EP0581145B2 - Verfahren und Vorrichtung zur Herstellung von Fasern, die während des Verspinnens störende Gase und/oder Dämpfe abgeben - Google Patents
Verfahren und Vorrichtung zur Herstellung von Fasern, die während des Verspinnens störende Gase und/oder Dämpfe abgeben Download PDFInfo
- Publication number
- EP0581145B2 EP0581145B2 EP93111453A EP93111453A EP0581145B2 EP 0581145 B2 EP0581145 B2 EP 0581145B2 EP 93111453 A EP93111453 A EP 93111453A EP 93111453 A EP93111453 A EP 93111453A EP 0581145 B2 EP0581145 B2 EP 0581145B2
- Authority
- EP
- European Patent Office
- Prior art keywords
- spinning
- spinning shaft
- gas
- shaft
- gases
- 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.)
- Expired - Lifetime
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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
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/08—Melt spinning methods
- D01D5/088—Cooling filaments, threads or the like, leaving the spinnerettes
- D01D5/092—Cooling filaments, threads or the like, leaving the spinnerettes in shafts or chimneys
-
- 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
- D01F6/76—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from other polycondensation products
- D01F6/765—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from other polycondensation products from polyarylene sulfides
Definitions
- thermoplastic polymers in which encapsulated spinning shafts are used are known per se.
- EP-A-147, 173 describes a melt spinning process of thermoplastic polymers, in which the polymer is extruded into a pressurized spinning shaft and is cooled within this shaft. Furthermore, an adapted device for carrying out the method is described, which has a specially designed outlet opening for the solidified filaments drawn off at high speed and with which a good sealing of the spinning shaft can be achieved. The device and the method are primarily aimed at producing a highly oriented multifilament yarn.
- EP-A-205,694 describes a melt spinning process of thermoplastic polymers, in which the polymer is extruded into a spinning shaft which is under a vacuum of less than 0.7 atm and is cooled within this shaft.
- the device for carrying out this method essentially relates to the device known from EP-A-147, 173 , to whose outlet side a vacuum pump is connected for the gas located in the spinning shaft.
- monomers and oligomers evaporating from the spun threads are removed from the spinning shaft by the gas flow, so that problems with residues deposited in the spinning shaft can be avoided.
- the device and the method are also aimed at producing a highly oriented multifilament yarn.
- melt spinning polymers are common interfering gases and / or vapors free.
- spinning polymers containing sulfur-containing Ingredients become strong smelling and possibly even harmful gases or vapors released. This problem is particularly pronounced when spinning multifilaments, as these result from the high surface of the molten capillaries release large quantities of such harmful gases.
- the present invention is based on the object occurring when spinning polymers to keep disturbing gases away from the environment remove.
- Fibers made of polymers that during disruptive gases and / or vapors from spinning such fibers are within the scope of this invention to understand those during melt spinning Gases and / or vapors released in the spinning shaft be escaping into the ambient air is not desired.
- gases and / or vapors released in the spinning shaft be escaping into the ambient air are not desired.
- gases and / or vaporous components include, for example, the so-called “spinning smoke” and especially gas and / or vaporous components, the sulfur-containing or halogen-containing, in particular chlorine-containing, or contain components containing sulfur and halogen.
- the polymers that make the latter gas and / or releasing vaporous constituents include sulphurous ones Polymers, such as polyarylene sulfides or polymers, the before or during spinning with halogen and / or sulfur-containing additives are.
- the process according to the invention is preferably used in the spinning of polyarylene sulfides or in the spinning of mixtures comprising polyarylene sulfides and other thermoplastic polymers.
- All filament-forming polymers which mainly have the recurring structural unit of the formula I can be used as polyarylene sulfides for use in the process according to the invention -Ar-S- in which Ar represents a divalent mono- or polynuclear aromatic radical, the free valences of which are in the p-position or in the m-position or in a parallel or angled position comparable to these positions.
- the polymers can also be partially crosslinked structures as long as they can be spun under the spinning conditions defined above.
- thermoplastics mixed with polyarylene sulfides can be used are polyester, such as polyethylene terephthalate; Poly- ⁇ -olefins, such as Polyethylene or polypropylene; partially or perfluorinated Polymers such as polytetrafluoroethylene; or to the Melting characteristics of the polyarylene sulfide customized polyether ketone.
- Polyarylene sulfides especially polyphenylene sulfides to polymers in which Ar is a p-phenylene radical represents.
- Preferred polyphenylene sulfides have a melt viscosity, measured at a shear rate of 1000 sec -1 ( ⁇ 1000 ), of 60 to 150 Pa * s at 320 ° C. and a melt viscosity, measured at a shear rate of 3000 sec -1 ( ⁇ 3000 ), of more than 50 Pa * s , the difference between ⁇ 1000 and ⁇ 3000 being more than 20 Pa * s .
- the polyarylene sulfide is usually subjected to a drying process before spinning.
- the polymer is generally dried in a finely divided form, such as powder or granule form, and in particular in the form of chips, preferably under vacuum. Usual drying times are between six and ten hours.
- the drying temperature is usually 120 to 160 ° C , preferably 120 to 140 ° C.
- the drying can also be carried out under inert gas.
- a polyarylene sulfide is particularly preferably used, whose water content is at most 0.01%, measured according to the Karl Fischer method. Using this raw material can be particularly set stable spinning conditions.
- thread-forming Polymers melt-spun, the melted Polymers using an extruder and a Spinning pump through a spinneret into a closed Spinning shaft is spun.
- the minimum delivery rate of polymer through the spinneret is preferably 0.5 g / (min * hole). Particularly preferred delivery rates are in the range of 0.7 to 1.3 g / (min * hole).
- the temperatures in the spinneret are usually 280 to 320 ° C., preferably 295 to 315 ° C.
- Typical number of holes in a spinneret are in the range from 50 to 500, in particular from 100 to 500.
- the shape of the nozzle holes can also be chosen as desired, for example triangular or rectangular, multilobal, oval or in particular round.
- Typical diameters of the nozzle holes are in the range from 0.25 to 0.65 mm.
- the nozzle holes are preferably in an annular nozzle arranged in the form of concentric circles.
- the spinning takes place in a closed Spinning shaft in a gas, especially in air, or also in an inert gas such as nitrogen.
- closed spinning shaft is to be understood in the context of this invention, a spinning shaft in which the supply and discharge of the blowing gas mainly, for example, more than 90 %, takes place via the supply and discharge lines for the blowing gas, and in which only a small part of the blowing gas leaves the spinning shaft through the outlet opening for the filaments formed.
- This outlet opening must therefore be designed in this way be that in addition to the high penetration speed the filaments formed also a good finish to prevent the contaminated blowing air from escaping allowed inside the spinning shaft.
- the freshly spun one Pass the thread out through a labyrinth seal or through perforated end plates, under or between which an additional auxiliary suction sucked off entrained blowing gas.
- the spinning shaft can be operated with negative pressure, external pressure or positive pressure.
- a slight negative pressure is maintained in the spinning shaft, preferably a negative pressure between 20 and 150 Pa, against the environment. In the event of leaks or pressure fluctuations, this variant prevents the contaminated blowing air from escaping immediately into the environment.
- the filaments created are after extrusion through the spinneret of a forced cooling in Subjected to spinning shaft by blowing with a gas. All the usual methods of Blowing are used. In addition to the possible Cross-blowing comes especially the central blowing in question. The blowing is particularly important preferred from the inside out.
- a gas can Inert gas, such as nitrogen. Is preferred Air.
- the spinning take-off speed of the filaments when leaving the spinning shaft can be more than 500 m / min, preferably between 800 and 5000 m / min, and in particular 1000 to 2000 m / min.
- Suitable adsorbents are silica gel or in particular activated carbon.
- the adsorbents are preferably in barrel form with supply and discharge and preferably, the required Fan-provided vessels used.
- Such Gas cleaning systems are commercially available in modular construction available.
- the spun ones are prepared Filaments aftertreated in a manner known per se. For this purpose they become, for example, an avivation, Drawing, which may also be multi-stage can and if necessary subjected to a fixation.
- the aftertreatment can be continued immediately after take off from the spinning machine or after an intermediate storage of the freshly spun Filaments.
- the obtained filaments either wound or in cut into staple fibers in a known manner.
- the invention also relates to a specially designed device according to claim 13 for carrying out the method according to the invention.
- Preferred embodiments of the device according to the invention are defined in claims 14 to 17 .
- thermoplastic polymer to be spun is melted via an extruder ( 1 ) and transported to a spinning pump ( 2 ).
- the extruder is fed with polymer chips, for example.
- the spinning pump ( 2 ) feeds the spin pack ( 3 ), which contains filters ( 4 ) and spinnerets ( 5 ).
- the spinnerets ( 5 ) open directly into a closed spinning shaft ( 6 ) which has at least one feed line ( 7 ) and one discharge line ( 8 ) for the blowing gas.
- 1 shows two discharge lines ( 8 ) for the blowing gas at the upper and lower ends of the spinning shaft.
- an auxiliary suction line ( 12 ) for the blowing gas is provided in this figure 1 , which is attached to the lower end of the spinning shaft next to the outlet opening for the filaments.
- all discharge lines for the blowing gas are equipped with a gas cleaning system ( 9 ). However, it is entirely possible to have all discharge lines lead to a gas cleaning system. The cleaned blowing air is drawn off from the gas cleaning system by pumps ( 18 ).
- FIG. 1 a central blowing device ( 11 ) is shown in FIG. 1 , from which the blowing gas ( 10 ) flows radially from the inside out through the filaments formed.
- blowing devices can be formed from pipes, the jacket of which has bores or other openings, such as slots or sieves, or which preferably consists of sintered metal.
- the central blowing from the inside out is particularly advantageous because with this embodiment a particularly stable running of the filaments enables becomes.
- the filaments ( 14 ) are prepared by means of application rollers ( 15 ), passed over a deflecting godet ( 16 ) and wound onto a spool ( 17 ). The spun filaments can then be sent for further processing.
- the blowing gas is expediently blown into the closed spinning shaft ( 6 ) via a fan through the feed line ( 7 ).
- At least one of the discharge lines ( 8 ) is equipped with a second fan, for example the suction line at the lower end of the spinning shaft in FIG. 1 .
- the pressure inside the spinning shaft can be regulated via the different performance of the fans in the supply and discharge lines.
- the spinning shaft must be used to operate the spinning system be opened during operation of the system.
- the spinning shaft preferably has its purpose below the spinneret has a device that opens of the spinning shaft when operating the system.
- a second powerful Suction in the area of the shaft opening under the nozzle, preferably on both sides under the Nozzle is attached when opening the shaft doors is turned on and the leakage of contaminated Blowing gas into the room in front of the shaft when open Door prevented.
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- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Mechanical Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Spinning Methods And Devices For Manufacturing Artificial Fibers (AREA)
- Artificial Filaments (AREA)
Description
Claims (17)
- Verfahren zur Herstellung von Fasern aus Polymeren, die während des Verspinnens störende Gase und/oder Dämpfe abgeben umfassend die Schritte:a) Extrudieren des geschmolzenen Polymeren durch eine Spinndüse in einen Spinnschacht,b) Anblasen der erhaltenen Filamente im Spinnschacht mit einem Gas,c) Abziehen der gebildeten Filamente aus dem Spinnschacht,d) Ableitung des Anblasgases aus dem Spinnschacht,
- Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß es sich bei dem Polymeren um ein Polyarylensulfid oder eine Mischung von Polyarylensulfiden oder eine Mischung von Polyarylensulfid und anderen thermoplastischen Polymeren handelt.
- Verfahren nach Anspruch 2, dadurch gekennzeichnet, daß es sich bei dem Polyarylensulfid um p-Polyphenylensuifid oder um eine Mischung von p-Polyphenylensulfiden handelt.
- Verfahren nach Anspruch 2, dadurch gekennzeichnet, daß Polyphenylensulfide eingesetzt werden, die bei 320°C eine Schmelzviskosität, gemessen mit einer Schergeschwindigkeit von 1000 sec-1 (η1000), von 60 bis 150 Pa*s und eine Schmelzviskosität, gemessen mit einer Schergeschwindigkeit von 3000 sec-1 (η3000), von mehr als 50 Pa*s aufweisen, wobei die Differenz von η1000 und η3000 mehr als 20 Pa*s beträgt.
- Verfahren nach Anspruch 2, dadurch gekennzeichnet, daß das Polyarylensulfid vor dem Verspinnen in feinverteilter Form getrocknet wird.
- Verfahren nach Anspruch 5, dadurch gekennzeichnet, daß die Trocknung unter Vakuum erfolgt, und daß die Trocknung durchgeführt wird, bis ein Wassergehalt des Polymeren von höchstens 0,01 %, gemessen nach der Methode nach Karl-Fischer, erreicht ist.
- Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß die Spinndüsen mehr als 100 Düsenlöcher aufweisen, die bevorzugt auf konzentrischen Kreisen angeordnet sind.
- Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß im Spinnschacht ein Unterdruck, insbesondere ein Unterdruck zwischen 20 und 150 Pa, gegen die Umgebung aufrechterhalten wird.
- Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß eine Förderleistung des Polymeren durch die Spinndüse von mindestens 0,5 g/(min*Loch) gewählt wird.
- Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß die ersponnenen Filamente mit einer Geschwindigkeit von mehr als 500 m/min, insbesondere von 800 bis 3000 m/min, aus dem Spinnschacht abgezogen werden.
- Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß das Anblasgas radial auf die ersponnenen Filamente einströmt, wobei die Anblasung insbesondere von innen nach außen erfolgt.
- Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß es sich bei dem Adsorptionsmittel für besagte störende Gase und/oder Dämpfe um Aktivkohle handelt.
- Vorrichtung zur Durchführung des Verfahrens nach den Ansprüchen 1 bis 12 zur Herstellung von schmelzgesponnen Filamenten, insbesondere von Multifilamenten aus Polymeren, die während des Verspinnens störende Gase und/oder Dämpfe abgeben umfassend Extruder (1), Spinnpumpe (2) und Spinnpack (3) aus Filter (4) und Spinndüsen (5), die in einen geschlossenen Spinnschacht (6) münden, welcher zumindest eine Zuführleitung (7) und eine Abführleitung (8) für das Anblasgas aufweist, wobei zumindest eine besagte Abführleitung (8) in ein Gasreinigungssystem (9) mündet, in welchem das Anblasgas (10) von besagten Gasen und/oder Dämpfen gereinigt wird.
- Vorrichtung nach Anspruch 13, dadurch gekennzeichnet, daß die Zuführleitung (7) in eine zentrale Anblasvorrichtung (11) mündet, von welcher das Anblasgas (10) radial von innen nach außen durch die gebildeten Filamente strömt.
- Vorrichtung nach Anspruch 13, dadurch gekennzeichnet, daß jeweils am oberen und am unteren Ende des Spinnschachtes (6) Absaugleitungen (8) für das Anblasgas vorgesehen sind, die in ein oder jeweils in ein Gasreinigungssystem (9) münden.
- Vorrichtung nach Anspruch 13, dadurch gekennzeichnet, daß neben der Austrittsöffnung für die Filamente am unteren Ende des Spinnschachtes eine zusätzliche Hilfsabsaugleitung (12) für das Anblasgas vorgesehen ist, das in ein Gasreinigungssystem (9) mündet.
- Vorrichtung nach Anspruch 15, dadurch gekennzeichnet, daß der Spinnschacht unterhalb der Spinndüse eine Vorrichtung aufweist, die ein Öffnen des Spinnschachtes beim Betrieb der Anlage gestattet und daß die am oberen Ende des Spinnschachtes (6) vorhandenen Absaugleitungen (8) für das Anblasgas mit einer leistungsstarken Absaugung versehen sind, die beim Öffnen der Schachttüren eingeschaltet wird und den Austritt von verunreinigtem Anblasgas in den Raum vor dem Schacht bei offener Türe verhindert.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE4224707 | 1992-07-25 | ||
DE4224707 | 1992-07-25 |
Publications (4)
Publication Number | Publication Date |
---|---|
EP0581145A2 EP0581145A2 (de) | 1994-02-02 |
EP0581145A3 EP0581145A3 (en) | 1994-08-10 |
EP0581145B1 EP0581145B1 (de) | 1997-10-08 |
EP0581145B2 true EP0581145B2 (de) | 2001-07-18 |
Family
ID=6464161
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP93111453A Expired - Lifetime EP0581145B2 (de) | 1992-07-25 | 1993-07-16 | Verfahren und Vorrichtung zur Herstellung von Fasern, die während des Verspinnens störende Gase und/oder Dämpfe abgeben |
Country Status (8)
Country | Link |
---|---|
US (1) | US5370833A (de) |
EP (1) | EP0581145B2 (de) |
JP (1) | JPH06158414A (de) |
AT (1) | ATE159057T1 (de) |
DE (1) | DE59307483D1 (de) |
DK (1) | DK0581145T4 (de) |
ES (1) | ES2110033T5 (de) |
GR (1) | GR3025234T3 (de) |
Families Citing this family (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5935512A (en) * | 1996-12-30 | 1999-08-10 | Kimberly-Clark Worldwide, Inc. | Nonwoven process and apparatus |
DE19830453A1 (de) * | 1998-07-08 | 2000-01-13 | Lurgi Zimmer Ag | Verfahren und Vorrichtung zum Transport von Dampf durch mindestens einen runden Spinndüsenschacht |
KR100391706B1 (ko) * | 2001-01-29 | 2003-07-12 | 덕산공조기계주식회사 | 섬유방사기용 환기 시스템 |
KR100468086B1 (ko) * | 2002-12-04 | 2005-01-26 | 난야 플라스틱스 코오퍼레이션 | 가는(細) 데니어 폴리에스터 중공예비연신사의 제조방법 및 그 방법으로 제조된 가는 데니어 폴리에스터 중공예비연신사 |
KR20040049722A (ko) * | 2002-12-07 | 2004-06-12 | 난야 플라스틱스 코오퍼레이션 | 복수개의 가는 데니어 폴리에스터 예비연신얀의 제조방법및 그 방법에 의하여 제조된 복수개의 가는 데니어폴리에스터 예비연신얀 |
US6926854B2 (en) * | 2003-06-25 | 2005-08-09 | Nan Ya Plastics Corporation | Process of making polyester fine denier multifilament |
CA2601751A1 (en) * | 2005-03-18 | 2006-09-21 | Diolen Industrial Fibers B.V. | Process for producing polyphenylene sulfide filament yarns |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
SU998605A1 (ru) † | 1981-01-16 | 1983-02-23 | Всесоюзный Научно-Исследовательский Институт Машин Для Производства Синтетических Волокон | Устройство дл охлаждени свежесформованной нити |
DE3629731A1 (de) † | 1985-09-18 | 1987-03-26 | Inventa Ag | Vorrichtung zum abkuehlen und praeparieren von schmelzgesponnenem spinngut |
DE3708168A1 (de) † | 1987-03-05 | 1988-09-15 | Inventa Ag | Vorrichtung zum abkuehlen und praeparieren von schmelzgesponnenem spinngut |
Family Cites Families (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2886848A (en) * | 1955-02-10 | 1959-05-19 | American Enka Corp | Blow box |
NL271547A (de) * | 1960-11-18 | |||
DE2009297C3 (de) * | 1970-02-27 | 1983-03-31 | Metallgesellschaft Ag, 6000 Frankfurt | Adsorptionsanlage zum Abscheiden von Schwefelverbindungen aus Gasen |
JPS52155216A (en) * | 1976-06-18 | 1977-12-23 | Mitsubishi Rayon Co Ltd | Process and apparatus for dry spinning |
JPS55137207A (en) * | 1979-04-13 | 1980-10-25 | Toray Ind Inc | Melt-spinning device for synthetic fiber |
DE3335735C2 (de) * | 1983-10-01 | 1986-11-27 | Werner H.K. Peters Maschinenfabrik Gmbh, 2000 Hamburg | Verfahren zur Herstellung von Wellpappe |
US4702871A (en) * | 1985-06-20 | 1987-10-27 | Toray Industries, Inc. | Method for melt-spinning thermoplastic polymer fibers |
US4780073A (en) * | 1985-06-20 | 1988-10-25 | Toray Industries, Inc. | Apparatus for melt-spinning thermoplastic polymer fibers |
-
1993
- 1993-07-16 DK DK93111453T patent/DK0581145T4/da active
- 1993-07-16 AT AT93111453T patent/ATE159057T1/de not_active IP Right Cessation
- 1993-07-16 ES ES93111453T patent/ES2110033T5/es not_active Expired - Lifetime
- 1993-07-16 EP EP93111453A patent/EP0581145B2/de not_active Expired - Lifetime
- 1993-07-16 DE DE59307483T patent/DE59307483D1/de not_active Expired - Fee Related
- 1993-07-26 JP JP5183896A patent/JPH06158414A/ja active Pending
- 1993-07-26 US US08/097,121 patent/US5370833A/en not_active Expired - Lifetime
-
1997
- 1997-10-31 GR GR970402870T patent/GR3025234T3/el unknown
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
SU998605A1 (ru) † | 1981-01-16 | 1983-02-23 | Всесоюзный Научно-Исследовательский Институт Машин Для Производства Синтетических Волокон | Устройство дл охлаждени свежесформованной нити |
DE3629731A1 (de) † | 1985-09-18 | 1987-03-26 | Inventa Ag | Vorrichtung zum abkuehlen und praeparieren von schmelzgesponnenem spinngut |
DE3708168A1 (de) † | 1987-03-05 | 1988-09-15 | Inventa Ag | Vorrichtung zum abkuehlen und praeparieren von schmelzgesponnenem spinngut |
Non-Patent Citations (9)
Title |
---|
Derwent Abstract der SU-A-998605 † |
Deutsche übersetzung der SU-A-998605 † |
Kirk-Othmer, Encyclopedia of Chemical Technology (1978), Vol. 1, S.544 + 545 † |
Römpps Chemie-Lexikon (1979), S.97 † |
Römpps Chemie-Lexikon (1981), S. 1414 † |
Ullmann's Encyclopedia of Industrial Chemistry (1987), Vol. A10, Chapter Fibers, General Production Technology, S. 511-566, insbes. S. 511, 535, 541, 542, 550, 552 † |
Ullmann's Encyclopedia of Industrial Chemistry (1989), Vol. A12, S. 183 + 184 † |
Ullmann's Encyklopädie der technischen Chemie (1972), Bd. 2, S.600, 613, 614 † |
Ullmann's Encyklopädie der technischen Chemie (1976), Bd. 11, S.249-290, insb. S.253, 264 † |
Also Published As
Publication number | Publication date |
---|---|
ES2110033T3 (es) | 1998-02-01 |
GR3025234T3 (en) | 1998-02-27 |
JPH06158414A (ja) | 1994-06-07 |
ATE159057T1 (de) | 1997-10-15 |
EP0581145A3 (en) | 1994-08-10 |
EP0581145B1 (de) | 1997-10-08 |
EP0581145A2 (de) | 1994-02-02 |
ES2110033T5 (es) | 2001-09-01 |
US5370833A (en) | 1994-12-06 |
DK0581145T4 (da) | 2001-11-12 |
DK0581145T3 (da) | 1998-05-18 |
DE59307483D1 (de) | 1997-11-13 |
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