CN104562226A - Defoaming method for preparing polyacrylonitrile stock solution - Google Patents
Defoaming method for preparing polyacrylonitrile stock solution Download PDFInfo
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- CN104562226A CN104562226A CN201310512705.7A CN201310512705A CN104562226A CN 104562226 A CN104562226 A CN 104562226A CN 201310512705 A CN201310512705 A CN 201310512705A CN 104562226 A CN104562226 A CN 104562226A
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- polyacrylonitrile
- defoaming
- polyacrylonitrile matrix
- deaeration still
- defoaming method
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- 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
- D01D1/10—Filtering or de-aerating the spinning solution or melt
- D01D1/103—De-aerating
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Abstract
The invention relates to a defoaming method for preparing a polyacrylonitrile stock solution, and aims at solving the problems that a stock solution in the prior art is not uniform, and an upper layer easily generates gel, or is even dried and hardened. According to the technical scheme, the defoaming method for preparing the polyacrylonitrile stock solution comprises the following steps: (a) starting a heating device, heating a defoaming kettle, starting a vacuum pump, vacuumizing the defoaming kettle, slowly conveying the polyacrylonitrile stock solution to the defoaming kettle from a demonomerisation kettle while vacuumizing, closing the vacuum pump after the polyacrylonitrile stock solution completely enters the defoaming kettle, introducing gas to the defoaming kettle, pressurizing and defoaming; (b) after pressurizing and defoaming are finished, starting the vacuum pump, vacuumizing the defoaming kettle, defoaming in vacuum, so as to obtain the final polyacrylonitrile stock solution, and the problems are relatively well solved; the defoaming method can be applied to industrial production of a carbon fiber precursor.
Description
Technical field
The present invention relates to a kind of defoaming method preparing polyacrylonitrile matrix.
Background technology
Carbon fiber can obtain through carbonization with polyacrylonitrile fibre, pitch fibers, viscose or phenolic fibre respectively, and polyacrylonitrile (PAN) base carbon fibre purposes is wherein the widest, consumption is maximum, with the fastest developing speed, has overwhelming superiority in carbon fiber is produced.In PAN base carbon fiber protofilament preparation process, the same with other most of artificial fibres all to relate to spinning solution hollow bubble remove problem.
Solution can produce bubble in polymerization or course of conveying; On the other hand because polymerization adopts azo compound to be initator, the nitrogen produced during decomposition is also mixed in stoste and forms bubble.Polyacrylonitrile matrix ratio of viscosities for carbon fiber spinning is higher, and under normal pressure inactive state, these bubbles not easily remove.Because the aperture of spinning head only has 0.05 ~ 1mm, the bubble of diameter 0.03 ~ 0.04mm exists in a large number in stoste, and spinning can not normally be carried out.Bubble diameter is greater than spinneret orifice footpath can cause broken filament, and forms lousiness, brings difficulty to spinning; Bubble diameter is less than spinneret orifice footpath, and gas bubbles left is causing cavity filament in fiber, and make fiber produce cavity, when drawing-off, easy fracture forms lousiness, fracture of wire, finally affects the intensity of finished product precursor and carbon fiber.So, the bubble in stoste thoroughly must be deviate from before spinning.
The factor affecting deaeration is a lot, mainly contains temperature, vacuum, viscosity and film thickness etc., and most domestic producer adopts intermittence polymerization, so deaeration is also intermittent, mostly adopts the method deaeration heating up and reduce pressure.After temperature rising, liquid viscosity declines and is conducive to micro-molecular gas effusion, and decompression can cause liquid level and hydraulic pressure interpolation, and expanded, the diffusion that are conducive to Small molecular bubble are equally deviate from.Discontinuous degassing generally needs continuous defoaming 12 ~ 48 hours, and vacuum pressure is-0.08 ~-0.1MPa.The drawback of adopting in this way is that inclined heated plate is long, and also a lot of solvent can be spun off together from solution under high negative pressure thus cause the upper strata excessive concentration of stoste, whole still stoste performance heterogeneity, epidermis produces gel, and even epidermis is dry and hard and can not spin.
Should ensure the homogeneity of spinning solution in precursor production process, otherwise under identical spinning condition, the performance difference of obtained precursor and the final carbon filament obtained is comparatively large, and CV value raises, and is unfavorable for that the continuous stabilization of precursor and carbon fiber is produced as far as possible.The generation of gel should be avoided as far as possible or reduce in the production process of spinning solution simultaneously.Gel increases the difficulty in filtration of spinning solution on the one hand, and filter pressure is increased, and the filter cloth replacing frequency increases, and is unfavorable for continuous seepage; On the other hand, larger gel easily blocks spinneret orifice, produces filament and lousiness.Less gel, due to different from other stoste performances in strand, finally becomes the defect in strand, affects the final performance of strand.
In order to improve the deaeration effect of acrylonitrile spinning solution, the mode that many manufacturing enterprises adopt the structure of transformation deaeration still to make stoste obtain specific area increase carries out deaeration, as patent CN101856570 just provides a kind of de-single defoaming device of acrylonitrile stoste, the method improves de-list in continuous seepage and deaeration efficiency to a certain extent, but because this equipment is applicable in continuous seepage, the stoste viscosity that is suitable for also smaller, it is not clearly that this height of acrylonitrile spinning solution for carbon fiber glues system effect.
Summary of the invention
The technical problem to be solved in the present invention is high temperature in conventional art, high vacuum deaeration easily makes stoste heterogeneity, produces the problem that gel is even dry and hard, provides a kind of defoaming method preparing polyacrylonitrile matrix newly.This defoaming method adopts two step method, has obtained spinning solution homogeneity better, the advantage that gel is less.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of defoaming method preparing polyacrylonitrile matrix, comprises the following steps:
A () starts heater, heated up by deaeration still; Start vavuum pump, deaeration still is vacuumized, vacuumizes while polyacrylonitrile matrix autospasy list still is slowly transported to deaeration still; All enter after deaeration still until polyacrylonitrile matrix, close vavuum pump, in deaeration still, pass into gas, carry out pressure debubble;
B () pressure debubble completes after, start vavuum pump, deaeration still is vacuumized and carries out vacuum defoamation and obtain final polyacrylonitrile matrix.
In technique scheme: in described step (a), polyacrylonitrile accounts for the weight ratio of polyacrylonitrile matrix is 10 ~ 30%; The temperature of polyacrylonitrile matrix is 50-70 DEG C; The viscosity of polyacrylonitrile matrix is 10 ~ 200Pa.s; The temperature of deaeration still is 50 ~ 70 DEG C; When carrying stoste in deaeration still, the vacuum of deaeration still remains on absolute pressure 1000 ~ 10000Pa; The stoste time range joined in deaeration still is 10 ~ 120min; The gas added to deaeration still after stoste all puts into deaeration still is at least one of nitrogen, helium, neon, argon gas, Krypton or xenon, and gas purity is 97 ~ 99.999%; In described step (a), deaeration still keeps pressure to be 0.01 ~ 0.5MPa, and maintains 15 ~ 36 hours; In described step (b), deaeration still is evacuated to absolute pressure 1000 ~ 10000Pa, and keeps carrying out vacuum defoamation in 1 ~ 30 hour.
The present invention adopts first by deaeration still pressurize 0.01-0.5MPa, 15-36 hour, vacuumize again, and keep vacuum to be absolute pressure 1000 ~ 10000Pa, 1-30 hour, because pressurize 0.01-0.5MPa can reduce the volatilization of sulfoxide, reduce the loss of sulfoxide in the stoste of top layer, and then increase the homogeneity of stoste, reduce the generation of gel, prevent stoste surface from solidifying dry and hard, while pressurize 0.01-0.5MPa also can prevent air from entering deaeration still, and then with polyacrylonitrile generation oxidative decomposition; After pressurize completes, vacuumizing 1-30 hour can remove the bubble in stoste, obtains homogeneity higher, the polyacrylonitrile matrix that gel is less.
Adopt the solution of the present invention, the polyacrylonitrile spinning solution bubble obtained is less, and homogeneity is higher, and gel is less, and the precursor intensity of spinning is higher, and CV value is less, achieves good technique effect.
Below by embodiment, the present invention is further elaborated:
Detailed description of the invention
[embodiment 1]
A kind of defoaming method preparing polyacrylonitrile matrix, comprise the following steps: start heater, deaeration still temperature is risen to 55 DEG C, start vavuum pump, deaeration still vacuum is remained on absolute pressure 3000Pa, and weight ratio polyacrylonitrile being accounted for polyacrylonitrile matrix is 18%, and temperature is 60 DEG C, viscosity is that the polyacrylonitrile matrix autospasy list still of 60Pa.s is slowly transported to deaeration still, and time of delivery is 30min; All enter after deaeration still until polyacrylonitrile matrix, close vavuum pump, deaeration still passes into nitrogen pressurization to 0.2MPa, and keeps 28 hours.After pressurize completes, start vavuum pump, keep vacuum within 12 hours, to obtain final polyacrylonitrile spinning solution in absolute pressure 2000Pa vacuum defoamation.Above-mentioned stoste is delivered to filter by measuring pump, through spinnerets ejection after filtration, enters coagulating bath and solidifies, then successively by hot water drawing-off, wash, oil, compacting by drying, steam drafting, HEAT SETTING and receipts silk obtain polyacrylonitrile fibril.In spinning process, before filter, pressure is 0.72MPa; The precursor intensity spun out is 5.63CN/dtex, and the CV of intensity is 6.1%.
[embodiment 2]
A kind of defoaming method preparing polyacrylonitrile matrix, comprise the following steps: start heater, deaeration still temperature is risen to 65 DEG C, start vavuum pump, deaeration still vacuum is remained on absolute pressure 2000Pa, and weight ratio polyacrylonitrile being accounted for polyacrylonitrile matrix is 22%, and temperature is 60 DEG C, viscosity is that the polyacrylonitrile matrix autospasy list still of 100Pa.s is slowly transported to deaeration still, and time of delivery is 50min; All enter after deaeration still until polyacrylonitrile matrix, close vavuum pump, deaeration still passes into argon pressurization to 0.1MPa, and keeps 24 hours.After pressurize completes, start vavuum pump, keep vacuum within 18 hours, to obtain final polyacrylonitrile spinning solution in absolute pressure 3000Pa vacuum defoamation.Above-mentioned stoste is delivered to filter by measuring pump, through spinnerets ejection after filtration, enters coagulating bath and solidifies, then successively by hot water drawing-off, wash, oil, compacting by drying, steam drafting, HEAT SETTING and receipts silk obtain polyacrylonitrile fibril.In spinning process, before filter, pressure is 0.82MPa; The precursor intensity spun out is 5.89CN/dtex, and the CV of intensity is 6.4%.
[embodiment 3]
A kind of defoaming method preparing polyacrylonitrile matrix, comprise the following steps: start heater, deaeration still temperature is risen to 60 DEG C, start vavuum pump, deaeration still vacuum is remained on absolute pressure 2000Pa, and weight ratio polyacrylonitrile being accounted for polyacrylonitrile matrix is 22%, and temperature is 65 DEG C, viscosity is that the polyacrylonitrile matrix autospasy list still of 80Pa.s is slowly transported to deaeration still, and time of delivery is 20min; All enter after deaeration still until polyacrylonitrile matrix, close vavuum pump, deaeration still passes into nitrogen pressurization to 0.3MPa, and keeps 20 hours.After pressurize completes, start vavuum pump, keep vacuum within 18 hours, to obtain final polyacrylonitrile spinning solution in absolute pressure 2000Pa vacuum defoamation.Above-mentioned stoste is delivered to filter by measuring pump, through spinnerets ejection after filtration, enters coagulating bath and solidifies, then successively by hot water drawing-off, wash, oil, compacting by drying, steam drafting, HEAT SETTING and receipts silk obtain polyacrylonitrile fibril.In spinning process, before filter, pressure is 0.76MPa; The precursor intensity spun out is 5.75CN/dtex, and the CV of intensity is 6.3%.
[embodiment 4]
A kind of defoaming method preparing polyacrylonitrile matrix, comprise the following steps: start heater, deaeration still temperature is risen to 65 DEG C, start vavuum pump, deaeration still vacuum is remained on absolute pressure 4000Pa, and weight ratio polyacrylonitrile being accounted for polyacrylonitrile matrix is 25%, and temperature is 60 DEG C, viscosity is that the polyacrylonitrile matrix autospasy list still of 110Pa.s is slowly transported to deaeration still, and time of delivery is 60min; All enter after deaeration still until polyacrylonitrile matrix, close vavuum pump, deaeration still passes into argon pressurization to 0.4MPa, and keeps 22 hours.After pressurize completes, start vavuum pump, keep vacuum within 16 hours, to obtain final polyacrylonitrile spinning solution in absolute pressure 3000Pa vacuum defoamation.Above-mentioned stoste is delivered to filter by measuring pump, through spinnerets ejection after filtration, enters coagulating bath and solidifies, then successively by hot water drawing-off, wash, oil, compacting by drying, steam drafting, HEAT SETTING and receipts silk obtain polyacrylonitrile fibril.In spinning process, before filter, pressure is 0.89MPa; The precursor intensity spun out is 5.97CN/dtex, and the CV of intensity is 6.6%.
[embodiment 5]
A kind of defoaming method preparing polyacrylonitrile matrix, comprise the following steps: start heater, deaeration still temperature is risen to 70 DEG C, start vavuum pump, deaeration still vacuum is remained on absolute pressure 5000Pa, and weight ratio polyacrylonitrile being accounted for polyacrylonitrile matrix is 25%, and temperature is 55 DEG C, viscosity is that the polyacrylonitrile matrix autospasy list still of 130Pa.s is slowly transported to deaeration still, and time of delivery is 80min; All enter after deaeration still until polyacrylonitrile matrix, close vavuum pump, deaeration still passes into nitrogen pressurization to 0.2MPa, and keeps 24 hours.After pressurize completes, start vavuum pump, keep vacuum within 20 hours, to obtain final polyacrylonitrile spinning solution in absolute pressure 4000Pa vacuum defoamation.Above-mentioned stoste is delivered to filter by measuring pump, through spinnerets ejection after filtration, enters coagulating bath and solidifies, then successively by hot water drawing-off, wash, oil, compacting by drying, steam drafting, HEAT SETTING and receipts silk obtain polyacrylonitrile fibril.In spinning process, before filter, pressure is 0.95MPa; The precursor intensity spun out is 6.03CN/dtex, and the CV of intensity is 6.5%.
[comparative example 1]
Start heater, deaeration still temperature is risen to 60 DEG C, start vavuum pump, deaeration still vacuum is remained on absolute pressure 3000Pa, and be that the polyacrylonitrile matrix autospasy list still of 80Pa.s is slowly transported to deaeration still by viscosity, time of delivery is 30min; After stoste has been carried, keep vacuum 48 hours.Above-mentioned stoste is delivered to filter by measuring pump, through spinnerets ejection after filtration, enters coagulating bath and solidifies, then successively by hot water drawing-off, wash, oil, compacting by drying, steam drafting, HEAT SETTING and receipts silk obtain polyacrylonitrile fibril.In spinning process, before filter, pressure is 0.89MPa; The precursor intensity spun out is 5.33CN/dtex, and the CV of intensity is 9.3%.
Claims (10)
1. prepare a defoaming method for polyacrylonitrile matrix, comprise the following steps:
A () starts heater, heated up by deaeration still; Start vavuum pump, deaeration still is vacuumized, vacuumizes while polyacrylonitrile matrix autospasy list still is slowly transported to deaeration still; All enter after deaeration still until polyacrylonitrile matrix, close vavuum pump, in deaeration still, pass into gas, carry out pressure debubble;
B () pressure debubble completes after, start vavuum pump, deaeration still is vacuumized and carries out vacuum defoamation and obtain final polyacrylonitrile matrix.
2. the defoaming method preparing polyacrylonitrile matrix according to claim 1, is characterized in that in described step (a), and the weight ratio that polyacrylonitrile accounts for polyacrylonitrile matrix is 10 ~ 30%.
3. the defoaming method preparing polyacrylonitrile matrix according to claim 1, is characterized in that in described step (a), and the temperature of polyacrylonitrile matrix is 50-70 DEG C.
4. the defoaming method preparing polyacrylonitrile matrix according to claim 1, is characterized in that in described step (a), and the viscosity of polyacrylonitrile matrix is 10 ~ 200Pa.s.
5. the defoaming method preparing polyacrylonitrile matrix according to claim 1, is characterized in that the temperature of deaeration still is 50 ~ 70 DEG C.
6. the defoaming method preparing polyacrylonitrile matrix according to claim 1, when it is characterized in that carrying stoste in deaeration still, the vacuum of deaeration still remains on absolute pressure 1000 ~ 10000Pa.
7. the defoaming method preparing polyacrylonitrile matrix according to claim 1, is characterized in that the stoste time joined in deaeration still is 10 ~ 120min.
8. the defoaming method preparing polyacrylonitrile matrix according to claim 1, is characterized in that the gas added in deaeration still is at least one in nitrogen, helium, neon, argon gas, Krypton or xenon; Gas purity is 97 ~ 99.999%.
9. the defoaming method preparing polyacrylonitrile matrix according to claim 1, is characterized in that keeping pressure to be 0.01 ~ 0.5MPa deaeration still in described step (a), and maintains 15 ~ 36 hours.
10. the defoaming method preparing polyacrylonitrile matrix according to claim 1, is characterized in that in described step (b), deaeration still is evacuated to absolute pressure 1000 ~ 10000Pa, and keeps carrying out vacuum defoamation in 1 ~ 30 hour.
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|---|---|---|---|---|
| CN101260172A (en) * | 2007-03-07 | 2008-09-10 | 中国科学院化学研究所 | Method for preparing super-high molecular weight polyacrylonitrile-base carbon fiber spinning primary fluid |
| JP2009235662A (en) * | 2008-03-05 | 2009-10-15 | Toray Ind Inc | Method for producing carbon fiber precursor fiber |
| CN101725072A (en) * | 2009-12-21 | 2010-06-09 | 山东海龙股份有限公司 | Defoaming method for high-temperature sticky cellulose/ionic liquid solution |
| CN101736411A (en) * | 2008-11-26 | 2010-06-16 | 中国科学院化学研究所 | Method for preparing polyacrylonitrile spinning solution for carbon fiber |
| CN101856570A (en) * | 2010-06-03 | 2010-10-13 | 西安康本材料有限公司 | Dynamic demonomerization and defoaming method and device for carbon fiber spinning solution |
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- 2013-10-28 CN CN201310512705.7A patent/CN104562226B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101260172A (en) * | 2007-03-07 | 2008-09-10 | 中国科学院化学研究所 | Method for preparing super-high molecular weight polyacrylonitrile-base carbon fiber spinning primary fluid |
| JP2009235662A (en) * | 2008-03-05 | 2009-10-15 | Toray Ind Inc | Method for producing carbon fiber precursor fiber |
| CN101736411A (en) * | 2008-11-26 | 2010-06-16 | 中国科学院化学研究所 | Method for preparing polyacrylonitrile spinning solution for carbon fiber |
| CN101725072A (en) * | 2009-12-21 | 2010-06-09 | 山东海龙股份有限公司 | Defoaming method for high-temperature sticky cellulose/ionic liquid solution |
| CN101856570A (en) * | 2010-06-03 | 2010-10-13 | 西安康本材料有限公司 | Dynamic demonomerization and defoaming method and device for carbon fiber spinning solution |
Non-Patent Citations (1)
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