KR950701940A - 1-올레핀 (공)중합용 지지촉매(supported catalyst for 1-olefin(s) (co)polymerization) - Google Patents
1-올레핀 (공)중합용 지지촉매(supported catalyst for 1-olefin(s) (co)polymerization)Info
- Publication number
- KR950701940A KR950701940A KR1019940704554A KR19940704554A KR950701940A KR 950701940 A KR950701940 A KR 950701940A KR 1019940704554 A KR1019940704554 A KR 1019940704554A KR 19940704554 A KR19940704554 A KR 19940704554A KR 950701940 A KR950701940 A KR 950701940A
- Authority
- KR
- South Korea
- Prior art keywords
- transition metal
- support material
- support
- catalyst
- integer
- Prior art date
Links
- 239000003054 catalyst Substances 0.000 title claims abstract 17
- 238000006116 polymerization reaction Methods 0.000 title abstract 2
- 239000000463 material Substances 0.000 claims abstract 12
- 229910052723 transition metal Inorganic materials 0.000 claims abstract 10
- 150000003624 transition metals Chemical class 0.000 claims abstract 10
- 150000001875 compounds Chemical class 0.000 claims abstract 5
- 150000001336 alkenes Chemical class 0.000 claims abstract 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical class O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract 3
- 239000012265 solid product Substances 0.000 claims abstract 3
- 238000004519 manufacturing process Methods 0.000 claims abstract 2
- 125000004432 carbon atom Chemical group C* 0.000 claims 6
- 239000004215 Carbon black (E152) Substances 0.000 claims 5
- 229930195733 hydrocarbon Natural products 0.000 claims 5
- 150000002430 hydrocarbons Chemical class 0.000 claims 5
- 229910052782 aluminium Inorganic materials 0.000 claims 3
- 239000002904 solvent Substances 0.000 claims 3
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims 2
- 229910052736 halogen Inorganic materials 0.000 claims 2
- 150000002367 halogens Chemical group 0.000 claims 2
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 2
- 125000005916 2-methylpentyl group Chemical group 0.000 claims 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims 1
- 125000000217 alkyl group Chemical group 0.000 claims 1
- -1 aluminum compound Chemical class 0.000 claims 1
- 229910052732 germanium Inorganic materials 0.000 claims 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 claims 1
- 239000012456 homogeneous solution Substances 0.000 claims 1
- 229910052739 hydrogen Inorganic materials 0.000 claims 1
- 239000001257 hydrogen Substances 0.000 claims 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 1
- 238000000034 method Methods 0.000 claims 1
- 238000003801 milling Methods 0.000 claims 1
- 239000003921 oil Substances 0.000 claims 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 claims 1
- 230000000379 polymerizing effect Effects 0.000 claims 1
- 229920001296 polysiloxane Polymers 0.000 claims 1
- 239000000843 powder Substances 0.000 claims 1
- 150000003254 radicals Chemical class 0.000 claims 1
- 229910052710 silicon Inorganic materials 0.000 claims 1
- 239000010703 silicon Substances 0.000 claims 1
- 239000000377 silicon dioxide Substances 0.000 claims 1
- 150000003623 transition metal compounds Chemical class 0.000 claims 1
- SQBBHCOIQXKPHL-UHFFFAOYSA-N tributylalumane Chemical compound CCCC[Al](CCCC)CCCC SQBBHCOIQXKPHL-UHFFFAOYSA-N 0.000 claims 1
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 claims 1
- ORYGRKHDLWYTKX-UHFFFAOYSA-N trihexylalumane Chemical compound CCCCCC[Al](CCCCCC)CCCCCC ORYGRKHDLWYTKX-UHFFFAOYSA-N 0.000 claims 1
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 claims 1
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical group C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 claims 1
- LFXVBWRMVZPLFK-UHFFFAOYSA-N trioctylalumane Chemical compound CCCCCCCC[Al](CCCCCCCC)CCCCCCCC LFXVBWRMVZPLFK-UHFFFAOYSA-N 0.000 claims 1
- CNWZYDSEVLFSMS-UHFFFAOYSA-N tripropylalumane Chemical compound CCC[Al](CCC)CCC CNWZYDSEVLFSMS-UHFFFAOYSA-N 0.000 claims 1
- USJZIJNMRRNDPO-UHFFFAOYSA-N tris-decylalumane Chemical compound CCCCCCCCCC[Al](CCCCCCCCCC)CCCCCCCCCC USJZIJNMRRNDPO-UHFFFAOYSA-N 0.000 claims 1
- 239000004711 α-olefin Substances 0.000 claims 1
- 229910052751 metal Inorganic materials 0.000 abstract 1
- 239000002184 metal Substances 0.000 abstract 1
- 239000000203 mixture Substances 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
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/54—Quaternary phosphonium compounds
- C07F9/5442—Aromatic phosphonium compounds (P-C aromatic linkage)
-
- 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
- C08F4/639—Component covered by group C08F4/62 containing a transition metal-carbon bond
- C08F4/63912—Component covered by group C08F4/62 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
- C08F4/639—Component covered by group C08F4/62 containing a transition metal-carbon bond
- C08F4/63916—Component covered by group C08F4/62 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
- C08F4/639—Component covered by group C08F4/62 containing a transition metal-carbon bond
- C08F4/6392—Component covered by group C08F4/62 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S526/00—Synthetic resins or natural rubbers -- part of the class 520 series
- Y10S526/943—Polymerization with metallocene catalysts
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Abstract
본 발명은 올레핀의 중합에 유용한 지지 촉매 조성물 및 그의 제조방법에 관한 것이다. 먼저 트리알칼알루미늄 화합물을 전이금속 메탈로센과 반응시킨 후 생성된 물질을 탈수되지 않은 지지물질과 반응-시켜 전이금속 밀리몰당 20q 이상의 지지물질을 함유하는 고체 생성물을 생성시킴으로써 촉매를 제조한다. 생성된 지지 촉매는 기존 기술에 의해 제조된 지지 촉매의 활성에 필적하는 활성을 가지며, 이는 기존의 공지된 메탈로센-알룸옥산 촉매에 사용되는 함량보다 20% 이상, 바람직하게는 50% 적은 활성 금속 함량에거 얻어진 것이다. 본 발명은 특히 6 내지 20중량%의 물이 흡수된 탈수되지 않은 실리카겔을 촉매 지지물질로서 사용하는데 관한 것이다.
Description
본 내용은 요부공개 건이므로 전문내용을 수록하지 않았음
Claims (10)
- 전이금속 메탈로센과 트리알킬알루미늄 화합물이 반응하는 탄화수소 용액으로 탈수되지 많은 지지물질을 처리함으로써 제조된 고체 생성물을 포함하며, 이때 상기 고체 생성물이 전이금속 밀리몰당 20q 이상의 탈수되지 않은 지지물질을 갖는 지지 촉매.
- 전이금속 화합물과 트리알길알루미늄 화합물이 반응하는 탄화수소용액으로 탈수되지 않은 지지물질을 처리함으로써 제조하고 전이금속 밀리몰당 20q 이상의 탈수되지 않은 고체 지지물질을 갖는 고체 생성물을 포함하는 지지 촉매를 사용하여 알파-올리펜을 단독으로 또는 기타 올레핀과 함계 접촉시키는 것을 포함하는 상기 알파-올레핀을 단독으로 또는 하나 이상의 기타 올레핀과 함께 중합시키는 방법.
- 탄화수소 용매중의 균질한 용액중에서 전이금속 메탈로센과 트리알킬알루미늄 화합물을 반응시키는 단계, 및 전이금속 밀리몰당 약 20q이상의 탈수되지 않은 지지물질의 양으로, 상기 균질한 용액에 탈수되지 않은 지지물질을 첨가하는 단계를 포함하는 지지 촉매를 제조하는 방법.
- 제1항 내지 제3항중 어느 한 항에 있어서, 지지 촉매가 탄화수소 용매 제거시 자유-유동 분말인 지지촉매.
- 제1항 내지 제4항중 어느 한 항에 있어서, 상기 전이금속 메탈로센이 상기 트리알킬알루디늄 화합물에 대해 100 내지 1000의 알루미늄 대 전이금속 원자비를 제공하는 양으로 탄화수소 용매에 존재하는 지지 촉매.
- 제1항 내지 제5항중 어느 한 항에 있어서, 상기 전이금속 메탈로센이 하기 일반식(Ⅰ), (Ⅱ) 또는 (Ⅲ)의 화합물인 지지 촉메 : Ⅰ. (C5HbR′4-b)2R″sMQg또는 Ⅱ. (C5HbR′4-b)2R″sMQg또는 Ⅲ. (C5HbR′4-b)2R″sMQ′상기 일반식(Ⅰ)에서, 각 R′은 동일하거나 또는 상이하며, 1 내지 20개의 탄소원자를 갖는 하이드로카빌기이고, M은 4b, 5b또는 6b족 전이금속이고, R은 1 내지 20개의 탄소원자를 갖는 하이드로카빌기 또는 하이드로 카복시기이며, X는 할로겐이고, "a"는 0 내지 5의 정수이고, "m"은 1 내지 3의 정수이며, "n"은 0 내지 3의 정수이며,"q"는 0 내지 3의 정수이고; 상기 일반식(Ⅱ) 또는 (Ⅲ)에서, 각 R′은 동일하거나 또는 상이하고, 수소, 또는 1 내지 20개의 탄소원자를 함유하는 하이드로카빌 라디칼, 실리콘-함유 하이드로카빌라디칼이고, R″은 C-C알킬렌 라디칼, 게르마늄 또는 실리콘 암유 라디칼, 또는 2개의 (C5) 고리를 가교시키는 포스핀 또는 아민 라디칼이고, Q는 1 내지 20개의 탄소원자를 갖는 하이드로카빌 라디칼, 1 내지 20개의 탄소원자를 갖는 하이드로카복시 라디칼 또는 할로겐이며, 동일하거나 또는 상이할수 있고, Q′은 1 내지 약 20개의 탄소원자를 갖는 알킬리덴 라디칼이며, "b"는 0 내지 4의 정수이며, "s"는 0 또는 1이고, "g"는 0 내지 3의 정수이고, M은 전술한 바와 같다.
- 제1항 내지 제6항중 어느 한 항에 있어서, 상기 트리알킬알루미늄이 트리메틸알루미늄, 트리에틸알루미늄, 트리프로필알루미늄, 트리-n-부틸알루미늄, 트리-이소부틸-알루미늄, 트리(2-메틸펜틸)알루미늄, 트리헥실알루미늄, 트리-n-옥틸알루미늄 및 트리-n-데실알루미늄으로 이루어진 군으로부터 선택되는 지지촉매.
- 제1항 내지 제7항중 어느 한 항에 있어서, 물 함량이 적어토 1.2 내지 0.8의 물 대 트리알킬알루미늄의 몰비를 제공하도록 하는 양으로 상기 탈수되지 않은 지지물질을 첨가한 지지촉매.
- 제1항 내지 제8항중 어느 한 항에 있어서, 상기 탈수되지 않은 지지물질을 전이금속 밀리몰딩 30q이상의 탈수되지 않은 지지물질의 양으로 첨가한 지지촉매.
- 제1항 내지 wp9항중 어느 한 항에 있어서, 상기탈수되지 않은 지지물질이 바람직하게는 6 내지 20중량%의 물 함량을 갖는 실리카인 지지촉매.※ 참고사항 : 최초출원 내용에 의하여 공개하는 것임.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US07/898,255 | 1992-06-15 | ||
| US07/898,255 US5238892A (en) | 1992-06-15 | 1992-06-15 | Supported catalyst for 1-olefin(s) (co)polymerization |
| PCT/US1993/003294 WO1993025586A1 (en) | 1992-06-15 | 1993-04-08 | Supported catalyst for 1-olefin(s) (co)polymerization |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| KR950701940A true KR950701940A (ko) | 1995-05-17 |
Family
ID=25409169
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| KR1019940704554A KR950701940A (ko) | 1992-06-15 | 1993-04-08 | 1-올레핀 (공)중합용 지지촉매(supported catalyst for 1-olefin(s) (co)polymerization) |
Country Status (10)
| Country | Link |
|---|---|
| US (2) | US5238892A (ko) |
| EP (1) | EP0646137B1 (ko) |
| JP (1) | JP3093795B2 (ko) |
| KR (1) | KR950701940A (ko) |
| CA (1) | CA2138138C (ko) |
| DE (1) | DE69306784T2 (ko) |
| ES (1) | ES2096918T3 (ko) |
| MX (1) | MX9302668A (ko) |
| RU (1) | RU94046338A (ko) |
| WO (1) | WO1993025586A1 (ko) |
Families Citing this family (137)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6025448A (en) | 1989-08-31 | 2000-02-15 | The Dow Chemical Company | Gas phase polymerization of olefins |
| US6538080B1 (en) | 1990-07-03 | 2003-03-25 | Bp Chemicals Limited | Gas phase polymerization of olefins |
| US6143854A (en) * | 1993-08-06 | 2000-11-07 | Exxon Chemical Patents, Inc. | Polymerization catalysts, their production and use |
| US5608019A (en) * | 1992-12-28 | 1997-03-04 | Mobil Oil Corporation | Temperature control of MW in olefin polymerization using supported metallocene catalyst |
| US5332706A (en) * | 1992-12-28 | 1994-07-26 | Mobil Oil Corporation | Process and a catalyst for preventing reactor fouling |
| US5602067A (en) * | 1992-12-28 | 1997-02-11 | Mobil Oil Corporation | Process and a catalyst for preventing reactor fouling |
| WO1995007939A1 (en) | 1993-09-17 | 1995-03-23 | Exxon Chemical Patents Inc. | Polymerization catalyst systems, their production and use |
| US5455741A (en) * | 1993-10-26 | 1995-10-03 | Pulse Engineering, Inc. | Wire-lead through hole interconnect device |
| US5614456A (en) * | 1993-11-15 | 1997-03-25 | Mobil Oil Corporation | Catalyst for bimodal molecular weight distribution ethylene polymers and copolymers |
| US5674795A (en) * | 1993-12-23 | 1997-10-07 | Union Carbide Chemicals & Plastics Technology Corporation | Spray dried, filled metallocene catalyst composition for use in polyolefin manufacture |
| US5629253A (en) * | 1994-04-26 | 1997-05-13 | Exxon Chemical Patents, Inc. | Polymerization catalyst systems, their production and use |
| ATE188972T1 (de) * | 1994-06-24 | 2000-02-15 | Exxon Chemical Patents Inc | Polymerisationskatalysatorsystem, ihre herstellung und gebrauch |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4808561A (en) * | 1985-06-21 | 1989-02-28 | Exxon Chemical Patents Inc. | Supported polymerization catalyst |
| WO1987003889A1 (en) * | 1985-12-24 | 1987-07-02 | Mitsui Petrochemical Industries, Ltd. | Process for polymerization of alpha-olefins |
| US4912075A (en) * | 1987-12-17 | 1990-03-27 | Exxon Chemical Patents Inc. | Method for preparing a supported metallocene-alumoxane catalyst for gas phase polymerization |
| US4925821A (en) * | 1987-12-17 | 1990-05-15 | Exxon Chemical Patents Inc. | Method for utilizing triethyaluminum to prepare an alumoxane support for an active metallocene catalyst |
| US4935397A (en) * | 1988-09-28 | 1990-06-19 | Exxon Chemical Patents Inc. | Supported metallocene-alumoxane catalyst for high pressure polymerization of olefins and a method of preparing and using the same |
| US4914253A (en) * | 1988-11-04 | 1990-04-03 | Exxon Chemical Patents Inc. | Method for preparing polyethylene wax by gas phase polymerization |
-
1992
- 1992-06-15 US US07/898,255 patent/US5238892A/en not_active Expired - Lifetime
-
1993
- 1993-04-08 JP JP06501446A patent/JP3093795B2/ja not_active Expired - Fee Related
- 1993-04-08 RU RU94046338/04A patent/RU94046338A/ru unknown
- 1993-04-08 WO PCT/US1993/003294 patent/WO1993025586A1/en active IP Right Grant
- 1993-04-08 ES ES93912149T patent/ES2096918T3/es not_active Expired - Lifetime
- 1993-04-08 CA CA002138138A patent/CA2138138C/en not_active Expired - Fee Related
- 1993-04-08 EP EP93912149A patent/EP0646137B1/en not_active Expired - Lifetime
- 1993-04-08 DE DE69306784T patent/DE69306784T2/de not_active Expired - Lifetime
- 1993-04-08 KR KR1019940704554A patent/KR950701940A/ko not_active Application Discontinuation
- 1993-04-14 US US08/046,676 patent/US5373072A/en not_active Expired - Lifetime
- 1993-05-06 MX MX9302668A patent/MX9302668A/es unknown
Also Published As
| Publication number | Publication date |
|---|---|
| CA2138138C (en) | 1998-01-06 |
| JPH07507828A (ja) | 1995-08-31 |
| CA2138138A1 (en) | 1993-12-23 |
| US5373072A (en) | 1994-12-13 |
| RU94046338A (ru) | 1996-10-27 |
| ES2096918T3 (es) | 1997-03-16 |
| WO1993025586A1 (en) | 1993-12-23 |
| EP0646137A1 (en) | 1995-04-05 |
| MX9302668A (es) | 1994-06-30 |
| JP3093795B2 (ja) | 2000-10-03 |
| DE69306784D1 (de) | 1997-01-30 |
| DE69306784T2 (de) | 1997-04-10 |
| US5238892A (en) | 1993-08-24 |
| EP0646137B1 (en) | 1996-12-18 |
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