EP2218807A1 - Wärmebehandlung zur Erhöhung der Druckstärke von PPTA-Filamenten - Google Patents
Wärmebehandlung zur Erhöhung der Druckstärke von PPTA-Filamenten Download PDFInfo
- Publication number
- EP2218807A1 EP2218807A1 EP09153014A EP09153014A EP2218807A1 EP 2218807 A1 EP2218807 A1 EP 2218807A1 EP 09153014 A EP09153014 A EP 09153014A EP 09153014 A EP09153014 A EP 09153014A EP 2218807 A1 EP2218807 A1 EP 2218807A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- ppta
- yarn
- filaments
- heat treatment
- compressive strength
- 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
- 229920003366 poly(p-phenylene terephthalamide) Polymers 0.000 title claims abstract description 45
- 238000010438 heat treatment Methods 0.000 title claims abstract description 41
- 238000000034 method Methods 0.000 claims abstract description 19
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000001301 oxygen Substances 0.000 claims abstract description 8
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 8
- 238000009987 spinning Methods 0.000 claims abstract description 7
- 238000001035 drying Methods 0.000 claims abstract description 5
- 238000005406 washing Methods 0.000 claims abstract description 5
- 239000004148 curcumin Substances 0.000 claims abstract description 4
- 230000007717 exclusion Effects 0.000 claims abstract description 4
- 230000003472 neutralizing effect Effects 0.000 claims abstract description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 9
- 239000004760 aramid Substances 0.000 description 6
- 229920003235 aromatic polyamide Polymers 0.000 description 6
- 125000003118 aryl group Chemical group 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 238000011282 treatment Methods 0.000 description 4
- 238000005259 measurement Methods 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000006835 compression Effects 0.000 description 2
- 238000007906 compression Methods 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- 229920003368 Kevlar® 29 Polymers 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000001112 coagulating effect Effects 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 238000000399 optical microscopy Methods 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000002166 wet spinning Methods 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
Classifications
-
- 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
- D01D10/00—Physical treatment of artificial filaments or the like during manufacture, i.e. during a continuous production process before the filaments have been collected
- D01D10/02—Heat treatment
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/58—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products
- D01F6/60—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polyamides
- D01F6/605—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polyamides from aromatic polyamides
Definitions
- the invention relates to a method for obtaining a PPTA [poly(para-phenylene terephthalamide)] yarn with increased compressive strength and to PPTA yarn thus obtained.
- Heating PPTA yarn is a common process to remove water that adheres to the yarn after neutralizations and washing during the spinning process. Such heating processes typically are performed at about 150 to 250 oC for typically not longer than a few seconds.
- Yarns spun from anisotropic solution of high molecular weight aromatic polyamides are known in literature.
- the process of making wholly aromatic polyamides is taught by Kwolek et al. in US 3,063,966 .
- the processing for spinning wholly aromatic polyamide yarns from anisotropic solutions is taught in US 3,154,610 and US 3,414,645 .
- the preparation of anisotropic dopes of aromatic polyamides is disclosed in US RE 30,352 .
- the present invention allows standard spin dope preparation and dry jet wet (air gap) spinning techniques that can be used without modifications of the aryl moieties as opposed to earlier described.
- Yarns were prepared from PPTA having a compressive strength as high as 1.3 GPa or even higher.
- the invention relates to a method for obtaining a PPTA yarn with increased compressive strength by the steps of air gap spinning a PPTA spin dope to PPTA filaments, bundling the filaments to the yarn, washing and optionally neutralizing and drying the yarn, characterized in that these steps are followed by applying a heat treatment to the PPTA yarn comprising heating the yarn at a temperature of 340 to 510 oC for 5 sec to 5 min under exclusion of oxygen.
- this method renders PPTA yarns having improved compressive strength by applying a heating process for a relatively long time at relatively low tensions.
- This heating step is in addition to the commonly used steps of making PPTA yarns, including air gap spinning, which includes coagulating the spun filaments and bundling these to yarn, followed by one or more of well-known process steps as washing, neutralizing, drying, winding and the like.
- the best compressive strength improvement is obtained when the heat treatment of the yarn is performed at a temperature of 360 to 480 oC for 20 sec to 2 min. It was found that the results improved at higher temperature at the lower end of the claimed time period, thus better results are obtained when the heat treatment is performed at a temperature of 410 to 440 oC for 20 sec to 1 min, or even better when performed at a temperature of 425 to 435 oC for 20 sec to 1 min. In general shorter heating times are used at higher heating temperatures.
- the heat treatment is performed at a tension of 0.02 to 3 cN/dtex, more preferably at a tension of 0.1 to 0.5 cN/dtex, and most preferably at a tension of 0.1 to 0.3 cN/dtex.
- the heating step of this invention is performed under exclusion of oxygen.
- the presence of oxygen during this treatment has a negative influence on the tenacity of the yarn.
- Oxygen therefore must be removed as good as possible from the heating device, such as an oven, for instance by flushing with inert gas such as nitrogen, helium, and the like.
- the amount of oxygen must be brought to less than 1 vol%, preferably less than 0.5 vol%.
- the PPTA yarns were spun from anisotropic solutions of aromatic polyamides in sulfuric acid, but other solvents such as NMP/calcium chloride can also be used.
- the aromatic polyamides were prepared using conventional polycondensation reaction techniques.
- the spin dopes could be prepared by mixing the polymer with sulfuric acid ice.
- the yarns can be spun via the known dry jet wet spinning procedure.
- the present method of the additional heat treatment may render PPTA yarns wherein the filaments have compressive strengths that have never been obtained earlier.
- the compressive strength of the filaments (of PPTA yarns) is higher than in the similar yarns not having undergone the additional heat treatment.
- the invention therefore has also to its objective PPTA yarns wherein the average compressive strength ⁇ c of its filaments is at least 0.8 + 2.5 * 10 -3 * (E-100) GPa, wherein E is the modulus in GPa.
- the term "average compressive strength" ( ⁇ c ) means the average of the measured compressive strength values of 3 filaments that are at randomly taken from the yarn.
- PPTA yarns with compressive strength 0.5 GPa at a modulus of 50 GPa have filaments with compressive strength 0.5 GPa at a modulus of 50 GPa, whereas this PPTA yarn after the heat treatment of this invention has a compressive strength of at least about 0.68 GPa.
- PPTA yarns with compressive strength 0.95 GPa or higher are yarns that have never been obtained earlier.
- PPTA yarns having filaments with compressive strengths of at least 0.95 GPa, more preferably of at least 1 GPa are therefore novel and also an objective of this invention. These yarns with extreme high compressive strength filaments are obtained by selecting optimum heating conditions with regard to temperature and heating time.
- the treatment was done in an oven of 3.66 m length.
- the oven was under nitrogen to a residual level of less than 0.3 vol% oxygen.
- Yarns were equilibrated at 21 °C and 65% RH.
- the compressive strength was determined via the elastica loop test (ELT) according to D.J. Sinclair, J. Appl. Phys., 21 (1950) 380 .
- ELT elastica loop test
- a filament is bent into a single asymmetric loop wherein the diameters are a few millimeters, immersed in paraffin, covered with a glass slide, which is then gradually contracted. Images were acquired during contraction, followed by measuring the c- and ⁇ -axes, wherein the c-axis is the largest diameter and the ⁇ -axis is the smallest diameter of the loop.
- the compressive strength ⁇ c is calculated from c*, which is determined by taking the intersection of two lines that can be drawn through the graph c/a before and after kink bend formation.
- the c* is obtained by semi-automatic drawing both lines.
- solid sulfuric acid having a concentration of 99.8% and high molecular weight PPTA were initially mixed at temperatures below 10 °C, Subsequently, the temperature of the polyamide sulfuric acid mixture was allowed to rise to room temperature resulting in a dry sandy mass, for use in making the spin dope.
- the PPTA and concentrated sulfuric acid can be mixed in a twinscrew extruder above room temperature to directly obtain the spin dope.
- PPTA spin dope was spun to filament yarn of different linear densities and finally washed and dried in the conventional manner.
- the yarn was heat treated in a tube oven at the temperatures and times as indicated in Table 1 in an inert environment (max. 0.25 vol.% O 2 ).
- the properties of these yarns are listed in Table 1.
- PPTA is poly(para-phenyleneterephthalamide);
- Comp. compression Table 1
- Mechanical properties of PPTA yarns after heat treatment Tension cN/dtex Heating time sec Temp °C Linear density dtex Tenacity mN/tex EAB % Modulus GPa Toughness J/g Comp.
Landscapes
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Mechanical Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Artificial Filaments (AREA)
- Inorganic Fibers (AREA)
- Yarns And Mechanical Finishing Of Yarns Or Ropes (AREA)
- Furnace Housings, Linings, Walls, And Ceilings (AREA)
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
ES09153014T ES2379506T3 (es) | 2009-02-17 | 2009-02-17 | Tratamiento térmico para alimentar la resistencia a la compresión de filamentos de PPTA |
PL09153014T PL2218807T3 (pl) | 2009-02-17 | 2009-02-17 | Obróbka cieplna dla zwiększenia wytrzymałości na ściskanie przędzy PPTA |
AT09153014T ATE545723T1 (de) | 2009-02-17 | 2009-02-17 | Wärmebehandlung zur erhöhung der druckstärke von ppta-filamenten |
DK09153014.7T DK2218807T3 (da) | 2009-02-17 | 2009-02-17 | Varmebehandling til forøgelse af trykstyrken af PPTA-filamenter |
EP09153014A EP2218807B1 (de) | 2009-02-17 | 2009-02-17 | Wärmebehandlung zur Erhöhung der Druckstärke von PPTA-Filamenten |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP09153014A EP2218807B1 (de) | 2009-02-17 | 2009-02-17 | Wärmebehandlung zur Erhöhung der Druckstärke von PPTA-Filamenten |
Publications (2)
Publication Number | Publication Date |
---|---|
EP2218807A1 true EP2218807A1 (de) | 2010-08-18 |
EP2218807B1 EP2218807B1 (de) | 2012-02-15 |
Family
ID=41069541
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP09153014A Active EP2218807B1 (de) | 2009-02-17 | 2009-02-17 | Wärmebehandlung zur Erhöhung der Druckstärke von PPTA-Filamenten |
Country Status (5)
Country | Link |
---|---|
EP (1) | EP2218807B1 (de) |
AT (1) | ATE545723T1 (de) |
DK (1) | DK2218807T3 (de) |
ES (1) | ES2379506T3 (de) |
PL (1) | PL2218807T3 (de) |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102286794A (zh) * | 2011-08-09 | 2011-12-21 | 中国石油化工股份有限公司 | 一种高性能纤维及其制备方法 |
CN102839480A (zh) * | 2012-10-02 | 2012-12-26 | 上海会博新材料科技有限公司 | 一种提高对位芳纶纤维在光缆增强中强度利用率的方法 |
CN112458583A (zh) * | 2020-10-22 | 2021-03-09 | 烟台泰和新材料股份有限公司 | 一种对位芳纶纤维及其制备方法和在制备熔融金属飞溅防护服装方面的应用 |
CN116005486A (zh) * | 2022-12-27 | 2023-04-25 | 东华大学 | 一种对位芳纶纸及其制备方法 |
Citations (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3063966A (en) | 1958-02-05 | 1962-11-13 | Du Pont | Process of making wholly aromatic polyamides |
US3154610A (en) | 1961-05-31 | 1964-10-27 | Celanese Corp | Process of wet spinning polyamides and prevention of gel formation |
US3414645A (en) | 1964-06-19 | 1968-12-03 | Monsanto Co | Process for spinning wholly aromatic polyamide fibers |
US3673143A (en) * | 1970-06-24 | 1972-06-27 | Du Pont | Optically anisotropic spinning dopes of polycarbonamides |
US3869430A (en) | 1971-08-17 | 1975-03-04 | Du Pont | High modulus, high tenacity poly(p-phenylene terephthalamide) fiber |
USRE30352E (en) | 1966-06-13 | 1980-07-29 | E. I. Du Pont De Nemours And Company | Optically anisotropic aromatic polyamide dopes |
EP0247889A2 (de) * | 1986-05-30 | 1987-12-02 | E.I. Du Pont De Nemours And Company | Poly-p-phenylenterephthalamidfaser mit hohem Modulus |
EP0388878A2 (de) * | 1989-03-20 | 1990-09-26 | E.I. Du Pont De Nemours And Company | On-Line-Faserbehandlung |
EP0759454A1 (de) * | 1994-05-11 | 1997-02-26 | Asahi Kasei Kogyo Kabushiki Kaisha | Paraaromatischer polyamidgegenstand und verfahren zu seiner herstellung |
US20040022981A1 (en) * | 2002-04-01 | 2004-02-05 | Carbon Nanotechnologies, Inc. | Composite of single-wall carbon nanotubes and aromatic polyamide and process for making the same |
JP2007297722A (ja) * | 2006-04-27 | 2007-11-15 | Du Pont Toray Co Ltd | ポリパラフェニレンテレフタルアミド繊維および製造方法ならびに用途 |
WO2008075751A1 (ja) * | 2006-12-15 | 2008-06-26 | Teijin Techno Products Limited | ヘテロ環含有芳香族ポリアミド繊維及びその製造方法、並びに該繊維から構成された布帛及び該繊維により補強された繊維強化複合材料 |
-
2009
- 2009-02-17 PL PL09153014T patent/PL2218807T3/pl unknown
- 2009-02-17 DK DK09153014.7T patent/DK2218807T3/da active
- 2009-02-17 AT AT09153014T patent/ATE545723T1/de active
- 2009-02-17 ES ES09153014T patent/ES2379506T3/es active Active
- 2009-02-17 EP EP09153014A patent/EP2218807B1/de active Active
Patent Citations (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3063966A (en) | 1958-02-05 | 1962-11-13 | Du Pont | Process of making wholly aromatic polyamides |
US3154610A (en) | 1961-05-31 | 1964-10-27 | Celanese Corp | Process of wet spinning polyamides and prevention of gel formation |
US3414645A (en) | 1964-06-19 | 1968-12-03 | Monsanto Co | Process for spinning wholly aromatic polyamide fibers |
USRE30352E (en) | 1966-06-13 | 1980-07-29 | E. I. Du Pont De Nemours And Company | Optically anisotropic aromatic polyamide dopes |
US3673143A (en) * | 1970-06-24 | 1972-06-27 | Du Pont | Optically anisotropic spinning dopes of polycarbonamides |
US3869430A (en) | 1971-08-17 | 1975-03-04 | Du Pont | High modulus, high tenacity poly(p-phenylene terephthalamide) fiber |
EP0247889A2 (de) * | 1986-05-30 | 1987-12-02 | E.I. Du Pont De Nemours And Company | Poly-p-phenylenterephthalamidfaser mit hohem Modulus |
EP0388878A2 (de) * | 1989-03-20 | 1990-09-26 | E.I. Du Pont De Nemours And Company | On-Line-Faserbehandlung |
EP0759454A1 (de) * | 1994-05-11 | 1997-02-26 | Asahi Kasei Kogyo Kabushiki Kaisha | Paraaromatischer polyamidgegenstand und verfahren zu seiner herstellung |
US20040022981A1 (en) * | 2002-04-01 | 2004-02-05 | Carbon Nanotechnologies, Inc. | Composite of single-wall carbon nanotubes and aromatic polyamide and process for making the same |
JP2007297722A (ja) * | 2006-04-27 | 2007-11-15 | Du Pont Toray Co Ltd | ポリパラフェニレンテレフタルアミド繊維および製造方法ならびに用途 |
WO2008075751A1 (ja) * | 2006-12-15 | 2008-06-26 | Teijin Techno Products Limited | ヘテロ環含有芳香族ポリアミド繊維及びその製造方法、並びに該繊維から構成された布帛及び該繊維により補強された繊維強化複合材料 |
Non-Patent Citations (4)
Title |
---|
D.J. SINCLAIR, J. APPL. PHYS., vol. 21, 1950, pages 380 |
D.J. SWEENEY, HIGH PERF. POLYM., vol. 14, 2002, pages 133 - 143 |
M.G. NORTHOLT; D.J. SIKKEMA, ADV. IN POL. SCI., vol. 98, 1990, pages 336 |
SWEENY, W.: "Improvements in compressive properties of high modulus yarns by crosslinking", J. POLYM. SCI., PART A: POLYM. CHEM., vol. 30, no. 6, 1992, pages 1111 - 1122 |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102286794A (zh) * | 2011-08-09 | 2011-12-21 | 中国石油化工股份有限公司 | 一种高性能纤维及其制备方法 |
CN102286794B (zh) * | 2011-08-09 | 2013-06-12 | 中国石油化工股份有限公司 | 一种纤维及其制备方法 |
CN102839480A (zh) * | 2012-10-02 | 2012-12-26 | 上海会博新材料科技有限公司 | 一种提高对位芳纶纤维在光缆增强中强度利用率的方法 |
CN112458583A (zh) * | 2020-10-22 | 2021-03-09 | 烟台泰和新材料股份有限公司 | 一种对位芳纶纤维及其制备方法和在制备熔融金属飞溅防护服装方面的应用 |
CN112458583B (zh) * | 2020-10-22 | 2021-09-17 | 烟台泰和新材料股份有限公司 | 一种对位芳纶纤维及其制备方法和在制备熔融金属飞溅防护服装方面的应用 |
CN116005486A (zh) * | 2022-12-27 | 2023-04-25 | 东华大学 | 一种对位芳纶纸及其制备方法 |
Also Published As
Publication number | Publication date |
---|---|
EP2218807B1 (de) | 2012-02-15 |
ES2379506T3 (es) | 2012-04-26 |
ATE545723T1 (de) | 2012-03-15 |
DK2218807T3 (da) | 2012-03-26 |
PL2218807T3 (pl) | 2012-05-31 |
ES2379506T8 (es) | 2012-06-11 |
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