KR950000742A - 에틸렌 및 프로필렌의 엘라스토머성 공중합체 및 그의 제조방법 - Google Patents
에틸렌 및 프로필렌의 엘라스토머성 공중합체 및 그의 제조방법 Download PDFInfo
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- KR950000742A KR950000742A KR1019940010320A KR19940010320A KR950000742A KR 950000742 A KR950000742 A KR 950000742A KR 1019940010320 A KR1019940010320 A KR 1019940010320A KR 19940010320 A KR19940010320 A KR 19940010320A KR 950000742 A KR950000742 A KR 950000742A
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- Prior art keywords
- propylene
- copolymer
- ethylene
- epe
- group
- Prior art date
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- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 title claims abstract 12
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 title claims abstract 11
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 title claims abstract 7
- 239000005977 Ethylene Substances 0.000 title claims abstract 7
- 238000000034 method Methods 0.000 title claims 4
- 229920001198 elastomeric copolymer Polymers 0.000 title claims 3
- 229920001577 copolymer Polymers 0.000 claims abstract 10
- 150000004291 polyenes Chemical class 0.000 claims abstract 3
- 125000001424 substituent group Chemical group 0.000 claims 7
- -1 aluminum organometallic compound Chemical class 0.000 claims 4
- 239000007795 chemical reaction product Substances 0.000 claims 3
- 150000001875 compounds Chemical class 0.000 claims 3
- 230000009257 reactivity Effects 0.000 claims 3
- 229910052782 aluminium Inorganic materials 0.000 claims 2
- 125000004432 carbon atom Chemical group C* 0.000 claims 2
- 239000003054 catalyst Substances 0.000 claims 2
- 239000000047 product Substances 0.000 claims 2
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 claims 2
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 claims 1
- 125000006736 (C6-C20) aryl group Chemical group 0.000 claims 1
- 125000003358 C2-C20 alkenyl group Chemical group 0.000 claims 1
- XPDKOTBKOLYRRS-UHFFFAOYSA-L [Cl-].[Cl-].C[Si](=[Zr+2](C1=CC=CC=2C3=CC=CC=C3CC1=2)C1=CC=CC=2C3=CC=CC=C3CC1=2)C Chemical compound [Cl-].[Cl-].C[Si](=[Zr+2](C1=CC=CC=2C3=CC=CC=C3CC1=2)C1=CC=CC=2C3=CC=CC=C3CC1=2)C XPDKOTBKOLYRRS-UHFFFAOYSA-L 0.000 claims 1
- 125000002877 alkyl aryl group Chemical group 0.000 claims 1
- 125000003710 aryl alkyl group Chemical group 0.000 claims 1
- 125000004429 atom Chemical group 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 claims 1
- 125000000753 cycloalkyl group Chemical group 0.000 claims 1
- 229910052736 halogen Inorganic materials 0.000 claims 1
- 125000005843 halogen group Chemical group 0.000 claims 1
- 150000002367 halogens Chemical class 0.000 claims 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims 1
- 230000006698 induction Effects 0.000 claims 1
- 239000000203 mixture Substances 0.000 claims 1
- 125000004817 pentamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 claims 1
- 238000006116 polymerization reaction Methods 0.000 claims 1
- 230000000379 polymerizing effect Effects 0.000 claims 1
- 238000004073 vulcanization Methods 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims 1
- 229910052726 zirconium Inorganic materials 0.000 claims 1
- 238000004132 cross linking Methods 0.000 abstract 1
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 abstract 1
- 239000012968 metallocene catalyst Substances 0.000 abstract 1
Classifications
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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
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
-
- 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
- C08F4/65908—Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with an ionising compound other than alumoxane, e.g. (C6F5)4B-X+
-
- 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
- C08F4/6592—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
- C08F4/65927—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 bridged
-
- 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)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Medicinal Preparation (AREA)
- Graft Or Block Polymers (AREA)
Abstract
(A) 공중합체 내 프로필렌의 몰 %함량(%P) 및 트리아드 비 EPE/(EPE+PPE+PPP)가 하기 관계를 만족하고 ;
0.01%P+EPE/(EPE+PPE+PPP)≥1
(B) 사슬내의 CH2기의 2% 미만이 (CH2)n서열(상기에서 n은 짝수이다)내에 존재함을 특징으로 하는, 에틸렌과 프로필렌, 및 임의로 소량의 폴리엔과의 비결정형 공중합체.
상기 공중합체는 가교기를 통해 함께 결합한 2개의 플루오레닐기를 갖는 특정 메탈로센 촉매의 존재하에 수행함으로서 수득가능하다.
Description
본 내용은 요부공개 건이므로 전문내용을 수록하지 않았음
Claims (9)
- (A) 공중합체 내 프로필렌의 몰 %함량(%P) 및 비 EPE/(EPE+PPE+PPP)(상기에, EPE, PPE 및 PPP는 각각 공중합체 내의 서열 에틸렌/프로필렉/에틸렌, 프로필렌/프로필렌/에틸렌 및 프로필렌/프로필렌/프로필렌을 나타낸다.)가 하기 관계를 만족하고 ;0.01%P+EPE/(EPE+PPE+PPP)≥1(B) 중합 사슬 내의 CH2기의 2% 미만이 (CH2)n서열(상기에서 n은 짝수이다)내에 존재함을 특징으로 하며, 에틸렌 유도단위 함량이 약 35~85몰%이고, 프로필렌 유도단위 함량이 약 10~60몰%인, 에틸렌과 프로필렌의 공중합체.
- 제1항에 있어서, 1 이상의 폴리엔으로부터 유도된 단위의 함량이 약 0~5몰%인 공중합체.
- 제1항 또는 제2항에 있어서, 반응도 비의 곱 r1r2(상기에서, r1은 프로필렌의 반응도 비이고, r2는 에틸렌의 반응도 비이다)가 0.1 미만인 공중합체.
- 제1항 또는 제2항에 있어서, 고유 점도()가 〉1.0인 공중합체.
- 제1항 또는 제2항에 있어서, 비 Mw/Mn가 3 미만인 공중합체.
- 제1항 내지 제5항 중 어느 한 항의 공중합체에 가황 공정을 수행함으로서 수득가능한 엘라스토머성 공중합체.
- 제6항의 엘라스토머성 공중합체로부터 수득된 성형품.
- (A)임의로 반응 생성물로서 일반식 AlR4 3또는 Al2R4 6(식중, 치환체 R4는 서로 동일하거나 상이하며 R1또는 할로겐이다)의 알루미늄 유기금속 화합물과 혼합된 하기일반식 (I)의 화합물 ;(식중, 치환체 R1는 서로 동일하거나 상이하며, 수소 원자, C1~C10알킬기, C3-C20시클로알킬기, C2-C20알케닐기, C6-C20아릴기, C7-C20알킬아릴기, 또는 C7-C20아릴알킬기이고, 임의로 2개의 인접 치환체 R1은 탄소수 5~8의 고리를 형성할 수 있으며, 추가로 치환체 R1은 Si 또는 Ge원자를 함유할 수 있고 ; M은 Ti, Zr 또는 Hf이고 ; 치환체 R2는, 서로 동일하거나 상이하며 할로겐 원자, -OH, -SH, R1, -OR1, -SR1, -NR1 2또는 PR1 2(식중, R1은 상기 정의한 바와 같다)이고 ; 기 R3는 〉CR1 2, 〉SiR1 2, 〉GeR1 2, 〉NR1또는 〉 PR1(식중, R1은 상기 정의한 바와같다)으로부터 선택되며, 임의로, R3가 〉CR1 2, 〉SiR1 2또는 〉GeR|1 2일 경우, 양 치환체 R1은 둘다 탄소수 3~8의 고리를 형성할 수 있다) 및 (B)일반식 AlR4 3또는 Al2R4 3또는 Al2R4 6(식중, 치환체 R4는 서로 동일하거나 상이하며 상기 정의한 바와 같다)의 알루미늄 유기금속 화합물 또는 메탈로센 알킬 양이온을 생성할 수 잇는 1종 이상의 화합물과 임의로 혼합된 알루목산간의 반응 생성물을 함유하는 촉매적 량의 촉매의 존재하에 에틸렌, 프로필렌 및 임의로 1종이상의 폴리엔과 혼합물을 중합반응시킴을 특징으로하는, 제1항 내지 제5항중 어느 한 항의 공중합체의 제조방법.
- 제8항에 있어서, 촉매가 ; (A)디메틸실란디일 -비스(플루오레닐)지르코늄 디클로라이드 및 (B)테트라이소부틸-디알루미녹산(TIBAO), 및 트리이소부틸 알루미늄(TIBAL) 및 물 간의 반응 생성물로부터 선택된 화합물간의 반응 생성물을 함유하는 제조방법.※ 참고사항 : 최초출원 내용에 의하여 공개하는 것임.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| ITMI93A001405 | 1993-06-30 | ||
| IT93MI001405A IT1264482B1 (it) | 1993-06-30 | 1993-06-30 | Copolimeri amorfi dell'etilene con propilene e procedimento per la loro preparazione |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| KR950000742A true KR950000742A (ko) | 1995-01-03 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| KR1019940010320A KR950000742A (ko) | 1993-06-30 | 1994-05-11 | 에틸렌 및 프로필렌의 엘라스토머성 공중합체 및 그의 제조방법 |
Country Status (16)
| Country | Link |
|---|---|
| US (2) | US6221992B1 (ko) |
| EP (1) | EP0632066B2 (ko) |
| JP (1) | JPH0733825A (ko) |
| KR (1) | KR950000742A (ko) |
| CN (1) | CN1051322C (ko) |
| AT (1) | ATE167880T1 (ko) |
| AU (1) | AU674208B2 (ko) |
| BR (1) | BR9401058A (ko) |
| CA (1) | CA2123336A1 (ko) |
| DE (1) | DE69411330T3 (ko) |
| ES (1) | ES2119014T3 (ko) |
| FI (1) | FI942157A (ko) |
| IL (1) | IL109435A (ko) |
| IT (1) | IT1264482B1 (ko) |
| NO (1) | NO303877B1 (ko) |
| RU (1) | RU2140426C1 (ko) |
Families Citing this family (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| IT1273420B (it) * | 1994-04-06 | 1997-07-08 | Spherilene Srl | Composti metallocenici, procedimento per la preparazione e loro utilizzo in catalizzatori per la polimerizzazione delle olefine |
| IT1273660B (it) * | 1994-07-20 | 1997-07-09 | Spherilene Srl | Procedimento per la preparazione di polimeri amorfi del propilene |
| IT1270125B (it) * | 1994-10-05 | 1997-04-28 | Spherilene Srl | Processo per la ( co) polimerizzazione di olefine |
| IT1275856B1 (it) | 1995-03-03 | 1997-10-24 | Spherilene Srl | Composti metallocenici bis-fluorenilici, procedimento per la loro preparazione e loro utilizzo in catalizzatori per la polimerizzazione |
| IT1275857B1 (it) * | 1995-03-03 | 1997-10-24 | Spherilene Srl | Copolimeri atattici del propilene con l'etilene |
| SG64939A1 (en) | 1995-07-17 | 2002-02-19 | Mitsui Chemicals Inc | Olefin polymerization catalyst, process for preparing olefin polymer, and olefin polymer |
| IT1282683B1 (it) * | 1996-02-23 | 1998-03-31 | Montell North America Inc | Mescole di bitume e di polimeri olefinici atti alla modifica dei bitumi |
| WO1999002569A1 (en) | 1997-07-14 | 1999-01-21 | The Board Of Trustees Of The Leland Stanford, Jr. University | CATALYSTS AND PROCESSES FOR THE SYNTHESIS OF ALTERNATING ETHYLENE/α-OLEFIN COPOLYMERS, AND ISOTACTIC COPOLYMERS THEREOF |
| US6225427B1 (en) | 1998-10-15 | 2001-05-01 | Uniroyal Chemical Company, Inc. | Olefin polymerization process employing metallocene catalyst provided by cocatalyst activation of a metallocene procatalyst |
| DE60024595T2 (de) | 1999-12-28 | 2006-07-27 | Basell Polyolefine Gmbh | Verfahren zur Herstellung von Ethylenpolymeren |
| US6835698B2 (en) * | 2000-02-09 | 2004-12-28 | Idemitsu Petrochemical Co., Ltd. | Ethylene-base copolymers, process for producing the same and lubricating oil compositions containing the same |
| US7622433B2 (en) | 2002-11-12 | 2009-11-24 | Mitsui Chemicals, Inc. | Lubricating oil composition and internal combustion engine oil |
| US7399737B2 (en) | 2005-06-13 | 2008-07-15 | Exxonmobil Chemical Patents Inc. | Lube additives |
| KR100994252B1 (ko) * | 2007-05-09 | 2010-11-12 | 주식회사 엘지화학 | 에틸렌 알파-올레핀 공중합체 |
| KR102363189B1 (ko) | 2018-01-11 | 2022-02-15 | 주식회사 엘지화학 | 혼성 담지 메탈로센 촉매를 이용한 폴리올레핀의 제조 방법 |
| WO2019139355A1 (ko) * | 2018-01-11 | 2019-07-18 | 주식회사 엘지화학 | 혼성 담지 메탈로센 촉매를 이용한 폴리올레핀의 제조방법 |
| CN116789884B (zh) * | 2023-08-28 | 2024-01-09 | 万华化学集团股份有限公司 | 高透光率的乙烯/α-烯烃共聚物 |
Family Cites Families (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5001205A (en) | 1988-06-16 | 1991-03-19 | Exxon Chemical Patents Inc. | Process for production of a high molecular weight ethylene α-olefin elastomer with a metallocene alumoxane catalyst |
| KR920006464B1 (ko) * | 1988-09-14 | 1992-08-07 | 미쓰이 세끼유 가가꾸 고오교오 가부시끼가이샤 | 올레핀중합용 촉매성분, 올레핀중합용 촉매 및 이 올레핀중합용 촉매를 사용한 올레핀의 중합방법 |
| DE69027652T2 (de) * | 1989-10-30 | 1996-11-28 | Fina Research | Verfahren zur Herstellung von syndiotaktischen Copolymeren aus Propylen und Olefinen |
| US5436305A (en) * | 1991-05-09 | 1995-07-25 | Phillips Petroleum Company | Organometallic fluorenyl compounds, preparation, and use |
| CA2068939C (en) * | 1991-05-20 | 1996-04-09 | Takashi Ueda | Olefin polymerization catalyst and olefin polymerization |
| US5292845A (en) * | 1992-01-23 | 1994-03-08 | Mitsui Petrochemical Industries, Ltd. | Ethylene/alpha-olefin/7-methyl-1,6-octadiene copolymer rubber and composition of the same |
| IT1254547B (it) * | 1992-03-23 | 1995-09-25 | Montecatini Tecnologie Srl | Copolimeri elastomerici dell'etilene con alfa-olefine. |
| ES2115061T3 (es) * | 1992-06-18 | 1998-06-16 | Montell Technology Company Bv | Procedimiento para la preparacion de un copolimero etilenico. |
| IT1264406B1 (it) * | 1993-05-11 | 1996-09-23 | Spherilene Srl | Copolimeri amorfi dell'etilene con alfa-olefine e procedimento per la loro preparazione |
| IT1264483B1 (it) * | 1993-06-30 | 1996-09-23 | Spherilene Srl | Copolimeri elastomerici dell'etilene con propilene |
-
1993
- 1993-06-30 IT IT93MI001405A patent/IT1264482B1/it active IP Right Grant
-
1994
- 1994-04-26 IL IL10943594A patent/IL109435A/xx not_active IP Right Cessation
- 1994-05-03 AU AU61848/94A patent/AU674208B2/en not_active Ceased
- 1994-05-04 DE DE69411330T patent/DE69411330T3/de not_active Expired - Fee Related
- 1994-05-04 ES ES94106975T patent/ES2119014T3/es not_active Expired - Lifetime
- 1994-05-04 EP EP94106975A patent/EP0632066B2/en not_active Expired - Lifetime
- 1994-05-04 AT AT94106975T patent/ATE167880T1/de active
- 1994-05-05 RU RU94015591A patent/RU2140426C1/ru active
- 1994-05-09 JP JP6095217A patent/JPH0733825A/ja not_active Ceased
- 1994-05-10 NO NO941741A patent/NO303877B1/no not_active IP Right Cessation
- 1994-05-10 FI FI942157A patent/FI942157A/fi unknown
- 1994-05-11 KR KR1019940010320A patent/KR950000742A/ko active IP Right Grant
- 1994-05-11 CN CN94106001A patent/CN1051322C/zh not_active Expired - Fee Related
- 1994-05-11 BR BR9401058A patent/BR9401058A/pt not_active Application Discontinuation
- 1994-05-11 CA CA002123336A patent/CA2123336A1/en not_active Abandoned
-
1997
- 1997-06-16 US US08/876,865 patent/US6221992B1/en not_active Expired - Fee Related
-
2000
- 2000-11-07 US US09/707,645 patent/US6448351B1/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| FI942157A0 (fi) | 1994-05-10 |
| ES2119014T3 (es) | 1998-10-01 |
| US6221992B1 (en) | 2001-04-24 |
| FI942157A (fi) | 1994-12-31 |
| DE69411330T2 (de) | 1999-01-07 |
| ATE167880T1 (de) | 1998-07-15 |
| US6448351B1 (en) | 2002-09-10 |
| EP0632066B1 (en) | 1998-07-01 |
| NO941741D0 (no) | 1994-05-10 |
| RU94015591A (ru) | 1996-04-20 |
| CN1096304A (zh) | 1994-12-14 |
| ITMI931405A0 (it) | 1993-06-30 |
| ITMI931405A1 (it) | 1994-12-30 |
| EP0632066B2 (en) | 2001-08-22 |
| AU6184894A (en) | 1995-01-12 |
| RU2140426C1 (ru) | 1999-10-27 |
| BR9401058A (pt) | 1994-12-27 |
| EP0632066A1 (en) | 1995-01-04 |
| DE69411330D1 (de) | 1998-08-06 |
| IL109435A0 (en) | 1994-07-31 |
| IT1264482B1 (it) | 1996-09-23 |
| DE69411330T3 (de) | 2002-05-16 |
| IL109435A (en) | 1999-07-14 |
| CA2123336A1 (en) | 1994-12-31 |
| CN1051322C (zh) | 2000-04-12 |
| NO303877B1 (no) | 1998-09-14 |
| JPH0733825A (ja) | 1995-02-03 |
| AU674208B2 (en) | 1996-12-12 |
| NO941741L (no) | 1995-01-02 |
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