EP2218807A1 - Wärmebehandlung zur Erhöhung der Druckstärke von PPTA-Filamenten - Google Patents

Wärmebehandlung zur Erhöhung der Druckstärke von PPTA-Filamenten Download PDF

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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
Application number
EP09153014A
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English (en)
French (fr)
Other versions
EP2218807B1 (de
Inventor
Alwin Knijnenberg
Leonardus Antonius Godfried Busscher
Theodorus Jacobus Dingemans
Johannes Bos
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Teijin Aramid BV
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Teijin Aramid BV
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Publication date
Application filed by Teijin Aramid BV filed Critical Teijin Aramid BV
Priority to AT09153014T priority Critical patent/ATE545723T1/de
Priority to PL09153014T priority patent/PL2218807T3/pl
Priority to EP09153014A priority patent/EP2218807B1/de
Priority to DK09153014.7T priority patent/DK2218807T3/da
Priority to ES09153014T priority patent/ES2379506T3/es
Publication of EP2218807A1 publication Critical patent/EP2218807A1/de
Application granted granted Critical
Publication of EP2218807B1 publication Critical patent/EP2218807B1/de
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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.
EP09153014A 2009-02-17 2009-02-17 Wärmebehandlung zur Erhöhung der Druckstärke von PPTA-Filamenten Active EP2218807B1 (de)

Priority Applications (5)

Application Number Priority Date Filing Date Title
AT09153014T ATE545723T1 (de) 2009-02-17 2009-02-17 Wärmebehandlung zur erhöhung der druckstärke von ppta-filamenten
PL09153014T PL2218807T3 (pl) 2009-02-17 2009-02-17 Obróbka cieplna dla zwiększenia wytrzymałości na ściskanie przędzy PPTA
EP09153014A EP2218807B1 (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
ES09153014T ES2379506T3 (es) 2009-02-17 2009-02-17 Tratamiento térmico para alimentar la resistencia a la compresión de filamentos de PPTA

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

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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 (3)

* Cited by examiner, † Cited by third party
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

Citations (12)

* Cited by examiner, † Cited by third party
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

Patent Citations (12)

* Cited by examiner, † Cited by third party
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

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* Cited by examiner, † Cited by third party
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 (5)

* Cited by examiner, † Cited by third party
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

Also Published As

Publication number Publication date
EP2218807B1 (de) 2012-02-15
ATE545723T1 (de) 2012-03-15
ES2379506T8 (es) 2012-06-11
DK2218807T3 (da) 2012-03-26
PL2218807T3 (pl) 2012-05-31
ES2379506T3 (es) 2012-04-26

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