymer aggregate that removal of contamination and not have dissolves etc.;
(4) solution after will filtering, be transported to the devolatilization device, under 40 ℃～70 ℃, being evacuated to vacuum is 0.05～0.1MPa devolatilization, remove bubble and lower boiling dilution solubilizer in the solution, improve the solid content of solution, obtain spinning solution, the mass percent of polyacrylonitrile is 10.5%～63.2% in the final spinning solution.
The molecular weight of the described polyacrylonitrile polymer of step (1) is: 50,000～200,000.
The described conventional organic solvents of step (1) is: dimethyl formamide, dimethylacetylamide or dimethyl sulfoxide (DMSO) etc.
The described dilution solubilizer of step (1) is: acetate, oxolane, ethyl acetate, acetone, benzinum, acetonitrile, nitromethane or dioxane etc.
The described devolatilization device of step (4) is: twin-screw degassing extruder, thin film evaporator or disk devolatilizer etc.
The polyacrylonitrile spinning solution for carbon fiber that utilizes the present invention to prepare, homogeneity is good, and the concentration height can prepare high-quality polyacrylonitrile fibril.
The specific embodiment
Embodiment 1
With molecular weight is that 50,000 polyacrylonitrile powder, dimethyl sulfoxide (DMSO) and oxolane are mixed to join in the dissolution kettle and dissolve, wherein: the mass percent of polyacrylonitrile powder is 24%, the mass percent of dimethyl sulfoxide (DMSO) is 64%, and the mass percent of oxolane is 12%; Dissolution kettle agitator speed 20rpm, solution temperature is 60 ℃, dissolution time is 5h.With the polymer solution that obtains after filtration, be transported in the thin film evaporator, under 60 ℃, keeping vacuum is that 0.05～0.1MPa removes oxolane, and the mass percent that can make polyacrylonitrile in the spinning solution is 27.3% spinning solution.
Embodiment 2
With molecular weight is that 120,000 polyacrylonitrile powder, dimethyl formamide and ethyl acetate are mixed to join in the dissolution kettle and dissolve, wherein: the mass percent of polyacrylonitrile powder is 15%, the dimethyl formamide mass percent is 75%, and the ethyl acetate mass percent is 10%; Dissolution kettle agitator speed 30rpm, solution temperature is 50 ℃, dissolution time is 3h.With the polymer solution that obtains after filtration, be transported to the twin-screw degassing extruder, under 50 ℃, keeping vacuum is that 0.05～0.1MPa removes ethyl acetate, and the mass percent that can make polyacrylonitrile in the spinning solution is 16.7% spinning solution.
Embodiment 3
With molecular weight is that 100,000 polyacrylonitrile powder, dimethyl sulfoxide (DMSO) and acetone are mixed to join in the dissolution kettle and dissolve, and wherein: the mass percent of polyacrylonitrile powder is 27%, and the mass percent of dimethyl sulfoxide (DMSO) is 48%, and the mass percent of acetone is 25%; Dissolution kettle agitator speed 50rpm, solution temperature is 40 ℃, dissolution time is 5h.With the polymer solution that obtains after filtration, be transported to the twin-screw degassing extruder, under 40 ℃, keeping vacuum is that 0.05～0.1MPa removes acetone, and the mass percent that can make polyacrylonitrile in the spinning solution is 36% spinning solution.
Embodiment 4
With molecular weight is that 50,000 polyacrylonitrile powder, dimethyl formamide and benzinum are mixed to join in the dissolution kettle and dissolve, wherein: the mass percent of polyacrylonitrile powder is 20%, the mass percent of dimethyl formamide is 65%, and the mass percent of benzinum is 15%; Dissolution kettle agitator speed 60rpm, solution temperature is 55 ℃, dissolution time is 8h.With the polymer solution that obtains after filtration, be transported to the disk devolatilizer, under 55 ℃, keeping vacuum is that 0.05～0.1MPa removes benzinum, and the mass percent that can make polyacrylonitrile in the spinning solution is 23.5% spinning solution.
Embodiment 5
With molecular weight is that 80,000 polyacrylonitrile powder, dimethylacetylamide and acetate are mixed to join in the dissolution kettle and dissolve, wherein: the mass percent of polyacrylonitrile powder is 22%, the mass percent of dimethylacetylamide is 63%, and the mass percent of acetate is 15%; Dissolution kettle agitator speed 40rpm, solution temperature is 60 ℃, dissolution time is 8h.With the polymer solution that obtains after filtration, be transported in the thin film evaporator, under 60 ℃, keeping vacuum is that 0.05～0.1MPa removes acetate, and the mass percent that can make polyacrylonitrile in the spinning solution is 25.9% spinning solution.
Claims (4)
1. the preparation method of a polyacrylonitrile spinning solution for carbon fiber is characterized in that, this method may further comprise the steps:
(1) with the polypropylene dedicated nitrile polymer powder of carbon fiber, organic solvent and dilution solubilizer join in the dissolution kettle;
Wherein, polyacrylonitrile polymer powder: organic solvent: the mass ratio of dilution solubilizer is 10～60: 35～85: 5～35;
(2) dissolution kettle of heating steps (1), in the stir speed (S.S.) of 10～100rpm, under 20 ℃～100 ℃ the temperature, dissolution time is 0.5～10 hour, and the polyacrylonitrile polymer powder is fully dissolved, and obtains polymer solution;
(3) polymer solution that step (2) is obtained is transported to filter, filters;
(4) solution after will filtering is transported to the devolatilization device, and under 40 ℃～70 ℃, being evacuated to vacuum is 0.05～0.1MPa devolatilization, removes bubble and dilution solubilizer in the solution, and the mass percent that obtains polyacrylonitrile in the spinning solution is 10.5%～63.2%;
Described dilution solubilizer is: acetate, oxolane, ethyl acetate, acetone, benzinum, acetonitrile, nitromethane or dioxane.
2. method according to claim 1 is characterized in that: the molecular weight of described polyacrylonitrile polymer is: 50,000～200,000.
3. method according to claim 1 is characterized in that: described organic solvent is: dimethyl formamide, dimethylacetylamide or dimethyl sulfoxide (DMSO).
4. method according to claim 1 is characterized in that: described devolatilization device is: twin-screw degassing extruder, thin film evaporator or disk devolatilizer.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103233298A (en) * | 2013-05-09 | 2013-08-07 | 上海大学 | Preparation method for high-carbon-content carbon fiber |
| CN103469316A (en) * | 2013-09-11 | 2013-12-25 | 中石化上海工程有限公司 | Defoaming method for PAN (Polyacrylonitrile) carbon fiber stock solution preparation |
| CN103668523A (en) * | 2012-09-19 | 2014-03-26 | 中国石油化工股份有限公司 | Production method of dry-process acrylic fiber |
| CN104562226A (en) * | 2013-10-28 | 2015-04-29 | 中国石油化工股份有限公司 | Defoaming method for preparing polyacrylonitrile stock solution |
| CN105225724A (en) * | 2014-06-30 | 2016-01-06 | 乐金显示有限公司 | Organic insulating material and comprise its flexible display |
| CN110699762A (en) * | 2019-11-20 | 2020-01-17 | 长春工业大学 | Preparation method of polyacrylonitrile spinning solution and preparation method of polyacrylonitrile fibers |
| CN111518311A (en) * | 2019-02-03 | 2020-08-11 | 中国石油天然气股份有限公司 | Method for recovering waste silk of polyacrylonitrile-based carbon fiber precursor |
| CN112831859A (en) * | 2021-02-18 | 2021-05-25 | 山东仁丰特种材料股份有限公司 | Preparation method of polyacrylonitrile fiber |
-
2008
- 2008-11-26 CN CN200810227312A patent/CN101736411A/en active Pending
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103668523A (en) * | 2012-09-19 | 2014-03-26 | 中国石油化工股份有限公司 | Production method of dry-process acrylic fiber |
| CN103233298A (en) * | 2013-05-09 | 2013-08-07 | 上海大学 | Preparation method for high-carbon-content carbon fiber |
| CN103233298B (en) * | 2013-05-09 | 2015-07-01 | 上海大学 | Preparation method for high-carbon-content carbon fiber |
| CN103469316A (en) * | 2013-09-11 | 2013-12-25 | 中石化上海工程有限公司 | Defoaming method for PAN (Polyacrylonitrile) carbon fiber stock solution preparation |
| CN103469316B (en) * | 2013-09-11 | 2016-02-24 | 中石化上海工程有限公司 | Produce the defoaming method of polyacrylonitrile-radical PAN carbon fiber stoste |
| CN104562226A (en) * | 2013-10-28 | 2015-04-29 | 中国石油化工股份有限公司 | Defoaming method for preparing polyacrylonitrile stock solution |
| CN104562226B (en) * | 2013-10-28 | 2017-06-20 | 中国石油化工股份有限公司 | The defoaming method of polyacrylonitrile matrix |
| CN105225724A (en) * | 2014-06-30 | 2016-01-06 | 乐金显示有限公司 | Organic insulating material and comprise its flexible display |
| CN111518311A (en) * | 2019-02-03 | 2020-08-11 | 中国石油天然气股份有限公司 | Method for recovering waste silk of polyacrylonitrile-based carbon fiber precursor |
| CN110699762A (en) * | 2019-11-20 | 2020-01-17 | 长春工业大学 | Preparation method of polyacrylonitrile spinning solution and preparation method of polyacrylonitrile fibers |
| CN112831859A (en) * | 2021-02-18 | 2021-05-25 | 山东仁丰特种材料股份有限公司 | Preparation method of polyacrylonitrile fiber |
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Application publication date: 20100616 |