NO310363B1 - Katalysatorsystem og fremgangsmåte til produksjon av polyolefin med bred molekylvektfordeling - Google Patents
Katalysatorsystem og fremgangsmåte til produksjon av polyolefin med bred molekylvektfordeling Download PDFInfo
- Publication number
- NO310363B1 NO310363B1 NO19952835A NO952835A NO310363B1 NO 310363 B1 NO310363 B1 NO 310363B1 NO 19952835 A NO19952835 A NO 19952835A NO 952835 A NO952835 A NO 952835A NO 310363 B1 NO310363 B1 NO 310363B1
- Authority
- NO
- Norway
- Prior art keywords
- metallocene
- fluorenyl
- dichloride
- carbon atoms
- bis
- Prior art date
Links
- 239000003054 catalyst Substances 0.000 title claims description 65
- 238000009826 distribution Methods 0.000 title claims description 45
- 238000000034 method Methods 0.000 title claims description 35
- 229920000098 polyolefin Polymers 0.000 title claims description 9
- 238000006116 polymerization reaction Methods 0.000 claims description 60
- 229920000642 polymer Polymers 0.000 claims description 58
- 239000007787 solid Substances 0.000 claims description 50
- -1 fluorenyl radical Chemical class 0.000 claims description 40
- ZSWFCLXCOIISFI-UHFFFAOYSA-N endo-cyclopentadiene Natural products C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 claims description 34
- 125000004432 carbon atom Chemical group C* 0.000 claims description 33
- 239000001257 hydrogen Substances 0.000 claims description 22
- 229910052739 hydrogen Inorganic materials 0.000 claims description 22
- 239000000203 mixture Substances 0.000 claims description 18
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 16
- 239000005977 Ethylene Substances 0.000 claims description 16
- 150000001336 alkenes Chemical class 0.000 claims description 16
- 150000003254 radicals Chemical class 0.000 claims description 16
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 claims description 15
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 14
- VPGLGRNSAYHXPY-UHFFFAOYSA-L zirconium(2+);dichloride Chemical compound Cl[Zr]Cl VPGLGRNSAYHXPY-UHFFFAOYSA-L 0.000 claims description 13
- 238000004519 manufacturing process Methods 0.000 claims description 12
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Chemical class C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 claims description 11
- RSPAIISXQHXRKX-UHFFFAOYSA-L 5-butylcyclopenta-1,3-diene;zirconium(4+);dichloride Chemical compound Cl[Zr+2]Cl.CCCCC1=CC=C[CH-]1.CCCCC1=CC=C[CH-]1 RSPAIISXQHXRKX-UHFFFAOYSA-L 0.000 claims description 10
- 125000001183 hydrocarbyl group Chemical group 0.000 claims description 9
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 9
- RBQGALRSGWYFMO-UHFFFAOYSA-L [Cl-].[Cl-].C1(C=CC=C1)[Zr+2]C1=CC=CC=2C3=CC=CC=C3CC1=2 Chemical group [Cl-].[Cl-].C1(C=CC=C1)[Zr+2]C1=CC=CC=2C3=CC=CC=C3CC1=2 RBQGALRSGWYFMO-UHFFFAOYSA-L 0.000 claims description 8
- 235000010290 biphenyl Nutrition 0.000 claims description 8
- 239000004305 biphenyl Substances 0.000 claims description 8
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 claims description 8
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 8
- 238000007334 copolymerization reaction Methods 0.000 claims description 7
- 150000002431 hydrogen Chemical group 0.000 claims description 7
- 229910052723 transition metal Inorganic materials 0.000 claims description 7
- 150000003624 transition metals Chemical class 0.000 claims description 7
- 229910052726 zirconium Inorganic materials 0.000 claims description 7
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 claims description 6
- 125000000962 organic group Chemical group 0.000 claims description 6
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 4
- UDGDYEXUYLDOKV-UHFFFAOYSA-L [Cl-].[Cl-].C[SiH](C)[Zr+2](C1=CC=CC=2C3=CC=CC=C3CC12)C1=CC=CC=2C3=CC=CC=C3CC12 Chemical compound [Cl-].[Cl-].C[SiH](C)[Zr+2](C1=CC=CC=2C3=CC=CC=C3CC12)C1=CC=CC=2C3=CC=CC=C3CC12 UDGDYEXUYLDOKV-UHFFFAOYSA-L 0.000 claims description 4
- 125000003454 indenyl group Chemical group C1(C=CC2=CC=CC=C12)* 0.000 claims description 4
- 125000001424 substituent group Chemical group 0.000 claims description 4
- HPYIUKIBUJFXII-UHFFFAOYSA-N Cyclopentadienyl radical Chemical class [CH]1C=CC=C1 HPYIUKIBUJFXII-UHFFFAOYSA-N 0.000 claims description 3
- 125000003545 alkoxy group Chemical group 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 229910052736 halogen Inorganic materials 0.000 claims description 3
- 150000002367 halogens Chemical class 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- WUFWYQJBDOMWKC-UHFFFAOYSA-L [Cl-].[Cl-].C1(C=CC2=CC=CC=C12)[Zr+2]C1(C(=C(C(=C1C)C)C)C)C Chemical compound [Cl-].[Cl-].C1(C=CC2=CC=CC=C12)[Zr+2]C1(C(=C(C(=C1C)C)C)C)C WUFWYQJBDOMWKC-UHFFFAOYSA-L 0.000 claims description 2
- QRRQMRJAMCZYOO-UHFFFAOYSA-L [Cl-].[Cl-].[Zr+2][SiH3] Chemical compound [Cl-].[Cl-].[Zr+2][SiH3] QRRQMRJAMCZYOO-UHFFFAOYSA-L 0.000 claims description 2
- 125000006267 biphenyl group Chemical group 0.000 claims description 2
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 238000006772 olefination reaction Methods 0.000 claims description 2
- 239000004711 α-olefin Substances 0.000 claims description 2
- LWUIVSCHIDJAKO-UHFFFAOYSA-L [Cl-].[Cl-].[Zr+2].C1(=CC=CC=2C3=CC=CC=C3CC12)C(CCC=C)(C)C1C=CC=C1 Chemical compound [Cl-].[Cl-].[Zr+2].C1(=CC=CC=2C3=CC=CC=C3CC12)C(CCC=C)(C)C1C=CC=C1 LWUIVSCHIDJAKO-UHFFFAOYSA-L 0.000 claims 2
- 125000003342 alkenyl group Chemical group 0.000 claims 2
- 125000002877 alkyl aryl group Chemical group 0.000 claims 2
- 125000003710 aryl alkyl group Chemical group 0.000 claims 2
- 125000003118 aryl group Chemical group 0.000 claims 2
- 125000004104 aryloxy group Chemical group 0.000 claims 2
- 125000004429 atom Chemical group 0.000 claims 2
- 229910052735 hafnium Inorganic materials 0.000 claims 2
- 229910052719 titanium Inorganic materials 0.000 claims 2
- HILIICNHOJSIPL-UHFFFAOYSA-L [Cl-].[Cl-].C1(=CC=CC=2C3=CC=CC=C3CC1=2)[Zr+2](C1C=CC=C1)=C Chemical compound [Cl-].[Cl-].C1(=CC=CC=2C3=CC=CC=C3CC1=2)[Zr+2](C1C=CC=C1)=C HILIICNHOJSIPL-UHFFFAOYSA-L 0.000 claims 1
- AICIQKYRDOALMR-UHFFFAOYSA-L [Cl-].[Cl-].CC1c2ccccc2-c2cccc([Zr++]c3cccc4-c5ccccc5C(C)c34)c12 Chemical compound [Cl-].[Cl-].CC1c2ccccc2-c2cccc([Zr++]c3cccc4-c5ccccc5C(C)c34)c12 AICIQKYRDOALMR-UHFFFAOYSA-L 0.000 claims 1
- 239000003446 ligand Substances 0.000 claims 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 45
- 239000000243 solution Substances 0.000 description 35
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 33
- 238000002474 experimental method Methods 0.000 description 21
- BRTALTYTFFNPAC-UHFFFAOYSA-N boroxin Chemical compound B1OBOBO1 BRTALTYTFFNPAC-UHFFFAOYSA-N 0.000 description 16
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 12
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical compound C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 10
- 239000000047 product Substances 0.000 description 10
- 239000002002 slurry Substances 0.000 description 10
- 150000001875 compounds Chemical class 0.000 description 9
- 229910052782 aluminium Inorganic materials 0.000 description 8
- 239000003085 diluting agent Substances 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- BFEGFEKPZJSMLC-UHFFFAOYSA-N COB1OBOBO1 Chemical compound COB1OBOBO1 BFEGFEKPZJSMLC-UHFFFAOYSA-N 0.000 description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 239000001282 iso-butane Substances 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- BZENIFADOHBVMR-UHFFFAOYSA-L [Cl-].[Cl-].CC1C2=CC=CC=C2C=2C=CC=C(C1=2)[Zr+2]C1C=CC=C1 Chemical compound [Cl-].[Cl-].CC1C2=CC=CC=C2C=2C=CC=C(C1=2)[Zr+2]C1C=CC=C1 BZENIFADOHBVMR-UHFFFAOYSA-L 0.000 description 5
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 5
- 238000010348 incorporation Methods 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 239000000155 melt Substances 0.000 description 4
- 239000012968 metallocene catalyst Substances 0.000 description 4
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- ASIUMUMCZDMVTE-UHFFFAOYSA-L [Cl-].[Cl-].C12=CC=CC=C2C2=CC=CC=C2C1[Zr+2]([SiH](C)C)C1C2=CC=CC=C2C2=CC=CC=C21 Chemical compound [Cl-].[Cl-].C12=CC=CC=C2C2=CC=CC=C2C1[Zr+2]([SiH](C)C)C1C2=CC=CC=C2C2=CC=CC=C21 ASIUMUMCZDMVTE-UHFFFAOYSA-L 0.000 description 3
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- 238000011156 evaluation Methods 0.000 description 3
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- 150000002430 hydrocarbons Chemical class 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 3
- 238000001542 size-exclusion chromatography Methods 0.000 description 3
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- QVRPRGWIJQKENN-UHFFFAOYSA-N 2,4,6-triethyl-1,3,5,2,4,6-trioxatriborinane Chemical compound CCB1OB(CC)OB(CC)O1 QVRPRGWIJQKENN-UHFFFAOYSA-N 0.000 description 2
- GBBSAMQTQCPOBF-UHFFFAOYSA-N 2,4,6-trimethyl-1,3,5,2,4,6-trioxatriborinane Chemical compound CB1OB(C)OB(C)O1 GBBSAMQTQCPOBF-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- KSJARYRXQGNKRM-UHFFFAOYSA-L [Cl-].[Cl-].C1(=CC=CC=2C3=CC=CC=C3CC12)[Zr+2]([SiH](C1=CC=CC=C1)C1=CC=CC=C1)C1=CC=CC=2C3=CC=CC=C3CC12 Chemical compound [Cl-].[Cl-].C1(=CC=CC=2C3=CC=CC=C3CC12)[Zr+2]([SiH](C1=CC=CC=C1)C1=CC=CC=C1)C1=CC=CC=2C3=CC=CC=C3CC12 KSJARYRXQGNKRM-UHFFFAOYSA-L 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 230000002902 bimodal effect Effects 0.000 description 2
- 238000000071 blow moulding Methods 0.000 description 2
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 2
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- 239000000376 reactant Substances 0.000 description 2
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- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 2
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- LWNGJAHMBMVCJR-UHFFFAOYSA-N (2,3,4,5,6-pentafluorophenoxy)boronic acid Chemical compound OB(O)OC1=C(F)C(F)=C(F)C(F)=C1F LWNGJAHMBMVCJR-UHFFFAOYSA-N 0.000 description 1
- AVQKDWGIJPBMTL-UHFFFAOYSA-L 1-[2-(1H-inden-1-yl)ethenyl]-9H-fluorene zirconium(2+) dichloride Chemical compound [Cl-].[Cl-].[Zr+2].C1(=CC=CC=2C3=CC=CC=C3CC12)C=CC1C=CC2=CC=CC=C12 AVQKDWGIJPBMTL-UHFFFAOYSA-L 0.000 description 1
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- 230000000704 physical effect Effects 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
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- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
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- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 description 1
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Classifications
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- 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
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- C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
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- 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
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Applications Claiming Priority (1)
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US08/305,243 US5594078A (en) | 1991-07-23 | 1994-09-13 | Process for producing broad molecular weight polyolefin |
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NO952835D0 NO952835D0 (no) | 1995-07-17 |
NO952835L NO952835L (no) | 1996-03-14 |
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NO19952835A NO310363B1 (no) | 1994-09-13 | 1995-07-17 | Katalysatorsystem og fremgangsmåte til produksjon av polyolefin med bred molekylvektfordeling |
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US (2) | US5594078A (hu) |
EP (1) | EP0705851B9 (hu) |
JP (1) | JPH08100018A (hu) |
KR (1) | KR100377078B1 (hu) |
CN (1) | CN1053676C (hu) |
AT (1) | ATE258194T1 (hu) |
AU (1) | AU677128B2 (hu) |
BG (1) | BG99794A (hu) |
BR (1) | BR9504008A (hu) |
CA (1) | CA2153520C (hu) |
CZ (1) | CZ235195A3 (hu) |
DE (1) | DE69532461T2 (hu) |
ES (1) | ES2210267T3 (hu) |
FI (1) | FI953456A (hu) |
HU (1) | HU218866B (hu) |
NO (1) | NO310363B1 (hu) |
PL (1) | PL310392A1 (hu) |
SG (1) | SG54082A1 (hu) |
SK (1) | SK112495A3 (hu) |
TW (1) | TW357157B (hu) |
ZA (1) | ZA957695B (hu) |
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- 1995-07-10 CA CA002153520A patent/CA2153520C/en not_active Expired - Lifetime
- 1995-07-17 NO NO19952835A patent/NO310363B1/no unknown
- 1995-07-17 FI FI953456A patent/FI953456A/fi unknown
- 1995-07-17 DE DE69532461T patent/DE69532461T2/de not_active Expired - Lifetime
- 1995-07-17 ES ES95111209T patent/ES2210267T3/es not_active Expired - Lifetime
- 1995-07-17 AT AT95111209T patent/ATE258194T1/de not_active IP Right Cessation
- 1995-07-17 EP EP95111209A patent/EP0705851B9/en not_active Expired - Lifetime
- 1995-07-18 HU HU9502155A patent/HU218866B/hu not_active IP Right Cessation
- 1995-07-19 BG BG99794A patent/BG99794A/bg unknown
- 1995-08-28 TW TW084108918A patent/TW357157B/zh not_active IP Right Cessation
- 1995-08-31 AU AU30371/95A patent/AU677128B2/en not_active Ceased
- 1995-09-01 SG SG1995001272A patent/SG54082A1/en unknown
- 1995-09-11 SK SK1124-95A patent/SK112495A3/sk unknown
- 1995-09-12 CN CN95116895A patent/CN1053676C/zh not_active Expired - Lifetime
- 1995-09-12 PL PL95310392A patent/PL310392A1/xx unknown
- 1995-09-12 KR KR1019950030166A patent/KR100377078B1/ko not_active IP Right Cessation
- 1995-09-12 CZ CZ952351A patent/CZ235195A3/cs unknown
- 1995-09-12 JP JP7233988A patent/JPH08100018A/ja active Pending
- 1995-09-13 BR BR9504008A patent/BR9504008A/pt not_active IP Right Cessation
- 1995-09-13 ZA ZA957695A patent/ZA957695B/xx unknown
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ES2210267T3 (es) | 2004-07-01 |
KR960010689A (ko) | 1996-04-20 |
BG99794A (bg) | 1996-06-28 |
CN1053676C (zh) | 2000-06-21 |
HUT72277A (en) | 1996-04-29 |
CA2153520A1 (en) | 1996-03-14 |
CN1123287A (zh) | 1996-05-29 |
SK112495A3 (en) | 1996-04-03 |
BR9504008A (pt) | 1996-09-24 |
CA2153520C (en) | 1999-08-31 |
AU677128B2 (en) | 1997-04-10 |
DE69532461T2 (de) | 2004-10-21 |
US5534473A (en) | 1996-07-09 |
FI953456A0 (fi) | 1995-07-17 |
PL310392A1 (en) | 1996-03-18 |
EP0705851A3 (en) | 1997-03-05 |
DE69532461D1 (de) | 2004-02-26 |
HU218866B (hu) | 2000-12-28 |
NO952835D0 (no) | 1995-07-17 |
AU3037195A (en) | 1996-04-04 |
EP0705851B1 (en) | 2004-01-21 |
ZA957695B (en) | 1996-04-15 |
CZ235195A3 (en) | 1996-04-17 |
FI953456A (fi) | 1996-03-14 |
EP0705851A2 (en) | 1996-04-10 |
SG54082A1 (en) | 1998-11-16 |
NO952835L (no) | 1996-03-14 |
KR100377078B1 (ko) | 2003-06-18 |
JPH08100018A (ja) | 1996-04-16 |
ATE258194T1 (de) | 2004-02-15 |
EP0705851B9 (en) | 2004-08-11 |
US5594078A (en) | 1997-01-14 |
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