CN1752300A - High shearing rate method for spinning poly-terephthaloyl p-phenylenediamine fibre - Google Patents
High shearing rate method for spinning poly-terephthaloyl p-phenylenediamine fibre Download PDFInfo
- Publication number
- CN1752300A CN1752300A CN 200510030946 CN200510030946A CN1752300A CN 1752300 A CN1752300 A CN 1752300A CN 200510030946 CN200510030946 CN 200510030946 CN 200510030946 A CN200510030946 A CN 200510030946A CN 1752300 A CN1752300 A CN 1752300A
- Authority
- CN
- China
- Prior art keywords
- ppta
- spinning
- double screw
- screw extruder
- extruder
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Artificial Filaments (AREA)
- Spinning Methods And Devices For Manufacturing Artificial Fibers (AREA)
Abstract
The invented method includes the following steps: uniformly mixing PPTA and concentrated sulfuric acid whose concentration is greater than 99% in mixing cylinder, preparing mixed solution in which PPTA content is 14%-24%; making the prepared PPTA mixed solution pass through twin screw extruder, further dissolving to form liquid crystal spinning solution, defoaming, fully mixing and regulating temperature, applying high shear stress to the defoamed PPTA spinning slurry in extruder machine head, filtering and metering, adopting dry-jet wet-spinning process to obtain the invented PPTA fibre.
Description
Technical field
The present invention relates to a kind of method that spins poly-terephthalate p-phenylenediamine (PPD) fiber, particularly relate to a kind of method of high-rate of shear spinning PPTA (PPTA) fiber.
Background technology
The Fanglun 1414 is a kind of typical aromatic polyamide fibre, p-aramid fiber or PPTA fiber are otherwise known as, have high-strength and high-modulus, high temperature resistant, excellent physical and mechanical performance such as creep is little, it is a class high-tech art fiber with the fastest developing speed in the fibrous material field in recent years, mainly be to be applied to fabrics for industrial use, particularly many lightweight, high performance products of requiring can only use this kind fiber.
Early seventies at first disclosed employing by du pont company and did spray-wet spinning PPTA/H in patent USP 3,767,756 last century
2SO
4The liquid crystal slurries have spinned the PPTA fiber of high-strength and high-modulus, but have existed PPTA/H
2SO
4Spinning solution stirs and deaeration difficult technologies problem at preparation process medium-high viscosity liquid crystal solution, both has been unfavorable for the industrial production of serialization, and PPTA is degrading again in dissolving and the deaeration process for a long time easily, thereby influences the PPTA quality of fibre.
Chinese patent (application number: disclose 200310109240) and adopted double-screw structure to improve the double screw extruder of design, realized quick dissolving and the deaeration new technology of PPTA in the concentrated sulfuric acid, avoided PPTA/H
2SO
4Long-time dissolving and deaeration cause the degraded of PPTA under higher temperature, spin out the PPTA fiber of high-strength and high-modulus, spinning speed be 80-150 rice/minute.Owing to adopted common shear rate and shear stress, polymer solution is difficult for forming liquid crystal, so spinning speed slow (only 80-150 rice/minute), production efficiency is lower.
Summary of the invention
Technical problem to be solved by this invention provides the method for the poly-terephthalate p-phenylenediamine (PPD) fiber of a kind of high-rate of shear spinning, to remedy the deficiencies in the prior art and defective, meets the demands of production and living.
In order to solve the problems of the technologies described above, the technical solution adopted in the present invention is: the method for the poly-terephthalate p-phenylenediamine (PPD) fiber of a kind of high-rate of shear spinning may further comprise the steps:
(1) being the PPTA resin (PPTA) of 4.5-8.5dl/g and concentration with inherent viscosity mixes greater than 99% the concentrated sulfuric acid, and the weight percentage that is mixed with PPTA is the mixed solution of 14%-24%;
(2) the PPTA mixed solution for preparing is finished the further dissolving of PPTA in the concentrated sulfuric acid and is formed fiber spinning from crystalline state solution, and it is carried out deaeration by double screw extruder in extruder;
(3) to fully mixing, regulate temperature through double screw extruder, taking off the PPTA spinning slurry of most bubble, apply shearing force, after filtration, after the metering, at 1*10 at cross-head
3s
-1-4.5*10
5s
-1High-rate of shear do down spray-wet spinning and make the Fanglun 1414.
As optimized technical scheme: the temperature of material in mixing drum, double screw extruder is controlled at 50-100 ℃; The time of staying was respectively 3-50 minute and 10-60 minute, made PPTA/H
2SO
4The time of staying in the temperature range of-Ding is to guarantee to form uniform fiber spinning from crystalline state solution.
Twin-screw diameter in the double screw extruder is 25-145mm, draw ratio is 30-80, screw speed is 10-200rpm, and the first half of two intermeshing double screw extruders in the double screw extruder, from the part the 30-80% of the screw rod total length that enters the mouth, be that kneading piece and a spot of reverse thread cover by various forward thread bush, different rotation directions combines, the total length of wherein mediating piece accounts for more than 30% of this partial-length, makes PPTA/H
2SO
4By constantly compress, effects such as expansion and axial back mixing are subjected to strong shearing and back mixing effect, to guarantee that material dissolves fully in double screw extruder.
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, make the PPTA/H2SO4 spinning solution in the outlet pushing course, pressure increases gradually, and the bubble in the solution is overflowed to the low direction of pressure, thereby reaches the purpose of deaeration.
The invention has the beneficial effects as follows: the present invention compared with prior art has the following advantages:
(1) deaeration of PPTA dissolving resin and spinning solution is finished in same double screw extruder, only need 30-60 minute time, can obtain that abundant mixing, adjustment are good, bubble takes off most PPTA spinning solution, and in the traditional handicraft PPTA resin in the concentrated sulfuric acid, at least need 3 hours 80-90 ℃ of following dissolving, the deaeration of slurries then needs the longer time, often reaches tens hours to tens hours, thereby this quick dissolving deaeration technology helps continuous spinning, the realization industrialization.
(2) twin-screw squeezes two intermeshing screw rods of machine, and its first half is made up of kneading piece and a spot of reverse thread cover of various forward thread bush, different rotation direction angles.Wherein, mediate the piece total length and account 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 the concentrated sulfuric acid greatly.
(3) latter half of twin-screw is made up of the thread bush that reduces gradually along Way out pitch in the double screw extruder, make the PPTA/H2SO4 spinning solution in the outlet pushing course, pressure increases gradually, and the bubble in the solution is overflowed to the low direction of pressure, thereby reaches the purpose of deaeration.
(4) temperature of double screw extruder can regulate and control as required.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, in the extremely 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) the PPTA spinning slurry through the double screw extruder head is imposed shearing force, spinning PPTA fiber on the one hand, helps the height-oriented of chain liquid crystal polymer under high-rate of shear, is beneficial to and obtains high-strength high-modulus fibre; On the other hand, because the shear shinning of liquid crystalline polymer solution, apparent viscosity descends, and makes spinning process more smooth, can further improve and spins speed, makes spinning speed improve 5-10 times, reach 400-1000 rice/minute.
(6) in a double screw extruder, PPTA dissolving resin, PPTA/H have been realized
2SO
4The deaeration of spinning solution and this three process of high-rate of shear spinning had both shortened the dissolving deaeration time greatly, were beneficial to again and carried high-speed spinning, thereby more help realizing industrialized continuous spinning, made the Fanglun 1414 of high-strength and high-modulus.
The specific embodiment
Below in conjunction with specific embodiment the present invention is further elaborated.
Embodiment 1
With 1.43 kilograms of inherent 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 is long to be to finish the PPTA resin at H in twin-screw by 1900mm
2SO
4In abundant dissolving and remove bubble in the spinning solution, through about 50 minutes,, bubble good to abundant mixing, adjustment at the head of extruder takes off most spinning solution and applies shearing force, after the filtration, through measuring pump, with 5.5 * 10
3s
-1Shear rate send into spinning head, the spinnerets specification is Φ 0.08 * 300 hole, through the air gap of 5mm layer, enter the coagulating bath spin duct, coagulation bath temperature is 5 ℃, and spinning speed is 550 meters/minute, 6 times of jet stretches, spun tow is sent into annealing device after the washing neutralization, handled for 10 seconds down at 525 ℃, reoiling is wound into tube, measures according to GB, and the TENSILE STRENGTH of gained PPTA fiber is 2.63Gpa, initial modulus is 184GPa, and extension at break is 1.43%.
Embodiment 2
With 1.43 kilograms of inherent viscosities is that the dry PPTA resin of 4.5dl/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 25mm that mixed material is clamp-oned diameter continuously, and draw ratio is 30, and rotating speed is in the double screw extruder of 10rpm, the temperature of control twin-screw is 50 ℃, the long 1500mm of screw rod first half wherein, latter half is long to be to finish the PPTA resin at H in twin-screw by 1750mm
2SO
4In abundant dissolving and remove bubble in the spinning solution, through about 35 minutes,, bubble good to abundant mixing, adjustment at the head of extruder takes off most spinning solution and applies shearing force, after the filtration, through measuring pump, with 4.5 * 10
5s
-1Shear rate send into spinning head, the spinnerets specification is Φ 0.08 * 300 hole, through the air gap of 5mm layer, enter the coagulating bath spin duct, coagulation bath temperature is 5 ℃, and spinning speed is 850 meters/minute, 6 times of jet stretches, spun tow is sent into annealing device after the washing neutralization, handled for 10 seconds down at 525 ℃, reoiling is wound into tube, measures according to GB, and the TENSILE STRENGTH of gained PPTA fiber is 2.75Gpa, initial modulus is 182GPa, and extension at break is 1.47%.
Embodiment 3
With 1.43 kilograms of inherent viscosities is that the dry PPTA resin of 8.5dl/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 145mm that mixed material is clamp-oned diameter continuously, and draw ratio is 80, and rotating speed is in the double screw extruder of 200rpm, the temperature of control twin-screw is 100 ℃, the long 1400mm of screw rod first half wherein, latter half is long to be to finish the PPTA resin at H in twin-screw by 1900mm
2SO
4In abundant dissolving and remove bubble in the spinning solution, through about 3 minutes,, bubble good to abundant mixing, adjustment at the head of extruder takes off most spinning solution and applies shearing force, after the filtration, through measuring pump, with 1.0 * 10
3s
-1Shear rate send into spinning head, the spinnerets specification is Φ 0.08 * 300 hole, through the air gap of 5mm layer, enter the coagulating bath spin duct, coagulation bath temperature is 5 ℃, and spinning speed is 550 meters/minute, 6 times of jet stretches, spun tow is sent into annealing device after the washing neutralization, handled for 10 seconds down at 525 ℃, reoiling is wound into tube, measures according to GB, and the TENSILE STRENGTH of gained PPTA fiber is 2.51Gpa, initial modulus is 176GPa, and extension at break is 1.45%.
The performance that table 1 is common spinning, dissolve deaeration and institute of the present invention spinning fibre fast relatively.
Table 1
| Sample | Intensity (GPa) | Modulus (GPa) | Extension at break (%) | Spinning speed (m/s) |
| Common spinning technique | 2.62 | 183 | 1.63 | 120 |
| Dissolve deaeration process implementing example 1 sample fast | 2.60 | 180 | 1.43 | 120 |
| Dissolve deaeration process implementing example 2 samples fast | 2.35 | 175 | 1.51 | 120 |
| The embodiment of the invention 1 sample | 2.63 | 184 | 1.43 | 550 |
| The embodiment of the invention 2 samples | 2.75 | 182 | 1.47 | 850 |
Claims (4)
1. the method for the poly-terephthalate p-phenylenediamine (PPD) fiber of high-rate of shear spinning is characterized in that, may further comprise the steps:
(1) being the PPTA resin of 4.5-8.5dl/g and concentration with inherent viscosity mixes in mixing drum greater than 99% the concentrated sulfuric acid, and the weight percentage that is mixed with PPTA is the mixed solution of 14%-24%;
(2) the PPTA mixed solution for preparing is finished the further dissolving of PPTA in the concentrated sulfuric acid and is formed fiber spinning from crystalline state solution, and it is carried out deaeration by double screw extruder in extruder;
(3) to fully mixing, regulate temperature through double screw extruder, taking off the PPTA spinning slurry of most bubble, apply shearing force, after filtration, after the metering, at 1*10 at cross-head
3s
-1-4.5*10
5s
-1High-rate of shear do down spray-wet spinning and make the Fanglun 1414.
2. method according to claim 1 is characterized in that: the temperature of material in mixing drum, double screw extruder is controlled at 50-100 ℃; The time of staying was respectively 3-50 minute and 10-60 minute.
3. method according to claim 1, it is characterized in that: the twin-screw diameter in the double screw extruder is 25-145mm, draw ratio is 30-80, screw speed is 10-200rpm, and the first half of two intermeshing double screw extruders in the double screw extruder, from the part the 30-80% of the screw rod total length that enters the mouth, be that kneading piece and a spot of reverse thread cover by various forward thread bush, different rotation directions combines, the total length of wherein mediating piece accounts for more than 30% of this partial-length.
4. method according to claim 1 is characterized in that: 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.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100309463A CN100427650C (en) | 2005-11-02 | 2005-11-02 | High shearing rate method for spinning poly-terephthaloyl p-phenylenediamine fibre |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100309463A CN100427650C (en) | 2005-11-02 | 2005-11-02 | High shearing rate method for spinning poly-terephthaloyl p-phenylenediamine fibre |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1752300A true CN1752300A (en) | 2006-03-29 |
| CN100427650C CN100427650C (en) | 2008-10-22 |
Family
ID=36679303
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2005100309463A Active CN100427650C (en) | 2005-11-02 | 2005-11-02 | High shearing rate method for spinning poly-terephthaloyl p-phenylenediamine fibre |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100427650C (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN101220530B (en) * | 2007-01-08 | 2011-06-22 | 上海艾麦达化纤科技有限公司 | Production of uniform polyphenylene terephthalamide fibre |
| 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 |
| CN101724935B (en) * | 2009-12-14 | 2011-09-14 | 中蓝晨光化工研究院有限公司 | Polyphenylene terephthalamide fibre and preparation method thereof |
| CN102268743A (en) * | 2011-05-06 | 2011-12-07 | 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 |
| CN104404644A (en) * | 2014-11-20 | 2015-03-11 | 东华大学 | Method for preparing spinning pulp through dissolution of PPTA resin with solid foamed sulfuric acid |
| CN109295506A (en) * | 2018-09-13 | 2019-02-01 | 清华大学 | A kind of p-aramid fiber spinning solution compounding system and its preparation method |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3767756A (en) * | 1972-06-30 | 1973-10-23 | Du Pont | Dry jet wet spinning process |
| JPH01111014A (en) * | 1987-10-21 | 1989-04-27 | Asahi Chem Ind Co Ltd | Dye-containing poly-p-phenylene terephthalamide fiber and production thereof |
| NL1000276C2 (en) * | 1995-05-02 | 1996-11-05 | Akzo Nobel Nv | Process for the production of fibers from poly (p-phenylene terephthalamide). |
| ATE399890T1 (en) * | 1998-10-22 | 2008-07-15 | Du Pont Toray Co Ltd | POLYPARAPHENYLENTEREPHTHALAMIDE FIBERS AND METHOD FOR PRODUCING THE SAME |
| CN1256474C (en) * | 2003-12-10 | 2006-05-17 | 中国石化仪征化纤股份有限公司 | Manufacturing method of poly p phenylene diamine terephthalamide fiber |
-
2005
- 2005-11-02 CN CNB2005100309463A patent/CN100427650C/en active Active
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101220530B (en) * | 2007-01-08 | 2011-06-22 | 上海艾麦达化纤科技有限公司 | Production of uniform polyphenylene terephthalamide fibre |
| 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 |
| CN101724935B (en) * | 2009-12-14 | 2011-09-14 | 中蓝晨光化工研究院有限公司 | Polyphenylene terephthalamide fibre and preparation method thereof |
| CN102268743A (en) * | 2011-05-06 | 2011-12-07 | 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 |
| 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 |
| 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 |
| CN104404644A (en) * | 2014-11-20 | 2015-03-11 | 东华大学 | Method for preparing spinning pulp through dissolution of PPTA resin with solid foamed sulfuric acid |
| 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 |
| CN109295506A (en) * | 2018-09-13 | 2019-02-01 | 清华大学 | A kind of p-aramid fiber spinning solution compounding system and its preparation method |
| CN109295506B (en) * | 2018-09-13 | 2020-07-28 | 清华大学 | Para-aramid spinning solution preparation system and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN100427650C (en) | 2008-10-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN100427650C (en) | High shearing rate method for spinning poly-terephthaloyl p-phenylenediamine fibre | |
| CN107224882B (en) | Preparation method of braided tube enhanced polyvinylidene fluoride hollow fiber membrane | |
| CN1298900C (en) | Cellulose multi-filament for tyre cord and its producing method | |
| JP4104596B2 (en) | Highly homogeneous cellulose solution and high strength lyocell fiber using the same | |
| CN102812168B (en) | Process for the manufacture of cellulose-based fibres and the fibres thus obtained | |
| CN1256474C (en) | Manufacturing method of poly p phenylene diamine terephthalamide fiber | |
| CN100395381C (en) | Method of continuously preparing poly terephthaloyl-p-phenylene diamine fibre | |
| JP2006138058A (en) | Method for producing cellulose fiber | |
| US10357725B2 (en) | Method for producing moulded articles | |
| CN110512294B (en) | Sheath-core type composite monofilament, production method and application thereof | |
| CN1060543C (en) | Method and apparatus for continuous making superhigh molecula polyethylene fibre | |
| CN1400342A (en) | Production method of high strength polyethylene fibre and fibre | |
| CN101736411A (en) | Method for preparing polyacrylonitrile spinning solution for carbon fiber | |
| CN101781808A (en) | Device for two-stage continuous dissolution, untwisting and spinning of homogeneous solution of ultra-high molecular weight polyethylene | |
| CN102560700B (en) | Para-aramid fine denier fiber and preparation method thereof | |
| CN1789503A (en) | Lyocell multi-filament for tire cord, tire cord and tire | |
| CN1158135C (en) | Preparation method of hollow fibre supermicro filtration membrane | |
| CN101220530B (en) | Production of uniform polyphenylene terephthalamide fibre | |
| CN103774253B (en) | A kind of wet spinning shaped device | |
| CN201092591Y (en) | Continuous defoaming device for manufacturing homogeneous Poly(p-phenyleneterephthalamide) fibre | |
| Song et al. | A comparative study on properties of cellulose/antarctic krill protein composite fiber by centrifugal spinning and wet spinning | |
| CN101608347A (en) | A kind of gradient coagulating bath device for preparing polyphenylene Ben Bing Er oxazole fiber | |
| Zhang et al. | Preparation and formation mechanism analysis of regenerated silk fibroin/polyvinyl alcohol blended fibers with waste silk quilt | |
| CA2923780A1 (en) | Method for producing a forming solution | |
| CN112095159B (en) | High-strength coarse denier polyvinyl alcohol fiber spun by wet method and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| EE01 | Entry into force of recordation of patent licensing contract |
Assignee: Puning Qiusheng Chemical Fiber Co., Ltd. Assignor: Donghua University Contract record no.: 2010440000497 Denomination of invention: High shearing rate method for spinning poly-terephthaloyl p-phenylenediamine fibre Granted publication date: 20081022 License type: Exclusive License Open date: 20060329 Record date: 20100517 |
|
| EM01 | Change of recordation of patent licensing contract |
Change date: 20110307 Contract record no.: 2010440000497 Assignee after: Guangdong Qiu Sheng Resources Co., Ltd. Assignee before: Puning Qiusheng Chemical Fiber Co., Ltd. |