CN104975357A - Preparation method of poly (p-phenylene terephthamide) spinning solution - Google Patents
Preparation method of poly (p-phenylene terephthamide) spinning solution Download PDFInfo
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- CN104975357A CN104975357A CN201410134721.1A CN201410134721A CN104975357A CN 104975357 A CN104975357 A CN 104975357A CN 201410134721 A CN201410134721 A CN 201410134721A CN 104975357 A CN104975357 A CN 104975357A
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Abstract
The invention relates to a preparation method of a poly (p-phenylene terephthamide) spinning solution. The preparation method comprises the steps that vacuum drying and freezing treatment are conducted on poly (p-phenylene terephthamide), and treated poly (p-phenylene terephthamide) is obtained; concentrated sulfuric acid is cooled, solidified and smashed; the treated poly (p-phenylene terephthamide) and treated concentrated sulfuric acid are mixed at a low temperature to obtain a solid solution, a vacuum condition is created, and the solid solution is heated up and dissolved to form the spinning solution. According to the preparation method of the poly (p-phenylene terephthamide) spinning solution, two powdered substances are fully mixed, the mixing efficiency is high, and the dissolving time is greatly reduced; the vacuum condition is created before the dissolving process is conducted, bubbles are not produced in the solution, the deaeration process is omitted, and degradation of the polymer is greatly slowed down; the whole dissolving process is simple and easy to carry out, and the industrial production of high-quality poly (p-phenylene terephthamide) fibers is facilitated.
Description
Technical field
The invention belongs to the preparation field of spinning solution, particularly a kind of preparation method of PPTA.
Background technology
Fanglun 1414 is called as p-aramid fiber or Fanglun l414 (PPTA), there is high-strength, Gao Mo, resistance to organic dissolution, the excellent properties such as light weight, intensity is 5-6 times of high-quality steel, modulus is 2-3 times of steel and glass fibre, and density is only 1/5 of steel, therefore, spun fiber has the good reputation of " artificial steel wire ", be widely used in defence and military, the special dimension such as Protective armor and Aero-Space.
Owing to having wide application background, so technology has state, the such as U.S. and Japan carry out strict blockade to its technology, and non-owner state all can the production technology of heavy industrialization in research and development.
The preparation of p-aramid fiber spinning solution is the important step of heavy industrialization, Chinese patent CN102268743 provides a kind of p-aramid fiber spinning solution technology of preparing, specifically add cosolvent and dry PPTA resin mixed dissolution in double screw extruder in concentrated sulfuric acid, obtain the uniform solution of high-efficiency dissolution, its shortcoming is the introducing of cosolvent perchloric acid, in spun fiber, chlorinty increases, considerably beyond Europe to aramid fiber chlorinty standard.Chinese patent CN1256474 relates to the manufacture method of Fanglun 1414, wherein, provide the preparation of spinning solution, method is mixed with the sulfuric acid being greater than 99% concentration by PPTA, enter in double screw extruder and carry out dissolving and deaeration, this method preparing spinning solution, the water that fouled sulfuric acid is brought into, can make dissolving difficulty also can cause the degraded of PPTA.
At present, the preparation of p-aramid fiber spinning solution is all according to a certain percentage p-aramid fiber powder and liquid sulfuric acid are put into reactor to stir, mixed dissolution.This soliqueous dissolution mechanism, dissolution time own is very long, and in atmosphere, stirring can make solution produce a large amount of bubbles, and deaeration needs for a long time, causes depolymerization, also can cause the degraded of polymer simultaneously.Solid-liquid two-phase mixtures, solution also may produce uneven phenomenon.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of preparation method of PPTA spinning solution, good effect of the present invention adopts freezing solidification to solvent, and two kinds of pulverous materials are fully mixed, mixing efficiency is high, and dissolution time greatly reduces; Make solution not produce bubble prior to the vacuum of course of dissolution, eliminate bubble removal step, significantly slow down the degraded situation of polymer; Whole dissolution process is simple, is conducive to the suitability for industrialized production of high-quality Fanglun 1414.
The preparation method of a kind of PPTA spinning solution of the present invention, comprising:
(1) vacuumize, freezing processing PPTA, obtain the PPTA after processing;
(2) by concentrated sulfuric acid cooling curing, crystallization forms solid, pulverizes;
(3) by above-mentioned PPTA and concentrated sulfuric acid low-temperature mixed, obtain solid solution, then application of vacuum, remove intergranular gases used, rising temperature for dissolving forms spinning solution; Wherein in spinning solution, PPTA concentration is 10-30wt%.
In described step (1), vacuumize is 80-120 DEG C, and freezing processing temperature is-15 DEG C ~ 5 DEG C.
PPTA powder is bone dry in the continuous vacuum drying apparatus of 80-120 DEG C in temperature.
In described step (1), the average particle size of PPTA is less than 150 orders; PPTA moisture content after process is less than 100ppm.
In described step (2), the concentration of the concentrated sulfuric acid is more than or equal to 100%.
In described step (2), concentrated sulfuric acid cooling curing temperature is-15 DEG C ~ 5 DEG C, preferably-5 DEG C ~ 5 DEG C; Pulverize as being ground into fine powder, granularity is not more than 200 orders.
In described step (3), low-temperature mixed temperature is-15 DEG C ~ 5 DEG C, preferably-10 DEG C ~ 5 DEG C.
Described step (3) rising temperature for dissolving process is carried out under vacuum, and vacuum overbottom pressure is not more than 10mmHg.
Rising temperature for dissolving is for being warming up to 80-100 DEG C in described step (3), and heating rate is 1 DEG C/min-3 DEG C/min.
Described rising temperature for dissolving is to 20-40 DEG C and stop 0.1-1h, is then warmed up to 80-100 DEG C, and heating rate is 1 DEG C/min-3 DEG C/min, preferably 1 DEG C/min-2 DEG C/min.
In described step (3), rising temperature for dissolving is carried out in dissolver, and dissolver is dissolution kettle or screw rod dissolving machine.
Described screw rod dissolving machine is twin-screw dissolving machine, three screw rod dissolving machines or four screw rod dissolving machines, preferred twin-screw dissolving machine.
Described dissolver with positive empty pump, can the twin-screw dissolving machine of temperature control.
In described spinning solution, PPTA concentration is preferably 15-25wt%, most preferably 16-20wt%.
Described whole dissolving agent process carries out under vacuum, and the spinning solution of formation does not have bubble completely.
Adopt freezing solidification to the solvent concentrated sulfuric acid in the present invention, and fully mixed by two kinds of pulverous materials, mixing efficiency is high, dissolution time greatly reduces, make solution not produce bubble prior to the vacuum of course of dissolution, eliminate bubble removal step, significantly slow down the degraded situation of polymer.
beneficial effect
(1) the preparation PPTA spinning solution of the present invention's employing, in course of dissolution, moisture is lower than 100ppm, and time decreased, reduces the degraded of polymer;
(2) the first premixed of the material of the present invention's two kinds of solid powder, mixing efficiency is high, and mixing is fully; Dissolution time can be reduced, and it is uniform and stable to dissolve formation spinning solution;
(3) the present invention adopts the method starting under vacuum to dissolve, and solution does not produce bubble, and eliminate deaeration step, technological process is short, and operation is simple, and production cost is controlled effectively; And from be dissolved into spinning solution and make required time and significantly reduce, effectively control the degraded of polymer, for the intensity improving finished fiber leaves huge technology space, be applicable to the industrialized production of PPTA.
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
High-precision measuring electronic scale is adopted to take the 8g PPTA powder (reduced inherent viscosity is 6.2dL/g) of 140 mesh sieves, being placed on temperature is that in the continuous vacuum drying apparatus of 120 DEG C, bone dry, to moisture 55ppm, cools and is refrigerated to-15 DEG C, adopt same weighing technique, take the sulfuric acid that 72g concentration is 100.2%, the concentrated sulfuric acid taken is placed in the freezing environment of-15 DEG C, cooling curing, then fine powder is ground into, cross 200 mesh sieves, two kinds of powder are added the mixing carrying out 1h in one-level double screw extruder, then be transported to secondary with vavuum pump under the vacuum condition of 10mmHg in overbottom pressure by mixed powder, can dissolve in the double screw extruder of temperature control, dissolution conditions, temperature is from-15 DEG C to being warmed up to 40 DEG C and stopping 10 minutes, finally be warmed up to 81 DEG C, programming rate 2 DEG C/min, whole course of dissolution 60min, what form not bubbles evenly can the solution of spinning, solution concentration is 10wt%, after testing, in solution, the reduced inherent viscosity of PPTA is 5.9dL/g.
Embodiment 2
Adopt high-precision measuring electronics to take 140 object 20g PPTA powder (reduced inherent viscosity is 6.2dL/g), being placed on temperature is be dried to moisture 100ppm in the Minton dryer of 82 DEG C, cools and is refrigerated to 5 DEG C, adopt same weighing technique, take the sulfuric acid that 48g concentration is 100.2%, the concentrated sulfuric acid taken is placed on freezing solidification in the coagulation system of 5 DEG C, then fine powder is ground into, cross 200 mesh sieves, two kinds of powder are added the mixing carrying out 1.5h in mixing kettle, then be under the vacuum of 9mmHg, mixed powder is transported to vavuum pump in overbottom pressure, can dissolve in the double screw extruder of temperature control, dissolution conditions, temperature is progressively raised to 20 DEG C from 5 DEG C, stop 1 hour, finally be warming up to 100 DEG C, programming rate 1 DEG C/min, whole course of dissolution dissolves 155min, being formed uniformly can the solution of spinning, solution concentration is 29.4wt%, in solution, the reduced inherent viscosity of PPTA is 5.2dL/g.
Embodiment 3
Adopt high-precision measuring electronic scale to take and get 140 object 12.5g PPTA powder (reduced inherent viscosity is 6.2dL/g), being placed on temperature is that in the Minton dryer of 102 DEG C, bone dry, to moisture 60ppm, cools and is refrigerated to-2 DEG C, adopt same weighing technique, take the 57.5g concentrated sulfuric acid that concentration is 100.5%, the concentrated sulfuric acid taken is placed in the cryocoagulation device of-2 DEG C, cooling curing, then fine powder is ground into, cross 200 orders, two kinds of powder are added in mixing kettle and carries out 1h and fully mix, then be under the vacuum of 8mmHg, mixed powder is transported to vavuum pump in overbottom pressure, can dissolve in the stirred tank of temperature control, vacuum overbottom pressure is kept to be the condition of 8mmHg in dissolving, temperature is progressively raised to 30 DEG C from-2 DEG C, stop 30 minutes, finally progressively be warmed up to 82 DEG C of programming rates, 1 DEG C/min, whole dissolution time 115min, being formed uniformly can the solution of spinning, solution concentration is 17.9wt%, in solution, the reduced inherent viscosity of PPTA is 5.7dL/g.
Comparative example
Adopt high-precision measuring electronic scale to take and get 140 object 12.5g PPTA powder (reduced inherent viscosity is 6.2dL/g), take the 57.5g concentrated sulfuric acid that concentration is 100.5% again, pour powder in concentrated sulfuric acid stirring and dissolving at ambient pressure, temperature is progressively raised to 82 DEG C from room temperature, programming rate 1 DEG C/min, 180min is about to required time when all dissolving, then employing conventional vacuum defoaming device removes the bubble in solution, being formed uniformly can the solution of spinning, de-aeration takes about 180min, solution concentration is 17.9wt%, in solution, the reduced inherent viscosity of PPTA is 4.6dL/g.
Claims (10)
1. a preparation method for PPTA spinning solution, comprising:
(1) vacuumize, freezing processing PPTA, obtain the PPTA after processing;
(2) by concentrated sulfuric acid cooling curing, pulverize;
(3) by above-mentioned PPTA and concentrated sulfuric acid low-temperature mixed, obtain solid solution, then application of vacuum, rising temperature for dissolving forms spinning solution; Wherein in spinning solution, PPTA concentration is 10-30wt%.
2. the preparation method of a kind of PPTA spinning solution according to claim 1, is characterized in that: in described step (1), vacuumize temperature is 80-120 DEG C, and freezing processing temperature is-15 DEG C ~ 5 DEG C.
3. the preparation method of a kind of PPTA spinning solution according to claim 1, is characterized in that: in described step (1), the average particle size of PPTA is less than 150 orders; PPTA moisture content after process is less than 100ppm.
4. the preparation method of a kind of PPTA spinning solution according to claim 1, is characterized in that: in described step (2), the concentration of the concentrated sulfuric acid is more than or equal to 100%.
5. the preparation method of a kind of PPTA spinning solution according to claim 1, is characterized in that: in described step (2), concentrated sulfuric acid cooling curing temperature is-15 DEG C ~ 5 DEG C; Pulverize as being ground into fine powder, granularity is not more than 200 orders.
6. the preparation method of a kind of PPTA spinning solution according to claim 1, is characterized in that: in described step (3), low-temperature mixed temperature is-15 DEG C ~ 5 DEG C.
7. the preparation method of a kind of PPTA spinning solution according to claim 1, is characterized in that: described step (3) rising temperature for dissolving process is carried out under vacuum, and vacuum overbottom pressure is not more than 10mmHg.
8. the preparation method of a kind of PPTA spinning solution according to claim 1, it is characterized in that: rising temperature for dissolving is that rising temperature for dissolving stops 0.1-1h to 20-40 DEG C in described step (3), then 80-100 DEG C is warmed up to, heating rate is 1 DEG C/min-3 DEG C/min.
9. the preparation method of a kind of PPTA spinning solution according to claim 1, is characterized in that: in described step (3), rising temperature for dissolving is carried out in dissolver, and dissolver is dissolution kettle or screw rod dissolving machine.
10. the preparation method of a kind of PPTA spinning solution according to claim 10, is characterized in that: described screw rod dissolving machine is twin-screw dissolving machine, three screw rod dissolving machines or four screw rod dissolving machines.
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4981619A (en) * | 1972-12-18 | 1974-08-06 | ||
| WO1996034732A1 (en) * | 1995-05-02 | 1996-11-07 | Akzo Nobel N.V. | Process for making fibres from poly(p-phenylene terephthalamide) |
| 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 |
| KR20070072042A (en) * | 2005-12-30 | 2007-07-04 | 주식회사 효성 | Process for preparing para-aramid fiber |
| 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 |
| CN103469314A (en) * | 2013-09-13 | 2013-12-25 | 东华大学 | Method for quickly preparing PPTA (poly-paraphenylene terephthalamide) resin liquid crystal spinning solution with ultrahigh molecular weight |
-
2014
- 2014-04-02 CN CN201410134721.1A patent/CN104975357A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4981619A (en) * | 1972-12-18 | 1974-08-06 | ||
| WO1996034732A1 (en) * | 1995-05-02 | 1996-11-07 | Akzo Nobel N.V. | Process for making fibres from poly(p-phenylene terephthalamide) |
| 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 |
| KR20070072042A (en) * | 2005-12-30 | 2007-07-04 | 주식회사 효성 | Process for preparing para-aramid fiber |
| 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 |
| CN103469314A (en) * | 2013-09-13 | 2013-12-25 | 东华大学 | Method for quickly preparing PPTA (poly-paraphenylene terephthalamide) resin liquid crystal spinning solution with ultrahigh molecular weight |
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