CN1256474C - Manufacturing method of poly p phenylene diamine terephthalamide fiber - Google Patents
Manufacturing method of poly p phenylene diamine terephthalamide fiber Download PDFInfo
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- CN1256474C CN1256474C CN 200310109240 CN200310109240A CN1256474C CN 1256474 C CN1256474 C CN 1256474C CN 200310109240 CN200310109240 CN 200310109240 CN 200310109240 A CN200310109240 A CN 200310109240A CN 1256474 C CN1256474 C CN 1256474C
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- ppta
- screw
- screw extruder
- twin
- double
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- 238000004519 manufacturing process Methods 0.000 title claims description 7
- 239000000835 fiber Substances 0.000 title abstract description 20
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 title abstract 2
- MHSKRLJMQQNJNC-UHFFFAOYSA-N terephthalamide Chemical compound NC(=O)C1=CC=C(C(N)=O)C=C1 MHSKRLJMQQNJNC-UHFFFAOYSA-N 0.000 title abstract 2
- 238000009987 spinning Methods 0.000 claims abstract description 34
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 16
- 239000011347 resin Substances 0.000 claims abstract description 16
- 229920005989 resin Polymers 0.000 claims abstract description 16
- 238000002166 wet spinning Methods 0.000 claims abstract description 5
- 229920003366 poly(p-phenylene terephthalamide) Polymers 0.000 claims description 39
- 239000000463 material Substances 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 11
- 238000004898 kneading Methods 0.000 claims description 4
- 238000005516 engineering process Methods 0.000 abstract description 5
- 239000004973 liquid crystal related substance Substances 0.000 abstract description 2
- 230000007928 solubilization Effects 0.000 abstract 4
- 238000005063 solubilization Methods 0.000 abstract 4
- 235000011149 sulphuric acid Nutrition 0.000 abstract 3
- 239000001117 sulphuric acid Substances 0.000 abstract 2
- RSWGJHLUYNHPMX-UHFFFAOYSA-N 1,4a-dimethyl-7-propan-2-yl-2,3,4,4b,5,6,10,10a-octahydrophenanthrene-1-carboxylic acid Chemical compound C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 abstract 1
- 230000002349 favourable effect Effects 0.000 abstract 1
- 239000000203 mixture Substances 0.000 abstract 1
- 238000004090 dissolution Methods 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 238000000137 annealing Methods 0.000 description 2
- 230000001112 coagulating effect Effects 0.000 description 2
- 230000015271 coagulation Effects 0.000 description 2
- 238000005345 coagulation Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004699 Ultra-high molecular weight polyethylene Substances 0.000 description 1
- 239000004760 aramid Substances 0.000 description 1
- 229920003235 aromatic polyamide Polymers 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 230000029087 digestion Effects 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000002657 fibrous material Substances 0.000 description 1
- 238000001891 gel spinning Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- -1 polyethylene Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 229920000785 ultra high molecular weight polyethylene Polymers 0.000 description 1
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- Artificial Filaments (AREA)
- Spinning Methods And Devices For Manufacturing Artificial Fibers (AREA)
Abstract
The present invention relates to a making method for poly p phenylene diamine terephthalamide (PPTA) fibers, which comprises: PPTA resin and sulphuric acid of which the concentration is larger than 99% are fully mixed; then the mixture is conveyed to a double-screw extruder for solubilization and deaeration; then a PPTA fiber is made by a dry spraying-wet spinning method. By rebuilding the double-screw structure of a double-screw extruder, the present invention achieves the technical purpose of the solubilization and the deaeration of a liquid crystal PPTA/H2SO4 solution with high viscosity, greatly shortens solubilization and deaeration time, relieves the problem that PPTA is degraded in sulphuric acid under a high-temperature solubilization condition, and is favorable for obtaining PPTA fibers with high strength and realizing the industrialization of spinning technology.
Description
Technical field
The present invention relates to textile technology field, be specifically related to the manufacture method of a kind of PPTA (PPTA) fiber.
Background technology
As everyone knows, the Fanglun 1414 is a kind of typical aromatic polyamide fibre, be called Fanglun l414 or PPTA fiber again, it has high-strength, Gao Mo, excellent properties such as high temperature resistant, it is a class tec fiber with fastest developing speed in the fibrous material in recent years, mainly use on fabrics for industrial use, particularly many product requirement lightweights, high performance occasion can only be used this kind fiber.
Last century, early seventies by the fiber spinning from crystalline state method that du pont company has at first been invented dry-jet wet-spinning, was made the PPTA fiber of this high-strength and high-modulus, but still existed PPTA/H so far
2SO
4The stirring of the preparation process medium-high viscosity liquid crystal of spinning solution and deaeration difficult technologies problem, generally, the PPTA resin dissolves under 80～90 ℃ of conditions in 99～100% sulfuric acid, needs 3 hours at least, and PPTA/H
2SO
4The deaeration of spinning solution often needs the longer time, reaches tens hours to tens hours, and not only bad for the industrial production of serialization, and PPTA degrading in dissolving and the deaeration process for a long time easily, thereby influences the intensity of PPTA fiber.
The inventor discloses in Chinese patent 95111657.6 and has a kind ofly carried out the Ultrastrength polyethylene fibre spinning apparatus of rapidly defoaming for full-bodied gel spinning solution, promptly adopts the double screw extruder deaeration, and the deaeration time is shortened dramatically.But the course of dissolution of ultra-high molecular weight polyethylene still carries out in the pressure dissolution kettle, needs 3～4 hours, and also easily makes macromolecular chain that violent degraded takes place under the high-temperature digestion condition, is unfavorable for obtaining high-intensity fiber.
Summary of the invention
The object of the invention is to overcome the shortcoming of above-mentioned existing PPTA spinning technique, by the improvement to screw-rod structure in the double screw extruder, provides a kind of quick dissolving and deaeration, the new technology of spinning high strength PPTA fiber.
The technical scheme of spinning PPTA provided by the invention comprises the following steps:
(1) the PPTA resin of inherent viscosity 4.0～8.5dl/g and concentration are added in the mixing drum greater than 99% sulfuric acid, the percentage by weight that makes PPTA is 14～24%, under 50～100 ℃, mixes 3～50 minutes;
(2) will mix the back material and clamp-on continuously in the double screw extruder, in twin-screw, finish the PPTA resin at H
2SO
4In dissolving and the deaeration of spinning solution;
(3) double screw extruder extrudes that abundant mixing, adjustment are good, bubble takes off most spinning solution, through measuring pump, filter after, do spray-wet spinning and obtain the PPTA fiber.
For realizing technical scheme of the present invention, the screw diameter that should satisfy double screw extruder is 25-145mm, and draw ratio is more than or equal to 30, and screw speed is 10～200rpm, the time of staying of mixed material in twin-screw is 10-60 minute, and gentle fully the finishing of assurance PPTA resin dissolves taken off to the greatest extent entirely.When screw diameter during less than 45mm, when promptly screw diameter is 25-45mm, can circulate to material, guarantee the time of staying of material in twin-screw.
The first half of two intermeshing twin-screws in the while double screw extruder of the present invention, from the screw rod total length that enters the mouth 30～80% part, kneading piece and a spot of reverse thread cover by various forward thread bush, different rotation directions are formed, wherein, the total length of mediating piece accounts for more than 30% of this partial-length, makes PPTA/H
2SO
4By constantly compress, effect such as expansion and axial back mixing is subjected to strong shearing and immixture, is beneficial to the PPTA dissolving resin.
The latter half of twin-screw is made up of the thread bush that reduces gradually along Way out pitch in the double screw extruder, makes PPTA/H
2SO
4Spinning solution is in the outlet pushing course, and pressure increases gradually, and the bubble in the solution is overflowed to the low direction of pressure, and reaches the purpose of deaeration.
Accompanying drawing 1 is a screw rod schematic diagram in the double screw extruder, and wherein AB is a first half, and D is the forward thread bush, and E is for mediating piece, and F is the reverse thread cover; BC is a latter half, and pitch reduces gradually along Way out.
The present invention compared with prior art has the following advantages:
(1) deaeration of PPTA dissolving resin and spinning solution is all finished in a double screw extruder, only need time of 30 minutes to 60 minutes can obtain that abundant mixing, adjustment are good, bubble takes off most PPTA spinning solution, then through measuring pump, filtration, do spray-wet spinning and obtain the PPTA fiber, thereby avoided in the traditional handicraft PPTA resin concentration greater than 99% sulfuric acid in, 80～90 ℃ of following dissolvings need 3 hours, PPTA/H at least
2SO
4The deaeration of spinning solution often needs the longer time, reaches tens hours to tens hours shortcoming, helps the continuous spinning of PPTA.
(2) two of double screw extruder intermeshing screw rods, its first half is made up of kneading piece and a spot of reverse thread cover of various forward thread bush, different rotation directions, wherein, the total length of mediating piece accounts for more than 30% of this partial-length, make screw rod have good automatic cleaning action and very high shear rate, make material can promptly reach microcosmic at short notice and mix, thereby can quicken the dissolution velocity of PPTA resin in sulfuric acid greatly.
(3) two of double screw extruder intermeshing screw rods, its latter half is made up of the thread bush that reduces gradually along Way out pitch, makes PPTA/H
2SO
4Spinning solution is in the outlet pushing course, and pressure increases gradually, and the bubble in the solution is overflowed to the low direction of pressure, and reaches the purpose of deaeration at short notice.
(4) temperature of twin-screw can regulate and control as required, and in by the twin-screw pushing course, constantly cut apart and reconfigured at as thin as a wafer solution between twin-screw and the outer sleeve, therefore at the utmost point in the short time, mixing, temperature adjustment constantly, can be mixed, be stabilized in the spinning solution of a certain design temperature, the effect that play stable spinning, improves fibre strength.
(5) owing in double screw extruder, carry out PPTA dissolving resin and PPTA/H
2SO
4The deaeration of spinning solution, the time of this twice workshop section is shortened greatly, only need 10 minutes to 60 minutes, so both helped realizing industrialized continuous spinning, can also avoid simultaneously macromolecular violent cracking in long-time dissolving, deaeration process, help obtaining high-intensity Fanglun 1414.
Description of drawings
Screw rod schematic diagram in Fig. 1 double screw extruder
The specific embodiment
Embodiment 1
With 1.43 kilograms of intrinsic viscosities is that the dry PPTA resin of 6.5dl/g and the sulfuric acid of 3.5 liters 100% add in the mixing drum of 10 liters, under 85 ℃, mix after 20 minutes, it is 55mm that mixed material is clamp-oned diameter continuously, and draw ratio is 60, and rotating speed is in the double screw extruder of 30rpm, the temperature of control twin-screw is 85 ℃, the long 1400mm of screw rod first half wherein, latter half length is 1900mm, finishes the PPTA resin at H in twin-screw
2SO
4In dissolving and the deaeration of spinning solution, extrude after 50 minutes that abundant mixing, adjustment are good, bubble takes off most spinning solution, after measuring pump, filtration, send into spinning head, the spinneret cap specification is 0.06 * 300 hole, through the air gap of 5cm layer, enters the coagulating bath spin duct, coagulation bath temperature is 5 ℃, 120 meters/minute of spinning speeds, 6 times of jet stretches, spun tow is after the washing neutralization, send into annealing device, handled for 10 seconds down at 525 ℃, reoiling is wound into tube, and gained PPTA fiber gets intensity 2.60GP, initial modulus 18OGP, extension at break 1.43%.
Embodiment 2
With 1.43 kilograms of intrinsic viscosities is that the dry PPTA resin of 5.3dl/g and the sulfuric acid of 3.5 liters 100% add in the mixing drum of 10 liters, under 85 ℃, mix after 5 minutes, it is 55mm that mixed material is clamp-oned diameter continuously, and draw ratio is 60, and rotating speed is in the double screw extruder of 50rpm, the long 1550mm of screw rod first half wherein, latter half length is 1750mm, and the temperature of control twin-screw is 85 ℃, finishes the PPTA resin at H in twin-screw
2SO
4In dissolving and the deaeration of spinning solution, extrude after 35 minutes that abundant mixing, adjustment are good, bubble takes off most spinning solution, after measuring pump, filtration, send into spinning head, the spinneret cap specification is 0.06 * 300 hole, through the air gap of 5cm layer, enters the coagulating bath spin duct, coagulation bath temperature is 5 ℃, 120 meters/minute of spinning speeds, 6 times of jet stretches, spun tow is after the washing neutralization, send into annealing device, handled for 10 seconds down at 525 ℃, reoiling is wound into tube, and gained PPTA fiber gets intensity 2.35GP, initial modulus 175GP, extension at break 1.51%.
The comparison of embodiment 3 common spinning process and the inventive method
Table 1 is with the comparison of common spinning process and this method
| Sample | Intensity (GPa) | Intensity cv (%) | The dissolving spinning time |
| Dissolving spinning method sample | 2.62 | 0.7 | 12 hours |
| Embodiment 1 sample | 2.6 | 0.66 | 4 hours |
| Embodiment 2 samples | 2.35 | 0.5 | 3.5 hour |
Claims (4)
1, a kind of Fanglun 1414's manufacture method is characterized in that this method comprises the following steps:
(1) being the PPTA resin of 4.0～8.5dl/g and concentration with inherent viscosity adds in the mixing drum greater than 99% sulfuric acid, the percentage by weight that makes PPTA is 14～24%, under 50～100 ℃, mixed 3～50 minutes;
(2) will mix the back material and clamp-on continuously in the double screw extruder, in twin-screw, finish the PPTA resin at H
2SO
4In dissolving and the deaeration of spinning solution;
(3) double screw extruder extrudes that abundant mixing, adjustment are good, bubble takes off most spinning solution, through measuring pump, filter after, do spray-wet spinning and obtain the Fanglun 1414;
The twin-screw diameter of wherein said double screw extruder is 25-145mm, and draw ratio is more than or equal to 30, and screw speed is 10～200rpm, and the time of staying of mixed material in twin-screw is 10-60 minute.
2, manufacture method according to claim 1 when the screw diameter that it is characterized in that wherein said double screw extruder is 25-45mm, circulates to material, and making the time of staying of mixed material in twin-screw is 10-60 minute.
3, manufacture method according to claim 1, the first half that it is characterized in that two intermeshing twin-screws in the wherein said double screw extruder, from the screw rod total length that enters the mouth 30～80% part, kneading piece and a spot of reverse thread cover by various forward thread bush, different rotation directions are formed, wherein, the total length of kneading piece accounts for more than 30% of this partial-length.
4, manufacture method according to claim 1 is characterized in that the latter half of twin-screw in the wherein said double screw extruder is made up of the thread bush that reduces gradually along Way out pitch.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200310109240 CN1256474C (en) | 2003-12-10 | 2003-12-10 | Manufacturing method of poly p phenylene diamine terephthalamide fiber |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200310109240 CN1256474C (en) | 2003-12-10 | 2003-12-10 | Manufacturing method of poly p phenylene diamine terephthalamide fiber |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1546757A CN1546757A (en) | 2004-11-17 |
| CN1256474C true CN1256474C (en) | 2006-05-17 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 200310109240 Expired - Lifetime CN1256474C (en) | 2003-12-10 | 2003-12-10 | Manufacturing method of poly p phenylene diamine terephthalamide fiber |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103143273A (en) * | 2013-03-05 | 2013-06-12 | 天津工业大学 | Preparation method of aromatic polymer porous membrane |
Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1650251A1 (en) * | 2004-10-22 | 2006-04-26 | Teijin Twaron B.V. | Method for dissolving PPTA in sulfuric acid using a twin screw extruder |
| CN100395381C (en) * | 2005-05-10 | 2008-06-18 | 东华大学 | Method of continuously preparing poly terephthaloyl-p-phenylene diamine fibre |
| CN100427650C (en) * | 2005-11-02 | 2008-10-22 | 东华大学 | High shearing rate method for spinning poly-terephthaloyl p-phenylenediamine fibre |
| CH700932B1 (en) * | 2007-05-14 | 2010-11-15 | List Holding Ag | Method and installation for producing a dope for the manufacture of a polymer fiber. |
| CN101555631B (en) * | 2008-04-10 | 2011-04-06 | 中国神马集团有限责任公司 | Industrial method for preparing PPTA spinning slurry with solid sulphuric acid |
| DE102009036915A1 (en) * | 2009-08-11 | 2011-02-24 | List Holding Ag | Process for treating a monomer, pre-polymer, polymer or a corresponding mixture |
| CN102268743B (en) * | 2011-05-06 | 2013-04-03 | 上海舟汉纤维材料科技有限公司 | Device and method for efficiently dissolving poly(p-phenytene terephthalamide) resin |
| CN102560700B (en) * | 2011-12-31 | 2014-12-10 | 苏州兆达特纤科技有限公司 | Para-aramid fine denier fiber and preparation method thereof |
| CN104975357A (en) * | 2014-04-02 | 2015-10-14 | 东华大学 | Preparation method of poly (p-phenylene terephthamide) spinning solution |
| CN104404644B (en) * | 2014-11-20 | 2017-02-22 | 东华大学 | Method for preparing spinning pulp through dissolution of PPTA resin with solid foamed sulfuric acid |
| CN110129912B (en) * | 2019-06-10 | 2021-10-26 | 黄河三角洲京博化工研究院有限公司 | Para-aramid fibrid and continuous production method thereof |
-
2003
- 2003-12-10 CN CN 200310109240 patent/CN1256474C/en not_active Expired - Lifetime
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103143273A (en) * | 2013-03-05 | 2013-06-12 | 天津工业大学 | Preparation method of aromatic polymer porous membrane |
| CN103143273B (en) * | 2013-03-05 | 2015-05-27 | 天津工业大学 | Preparation method of aromatic polymer porous membrane |
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| Publication number | Publication date |
|---|---|
| CN1546757A (en) | 2004-11-17 |
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