CN104404644A - Method for preparing spinning pulp through dissolution of PPTA resin with solid foamed sulfuric acid - Google Patents
Method for preparing spinning pulp through dissolution of PPTA resin with solid foamed sulfuric acid Download PDFInfo
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- CN104404644A CN104404644A CN201410667832.9A CN201410667832A CN104404644A CN 104404644 A CN104404644 A CN 104404644A CN 201410667832 A CN201410667832 A CN 201410667832A CN 104404644 A CN104404644 A CN 104404644A
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- sulfuric acid
- ppta
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Abstract
The invention relates to a method for preparing spinning pulp through dissolution of PPTA resin with solid foamed sulfuric acid. The method comprises steps as follows: the solid foamed sulfuric acid is cooled to the temperature of subzero 10 DEG C-0 DEG C, crushed and then mixed with the dried PPTA resin, dissolution and pre-defoaming are performed, and a pre-defoamed PPTA resin/sulfuric acid liquid crystal solution is obtained; the pre-defoamed PPTA resin/sulfuric acid liquid crystal solution is sheared and kneaded, and the spinning pulp is obtained. The method is good in mixing effect and short in dissolution time, the dissolution speed of the resin is increased, and the uniformity of the liquid crystal pulp is improved.
Description
Technical field
The invention belongs to the preparation field of PPTA spinning solution, particularly a kind of by the method for solid-state foaming sulfuric acid dissolution PPTA resin-made for spinning pulp.
Background technology
PPTA (PPTA) fiber is a kind of high-performance fiber being widely used in every field.It is obtained by dry-jet wet-spinning by the liquid crystal solution of PPTA resin/concentrated sulfuric acid.One of the key point and difficult point of PPTA fiber fabrication process are the preparations of PPTA resin/sulfuric acid fiber spinning from crystalline state slurries.Traditional slurries preparation method be by PPTA resin drop into preheating the concentrated sulfuric acid in rapidly stir, heating for dissolving.But because the acidity of sulfuric acid is very strong, resin contacts with it rear surface and dissolves rapidly, generates heat, thus occurs serious clustering phenomena, cause the resin be coated in agglomerate to be difficult to absorption sulfuric acid, thus mix further and dissolve.In recent years, there are some researchs with preparing PPTA spinning slurry with solid sulphuric acid and patent, mainly comprise: granular solid sulphuric acid fully mixes with dry PPTA resin by (1).(2) mixture intensification will be obtained mediate, shear, form liquid crystal slurries.The mode of solid-solid blend is conducive to the harm reducing resin conglomeration, improves the uniformity of slurries.But because resinous powder particles is less, proportion is less than sulfuric acid particle, the mixture form therefore formed is that sulfuric acid particle surface has adsorbed a lot of resin particles, is equivalent to sulfuric acid and is dispersed in resin, still there will be clustering phenomena to a certain degree.
Summary of the invention
Technical problem to be solved by this invention is to provide the method for a kind of solid-state foaming sulfuric acid dissolution PPTA resin-made for spinning pulp, and the inventive method good mixing effect, dissolution time is short, improves the dissolution velocity of resin and the uniformity of liquid crystal slurries.
Of the present invention a kind of by solid-state foaming sulfuric acid dissolution PPTA resin-made for the method for spinning pulp, comprising:
(1) be that the concentrated sulfuric acid of 99.8-100.2% is cooled to 8-10 DEG C by concentration, under the condition that sulfuric acid keeps liquid, foaming, cooling obtains solid-state foaming sulfuric acid; Wherein foam as using SO
3with N
2mist foam;
(2) above-mentioned solid-state foaming sulfuric acid is cooled to-10 DEG C ~ 0 DEG C, pulverizes, then with dry PPTA PPTA mixed with resin, vacuumize, dissolve, obtain the PPTA resin/sulfuric acid liquid crystal solution of deaeration;
(3) PPTA of above-mentioned pre-deaeration resin/sulfuric acid liquid crystal solution is carried out shearing, mediating, obtain spinning pulp.
In described step (1), the pressure of mist is 0.5 ~ 5Mpa; SO in mist
3and N
2the ratio of volume be 1:3 ~ 1:20.
In described step (2), the logarithmic specific concentration viscosity of PPTA resin is 4.0-8.0dl/g.
In described step (2), solution temperature is 60 ~ 85 DEG C, and dissolution time is 0.5-1h.
Be mixed in described step (2) and mix in agitator.
Shearing in described step (3), kneading, deaeration are carried out in twin-screw or multiaxis kneader, and the time is 3 ~ 30min.In described step (3), the mass percentage concentration of spinning pulp is 18 ~ 23%.
The solid-state foaming concentrated sulfuric acid preparation method of step (1) is: by concentration be 99.8 ~ 100.2% sulfuric acid add in the foam device with chuck, in foam maker chuck, pass into freezing liquid, make sulfuric acid keep liquid condition, temperature remains on 10 DEG C.In sulfuric acid, inject the gaseous mixture of SO3 and N2 of 0.5 ~ 5Mpa, sulfuric acid is foamed and lowers the temperature in foaming process to condense into solid, wherein SO in gaseous mixture
3and N
2the ratio of volume be 1/3 ~ 1/20.
The present invention's volume ratio is 1/3 ~ 1/20, and pressure is the SO of 0.5 ~ 5Mpa
3and N
2mist as the foamed gas of sulfuric acid, N
2existence can reduce the oxidative degradation of resin, SO
3the moisture entered in course of dissolution can be absorbed and become sulfuric acid, the dissolving of resin can not be affected.
First the present invention carries out foamed solidification to sulfuric acid, greatly reduces the proportion of sulfuric acid, and blowing agent is SO simultaneously
3, utilize SO
3adsorbable a small amount of moisture content becomes sulfuric acid, thus the concentration of the concentrated sulfuric acid can be relaxed, also can suitably be relaxed PPTA moisture content, again solid-state sulfuric acid is pulverized, mix with resin, the mixture form then formed is that sulfuric acid particle surface adsorbs many tiny sulfuric acid particles, is equivalent to resin dispersion in sulfuric acid.The inventive method good mixing effect, alleviates the degraded of resin, shortens dissolution time, substantially increases the uniformity of solution.
Method of the present invention adopts the solid-state foaming sulfuric acid pulverized to be raw material, and relative to the direct freezing sulfuric acid particle obtained, proportion is less, larger with resin contact area, clustering phenomena when avoiding dissolving resin to dissolve better.The inventive method not only increases the dissolution velocity of resin and the uniformity of spinning slurry, and the less to a great extent degraded of resin.
beneficial effect
(1) method of the present invention adopts the solid-state foaming sulfuric acid pulverized to be raw material, and relative to the direct freezing sulfuric acid particle obtained, proportion is less, larger with resin contact area, clustering phenomena when avoiding dissolving resin to dissolve better;
(2) the inventive method not only increases the dissolution velocity of resin and the uniformity of spinning slurry, and decreases the degraded of resin to a great extent.
Detailed description of the invention
Below in conjunction with specific embodiment, set forth the present invention further.Should be understood that these embodiments are only not used in for illustration of the present invention to limit the scope of the invention.In addition should be understood that those skilled in the art can make various changes or modifications the present invention, and these equivalent form of values fall within the application's appended claims limited range equally after the content of having read the present invention's instruction.
Embodiment 1
(1) liquid sulfuric acid being 99.8% by 180 kilograms of concentration adds in foam maker and is cooled to 10 DEG C, keeps sulfuric acid to become liquid condition.The SO of 1Mpa is passed into rapidly in freezing liquid sulfuric acid
3and N
2gaseous mixture, SO in gaseous mixture
3and N
2the ratio of volume be 1/5.Freezing liquid sulfuric acid expands in the impact lower volume of gas, and due to the disturbance of external force, the sulfuric acid close to freezing point is further cooled and quick solidification, forms the solid-state sulfuric acid of foaming.
(2) reduce temperature further to-10 DEG C, the solid-state sulfuric acid of foaming is ground into tiny particle further.
(3) by solid-state for the foaming of pulverizing sulfuric acid and 45 kilograms of logarithmic viscosity numbers be 7.0 PPTA powdery resin drop in multiaxis planetary stirrer and fully mix.
(4) keep agitator running, and vacuumize, mixture is warming up to 85 DEG C simultaneously and dissolves, after 1h, obtain the liquid crystal solution of PPTA/ sulfuric acid.
(5) liquid crystal solution obtained is pumped in multiaxis kneader shear further, mediate, obtain uniform and stable after 0.5h and completed the PPTA/ sulfuric acid spin slurries of deaeration.
(6) from PPTA powder contact to the liquid concentrated sulfuric acid to obtained can the slurries overall process 1.5h consuming time of spinning, in slurries, the logarithmic viscosity number of PPTA is 6.7.
Embodiment 2
(1) liquid sulfuric acid being 100.2% by 195 kilograms of concentration adds in foam maker and is cooled to 10 DEG C, keeps sulfuric acid to become liquid condition.The SO of 5Mpa is passed into rapidly in freezing liquid sulfuric acid
3and N
2gaseous mixture, SO in gaseous mixture
3and N
2the ratio of volume be 1/20.Freezing liquid sulfuric acid expands in the impact lower volume of gas, and due to the disturbance of external force, the sulfuric acid close to freezing point is further cooled and quick solidification, forms the solid-state sulfuric acid of foaming.
(2) reduce temperature to 0 DEG C further, the solid-state sulfuric acid of foaming is ground into tiny particle further.
(3) by solid-state for the foaming of pulverizing sulfuric acid and 45 kilograms of logarithmic viscosity numbers be 4.0 PPTA powdery resin drop in multiaxis planetary stirrer and fully mix.
(4) keep agitator running, vacuumize and progressively mixture is warming up to 60 DEG C and dissolve, after 0.8h, obtain the liquid crystal solution of PPTA/ sulfuric acid.
(5) liquid crystal solution obtained is pumped in twin-screw shear further, mediate, after 0.5h, obtain uniform and stable PPTA/ sulfuric acid spin slurries.
(6) from PPTA powder contact to the liquid concentrated sulfuric acid to obtained can the slurries overall process of spinning be consuming time is less than 1.5h, in slurries, the logarithmic viscosity number of PPTA is 3.8.
Reference examples 1
(1) it is fully mix in the dry PPTA powdery resin input multiaxis planetary stirrer of 7.0 that the liquid sulfuric acid being 100.8% to 180 kilograms of concentration adds 45 kilograms of logarithmic viscosity numbers.Mixture is progressively warming up to 85 DEG C to dissolve simultaneously, after 4h, obtains the liquid crystal solution of PPTA/ sulfuric acid.
(2) solution obtained is carried out vacuum defoamation to continue to shear, mediate 3h simultaneously, obtain the uniform and stable PPTA/ sulfuric acid spin slurries also having completed deaeration.
(3) from PPTA powder contact to the liquid concentrated sulfuric acid to obtained can the slurries overall process 7h consuming time of spinning, in PPTA slurries processed, the logarithmic viscosity number of PPTA is 5.7.
Reference examples 2
(1) liquid sulfuric acid being 100.2% by 195 kilograms of concentration is cooled to 0 DEG C, and the concentrated sulfuric acid is solidified, and solid-state sulfate powder is broken into particle.
(2) by the solid-state sulfuric acid pulverized and 45 kilograms of logarithmic viscosity numbers be 4.0 dry PPTA powdery resin drop in multiaxis planetary stirrer and fully mix.
(4) keep agitator running, vacuumize and progressively mixture is warming up to 60 DEG C and dissolve, after 1.5h, obtain the liquid crystal solution of PPTA/ sulfuric acid.
(5) liquid crystal solution obtained is pumped in twin-screw shear further, mediate, after 0.5h, obtain uniform and stable PPTA/ sulfuric acid spin slurries.
(6) from PPTA powder contact to the liquid concentrated sulfuric acid to obtained can the slurries overall process 2h consuming time of spinning, be greater than this patent and implement 2 such as spent times more than 1/3, in slurries, the logarithmic viscosity number of PPTA is 3.7.
Claims (7)
1. by solid-state foaming sulfuric acid dissolution PPTA resin-made for a method for spinning pulp, comprising:
(1) be that the concentrated sulfuric acid of 99.8-100.2% is cooled to 8-10 DEG C by concentration, under the condition that sulfuric acid keeps liquid, foaming, cooling obtains solid-state foaming sulfuric acid; Wherein foam as using SO
3with N
2mist foam;
(2) above-mentioned solid-state foaming sulfuric acid is cooled to-10 DEG C ~ 0 DEG C, pulverizes, then with dry PPTA PPTA mixed with resin, vacuumize, dissolve, obtain the PPTA resin/sulfuric acid liquid crystal solution of deaeration;
(3) the PPTA resin/sulfuric acid liquid crystal solution of above-mentioned deaeration is carried out shearing, mediating, obtain spinning pulp.
2. according to claim 1 a kind of by solid-state foaming sulfuric acid dissolution PPTA resin-made for the method for spinning pulp, it is characterized in that: the pressure of mist is 0.5 ~ 5Mpa in described step (1); SO in mist
3and N
2the ratio of volume be 1:3 ~ 1:20.
3. according to claim 1 a kind of by solid-state foaming sulfuric acid dissolution PPTA resin-made for the method for spinning pulp, it is characterized in that: the logarithmic specific concentration viscosity of PPTA resin is 4.0-8.0dl/g in described step (2).
4. according to claim 1 a kind of by solid-state foaming sulfuric acid dissolution PPTA resin-made for the method for spinning pulp, it is characterized in that: solution temperature is 60 ~ 85 DEG C in described step (2), and dissolution time is 0.5-1h.
5. according to claim 1 a kind of by the method for solid-state foaming sulfuric acid dissolution PPTA resin-made for spinning pulp, it is characterized in that: shearing in described step (3), kneading, deaeration are carried out in extruder or multiaxis kneader, and the time is 3 ~ 30min.
6. according to claim 6 a kind of by solid-state foaming sulfuric acid dissolution PPTA resin-made for the method for spinning pulp, it is characterized in that: described extruder is double screw extruder.
7. according to claim 1 a kind of by solid-state foaming sulfuric acid dissolution PPTA resin-made for the method for spinning pulp, it is characterized in that: the mass percentage concentration of spinning pulp is 18 ~ 23% in described step (3).
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410667832.9A CN104404644B (en) | 2014-11-20 | 2014-11-20 | Method for preparing spinning pulp through dissolution of PPTA resin with solid foamed sulfuric acid |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410667832.9A CN104404644B (en) | 2014-11-20 | 2014-11-20 | Method for preparing spinning pulp through dissolution of PPTA resin with solid foamed sulfuric acid |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104404644A true CN104404644A (en) | 2015-03-11 |
| CN104404644B CN104404644B (en) | 2017-02-22 |
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1546757A (en) * | 2003-12-10 | 2004-11-17 | 中国石化仪征化纤股份有限公司 | Manufacturing method of poly p phenylene diamine terephthalamide fiber |
| CN1752300A (en) * | 2005-11-02 | 2006-03-29 | 东华大学 | High shearing rate method for spinning poly-terephthaloyl p-phenylenediamine fibre |
| WO2008095632A1 (en) * | 2007-02-03 | 2008-08-14 | Teijin Aramid B.V. | Method for dissolving aramid polymer in sulfuric acid using a double shaft kneader |
| CN101555631A (en) * | 2008-04-10 | 2009-10-14 | 中国神马集团有限责任公司 | Industrial method for preparing PPTA spinning slurry with solid sulphuric acid |
| CN101724935A (en) * | 2009-12-14 | 2010-06-09 | 中蓝晨光化工研究院有限公司 | Polyphenylene terephthalamide fibre and preparation method thereof |
| CN102154727A (en) * | 2011-05-23 | 2011-08-17 | 蓝星（成都）新材料有限公司 | High-intensity poly(terephthaloyl-p-phenylene diamine) (PPTA) fiber and preparation method thereof |
-
2014
- 2014-11-20 CN CN201410667832.9A patent/CN104404644B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1546757A (en) * | 2003-12-10 | 2004-11-17 | 中国石化仪征化纤股份有限公司 | Manufacturing method of poly p phenylene diamine terephthalamide fiber |
| CN1752300A (en) * | 2005-11-02 | 2006-03-29 | 东华大学 | High shearing rate method for spinning poly-terephthaloyl p-phenylenediamine fibre |
| WO2008095632A1 (en) * | 2007-02-03 | 2008-08-14 | Teijin Aramid B.V. | Method for dissolving aramid polymer in sulfuric acid using a double shaft kneader |
| CN101555631A (en) * | 2008-04-10 | 2009-10-14 | 中国神马集团有限责任公司 | Industrial method for preparing PPTA spinning slurry with solid sulphuric acid |
| CN101724935A (en) * | 2009-12-14 | 2010-06-09 | 中蓝晨光化工研究院有限公司 | Polyphenylene terephthalamide fibre and preparation method thereof |
| CN102154727A (en) * | 2011-05-23 | 2011-08-17 | 蓝星（成都）新材料有限公司 | High-intensity poly(terephthaloyl-p-phenylene diamine) (PPTA) fiber and preparation method thereof |
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|---|---|
| CN104404644B (en) | 2017-02-22 |
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