ATE81512T1 - Katalysator zur polymerisierung von alpha-olefin und verfahren. - Google Patents
Katalysator zur polymerisierung von alpha-olefin und verfahren.Info
- Publication number
- ATE81512T1 ATE81512T1 AT87905645T AT87905645T ATE81512T1 AT E81512 T1 ATE81512 T1 AT E81512T1 AT 87905645 T AT87905645 T AT 87905645T AT 87905645 T AT87905645 T AT 87905645T AT E81512 T1 ATE81512 T1 AT E81512T1
- Authority
- AT
- Austria
- Prior art keywords
- alpha
- olefins
- transition metal
- solid catalyst
- cpd
- Prior art date
Links
- 239000004711 α-olefin Substances 0.000 title abstract 6
- 238000000034 method Methods 0.000 title abstract 2
- 239000002685 polymerization catalyst Substances 0.000 title 1
- 239000011949 solid catalyst Substances 0.000 abstract 3
- 229910052723 transition metal Inorganic materials 0.000 abstract 3
- 150000003624 transition metals Chemical class 0.000 abstract 3
- 125000000217 alkyl group Chemical group 0.000 abstract 2
- 125000003118 aryl group Chemical group 0.000 abstract 2
- 239000003054 catalyst Substances 0.000 abstract 2
- 125000001485 cycloalkadienyl group Chemical group 0.000 abstract 2
- 229910052735 hafnium Inorganic materials 0.000 abstract 2
- 125000005843 halogen group Chemical group 0.000 abstract 2
- 229910052719 titanium Inorganic materials 0.000 abstract 2
- 229910052726 zirconium Inorganic materials 0.000 abstract 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 abstract 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract 1
- 239000004215 Carbon black (E152) Substances 0.000 abstract 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 abstract 1
- 239000005977 Ethylene Substances 0.000 abstract 1
- 101100240985 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) nrc-2 gene Proteins 0.000 abstract 1
- 125000003710 aryl alkyl group Chemical group 0.000 abstract 1
- 229910052796 boron Inorganic materials 0.000 abstract 1
- 229910052799 carbon Inorganic materials 0.000 abstract 1
- 239000000969 carrier Substances 0.000 abstract 1
- 125000000753 cycloalkyl group Chemical group 0.000 abstract 1
- 229930195733 hydrocarbon Natural products 0.000 abstract 1
- 150000002430 hydrocarbons Chemical group 0.000 abstract 1
- 229910052809 inorganic oxide Inorganic materials 0.000 abstract 1
- 229910052744 lithium Inorganic materials 0.000 abstract 1
- 229910052749 magnesium Inorganic materials 0.000 abstract 1
- 125000002370 organoaluminium group Chemical group 0.000 abstract 1
- 229910052725 zinc Inorganic materials 0.000 abstract 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F110/02—Ethene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/62—Refractory metals or compounds thereof
- C08F4/64—Titanium, zirconium, hafnium or compounds thereof
- C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
- C08F4/65912—Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with an organoaluminium compound
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/62—Refractory metals or compounds thereof
- C08F4/64—Titanium, zirconium, hafnium or compounds thereof
- C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
- C08F4/65916—Component covered by group C08F4/64 containing a transition metal-carbon bond supported on a carrier, e.g. silica, MgCl2, polymer
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/62—Refractory metals or compounds thereof
- C08F4/64—Titanium, zirconium, hafnium or compounds thereof
- C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
- C08F4/6592—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/62—Refractory metals or compounds thereof
- C08F4/64—Titanium, zirconium, hafnium or compounds thereof
- C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
- C08F4/6592—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring
- C08F4/65922—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring containing at least two cyclopentadienyl rings, fused or not
- C08F4/65925—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring containing at least two cyclopentadienyl rings, fused or not two cyclopentadienyl rings being mutually non-bridged
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Applications Claiming Priority (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP19803786 | 1986-08-26 | ||
| JP19803886A JPH0832735B2 (ja) | 1986-08-26 | 1986-08-26 | オレフインの重合方法 |
| JP61203638A JP2530624B2 (ja) | 1986-09-01 | 1986-09-01 | オレフインの重合方法 |
| JP3459187A JPH0780936B2 (ja) | 1986-08-26 | 1987-02-19 | オレフインの重合方法 |
| PCT/JP1987/000629 WO1988001626A1 (fr) | 1986-08-26 | 1987-08-26 | CATALYSEUR DE POLYMERISATION D'alpha-OLEFINE ET PROCEDE DE POLYMERISATION |
| EP87905645A EP0279863B1 (de) | 1986-08-26 | 1987-08-26 | Katalysator zur polymerisierung von alpha-olefin und verfahren |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| ATE81512T1 true ATE81512T1 (de) | 1992-10-15 |
Family
ID=27459955
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| AT87905645T ATE81512T1 (de) | 1986-08-26 | 1987-08-26 | Katalysator zur polymerisierung von alpha-olefin und verfahren. |
Country Status (5)
| Country | Link |
|---|---|
| EP (1) | EP0279863B1 (de) |
| AT (1) | ATE81512T1 (de) |
| CA (1) | CA1319142C (de) |
| DE (1) | DE3782243T2 (de) |
| WO (1) | WO1988001626A1 (de) |
Families Citing this family (126)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0812862B1 (de) * | 1986-09-24 | 2002-11-13 | Mitsui Chemicals, Inc. | Olefinpolymerisationsverfahren |
| MY103812A (en) † | 1988-02-12 | 1993-09-30 | Mitsui Chemicals Inc | Olefin polymerization catalyst and process for the polymerization of olefins. |
| CA2034759C (en) * | 1988-08-01 | 2003-06-03 | Won R. Song | Novel ethylene alpha-olefin polymer substituted mono- and dicarboxylic acid dispersant additives |
| US5229022A (en) * | 1988-08-01 | 1993-07-20 | Exxon Chemical Patents Inc. | Ethylene alpha-olefin polymer substituted mono- and dicarboxylic acid dispersant additives (PT-920) |
| US5759967A (en) * | 1988-08-01 | 1998-06-02 | Exxon Chemical Patents Inc | Ethylene α-olefin/diene interpolymer-substituted carboxylic acid dispersant additives |
| US5277833A (en) * | 1988-08-01 | 1994-01-11 | Exxon Chemical Patents Inc. | Ethylene alpha-olefin polymer substituted mono-and dicarboxylic acid lubricant dispersant additives |
| US5266223A (en) * | 1988-08-01 | 1993-11-30 | Exxon Chemical Patents Inc. | Ethylene alpha-olefin polymer substituted mono-and dicarboxylic acid dispersant additives |
| US5200103A (en) * | 1988-08-01 | 1993-04-06 | Exxon Chemical Patents Inc. | Ethylene alpha-olefin copolymer substituted Mannich base lubricant dispsersant additives |
| US5017299A (en) * | 1988-08-01 | 1991-05-21 | Exxon Chemical Patents, Inc. | Novel ethylene alpha-olefin copolymer substituted Mannich base lubricant dispersant additives |
| US5186851A (en) * | 1988-08-01 | 1993-02-16 | Exxon Chemical Patents Inc. | Ethylene alpha-olefin copolymer substituted mannich base lubricant dispersant additives |
| US5128056A (en) * | 1988-08-01 | 1992-07-07 | Exxon Chemical Patents Inc. | Ethylene alpha-olefin copolymer substituted amino phenol mannich base lubricant dispersant additives |
| US5345002A (en) * | 1988-08-01 | 1994-09-06 | Exxon Chemical Patents Inc. | Ethylene alpha-olefin copolymer substituted hydroxy aromatic compounds |
| US5350532A (en) * | 1988-08-01 | 1994-09-27 | Exxon Chemical Patents Inc. | Borated ethylene alpha-olefin polymer substituted mono- and dicarboxylic acid dispersant additives |
| US5225091A (en) * | 1988-08-01 | 1993-07-06 | Exxon Chemical Patents Inc. | Ethylene alpha-olefin polymer substituted thiocarboxylic acid lubricant dispersant additives |
| US4914253A (en) * | 1988-11-04 | 1990-04-03 | Exxon Chemical Patents Inc. | Method for preparing polyethylene wax by gas phase polymerization |
| EP0955322A3 (de) * | 1988-12-26 | 1999-12-08 | Mitsui Chemicals, Inc. | Olefincopolymere und Verfahren zur Herstellung davon |
| IL96810A0 (en) † | 1990-01-02 | 1991-09-16 | Exxon Chemical Patents Inc | Supported ionic metallocene catalysts for olefin polymerization and methods for the preparation thereof |
| US5225092A (en) * | 1990-02-01 | 1993-07-06 | Exxon Chemical Patents Inc. | Ethylene alpha-olefin polymer substituted amine dispersant additives |
| US5151204A (en) * | 1990-02-01 | 1992-09-29 | Exxon Chemical Patents Inc. | Oleaginous compositions containing novel ethylene alpha-olefin polymer viscosity index improver additive |
| DE69222700T2 (de) * | 1991-07-11 | 1998-03-26 | Idemitsu Kosan Co | Verfahren zur Herstellung von Polymeren auf Olefinbasis und Olefin-Polymerisationskatalysatoren |
| DE69224600T2 (de) * | 1991-11-12 | 1998-08-27 | Nippon Oil Co Ltd | Katalysatorbestandteile für Olefinpolymerisation |
| EP0618931B2 (de) † | 1991-12-23 | 2000-11-02 | Exxon Chemical Patents Inc. | Modifizierte monocyclopentadienyl-uebergangsmetal/aluminoxan katalysatorsystem fuer olefinpolymerisation |
| US6143854A (en) | 1993-08-06 | 2000-11-07 | Exxon Chemical Patents, Inc. | Polymerization catalysts, their production and use |
| US5240894A (en) * | 1992-05-18 | 1993-08-31 | Exxon Chemical Patents Inc. | Method for making and using a supported metallocene catalyst system |
| IT1256603B (it) * | 1992-10-30 | 1995-12-12 | Enichem Polimeri | Catalizzatore e procedimento per (co) polimerizzare le alfa-olefine |
| DE69307472T2 (de) * | 1992-11-10 | 1997-05-15 | Mitsubishi Chem Corp | Verfahren zur Herstellung von Alpha-Olefinpolymeren |
| CA2110463C (en) * | 1992-12-17 | 2005-02-08 | Jacob Emert | Gel-free ethylene interpolymer dispersant additives useful in oleaginous compositions |
| CA2110649C (en) * | 1992-12-17 | 2004-10-26 | Jacob Emert | Gel-free alpha-olefin dispersant additives useful in oleaginous compositions |
| JP3300357B2 (ja) † | 1993-03-25 | 2002-07-08 | モービル・オイル・コーポレーション | 粒状の樹脂を形成する方法 |
| JPH08509773A (ja) † | 1993-04-26 | 1996-10-15 | エクソン・ケミカル・パテンツ・インク | 流動床におけるモノマーの重合プロセス |
| IT1264680B1 (it) | 1993-07-07 | 1996-10-04 | Spherilene Srl | Catalizzatori supportati per la polimerizzazione delle olefine |
| US5422325A (en) * | 1993-09-17 | 1995-06-06 | Exxon Chemical Patents Inc. | Supported polymerization catalysts, their production and use |
| FI96866C (fi) | 1993-11-05 | 1996-09-10 | Borealis As | Tuettu olefiinipolymerointikatalyytti, sen valmistus ja käyttö |
| FI95276C (fi) * | 1993-12-03 | 1996-01-10 | Borealis As | Olefiinien polymerointikatalyytti ja menetelmä sen valmistamiseksi |
| US5491207A (en) * | 1993-12-14 | 1996-02-13 | Exxon Chemical Patents Inc. | Process of producing high molecular weight ethylene-α-olefin elastomers with an indenyl metallocene catalyst system |
| US5595950A (en) * | 1993-12-20 | 1997-01-21 | Exxon Chemical Patents, Inc. | Polymerization catalyst systems, their production and use |
| US6391817B1 (en) | 1993-12-28 | 2002-05-21 | Exxonmobil Chemical Patents Inc. | Method for producing a prepolymerized catalyst |
| DE4406964A1 (de) * | 1994-03-03 | 1995-09-07 | Basf Ag | Geträgerte Metalloxenkomplexe mit heterofunktionellen Gruppen am Cyclopentadienylsystem als Katalysatorsysteme |
| TW454020B (en) † | 1994-08-09 | 2001-09-11 | Mitsui Chemicals Inc | Olefin polymerization catalyst |
| CA2223258A1 (en) * | 1995-07-06 | 1997-01-23 | Exxon Chemical Patents, Inc. | Method for producing prepolymerized, supported metallocene catalyst systems |
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| EP0816394B1 (de) * | 1996-06-26 | 2002-01-30 | BP Chemicals S.N.C. | Verfahren zur Ethylenpolymerisation in der Gasphase |
| ES2171640T3 (es) | 1996-06-26 | 2002-09-16 | Bp Chem Int Ltd | Procedimiento para la polimerizacion de etileno en fase gaseosa. |
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| RU2307838C2 (ru) * | 2001-09-14 | 2007-10-10 | Бп Корпорейшн Норт Америка Инк. | Латентные металлоценовые каталитические системы для полимеризации олефинов |
| EP1323747A1 (de) | 2001-12-19 | 2003-07-02 | Borealis Technology Oy | Herstellung von Katalysatoren für die Olefinpolymerisation |
| ATE422508T1 (de) | 2001-12-19 | 2009-02-15 | Borealis Tech Oy | Herstellung von geträgerten katalysatoren für die olefinpolymerisation |
| WO2004041909A1 (ja) | 2002-11-05 | 2004-05-21 | Meisei Chemical Works, Ltd. | エチレンオキシド用重合触媒組成物および当該組成物を用いたポリ(エチレンオキシド)の製造方法 |
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| US6953764B2 (en) | 2003-05-02 | 2005-10-11 | Dow Global Technologies Inc. | High activity olefin polymerization catalyst and process |
| JP5561933B2 (ja) | 2005-06-16 | 2014-07-30 | ザ ルブリゾル コーポレイション | 燃料における使用のための四級アンモニウム塩洗浄剤 |
| EP1803747A1 (de) | 2005-12-30 | 2007-07-04 | Borealis Technology Oy | Oberflächemodifizierte Polymerisationskatalysatoren zur Herstellung von Polyolefinfilmen mit niedrigem Gelgehalt |
| EP1847555A1 (de) | 2006-04-18 | 2007-10-24 | Borealis Technology Oy | Mehrfach verzweigtes Polypropylen |
| US7563368B2 (en) | 2006-12-12 | 2009-07-21 | Cummins Filtration Ip Inc. | Filtration device with releasable additive |
| EP1939226B1 (de) | 2006-12-28 | 2013-07-17 | Borealis Technology Oy | Verfahren zur Polymerherstellung, Verfahren zur Herstellung eines prepolymerisierten Katalysators, prepolymerisierter Katalysator und seine Verwendung |
| TW200932762A (en) | 2007-10-22 | 2009-08-01 | Univation Tech Llc | Polyethylene compositions having improved properties |
| EP2119732A1 (de) | 2008-05-16 | 2009-11-18 | Borealis Technology Oy | Metallocen-Katalysator-Zusammensetzungen mit verbesserten Eigenschaften, Verfahren zu ihrer Herstellung und ihre Verwendung zur Herstellung von Polyolefin-Homo- oder Copolymeren |
| US8702995B2 (en) | 2008-05-27 | 2014-04-22 | Dober Chemical Corp. | Controlled release of microbiocides |
| US8591747B2 (en) | 2008-05-27 | 2013-11-26 | Dober Chemical Corp. | Devices and methods for controlled release of additive compositions |
| US7883638B2 (en) | 2008-05-27 | 2011-02-08 | Dober Chemical Corporation | Controlled release cooling additive compositions |
| JP5346088B2 (ja) | 2008-09-25 | 2013-11-20 | バーゼル・ポリオレフィン・ゲーエムベーハー | 耐衝撃性lldpe組成物及びそれから製造されるフィルム |
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-
1987
- 1987-08-26 EP EP87905645A patent/EP0279863B1/de not_active Expired - Lifetime
- 1987-08-26 WO PCT/JP1987/000629 patent/WO1988001626A1/ja not_active Ceased
- 1987-08-26 DE DE8787905645T patent/DE3782243T2/de not_active Expired - Fee Related
- 1987-08-26 AT AT87905645T patent/ATE81512T1/de not_active IP Right Cessation
-
1988
- 1988-04-18 CA CA000564390A patent/CA1319142C/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| DE3782243T2 (de) | 1993-03-04 |
| EP0279863A1 (de) | 1988-08-31 |
| EP0279863B1 (de) | 1992-10-14 |
| WO1988001626A1 (fr) | 1988-03-10 |
| CA1319142C (en) | 1993-06-15 |
| DE3782243D1 (de) | 1992-11-19 |
| EP0279863A4 (de) | 1988-08-29 |
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| UEP | Publication of translation of european patent specification | ||
| REN | Ceased due to non-payment of the annual fee | ||
| RZN | Patent revoked | ||
| RZN | Patent revoked |