FI113544B - Menetelmä olefiinin polymeroimiseksi - Google Patents
Menetelmä olefiinin polymeroimiseksi Download PDFInfo
- Publication number
- FI113544B FI113544B FI923337A FI923337A FI113544B FI 113544 B FI113544 B FI 113544B FI 923337 A FI923337 A FI 923337A FI 923337 A FI923337 A FI 923337A FI 113544 B FI113544 B FI 113544B
- Authority
- FI
- Finland
- Prior art keywords
- fluorenyl
- ethane
- process according
- zirconium dichloride
- dichloride
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims abstract description 39
- 230000008569 process Effects 0.000 title claims description 30
- 150000001336 alkenes Chemical class 0.000 title claims description 19
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 title claims description 13
- 230000000379 polymerizing effect Effects 0.000 title claims description 4
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 claims abstract description 38
- -1 fluorenyl radical Chemical class 0.000 claims description 115
- 239000003054 catalyst Substances 0.000 claims description 48
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 37
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Natural products CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 35
- 150000001875 compounds Chemical class 0.000 claims description 35
- VPGLGRNSAYHXPY-UHFFFAOYSA-L zirconium(2+);dichloride Chemical compound Cl[Zr]Cl VPGLGRNSAYHXPY-UHFFFAOYSA-L 0.000 claims description 25
- 238000006243 chemical reaction Methods 0.000 claims description 22
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 21
- 239000002904 solvent Substances 0.000 claims description 21
- WYURNTSHIVDZCO-UHFFFAOYSA-N tetrahydrofuran Substances C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 21
- 229910052751 metal Inorganic materials 0.000 claims description 20
- 239000002184 metal Substances 0.000 claims description 20
- 229910052783 alkali metal Inorganic materials 0.000 claims description 19
- 125000004432 carbon atom Chemical group C* 0.000 claims description 18
- 150000003254 radicals Chemical class 0.000 claims description 16
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical group CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 15
- ZSWFCLXCOIISFI-UHFFFAOYSA-N endo-cyclopentadiene Natural products C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 claims description 14
- 150000003623 transition metal compounds Chemical class 0.000 claims description 14
- 125000001183 hydrocarbyl group Chemical group 0.000 claims description 11
- 229910052739 hydrogen Inorganic materials 0.000 claims description 11
- 150000003839 salts Chemical class 0.000 claims description 11
- 239000001257 hydrogen Substances 0.000 claims description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 8
- KUNZSLJMPCDOGI-UHFFFAOYSA-L [Cl-].[Cl-].[Hf+2] Chemical compound [Cl-].[Cl-].[Hf+2] KUNZSLJMPCDOGI-UHFFFAOYSA-L 0.000 claims description 8
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 claims description 7
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 claims description 7
- 229910052735 hafnium Inorganic materials 0.000 claims description 7
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- 239000000460 chlorine Substances 0.000 claims description 6
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Natural products C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 5
- HVYLDTQYKHSBCX-UHFFFAOYSA-L [Cl-].[Cl-].[Zr+2].C1(=CC=CC=2C3=CC=CC=C3CC12)CC(C1C=CC2=CC=CC=C12)C Chemical compound [Cl-].[Cl-].[Zr+2].C1(=CC=CC=2C3=CC=CC=C3CC12)CC(C1C=CC2=CC=CC=C12)C HVYLDTQYKHSBCX-UHFFFAOYSA-L 0.000 claims description 5
- XLJVZPGYLPEDNO-UHFFFAOYSA-L [Cl-].[Cl-].[Zr+2].C12=CC=CC=C2CC2=C1C=CC=C2CCC1=CC=CC2=C1CC1=CC=CC=C12 Chemical compound [Cl-].[Cl-].[Zr+2].C12=CC=CC=C2CC2=C1C=CC=C2CCC1=CC=CC2=C1CC1=CC=CC=C12 XLJVZPGYLPEDNO-UHFFFAOYSA-L 0.000 claims description 5
- 229910052736 halogen Inorganic materials 0.000 claims description 5
- 150000002367 halogens Chemical class 0.000 claims description 5
- 150000002739 metals Chemical class 0.000 claims description 5
- 229910052801 chlorine Inorganic materials 0.000 claims description 4
- 125000003454 indenyl group Chemical group C1(C=CC2=CC=CC=C12)* 0.000 claims description 4
- 230000000737 periodic effect Effects 0.000 claims description 4
- 229910052719 titanium Inorganic materials 0.000 claims description 4
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 claims description 4
- FWLPMMZOQSPPPH-UHFFFAOYSA-N 2-tert-butyl-1-[2-(2-tert-butyl-9h-fluoren-1-yl)ethyl]-9h-fluorene Chemical compound C1=CC=C2C3=CC=C(C(C)(C)C)C(CCC4=C5C(C6=CC=CC=C6C5)=CC=C4C(C)(C)C)=C3CC2=C1 FWLPMMZOQSPPPH-UHFFFAOYSA-N 0.000 claims description 3
- OXUITWROQHDFEV-UHFFFAOYSA-L 4-tert-butyl-1-[2-(4-tert-butyl-9H-fluoren-1-yl)ethyl]-9H-fluorene zirconium(2+) dichloride Chemical compound [Cl-].[Cl-].[Zr+2].C(C)(C)(C)C1=CC=C(C=2CC3=CC=CC=C3C12)CCC1=CC=C(C=2C3=CC=CC=C3CC12)C(C)(C)C OXUITWROQHDFEV-UHFFFAOYSA-L 0.000 claims description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 3
- 229910007926 ZrCl Inorganic materials 0.000 claims description 3
- NEHMKBQYUWJMIP-UHFFFAOYSA-N anhydrous methyl chloride Natural products ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 claims description 3
- 125000005842 heteroatom Chemical group 0.000 claims description 3
- 229910052726 zirconium Inorganic materials 0.000 claims description 3
- 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 2
- ALKCHKDQKMSZIC-UHFFFAOYSA-L [Cl-].[Cl-].[Hf+2].C1(=CC=CC=2C3=CC=CC=C3CC12)CCC1=CC=CC=2C3=CC=CC=C3CC12 Chemical compound [Cl-].[Cl-].[Hf+2].C1(=CC=CC=2C3=CC=CC=C3CC12)CCC1=CC=CC=2C3=CC=CC=C3CC12 ALKCHKDQKMSZIC-UHFFFAOYSA-L 0.000 claims description 2
- MZWBBNXTXXTYFZ-UHFFFAOYSA-L [Cl-].[Cl-].[Hf+2].CC1=C(C=CC=2C3=CC=CC=C3CC12)CCC1=C(C=2CC3=CC=CC=C3C2C=C1)C Chemical compound [Cl-].[Cl-].[Hf+2].CC1=C(C=CC=2C3=CC=CC=C3CC12)CCC1=C(C=2CC3=CC=CC=C3C2C=C1)C MZWBBNXTXXTYFZ-UHFFFAOYSA-L 0.000 claims description 2
- XFZVZHATBHSZAE-UHFFFAOYSA-L [Cl-].[Cl-].[Hf+2].CC1=CC=C(C=2CC3=CC=CC=C3C12)CCC1=CC=C(C=2C3=CC=CC=C3CC12)C Chemical compound [Cl-].[Cl-].[Hf+2].CC1=CC=C(C=2CC3=CC=CC=C3C12)CCC1=CC=C(C=2C3=CC=CC=C3CC12)C XFZVZHATBHSZAE-UHFFFAOYSA-L 0.000 claims description 2
- HFOHQVSXHMUCJW-UHFFFAOYSA-L [Cl-].[Cl-].[Zr+2].C(C)(C)(C)C1=C(C=2CC3=CC(=CC=C3C2C(=C1)C)C(C)(C)C)CCC1=C(C=C(C=2C3=CC=C(C=C3CC12)C(C)(C)C)C)C(C)(C)C Chemical compound [Cl-].[Cl-].[Zr+2].C(C)(C)(C)C1=C(C=2CC3=CC(=CC=C3C2C(=C1)C)C(C)(C)C)CCC1=C(C=C(C=2C3=CC=C(C=C3CC12)C(C)(C)C)C)C(C)(C)C HFOHQVSXHMUCJW-UHFFFAOYSA-L 0.000 claims description 2
- YQANMNHJLUCAKC-UHFFFAOYSA-L [Cl-].[Cl-].[Zr+2].C1(=CC=CC=2C3=CC=CC=C3CC12)CC(C1=CC=CC=2C3=CC=CC=C3CC12)C Chemical compound [Cl-].[Cl-].[Zr+2].C1(=CC=CC=2C3=CC=CC=C3CC12)CC(C1=CC=CC=2C3=CC=CC=C3CC12)C YQANMNHJLUCAKC-UHFFFAOYSA-L 0.000 claims description 2
- SYWUCUBHFOLOEG-UHFFFAOYSA-L [Cl-].[Cl-].[Zr+2].CC1=CC=C(C=2CC3=CC=CC=C3C12)CCC1=C(C=2CC3=CC=CC=C3C2C=C1)C Chemical compound [Cl-].[Cl-].[Zr+2].CC1=CC=C(C=2CC3=CC=CC=C3C12)CCC1=C(C=2CC3=CC=CC=C3C2C=C1)C SYWUCUBHFOLOEG-UHFFFAOYSA-L 0.000 claims description 2
- 125000001931 aliphatic group Chemical group 0.000 claims description 2
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- HZVOZRGWRWCICA-UHFFFAOYSA-N methanediyl Chemical compound [CH2] HZVOZRGWRWCICA-UHFFFAOYSA-N 0.000 claims description 2
- 125000003944 tolyl group Chemical group 0.000 claims description 2
- 239000004711 α-olefin Substances 0.000 claims description 2
- QVRBGKYLLCLCHL-UHFFFAOYSA-N 5-methylcyclopenta-1,3-diene Chemical compound CC1C=CC=C1 QVRBGKYLLCLCHL-UHFFFAOYSA-N 0.000 claims 2
- HSWMTFMIJVZLGW-UHFFFAOYSA-L 1-[2-(9H-fluoren-1-yl)ethyl]-9H-fluorene vanadium(2+) dichloride Chemical compound [Cl-].[Cl-].[V+2].C1(=CC=CC=2C3=CC=CC=C3CC12)CCC1=CC=CC=2C3=CC=CC=C3CC12 HSWMTFMIJVZLGW-UHFFFAOYSA-L 0.000 claims 1
- PRIGFEJKMMRJSF-UHFFFAOYSA-M 1-fluoro-2,4,6-trimethylpyridin-1-ium;trifluoromethanesulfonate Chemical compound [O-]S(=O)(=O)C(F)(F)F.CC1=CC(C)=[N+](F)C(C)=C1 PRIGFEJKMMRJSF-UHFFFAOYSA-M 0.000 claims 1
- APRHBMYIKSADHX-UHFFFAOYSA-L 4-methyl-1-[2-(4-methyl-9H-fluoren-1-yl)ethyl]-9H-fluorene zirconium(2+) dichloride Chemical compound [Cl-].[Cl-].[Zr+2].CC1=CC=C(C=2CC3=CC=CC=C3C12)CCC1=CC=C(C=2C3=CC=CC=C3CC12)C APRHBMYIKSADHX-UHFFFAOYSA-L 0.000 claims 1
- VSUIFXKFQOGXGU-UHFFFAOYSA-K [Cl-].[Cl-].[Cl-].[Zr+3].C(C1=CC=CC1)c1cccc-2c1Cc1ccccc-21 Chemical compound [Cl-].[Cl-].[Cl-].[Zr+3].C(C1=CC=CC1)c1cccc-2c1Cc1ccccc-21 VSUIFXKFQOGXGU-UHFFFAOYSA-K 0.000 claims 1
- JEOKVXVDNOAQDX-UHFFFAOYSA-L [Cl-].[Cl-].[Hf+2].C1(=CC=CC=2C3=CC=CC=C3CC12)CC(C1C=CC2=CC=CC=C12)C Chemical compound [Cl-].[Cl-].[Hf+2].C1(=CC=CC=2C3=CC=CC=C3CC12)CC(C1C=CC2=CC=CC=C12)C JEOKVXVDNOAQDX-UHFFFAOYSA-L 0.000 claims 1
- QMGSQNXGEMEXOK-UHFFFAOYSA-L [Cl-].[Cl-].[Hf+2].C1(=CC=CC=2C3=CC=CC=C3CC12)CCCC1=CC=CC=2C3=CC=CC=C3CC12 Chemical compound [Cl-].[Cl-].[Hf+2].C1(=CC=CC=2C3=CC=CC=C3CC12)CCCC1=CC=CC=2C3=CC=CC=C3CC12 QMGSQNXGEMEXOK-UHFFFAOYSA-L 0.000 claims 1
- CYSNCVJNJFWYEM-UHFFFAOYSA-L [Cl-].[Cl-].[Zr+2].C(C)(C)(C)C1=C(C=2CC3=CC(=CC=C3C2C=C1)C(C)(C)C)CCC1=CC=CC=2C3=CC=CC=C3CC12 Chemical compound [Cl-].[Cl-].[Zr+2].C(C)(C)(C)C1=C(C=2CC3=CC(=CC=C3C2C=C1)C(C)(C)C)CCC1=CC=CC=2C3=CC=CC=C3CC12 CYSNCVJNJFWYEM-UHFFFAOYSA-L 0.000 claims 1
- BPDKGUAQIAHLJD-UHFFFAOYSA-L [Cl-].[Cl-].[Zr+2].C(C)C1=C(C=2CC3=CC=CC=C3C2C=C1)CCC1=C(C=CC=2C3=CC=CC=C3CC12)CC Chemical compound [Cl-].[Cl-].[Zr+2].C(C)C1=C(C=2CC3=CC=CC=C3C2C=C1)CCC1=C(C=CC=2C3=CC=CC=C3CC12)CC BPDKGUAQIAHLJD-UHFFFAOYSA-L 0.000 claims 1
- KFGGSYPWRALCMB-UHFFFAOYSA-L [Cl-].[Cl-].[Zr+2].C1(=CC=CC=2C3=CC=CC=C3CC12)CCCC1=CC=CC=2C3=CC=CC=C3CC12 Chemical compound [Cl-].[Cl-].[Zr+2].C1(=CC=CC=2C3=CC=CC=C3CC12)CCCC1=CC=CC=2C3=CC=CC=C3CC12 KFGGSYPWRALCMB-UHFFFAOYSA-L 0.000 claims 1
- NFGGRRGHUTVQCF-UHFFFAOYSA-L [Cl-].[Cl-].[Zr+2].CC1=C(C=C(C=2C3=CC=CC=C3CC12)C)CCC1=C(C=2CC3=CC=CC=C3C2C(=C1)C)C Chemical compound [Cl-].[Cl-].[Zr+2].CC1=C(C=C(C=2C3=CC=CC=C3CC12)C)CCC1=C(C=2CC3=CC=CC=C3C2C(=C1)C)C NFGGRRGHUTVQCF-UHFFFAOYSA-L 0.000 claims 1
- YZVPACIIQNMYBS-UHFFFAOYSA-N [Zr].C1(=CC=CC=2C3=CC=CC=C3CC12)CC(C1C=C(C=C1)C)C Chemical compound [Zr].C1(=CC=CC=2C3=CC=CC=C3CC12)CC(C1C=C(C=C1)C)C YZVPACIIQNMYBS-UHFFFAOYSA-N 0.000 claims 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 claims 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims 1
- 125000005982 diphenylmethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])(*)C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 claims 1
- WCYWZMWISLQXQU-UHFFFAOYSA-N methyl Chemical compound [CH3] WCYWZMWISLQXQU-UHFFFAOYSA-N 0.000 claims 1
- 229940050176 methyl chloride Drugs 0.000 claims 1
- 229920000642 polymer Polymers 0.000 abstract description 38
- 238000006116 polymerization reaction Methods 0.000 abstract description 36
- 239000002685 polymerization catalyst Substances 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 33
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 21
- 239000007787 solid Substances 0.000 description 21
- 238000002360 preparation method Methods 0.000 description 19
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N o-biphenylenemethane Natural products C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 description 16
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 14
- 239000011541 reaction mixture Substances 0.000 description 11
- DVSDBMFJEQPWNO-UHFFFAOYSA-N methyllithium Chemical compound C[Li] DVSDBMFJEQPWNO-UHFFFAOYSA-N 0.000 description 10
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 10
- 229910052723 transition metal Inorganic materials 0.000 description 10
- 150000003624 transition metals Chemical class 0.000 description 10
- 239000007788 liquid Substances 0.000 description 9
- 239000000178 monomer Substances 0.000 description 9
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 8
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 8
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 8
- 239000005977 Ethylene Substances 0.000 description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 8
- 239000003085 diluting agent Substances 0.000 description 8
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 241000723368 Conium Species 0.000 description 7
- YLQWCDOCJODRMT-UHFFFAOYSA-N fluoren-9-one Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3C2=C1 YLQWCDOCJODRMT-UHFFFAOYSA-N 0.000 description 7
- 239000003446 ligand Substances 0.000 description 7
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 7
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 7
- PBKONEOXTCPAFI-UHFFFAOYSA-N 1,2,4-trichlorobenzene Chemical compound ClC1=CC=C(Cl)C(Cl)=C1 PBKONEOXTCPAFI-UHFFFAOYSA-N 0.000 description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- GVEPBJHOBDJJJI-UHFFFAOYSA-N fluoranthene Chemical compound C1=CC(C2=CC=CC=C22)=C3C2=CC=CC3=C1 GVEPBJHOBDJJJI-UHFFFAOYSA-N 0.000 description 6
- GKEUODMJRFDLJY-UHFFFAOYSA-N 1-Methylfluorene Chemical compound C12=CC=CC=C2CC2=C1C=CC=C2C GKEUODMJRFDLJY-UHFFFAOYSA-N 0.000 description 5
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 5
- 238000005481 NMR spectroscopy Methods 0.000 description 5
- 239000004743 Polypropylene Substances 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 125000000896 monocarboxylic acid group Chemical group 0.000 description 5
- 229910052763 palladium Inorganic materials 0.000 description 5
- 229920001155 polypropylene Polymers 0.000 description 5
- 239000002244 precipitate Substances 0.000 description 5
- 238000001542 size-exclusion chromatography Methods 0.000 description 5
- 125000001424 substituent group Chemical group 0.000 description 5
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 description 5
- JQGUJNDHLZJSKL-UHFFFAOYSA-N 1-(cyclopenta-2,4-dien-1-ylmethyl)-9H-fluorene Chemical compound C(C1C=CC=C1)C1=CC=CC2=C1CC1=CC=CC=C21 JQGUJNDHLZJSKL-UHFFFAOYSA-N 0.000 description 4
- 229910010082 LiAlH Inorganic materials 0.000 description 4
- 229910010084 LiAlH4 Inorganic materials 0.000 description 4
- 238000001460 carbon-13 nuclear magnetic resonance spectrum Methods 0.000 description 4
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000000605 extraction Methods 0.000 description 4
- 125000005843 halogen group Chemical group 0.000 description 4
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 4
- 239000012280 lithium aluminium hydride Substances 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical compound C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- WLRLVPXYOKGSAJ-UHFFFAOYSA-L 1-[2-(1H-inden-1-yl)ethyl]-9H-fluorene zirconium(2+) dichloride Chemical compound [Cl-].[Cl-].[Zr+2].C1(=CC=CC=2C3=CC=CC=C3CC12)CCC1C=CC2=CC=CC=C12 WLRLVPXYOKGSAJ-UHFFFAOYSA-L 0.000 description 3
- IAGPYKKRRMNDCQ-UHFFFAOYSA-N 2-ethyl-9h-fluorene Chemical compound C1=CC=C2C3=CC=C(CC)C=C3CC2=C1 IAGPYKKRRMNDCQ-UHFFFAOYSA-N 0.000 description 3
- OPFILOLCFWFBNT-UHFFFAOYSA-N 4-methyl-9h-fluorene Chemical compound C1C2=CC=CC=C2C2=C1C=CC=C2C OPFILOLCFWFBNT-UHFFFAOYSA-N 0.000 description 3
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
- GDBQHVXXKJIZSM-UHFFFAOYSA-L Cl[Zr]Cl.C(C1C=CC=C1)C1=CC=CC2=C1CC1=CC=CC=C21 Chemical compound Cl[Zr]Cl.C(C1C=CC=C1)C1=CC=CC2=C1CC1=CC=CC=C21 GDBQHVXXKJIZSM-UHFFFAOYSA-L 0.000 description 3
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- BMTKGBCFRKGOOZ-UHFFFAOYSA-K cyclopenta-1,3-diene;zirconium(4+);trichloride Chemical compound [Cl-].[Cl-].[Cl-].[Zr+4].C=1C=C[CH-]C=1 BMTKGBCFRKGOOZ-UHFFFAOYSA-K 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- HJXBDPDUCXORKZ-UHFFFAOYSA-N diethylalumane Chemical compound CC[AlH]CC HJXBDPDUCXORKZ-UHFFFAOYSA-N 0.000 description 1
- YNLAOSYQHBDIKW-UHFFFAOYSA-M diethylaluminium chloride Chemical compound CC[Al](Cl)CC YNLAOSYQHBDIKW-UHFFFAOYSA-M 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- UHAACAAEIMGXFS-UHFFFAOYSA-N ethylaluminum(2+);oxygen(2-) Chemical compound [O-2].CC[Al+2] UHAACAAEIMGXFS-UHFFFAOYSA-N 0.000 description 1
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- 230000008020 evaporation Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical compound [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 description 1
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- 238000004817 gas chromatography Methods 0.000 description 1
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- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- PDPJQWYGJJBYLF-UHFFFAOYSA-J hafnium tetrachloride Chemical compound Cl[Hf](Cl)(Cl)Cl PDPJQWYGJJBYLF-UHFFFAOYSA-J 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000012456 homogeneous solution Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
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- CBOIHMRHGLHBPB-UHFFFAOYSA-N hydroxymethyl Chemical compound O[CH2] CBOIHMRHGLHBPB-UHFFFAOYSA-N 0.000 description 1
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- 150000002469 indenes Chemical class 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
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- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
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- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
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- 229910052987 metal hydride Inorganic materials 0.000 description 1
- 150000004681 metal hydrides Chemical class 0.000 description 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N methanol Substances OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 1
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 1
- UEEXYHHZSOEEDG-UHFFFAOYSA-N methylaluminum(2+);oxygen(2-) Chemical compound [O-2].[Al+2]C UEEXYHHZSOEEDG-UHFFFAOYSA-N 0.000 description 1
- 230000011987 methylation Effects 0.000 description 1
- 238000007069 methylation reaction Methods 0.000 description 1
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- AFFLGGQVNFXPEV-UHFFFAOYSA-N n-decene Natural products CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid group Chemical group C(CCCCCCC\C=C/CCCCCCCC)(=O)O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- XMGMFRIEKMMMSU-UHFFFAOYSA-N phenylmethylbenzene Chemical group C=1C=CC=CC=1[C]C1=CC=CC=C1 XMGMFRIEKMMMSU-UHFFFAOYSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 210000002966 serum Anatomy 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 125000005156 substituted alkylene group Chemical group 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 239000006188 syrup Substances 0.000 description 1
- 235000020357 syrup Nutrition 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- ZWYDDDAMNQQZHD-UHFFFAOYSA-L titanium(ii) chloride Chemical compound [Cl-].[Cl-].[Ti+2] ZWYDDDAMNQQZHD-UHFFFAOYSA-L 0.000 description 1
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
Classifications
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- 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
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- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
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- 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
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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
- 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
- C08F4/63922—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 containing at least two cyclopentadienyl rings, fused or not
-
- 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
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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
- 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
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- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
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- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
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Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US73485391 | 1991-07-23 | ||
US07/734,853 US5436305A (en) | 1991-05-09 | 1991-07-23 | Organometallic fluorenyl compounds, preparation, and use |
Publications (3)
Publication Number | Publication Date |
---|---|
FI923337A0 FI923337A0 (fi) | 1992-07-22 |
FI923337A FI923337A (fi) | 1993-01-24 |
FI113544B true FI113544B (fi) | 2004-05-14 |
Family
ID=24953348
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
FI923337A FI113544B (fi) | 1991-07-23 | 1992-07-22 | Menetelmä olefiinin polymeroimiseksi |
Country Status (21)
Country | Link |
---|---|
US (1) | US5436305A (de) |
EP (1) | EP0524624B1 (de) |
JP (2) | JP2791247B2 (de) |
KR (1) | KR100192683B1 (de) |
CN (1) | CN1068829A (de) |
AT (1) | ATE217637T1 (de) |
AU (1) | AU649821B2 (de) |
CZ (1) | CZ230392A3 (de) |
DE (1) | DE69232608T2 (de) |
DK (1) | DK0524624T3 (de) |
ES (1) | ES2176180T3 (de) |
FI (1) | FI113544B (de) |
HU (1) | HU212903B (de) |
IE (1) | IE922381A1 (de) |
MX (1) | MX9202788A (de) |
NO (1) | NO304553B1 (de) |
PL (1) | PL295385A1 (de) |
RO (1) | RO111683B1 (de) |
SG (1) | SG44707A1 (de) |
SK (1) | SK230392A3 (de) |
ZA (1) | ZA923987B (de) |
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-
1991
- 1991-07-23 US US07/734,853 patent/US5436305A/en not_active Expired - Lifetime
-
1992
- 1992-04-09 CN CN92102617A patent/CN1068829A/zh active Pending
- 1992-05-20 AU AU17002/92A patent/AU649821B2/en not_active Ceased
- 1992-06-01 ZA ZA923987A patent/ZA923987B/xx unknown
- 1992-06-11 MX MX9202788A patent/MX9202788A/es unknown
- 1992-06-20 KR KR1019920010768A patent/KR100192683B1/ko not_active IP Right Cessation
- 1992-06-22 JP JP4163092A patent/JP2791247B2/ja not_active Expired - Fee Related
- 1992-07-22 RO RO92-01007A patent/RO111683B1/ro unknown
- 1992-07-22 FI FI923337A patent/FI113544B/fi not_active IP Right Cessation
- 1992-07-22 NO NO922910A patent/NO304553B1/no unknown
- 1992-07-22 IE IE238192A patent/IE922381A1/en not_active Application Discontinuation
- 1992-07-23 DE DE69232608T patent/DE69232608T2/de not_active Expired - Fee Related
- 1992-07-23 AT AT92112582T patent/ATE217637T1/de not_active IP Right Cessation
- 1992-07-23 EP EP92112582A patent/EP0524624B1/de not_active Expired - Lifetime
- 1992-07-23 DK DK92112582T patent/DK0524624T3/da active
- 1992-07-23 CZ CS922303A patent/CZ230392A3/cs unknown
- 1992-07-23 SG SG1996006065A patent/SG44707A1/en unknown
- 1992-07-23 SK SK2303-92A patent/SK230392A3/sk unknown
- 1992-07-23 PL PL29538592A patent/PL295385A1/xx unknown
- 1992-07-23 HU HU9202412A patent/HU212903B/hu not_active IP Right Cessation
- 1992-07-23 ES ES92112582T patent/ES2176180T3/es not_active Expired - Lifetime
-
1998
- 1998-02-19 JP JP10037503A patent/JP3111176B2/ja not_active Expired - Fee Related
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SK230392A3 (en) | 1995-05-10 |
CZ230392A3 (en) | 1993-02-17 |
DE69232608D1 (de) | 2002-06-20 |
HUT63972A (en) | 1993-11-29 |
HU212903B (en) | 1996-12-30 |
JP3111176B2 (ja) | 2000-11-20 |
EP0524624B1 (de) | 2002-05-15 |
JPH10226695A (ja) | 1998-08-25 |
DK0524624T3 (da) | 2002-08-26 |
PL295385A1 (en) | 1993-04-05 |
IE922381A1 (en) | 1993-01-27 |
AU649821B2 (en) | 1994-06-02 |
JPH05239082A (ja) | 1993-09-17 |
AU1700292A (en) | 1993-03-11 |
CN1068829A (zh) | 1993-02-10 |
MX9202788A (es) | 1993-01-01 |
ZA923987B (en) | 1993-02-24 |
FI923337A0 (fi) | 1992-07-22 |
RO111683B1 (ro) | 1996-12-30 |
FI923337A (fi) | 1993-01-24 |
US5436305A (en) | 1995-07-25 |
KR100192683B1 (ko) | 1999-06-15 |
NO922910L (no) | 1993-01-25 |
EP0524624A2 (de) | 1993-01-27 |
NO922910D0 (no) | 1992-07-22 |
ATE217637T1 (de) | 2002-06-15 |
ES2176180T3 (es) | 2002-12-01 |
DE69232608T2 (de) | 2002-11-28 |
JP2791247B2 (ja) | 1998-08-27 |
NO304553B1 (no) | 1999-01-11 |
SG44707A1 (en) | 1997-12-19 |
KR930002361A (ko) | 1993-02-23 |
EP0524624A3 (en) | 1993-05-05 |
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