KR970703815A - 올레핀 중합반응 촉매(olefin polymerization catalyst) - Google Patents
올레핀 중합반응 촉매(olefin polymerization catalyst) Download PDFInfo
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- KR970703815A KR970703815A KR1019960707287A KR19960707287A KR970703815A KR 970703815 A KR970703815 A KR 970703815A KR 1019960707287 A KR1019960707287 A KR 1019960707287A KR 19960707287 A KR19960707287 A KR 19960707287A KR 970703815 A KR970703815 A KR 970703815A
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- South Korea
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- tetraisopropoxide
- oxygen atom
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- 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
- 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
- C08F4/642—Component covered by group C08F4/64 with an organo-aluminium compound
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/12—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides
- B01J31/122—Metal aryl or alkyl compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/12—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides
- B01J31/128—Mixtures of organometallic compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/12—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides
- B01J31/14—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides of aluminium or boron
- B01J31/143—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides of aluminium or boron of aluminium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
- B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
- B01J31/1815—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine with more than one complexing nitrogen atom, e.g. bipyridyl, 2-aminopyridine
- B01J31/182—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine with more than one complexing nitrogen atom, e.g. bipyridyl, 2-aminopyridine comprising aliphatic or saturated rings
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/2208—Oxygen, e.g. acetylacetonates
- B01J31/2226—Anionic ligands, i.e. the overall ligand carries at least one formal negative charge
- B01J31/223—At least two oxygen atoms present in one at least bidentate or bridging ligand
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/2208—Oxygen, e.g. acetylacetonates
- B01J31/2226—Anionic ligands, i.e. the overall ligand carries at least one formal negative charge
- B01J31/2243—At least one oxygen and one nitrogen atom present as complexing atoms in an at least bidentate or bridging ligand
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/10—Polymerisation reactions involving at least dual use catalysts, e.g. for both oligomerisation and polymerisation
- B01J2231/12—Olefin polymerisation or copolymerisation
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/40—Complexes comprising metals of Group IV (IVA or IVB) as the central metal
- B01J2531/46—Titanium
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/40—Complexes comprising metals of Group IV (IVA or IVB) as the central metal
- B01J2531/48—Zirconium
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/40—Complexes comprising metals of Group IV (IVA or IVB) as the central metal
- B01J2531/49—Hafnium
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/50—Complexes comprising metals of Group V (VA or VB) as the central metal
- B01J2531/56—Vanadium
-
- 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
- C08F2410/00—Features related to the catalyst preparation, the catalyst use or to the deactivation of the catalyst
- C08F2410/04—Dual catalyst, i.e. use of two different catalysts, where none of the catalysts is a metallocene
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Catalysts (AREA)
Abstract
Description
Claims (5)
- 하기 (A) 및 (B)를 포함하는 올레핀 중합반응 및 공중합반응용 촉매; (A) LMX2LMXY, L'MX 및 L2M으로 이루어진 군중에서 선택된 실험식으로 표시되는 착물(식중, M은 Ti, V, Zr 또는 Hf로 이루어진 군중에서 선택되고; X는 알콕시 또는 아릴옥시기 또는 할로겐 원자이고; Y는 X와는 상이한 산소 원자 또는 알콕시 또는 아릴옥시기 또는 할로겐 원자이며; L은 2자리 배위 리간드 Z-R-Z 또는 Z-R-W-R-Z이고, 이때 R은 무치환 또는 알킬-치환된 알킬렌, 시클로알킬렌 또는 아릴렌 기이고, W는 CH2,O, S, N-R' 또는 SiR'2이고, R'는 알킬 또는 아릴기이고, Z는 산소원자, 황원자, N-H기 또는 C(=O)-O기이며; L'는 3자리 배위 리간드또는이고, 이때 U는 Z와는 상이한 것으로서, 산소원자, 황원자, N-H또는 C(=O)-O기이고, R"는 알킬렌, 시클로알킬렌 또는 아릴렌기임); 및 (B) [Al] :[Mg] 몰 비율이 1 이상인 알킬알루미늄 할라이드와 유기 마그네슘 화합물의 배합물.
- 제1항에 있어서, L과 L'가 각각 1,2,6-헥산트리올; 1,5-헥산디올;디글리콜산;캄포르산;2-히드록시벤질알코올;1,1'-비-2-나프톨;비스(2-히드록시페닐)메탄;2,2'-비페놀;디펜산;시스-1,2-디아미노시클로헥산;1,4,7-트리아자시클로노난;디에탄올아민;L-글루탐산;1-[N,N-비스(2-히드록시에틸)아미노]-2-프로판올로부터 선택되는 촉매.
- 제1항 또는 제2항에 있어서, 상기 착물(A)가 리간드 L EH는 L'와 티타늄 테트라이소프로폭사이드, 티타늄 테트라클로라이드, 지르코늄 테트라이소프로폭사이드 또는 바나딜 테트라이소프로폭사이드의 반응 생성물인 촉매.
- 제1항 내지 제3항 중 어느 한항에 있어서, 상기 디알킬알루미늄 할라이드가 디메틸알루미늄 클로라이드. 디에틸 알루미늄 클로라이드, 및 디이소부틸알루미늄 클로라이드로부터 선택되는 촉매.
- 제1항 내지 제4항 중 어느 한 항에 있어서, 상기 유기마그네슘 화합물이 디부틸마그네슘인 촉메.※ 참고사항 : 최초출원 내용에 의하여 공개하는 것임.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US08/264,206 US5506184A (en) | 1994-06-22 | 1994-06-22 | Olefin polymerization catalyst system |
| US08/264,206 | 1994-06-22 | ||
| PCT/US1995/006794 WO1995035164A1 (en) | 1994-06-22 | 1995-05-26 | Olefin polymerization catalyst |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| KR970703815A true KR970703815A (ko) | 1997-08-09 |
| KR100342985B1 KR100342985B1 (ko) | 2002-12-05 |
Family
ID=23005039
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| KR1019960707287A Expired - Fee Related KR100342985B1 (ko) | 1994-06-22 | 1995-05-26 | 올레핀중합반응촉매 |
Country Status (11)
| Country | Link |
|---|---|
| US (1) | US5506184A (ko) |
| EP (1) | EP0766600B1 (ko) |
| JP (2) | JP3832855B2 (ko) |
| KR (1) | KR100342985B1 (ko) |
| CN (1) | CN1080729C (ko) |
| AU (1) | AU700820B2 (ko) |
| DE (1) | DE69514803T2 (ko) |
| ES (1) | ES2142485T3 (ko) |
| TW (1) | TW412545B (ko) |
| WO (1) | WO1995035164A1 (ko) |
| ZA (1) | ZA954658B (ko) |
Families Citing this family (24)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6245705B1 (en) | 1993-11-18 | 2001-06-12 | Univation Technologies | Cocatalysts for metallocene-based olefin polymerization catalyst systems |
| US5869585A (en) * | 1995-10-30 | 1999-02-09 | Mobil Oil Corporation | Multi-component catalyst systems for olefin polymerization |
| US6169152B1 (en) | 1996-07-05 | 2001-01-02 | Jsr Corporation | Olefin polymerization catalyst comprising transition metal compound containing a cyclic ligand having at least two nitrogen atoms in its main chain skeleton |
| KR100223105B1 (ko) * | 1996-10-09 | 1999-10-15 | 유현식 | 올레핀 중합용 촉매와 이를 이용한 올레핀 중합방법 |
| FI973451A0 (fi) | 1997-08-22 | 1997-08-22 | Borealis As | Ny organometalfoerening och metod foer polymerisation av olefiner med hjaelp av en katalytkomposition som innehaoller denna organometalfoerening |
| US6015766A (en) * | 1997-12-18 | 2000-01-18 | Mobil Oil Corporation | Catalyst systems for olefin polymerization based on metallocene complexes and oligoalkylaluminates with sterically hindered alkyl groups as cocatalysts |
| US6153550A (en) * | 1997-12-18 | 2000-11-28 | Mobile Oil Corporation | Olefin polymerization catalyst based on metallocene complexes and perfluorinated oligoaryl derivatives of aluminates |
| US6232257B1 (en) * | 1998-03-20 | 2001-05-15 | The Penn State-Research Foundation | Preparation of highly branched, liquid polymers of ethylene and/or α-olefins in the presence of aluminum-based catalyst systems |
| KR100287955B1 (ko) * | 1998-06-08 | 2001-05-02 | 유현식 | 올레핀계 또는 스티렌계 중합용 신규 메탈로센 촉매 및 이를 이용한 중합방법 |
| US6706827B1 (en) | 1998-06-08 | 2004-03-16 | Samsung Atofina Co. Ltd. | Metallocene catalysts for olefin or styrene polymerization and polymerization method using the metallocene catalysts |
| US6274684B1 (en) * | 1999-10-22 | 2001-08-14 | Univation Technologies, Llc | Catalyst composition, method of polymerization, and polymer therefrom |
| US6300439B1 (en) | 1999-11-08 | 2001-10-09 | Univation Technologies, Llc | Group 15 containing transition metal catalyst compounds, catalyst systems and their use in a polymerization process |
| FR2802833B1 (fr) * | 1999-12-24 | 2002-05-10 | Inst Francais Du Petrole | Composition catalytique et procede pour l'oligomerisation de l'ethylene, en particulier en hexene-1 |
| DE10145453A1 (de) * | 2001-09-14 | 2003-06-05 | Basell Polyolefine Gmbh | Monocyclopentadienylkomplexe mit einem kondensierten Heterocyclus |
| US7834112B2 (en) * | 2001-09-14 | 2010-11-16 | Basell Polyolefine Gmbh | Method of polymerization of olefins |
| US6967184B2 (en) * | 2004-02-17 | 2005-11-22 | Univation Technologies, Llc | Fluoroalcohol leaving group for non-metallocene olefin polymerization catalysts |
| EP1805226A1 (en) * | 2004-10-29 | 2007-07-11 | Exxonmobil Chemical Patents Inc. | Catalyst compound containing divalent tridentate ligand |
| JP5268040B2 (ja) * | 2005-04-07 | 2013-08-21 | 独立行政法人物質・材料研究機構 | 顔料用黄色系色素組成物及びその製造方法 |
| CN102585057B (zh) * | 2011-01-05 | 2013-12-04 | 中国石油化工股份有限公司 | 一种用于乙烯聚合反应的催化剂 |
| BR112014026674B8 (pt) * | 2012-04-27 | 2021-10-05 | Albemarle Corp | Composição de precursor de ativador e processo de formação |
| US12012475B2 (en) | 2018-11-06 | 2024-06-18 | Dow Global Technologies Llc | Method of olefin polymerization using alkane-soluble non-metallocene precatalyst |
| JP7524170B2 (ja) | 2018-11-06 | 2024-07-29 | ダウ グローバル テクノロジーズ エルエルシー | アルカン可溶性非メタロセンプレ触媒 |
| SG11202103831TA (en) | 2018-11-06 | 2021-05-28 | Dow Global Technologies Llc | Alkane-soluble non-metallocene precatalysts |
| CN116490268B (zh) * | 2020-09-14 | 2026-01-13 | 切弗朗菲利浦化学公司 | 由烃通过过渡金属催化生产醇和羰基化合物 |
Family Cites Families (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4452914A (en) * | 1982-08-13 | 1984-06-05 | The Dow Chemical Company | Titanium complexes and catalysts prepared therefrom |
| US4482639A (en) * | 1982-09-15 | 1984-11-13 | The Standard Oil Company | Catalysts for the polymerization of ethylene |
| US4820786A (en) * | 1983-08-29 | 1989-04-11 | Chevron Research Company | Process for the preparation of linear low density polyethylene |
| US4528339A (en) * | 1983-12-27 | 1985-07-09 | The Dow Chemical Company | Polymerization of olefins employing catalysts prepared from novel titanium compounds |
| US4622309A (en) * | 1983-12-27 | 1986-11-11 | The Dow Chemical Company | Novel titanium complexes and catalysts prepared therefrom |
| US4555497A (en) * | 1984-10-26 | 1985-11-26 | The Dow Chemical Company | Titanium complexes and catalysts prepared therefrom |
| US5280000A (en) * | 1985-10-11 | 1994-01-18 | Sumitomo Chemical Company, Limited | Catalyst for olefin polymerization and process for producing olefin polymer using the catalyst |
| US5043408A (en) * | 1989-06-26 | 1991-08-27 | Sumitomo Chemical Company, Limited | Ethylene-aromatic vinyl compound alternating copolymer and process for the production thereof |
| US5086135A (en) * | 1989-12-26 | 1992-02-04 | Mobil Oil Corporation | Zirconium-based catalyst composition for polymerizing olefins and polymerization therewith |
-
1994
- 1994-06-22 US US08/264,206 patent/US5506184A/en not_active Expired - Lifetime
-
1995
- 1995-05-26 KR KR1019960707287A patent/KR100342985B1/ko not_active Expired - Fee Related
- 1995-05-26 AU AU26554/95A patent/AU700820B2/en not_active Ceased
- 1995-05-26 EP EP95921489A patent/EP0766600B1/en not_active Expired - Lifetime
- 1995-05-26 CN CN95193662A patent/CN1080729C/zh not_active Expired - Fee Related
- 1995-05-26 DE DE69514803T patent/DE69514803T2/de not_active Expired - Fee Related
- 1995-05-26 WO PCT/US1995/006794 patent/WO1995035164A1/en not_active Ceased
- 1995-05-26 JP JP50221296A patent/JP3832855B2/ja not_active Expired - Fee Related
- 1995-05-26 ES ES95921489T patent/ES2142485T3/es not_active Expired - Lifetime
- 1995-06-06 ZA ZA954658A patent/ZA954658B/xx unknown
- 1995-06-07 TW TW084105719A patent/TW412545B/zh not_active IP Right Cessation
-
2006
- 2006-04-18 JP JP2006114672A patent/JP2006193754A/ja active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| EP0766600B1 (en) | 2000-01-26 |
| US5506184A (en) | 1996-04-09 |
| EP0766600A1 (en) | 1997-04-09 |
| ZA954658B (en) | 1996-12-06 |
| ES2142485T3 (es) | 2000-04-16 |
| DE69514803T2 (de) | 2000-10-12 |
| AU2655495A (en) | 1996-01-15 |
| DE69514803D1 (de) | 2000-03-02 |
| CN1080729C (zh) | 2002-03-13 |
| KR100342985B1 (ko) | 2002-12-05 |
| CN1165488A (zh) | 1997-11-19 |
| JP3832855B2 (ja) | 2006-10-11 |
| TW412545B (en) | 2000-11-21 |
| JPH10501840A (ja) | 1998-02-17 |
| JP2006193754A (ja) | 2006-07-27 |
| WO1995035164A1 (en) | 1995-12-28 |
| EP0766600A4 (en) | 1997-12-10 |
| AU700820B2 (en) | 1999-01-14 |
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