MXPA00004295A - Method for producing fulvene metal complexes - Google Patents
Method for producing fulvene metal complexesInfo
- Publication number
- MXPA00004295A MXPA00004295A MXPA/A/2000/004295A MXPA00004295A MXPA00004295A MX PA00004295 A MXPA00004295 A MX PA00004295A MX PA00004295 A MXPA00004295 A MX PA00004295A MX PA00004295 A MXPA00004295 A MX PA00004295A
- Authority
- MX
- Mexico
- Prior art keywords
- carbon atoms
- group
- formula
- fulvene
- reaction
- Prior art date
Links
- PGTKVMVZBBZCKQ-UHFFFAOYSA-N fulvene Chemical compound C=C1C=CC=C1 PGTKVMVZBBZCKQ-UHFFFAOYSA-N 0.000 title claims abstract description 37
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 30
- 239000002184 metal Substances 0.000 title claims abstract description 30
- 238000004519 manufacturing process Methods 0.000 title abstract 2
- 150000001875 compounds Chemical class 0.000 claims abstract description 19
- 150000001993 dienes Chemical class 0.000 claims abstract description 9
- 150000001336 alkenes Chemical class 0.000 claims abstract description 8
- 125000004432 carbon atoms Chemical group C* 0.000 claims description 69
- -1 fulvene compound Chemical class 0.000 claims description 45
- 238000006243 chemical reaction Methods 0.000 claims description 38
- 229910052739 hydrogen Inorganic materials 0.000 claims description 27
- 238000006116 polymerization reaction Methods 0.000 claims description 22
- 238000000034 method Methods 0.000 claims description 18
- 125000003118 aryl group Chemical group 0.000 claims description 11
- 239000003638 reducing agent Substances 0.000 claims description 11
- RTAQQCXQSZGOHL-UHFFFAOYSA-N titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 11
- 239000010936 titanium Substances 0.000 claims description 11
- 229910052719 titanium Inorganic materials 0.000 claims description 11
- 239000004215 Carbon black (E152) Substances 0.000 claims description 10
- 125000000217 alkyl group Chemical group 0.000 claims description 10
- 239000001257 hydrogen Substances 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 10
- 230000027455 binding Effects 0.000 claims description 9
- QCWXUUIWCKQGHC-UHFFFAOYSA-N zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 9
- 229910052726 zirconium Inorganic materials 0.000 claims description 9
- 125000002877 alkyl aryl group Chemical group 0.000 claims description 8
- 239000003446 ligand Substances 0.000 claims description 8
- 239000003426 co-catalyst Substances 0.000 claims description 7
- VBJZVLUMGGDVMO-UHFFFAOYSA-N Hafnium Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 claims description 6
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 6
- 229910052735 hafnium Inorganic materials 0.000 claims description 6
- 125000002097 pentamethylcyclopentadienyl group Chemical group 0.000 claims description 6
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 claims description 6
- 230000003197 catalytic Effects 0.000 claims description 5
- 229910052804 chromium Inorganic materials 0.000 claims description 5
- VYZAMTAEIAYCRO-UHFFFAOYSA-N chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 5
- 239000011651 chromium Substances 0.000 claims description 5
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 5
- 229910052758 niobium Inorganic materials 0.000 claims description 5
- 239000010955 niobium Substances 0.000 claims description 5
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims description 5
- 229910052715 tantalum Inorganic materials 0.000 claims description 5
- 229910052720 vanadium Inorganic materials 0.000 claims description 5
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium(0) Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 5
- 125000003342 alkenyl group Chemical group 0.000 claims description 4
- 125000003545 alkoxy group Chemical group 0.000 claims description 4
- 125000003277 amino group Chemical group 0.000 claims description 4
- 125000005018 aryl alkenyl group Chemical group 0.000 claims description 4
- 125000004104 aryloxy group Chemical group 0.000 claims description 4
- 125000004429 atoms Chemical group 0.000 claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 4
- 239000012429 reaction media Substances 0.000 claims description 4
- 150000003623 transition metal compounds Chemical class 0.000 claims description 4
- 230000004913 activation Effects 0.000 claims description 3
- 229910052783 alkali metal Inorganic materials 0.000 claims description 3
- 150000001340 alkali metals Chemical class 0.000 claims description 3
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 3
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- 150000004696 coordination complex Chemical class 0.000 claims description 3
- 229910052744 lithium Inorganic materials 0.000 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 230000003647 oxidation Effects 0.000 claims description 3
- 238000007254 oxidation reaction Methods 0.000 claims description 3
- 229910052768 actinide Inorganic materials 0.000 claims description 2
- 150000001255 actinides Chemical class 0.000 claims description 2
- 125000001931 aliphatic group Chemical group 0.000 claims description 2
- 125000000304 alkynyl group Chemical group 0.000 claims description 2
- 150000001408 amides Chemical class 0.000 claims description 2
- 125000000129 anionic group Chemical group 0.000 claims description 2
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 2
- 125000003709 fluoroalkyl group Chemical group 0.000 claims description 2
- 125000004407 fluoroaryl group Chemical group 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 125000005843 halogen group Chemical group 0.000 claims description 2
- 150000002367 halogens Chemical class 0.000 claims description 2
- 125000005842 heteroatoms Chemical group 0.000 claims description 2
- 229910052747 lanthanoid Inorganic materials 0.000 claims description 2
- 150000002602 lanthanoids Chemical class 0.000 claims description 2
- 230000001264 neutralization Effects 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 230000000737 periodic Effects 0.000 claims description 2
- 229910052717 sulfur Inorganic materials 0.000 claims description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims 2
- 150000002431 hydrogen Chemical class 0.000 claims 2
- 125000000837 carbohydrate group Chemical group 0.000 claims 1
- 229910052799 carbon Inorganic materials 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract description 16
- UHOVQNZJYSORNB-MZWXYZOWSA-N Deuterated benzene Chemical compound [2H]C1=C([2H])C([2H])=C([2H])C([2H])=C1[2H] UHOVQNZJYSORNB-MZWXYZOWSA-N 0.000 description 44
- WYURNTSHIVDZCO-UHFFFAOYSA-N tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 36
- 239000011777 magnesium Substances 0.000 description 35
- FYYHWMGAXLPEAU-UHFFFAOYSA-N magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 34
- 229910052749 magnesium Inorganic materials 0.000 description 34
- 239000000243 solution Substances 0.000 description 33
- VLKZOEOYAKHREP-UHFFFAOYSA-N hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 27
- YXFVVABEGXRONW-UHFFFAOYSA-N toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 26
- 239000012265 solid product Substances 0.000 description 19
- 230000015572 biosynthetic process Effects 0.000 description 17
- 238000001704 evaporation Methods 0.000 description 17
- 238000003786 synthesis reaction Methods 0.000 description 17
- 230000002194 synthesizing Effects 0.000 description 17
- 239000005977 Ethylene Substances 0.000 description 13
- VGGSQFUCUMXWEO-UHFFFAOYSA-N ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 13
- 238000001914 filtration Methods 0.000 description 13
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 12
- 239000008079 hexane Substances 0.000 description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 12
- WXACXMWYHXOSIX-UHFFFAOYSA-N 5-propan-2-ylidenecyclopenta-1,3-diene Chemical compound CC(C)=C1C=CC=C1 WXACXMWYHXOSIX-UHFFFAOYSA-N 0.000 description 9
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 9
- BULLHRADHZGONG-UHFFFAOYSA-N [cyclopenta-2,4-dien-1-ylidene(phenyl)methyl]benzene Chemical group C1=CC=CC1=C(C=1C=CC=CC=1)C1=CC=CC=C1 BULLHRADHZGONG-UHFFFAOYSA-N 0.000 description 8
- 238000005160 1H NMR spectroscopy Methods 0.000 description 7
- 229910010062 TiCl3 Inorganic materials 0.000 description 7
- 238000002425 crystallisation Methods 0.000 description 7
- 230000005712 crystallization Effects 0.000 description 7
- 150000002234 fulvenes Chemical class 0.000 description 7
- 238000000926 separation method Methods 0.000 description 7
- RYLMKTLFCIGRQD-UHFFFAOYSA-N 2,3,4,5-tetramethylfulvene Chemical compound CC1=C(C)C(=C)C(C)=C1C RYLMKTLFCIGRQD-UHFFFAOYSA-N 0.000 description 6
- XKRFYHLGVUSROY-UHFFFAOYSA-N argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 description 6
- MZRVEZGGRBJDDB-UHFFFAOYSA-N n-butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 6
- 125000000538 pentafluorophenyl group Chemical group FC1=C(F)C(F)=C(*)C(F)=C1F 0.000 description 6
- 238000001149 thermolysis Methods 0.000 description 6
- 229910007926 ZrCl Inorganic materials 0.000 description 5
- 238000007792 addition Methods 0.000 description 5
- QOXHZZQZTIGPEV-UHFFFAOYSA-K cyclopenta-1,3-diene;titanium(4+);trichloride Chemical compound Cl[Ti+](Cl)Cl.C=1C=C[CH-]C=1 QOXHZZQZTIGPEV-UHFFFAOYSA-K 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- MCULRUJILOGHCJ-UHFFFAOYSA-N Triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 description 4
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 4
- 238000007334 copolymerization reaction Methods 0.000 description 4
- 125000004435 hydrogen atoms Chemical class [H]* 0.000 description 4
- LWNDMGJQHFFEPE-UHFFFAOYSA-N methylcyclohexane;titanium;toluene Chemical compound [Ti].C[C-]1[CH-][CH-][CH-][CH-][CH-]1.CC1=CC=CC=C1 LWNDMGJQHFFEPE-UHFFFAOYSA-N 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 4
- XJDNKRIXUMDJCW-UHFFFAOYSA-J Titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 3
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- BZKBCQXYZZXSCO-UHFFFAOYSA-N sodium hydride Chemical compound [H-].[Na+] BZKBCQXYZZXSCO-UHFFFAOYSA-N 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- 229910052723 transition metal Inorganic materials 0.000 description 3
- 150000003624 transition metals Chemical class 0.000 description 3
- GONLXCSZJHTGIC-UHFFFAOYSA-N 1-tert-butyl-5-methylidenecyclopenta-1,3-diene Chemical compound CC(C)(C)C1=CC=CC1=C GONLXCSZJHTGIC-UHFFFAOYSA-N 0.000 description 2
- CSFFJSOWDFOFON-UHFFFAOYSA-N 5-(2,2-dimethylpropylidene)cyclopenta-1,3-diene Chemical compound CC(C)(C)C=C1C=CC=C1 CSFFJSOWDFOFON-UHFFFAOYSA-N 0.000 description 2
- GMXJULBTMDZPHU-UHFFFAOYSA-N 5-ethylidene-1,2,3,4-tetramethylcyclopenta-1,3-diene Chemical compound CC=C1C(C)=C(C)C(C)=C1C GMXJULBTMDZPHU-UHFFFAOYSA-N 0.000 description 2
- KDUIUFJBNGTBMD-VXMYFEMYSA-N Cyclooctatetraene Chemical group C1=C\C=C/C=C\C=C1 KDUIUFJBNGTBMD-VXMYFEMYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N HCl Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- NNPPMTNAJDCUHE-UHFFFAOYSA-N Isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 2
- SRTHRWZAMDZJOS-UHFFFAOYSA-N Lithium hydride Chemical compound [H-].[Li+] SRTHRWZAMDZJOS-UHFFFAOYSA-N 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L MgCl2 Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N Octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene (PE) Substances 0.000 description 2
- 238000004639 Schlenk technique Methods 0.000 description 2
- 229910003074 TiCl4 Inorganic materials 0.000 description 2
- VOITXYVAKOUIBA-UHFFFAOYSA-N Triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 2
- OBAJXDYVZBHCGT-UHFFFAOYSA-N Tris(pentafluorophenyl)borane Chemical compound FC1=C(F)C(F)=C(F)C(F)=C1B(C=1C(=C(F)C(F)=C(F)C=1F)F)C1=C(F)C(F)=C(F)C(F)=C1F OBAJXDYVZBHCGT-UHFFFAOYSA-N 0.000 description 2
- PFXYQVJESZAMSV-UHFFFAOYSA-K Zirconium(III) chloride Chemical compound Cl[Zr](Cl)Cl PFXYQVJESZAMSV-UHFFFAOYSA-K 0.000 description 2
- 229910007930 ZrCl3 Inorganic materials 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 150000004645 aluminates Chemical class 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- SMYKVLBUSSNXMV-UHFFFAOYSA-J aluminum;tetrahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[Al+3] SMYKVLBUSSNXMV-UHFFFAOYSA-J 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 150000001642 boronic acid derivatives Chemical class 0.000 description 2
- 150000001925 cycloalkenes Chemical class 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 150000004795 grignard reagents Chemical class 0.000 description 2
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 2
- 125000003454 indenyl group Chemical group C1(C=CC2=CC=CC=C12)* 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 150000008040 ionic compounds Chemical class 0.000 description 2
- 239000001282 iso-butane Substances 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052987 metal hydride Inorganic materials 0.000 description 2
- 150000004681 metal hydrides Chemical class 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N n-heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 125000002524 organometallic group Chemical group 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 230000001681 protective Effects 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- QKUVGYVQJVSFKW-UHFFFAOYSA-N (2,4-dimethyl-3-methylidene-5-phenylcyclopenta-1,4-dien-1-yl)benzene Chemical compound CC=1C(=C)C(C)=C(C=2C=CC=CC=2)C=1C1=CC=CC=C1 QKUVGYVQJVSFKW-UHFFFAOYSA-N 0.000 description 1
- JWCQJEMOTHGHHH-UHFFFAOYSA-N (3-methylidene-2,4,5-triphenylcyclopenta-1,4-dien-1-yl)benzene Chemical compound C=C1C(C=2C=CC=CC=2)=C(C=2C=CC=CC=2)C(C=2C=CC=CC=2)=C1C1=CC=CC=C1 JWCQJEMOTHGHHH-UHFFFAOYSA-N 0.000 description 1
- XVKBVPBNHWUILZ-UHFFFAOYSA-N (3-methylidene-2-phenylcyclopenta-1,4-dien-1-yl)benzene Chemical compound C=C1C=CC(C=2C=CC=CC=2)=C1C1=CC=CC=C1 XVKBVPBNHWUILZ-UHFFFAOYSA-N 0.000 description 1
- RNGRSVBIFDGEJJ-UHFFFAOYSA-N (3-methylidene-5-phenylcyclopenta-1,4-dien-1-yl)benzene Chemical compound C=1C(=C)C=C(C=2C=CC=CC=2)C=1C1=CC=CC=C1 RNGRSVBIFDGEJJ-UHFFFAOYSA-N 0.000 description 1
- DUOLVCQVQGYWKL-UHFFFAOYSA-N (5-benzylidene-2,3-diphenylcyclopenta-1,3-dien-1-yl)benzene Chemical compound C=1C=CC=CC=1C=C1C=C(C=2C=CC=CC=2)C(C=2C=CC=CC=2)=C1C1=CC=CC=C1 DUOLVCQVQGYWKL-UHFFFAOYSA-N 0.000 description 1
- OJOWICOBYCXEKR-KRXBUXKQSA-N (5E)-5-ethylidenebicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(=C/C)/CC1C=C2 OJOWICOBYCXEKR-KRXBUXKQSA-N 0.000 description 1
- ZGXMNEKDFYUNDQ-GQCTYLIASA-N (5E)-hepta-1,5-diene Chemical compound C\C=C\CCC=C ZGXMNEKDFYUNDQ-GQCTYLIASA-N 0.000 description 1
- POILWHVDKZOXJZ-ARJAWSKDSA-M (Z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 description 1
- QCEOZLISXJGWSW-UHFFFAOYSA-K 1,2,3,4,5-pentamethylcyclopentane;trichlorotitanium Chemical compound [Cl-].[Cl-].[Cl-].CC1=C(C)C(C)([Ti+3])C(C)=C1C QCEOZLISXJGWSW-UHFFFAOYSA-K 0.000 description 1
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-Hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 1
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-Octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 1
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 1
- RYWQKMKTWPCXJL-UHFFFAOYSA-N 1-cyclopenta-2,4-dien-1-ylidene-N,N,N',N'-tetramethylmethanediamine Chemical compound CN(C)C(N(C)C)=C1C=CC=C1 RYWQKMKTWPCXJL-UHFFFAOYSA-N 0.000 description 1
- UJXXVGXQTXQALL-UHFFFAOYSA-N 1-cyclopenta-2,4-dien-1-ylidene-N,N-dimethylmethanamine Chemical compound CN(C)C=C1C=CC=C1 UJXXVGXQTXQALL-UHFFFAOYSA-N 0.000 description 1
- IHTWCYWTBONHAN-UHFFFAOYSA-N 2,3-dimethyl-5-methylidenecyclopenta-1,3-diene Chemical compound CC1=CC(=C)C=C1C IHTWCYWTBONHAN-UHFFFAOYSA-N 0.000 description 1
- BHNQYGJTXLQHMK-UHFFFAOYSA-N 2,6-bis(2-methylpropyl)oxaluminane Chemical group CC(C)CC1CCC[Al](CC(C)C)O1 BHNQYGJTXLQHMK-UHFFFAOYSA-N 0.000 description 1
- AQZWEFBJYQSQEH-UHFFFAOYSA-N 2-methyloxaluminane Chemical class C[Al]1CCCCO1 AQZWEFBJYQSQEH-UHFFFAOYSA-N 0.000 description 1
- BBDKZWKEPDTENS-UHFFFAOYSA-N 4-Vinylcyclohexene Chemical compound C=CC1CCC=CC1 BBDKZWKEPDTENS-UHFFFAOYSA-N 0.000 description 1
- FYZHLRMYDRUDES-UHFFFAOYSA-N 5,7-dimethylocta-1,6-diene Chemical compound CC(C)=CC(C)CCC=C FYZHLRMYDRUDES-UHFFFAOYSA-N 0.000 description 1
- GTZQESAMRQJMPF-UHFFFAOYSA-N 5-(2-methylpropylidene)cyclopenta-1,3-diene Chemical compound CC(C)C=C1C=CC=C1 GTZQESAMRQJMPF-UHFFFAOYSA-N 0.000 description 1
- INYHZQLKOKTDAI-UHFFFAOYSA-N 5-ethenylbicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(C=C)CC1C=C2 INYHZQLKOKTDAI-UHFFFAOYSA-N 0.000 description 1
- LMDOZFCKTSEGMJ-UHFFFAOYSA-N 5-methylidene-2,3-di(propan-2-yl)cyclopenta-1,3-diene Chemical compound CC(C)C1=CC(=C)C=C1C(C)C LMDOZFCKTSEGMJ-UHFFFAOYSA-N 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N Aluminium hydride Chemical compound [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 210000001772 Blood Platelets Anatomy 0.000 description 1
- KOTQLLUQLXWWDK-UHFFFAOYSA-N Chromium hexacarbonyl Chemical group O#C[Cr](C#O)(C#O)(C#O)(C#O)C#O KOTQLLUQLXWWDK-UHFFFAOYSA-N 0.000 description 1
- HGCIXCUEYOPUTN-UHFFFAOYSA-N Cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 description 1
- WJTCGQSWYFHTAC-UHFFFAOYSA-N Cyclooctane Chemical compound C1CCCCCCC1 WJTCGQSWYFHTAC-UHFFFAOYSA-N 0.000 description 1
- LPIQUOYDBNQMRZ-UHFFFAOYSA-N Cyclopentene Chemical compound C1CC=CC1 LPIQUOYDBNQMRZ-UHFFFAOYSA-N 0.000 description 1
- RAABOESOVLLHRU-UHFFFAOYSA-N Diazene Chemical compound N=N RAABOESOVLLHRU-UHFFFAOYSA-N 0.000 description 1
- HECLRDQVFMWTQS-UHFFFAOYSA-N Dicyclopentadiene Chemical compound C1C2C3CC=CC3C1C=C2 HECLRDQVFMWTQS-UHFFFAOYSA-N 0.000 description 1
- YNLAOSYQHBDIKW-UHFFFAOYSA-M Diethylaluminium chloride Chemical compound CC[Al](Cl)CC YNLAOSYQHBDIKW-UHFFFAOYSA-M 0.000 description 1
- SDIXRDNYIMOKSG-UHFFFAOYSA-L Disodium methyl arsenate Chemical compound [Na+].[Na+].C[As]([O-])([O-])=O SDIXRDNYIMOKSG-UHFFFAOYSA-L 0.000 description 1
- KDRVTEPPBMBHHA-UHFFFAOYSA-N FC1=C(F)C(F)=C(F)C(F)=C1BC1=C(F)C(F)=C(F)C(F)=C1F Chemical compound FC1=C(F)C(F)=C(F)C(F)=C1BC1=C(F)C(F)=C(F)C(F)=C1F KDRVTEPPBMBHHA-UHFFFAOYSA-N 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
- 238000004566 IR spectroscopy Methods 0.000 description 1
- QWTDNUCVQCZILF-UHFFFAOYSA-N Isopentane Chemical compound CCC(C)C QWTDNUCVQCZILF-UHFFFAOYSA-N 0.000 description 1
- 229910000799 K alloy Inorganic materials 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- KMKBZNSIJQWHJA-UHFFFAOYSA-N Molybdenum hexacarbonyl Chemical group O#C[Mo](C#O)(C#O)(C#O)(C#O)C#O KMKBZNSIJQWHJA-UHFFFAOYSA-N 0.000 description 1
- JFNLZVQOOSMTJK-UHFFFAOYSA-N Norbornene Chemical compound C1C2CCC1C=C2 JFNLZVQOOSMTJK-UHFFFAOYSA-N 0.000 description 1
- 240000007817 Olea europaea Species 0.000 description 1
- YWAKXRMUMFPDSH-UHFFFAOYSA-N Pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 1
- PMJHHCWVYXUKFD-SNAWJCMRSA-N Piperylene Chemical compound C\C=C\C=C PMJHHCWVYXUKFD-SNAWJCMRSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- NCVIXNVCXNGGBW-UHFFFAOYSA-N Sodium naphthalenide Chemical compound [Na+].C1=CC=CC2=C[CH][CH-]C=C21 NCVIXNVCXNGGBW-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- JLTRXTDYQLMHGR-UHFFFAOYSA-N Trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 description 1
- JUOXOUBQXJJXAO-UHFFFAOYSA-N [Mg].C=CC=C Chemical compound [Mg].C=CC=C JUOXOUBQXJJXAO-UHFFFAOYSA-N 0.000 description 1
- 230000003213 activating Effects 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N al2o3 Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910000573 alkali metal alloy Inorganic materials 0.000 description 1
- 229910000941 alkaline earth metal alloy Inorganic materials 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminum Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- GRJWDJVTZAUGDZ-UHFFFAOYSA-N anthracene;magnesium Chemical compound [Mg].C1=CC=CC2=CC3=CC=CC=C3C=C21 GRJWDJVTZAUGDZ-UHFFFAOYSA-N 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- AZWXAPCAJCYGIA-UHFFFAOYSA-N bis(2-methylpropyl)alumane Chemical compound CC(C)C[AlH]CC(C)C AZWXAPCAJCYGIA-UHFFFAOYSA-N 0.000 description 1
- SJBIACKVFNCVOM-UHFFFAOYSA-M bis(2-methylpropyl)alumanylium;fluoride Chemical compound CC(C)C[Al](F)CC(C)C SJBIACKVFNCVOM-UHFFFAOYSA-M 0.000 description 1
- XGIUDIMNNMKGDE-UHFFFAOYSA-N bis(trimethylsilyl)azanide Chemical compound C[Si](C)(C)[N-][Si](C)(C)C XGIUDIMNNMKGDE-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 1
- KAKZBPTYRLMSJV-UHFFFAOYSA-N butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 150000004292 cyclic ethers Chemical class 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 239000004914 cyclooctane Substances 0.000 description 1
- MIODROMBEUMZIF-UHFFFAOYSA-N cyclopenta-2,4-dien-1-ylidenecyclohexane Chemical compound C1CCCCC1=C1C=CC=C1 MIODROMBEUMZIF-UHFFFAOYSA-N 0.000 description 1
- IGSGWPUSCLPKER-UHFFFAOYSA-N cyclopenta-2,4-dien-1-ylidenemethylbenzene Chemical compound C=1C=CC=CC=1C=C1C=CC=C1 IGSGWPUSCLPKER-UHFFFAOYSA-N 0.000 description 1
- JZLAYHCMSHSZKE-UHFFFAOYSA-N cyclopenta-2,4-dien-1-ylidenemethylcyclohexane Chemical compound C1CCCCC1C=C1C=CC=C1 JZLAYHCMSHSZKE-UHFFFAOYSA-N 0.000 description 1
- 239000002274 desiccant Substances 0.000 description 1
- PBGGNZZGJIKBMJ-UHFFFAOYSA-N di(propan-2-yl)azanide Chemical compound CC(C)[N-]C(C)C PBGGNZZGJIKBMJ-UHFFFAOYSA-N 0.000 description 1
- 150000001983 dialkylethers Chemical class 0.000 description 1
- 229910000071 diazene Inorganic materials 0.000 description 1
- UZBQIPPOMKBLAS-UHFFFAOYSA-N diethylazanide Chemical compound CC[N-]CC UZBQIPPOMKBLAS-UHFFFAOYSA-N 0.000 description 1
- XTHFKEDIFFGKHM-UHFFFAOYSA-N dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 1
- JLTDJTHDQAWBAV-UHFFFAOYSA-O dimethyl(phenyl)azanium Chemical compound C[NH+](C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-O 0.000 description 1
- BQWOMAQHJXIFPQ-UHFFFAOYSA-Q dimethyl(phenyl)azanium;borate Chemical compound [O-]B([O-])[O-].C[NH+](C)C1=CC=CC=C1.C[NH+](C)C1=CC=CC=C1.C[NH+](C)C1=CC=CC=C1 BQWOMAQHJXIFPQ-UHFFFAOYSA-Q 0.000 description 1
- HWMVBKIXMMJLCU-UHFFFAOYSA-N dimethyl-(2,3,4,5,6-pentafluorophenyl)-[2,3,4-tris(2,3,4,5,6-pentafluorophenyl)phenyl]azanium Chemical compound FC=1C(F)=C(F)C(F)=C(F)C=1[N+](C)(C)C(C(=C1C=2C(=C(F)C(F)=C(F)C=2F)F)C=2C(=C(F)C(F)=C(F)C=2F)F)=CC=C1C1=C(F)C(F)=C(F)C(F)=C1F HWMVBKIXMMJLCU-UHFFFAOYSA-N 0.000 description 1
- QKIUAMUSENSFQQ-UHFFFAOYSA-N dimethylazanide Chemical compound C[N-]C QKIUAMUSENSFQQ-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- PRBHEGAFLDMLAL-UHFFFAOYSA-N hexa-1,4-diene Chemical compound CC=CCC=C PRBHEGAFLDMLAL-UHFFFAOYSA-N 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- VQTUBCCKSQIDNK-UHFFFAOYSA-N isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- HPQVWDOOUQVBTO-UHFFFAOYSA-N lithium aluminium hydride Substances [Li+].[Al-] HPQVWDOOUQVBTO-UHFFFAOYSA-N 0.000 description 1
- OCZDCIYGECBNKL-UHFFFAOYSA-N lithium;alumanuide Chemical compound [Li+].[AlH4-] OCZDCIYGECBNKL-UHFFFAOYSA-N 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- 229910012375 magnesium hydride Inorganic materials 0.000 description 1
- RHLWKNJTVXDVHU-UHFFFAOYSA-N magnesium;hydride Chemical compound [H-].[H-].[Mg+2] RHLWKNJTVXDVHU-UHFFFAOYSA-N 0.000 description 1
- 238000001819 mass spectrum Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N o-xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-M phenolate Chemical compound [O-]C1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-M 0.000 description 1
- 229940031826 phenolate Drugs 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- ASRAWSBMDXVNLX-UHFFFAOYSA-N pyrazolate Chemical compound C=1C=C(Cl)C=C(Cl)C=1C(=O)C=1C(C)=NN(C)C=1OS(=O)(=O)C1=CC=C(C)C=C1 ASRAWSBMDXVNLX-UHFFFAOYSA-N 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 125000005373 siloxane group Chemical group [SiH2](O*)* 0.000 description 1
- 229910001023 sodium amalgam Inorganic materials 0.000 description 1
- YOQDYZUWIQVZSF-UHFFFAOYSA-N sodium borohydride Substances [BH4-].[Na+] YOQDYZUWIQVZSF-UHFFFAOYSA-N 0.000 description 1
- 229910000033 sodium borohydride Inorganic materials 0.000 description 1
- ODGROJYWQXFQOZ-UHFFFAOYSA-N sodium;boron(1-) Chemical compound [B-].[Na+] ODGROJYWQXFQOZ-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000004071 soot Substances 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- BIUNYMXQLNNMJR-UHFFFAOYSA-N tetrakis(2,3,4,5,6-pentafluorophenyl)boranuide Chemical compound FC1=C(F)C(F)=C(F)C(F)=C1[B-](C=1C(=C(F)C(F)=C(F)C=1F)F)(C=1C(=C(F)C(F)=C(F)C=1F)F)C1=C(F)C(F)=C(F)C(F)=C1F BIUNYMXQLNNMJR-UHFFFAOYSA-N 0.000 description 1
- 150000007944 thiolates Chemical class 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- ZFHUWUDEFBXODN-UHFFFAOYSA-N tris(2,3,4,5,6-pentafluorophenyl)-(2,3,4,5,6-pentafluoro-1-tritylcyclohexa-2,4-dien-1-yl)boranuide Chemical compound FC1C(F)=C(F)C(F)=C(F)C1(C(C=1C=CC=CC=1)(C=1C=CC=CC=1)C=1C=CC=CC=1)[B-](C=1C(=C(F)C(F)=C(F)C=1F)F)(C=1C(=C(F)C(F)=C(F)C=1F)F)C1=C(F)C(F)=C(F)C(F)=C1F ZFHUWUDEFBXODN-UHFFFAOYSA-N 0.000 description 1
- POHPFVPVRKJHCR-UHFFFAOYSA-N tris(2,3,4,5,6-pentafluorophenyl)alumane Chemical compound FC1=C(F)C(F)=C(F)C(F)=C1[Al](C=1C(=C(F)C(F)=C(F)C=1F)F)C1=C(F)C(F)=C(F)C(F)=C1F POHPFVPVRKJHCR-UHFFFAOYSA-N 0.000 description 1
- 238000005429 turbidity Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Abstract
The invention relates to a method for producing fulvene metal complexes, to novel metal complexes and to the use of said complexes as catalysts for polymerising unsaturated compounds, especially for polymerising and copolymerising olefins and/or dienes.
Description
PROCEDURE FOR OBTAINING FULVENO METALLIC COMPLEXES
Field of the invention.
The present invention relates to a process for obtaining fulvene metal complexes, to new metal complexes of floccene as well as to their use as catalysts for the polymerization of unsaturated compounds, especially for the polymerization and for the copolymerization of olefins and / or of dienes.
Background of the invention
Metal complexes with cyclopentadienyl ligands have been intensively investigated since the discovery of ferrocene. The use of cyclopentadienyl metal complexes, in particular the use of metallocene complexes in admixture with activating co-catalysts, preferably alumoxanes, has long been known for the polymerization of olefins and diolefins (for example EP-A 69 951, 129 368 351
REF .: 119683 392,485 821,485 823). The metallocenes have been revealed as specific catalysts, with high activity in the polymerization of olefins. To increase the activity, the selectivity, to control the microstructure, the molecular weights and the molecular weight distribution, a plurality of metallocene catalysts or metallocene catalyst systems for the polymerization of olefinic compounds has been developed in recent years.
In relation to metal complexes with fulvene ligands there is little knowledge.
In the J. Am. Chem. Soc. 1997 publication,
119.5132, polymerization catalysts for zwitterionic olefins, which are formed by the reaction of special compounds of (? 6-2, 3,4,5-tetramethylcyclopentadienyl-1-methylene) (? 5-pentamethyl-cyclo-penta- dienyl) zirconium with tris- (pentafluorophenyl) boron or with bis (pentafluoro-phenyl) borane. The synthesis of the compounds of (? 6-2,3,4, 5-tetramethylcyclopentadienyl-1-methylene) (? 5-pentamethylcyclopentadienyl) zirconium is very expensive, a metallocene having to be prepared with ligands of pentamethylcyclopentadienyl, which decomposes in the last stage of the synthesis by a thermolysis reaction. Such thermolysis reactions are described in the literature.
According to Bercaw et al., JACS (1972), 94, 1219 is formed, by thermolysis of bis (? 5-pentamethylcyclopentadienyl) -thitanedimethyl, the fulvene compound of (? 6-2, 3,4,5-tetramethylcyclo? Entadienil) -1-methylene) (? 5-penta-methylcyclopentadienyl) titanmethyl. The thermolysis of pentamethylcyclopentadienyl complexes of zirconium and hafnium is described in the publication by J. Marks et al., JACS (1988), 110, 7701. By means of the thermolysis of bis ((5-pentamethylcyclopentadienyl) zirconiodiphenyl, the fulvene complex of (6-2, 3,4,5-tetramethylcyclopentadienyl-1-methylene) (5-pentamethyl-cyclopentadienyl) zirconiofenyl is formed.
The preparation of the fulvene complexes according to the thermal process is limited to a few structural variants. The thermal process does not always lead to unitary products. It has been described by 0. Wiikinson et al. in J. Chem. Soc. 1960, 1321-1324 the reaction of 6,6-dialkyl-funne with chromium hexacarbonyl or with molybdenum hexacarbonyl. In place of the metallic fulvene complexes, however, cyclopentadienyl metal complexes are obtained. It is described in the J. Chem. Soc. Dalton Trans. (1985), 2037 by M. L. H. Oreen et al., The synthesis of bis (6,6,6,6-difenylfulvene) titanium by reaction of bis (toluene) titanium with 6,6, diphenylfulvene. However, bis (toluene) titanium must be prepared by metal atomic evaporation techniques, which are complicated and expensive. For this, metallic titanium is evaporated and condensed in a matrix together with gaseous toluene. The yield in bis (toluene) titanium is very low. The bis (toluene) titanium is therefore accessible only in a limited proportion. Thus, there was the task of finding an improved process for obtaining fulvene metal complexes, which avoided the aforementioned drawbacks. It has now been found, surprisingly, that fulvene metal complexes can be prepared by reaction of a fulvene compound with a suitable complex of transition metal in the presence of a reducing agent.
Detailed description of the invention. The object of the present invention is therefore a process for the preparation of fulvene metal complexes of the formula (la)
or of the formula (Ib)
??? L..M (Ib), where M means a metal of the groups Illb, IVb, Vb, or of the lanthanides or of the actinides of the periodic system of the elements according to IUPAC, A means an anionic ligand, if appropriate or several times bridged, X means hydrogen, means an alkyl group with 1 to 10 carbon atoms, an alkoxy group with 1 to 10 carbon atoms, an aryl group with 6 to 10 carbon atoms, an aryloxy group with 6 to 10 carbon atoms, an alkenyl group with 2 to 10 carbon atoms, an arylalkyl group with 7 to 40 carbon atoms, an alkylaryl group with 7 to 40 carbon atoms, an arylalkenyl group with 8 to 40 carbon atoms, a group silyl substituted by a hydrocarbon radical having 1 to 10 carbon atoms, a halogen atom or an amide of the formula NR72, L denotes a neutral ligand, RX, R2, R3, R4, R5, R6 are the same or different and mean hydrogen , halogen, a cyano group, an alkyl group with 1 to 20 carbon atoms, a fluoroalkyl group with the ß carbon atoms, a fluoroaryl group with 6 to 10 carbon atoms, an alkoxy group with 1 to 10 carbon atoms / an aryl group with 6 to 20 carbon atoms , an aryloxy group with 6 to 10 carbon atoms, an alkenyl group with 2 to 10 carbon atoms, an arylalkyl group with 7 to 40 carbon atoms, an alkylaryl group with 7 to 40 carbon atoms, an arylalkenyl group with 8 up to 40 carbon atoms, an alkynyl group with 2 to 10 carbon atoms, a silyl group substituted by hydrocarbon radicals with 1 to 10 carbon atoms, an amino group optionally substituted by hydrocarbon radicals with 1 to 20 carbon atoms, or R, R2, R3, R4, R5, R6 respectively form, together with the atoms to which they are linked, one or more aliphatic or aromatic ring systems, which may contain one or more heteroatoms (O, N, S) and which have from 5 to 10 carbon atoms, R7 means hydrogen, an alkyl group with 1 to 20 carbon atoms, an aryl group with 6 to 20 carbon atoms, an arylalkyl group with 7 to 40 carbon atoms, an alkylaryl group with 7 to 10 carbon atoms, up to 40 carbon atoms, a silyl group substituted by hydrocarbon radicals with 1 to 10 carbon atoms, an amino group optionally substituted by hydrocarbon radicals with 1 to 20 carbon atoms, m, p means the numbers 0, 1, 2 , 3 or 4, which are produced by the valence and the linked state of M, as well as k means the numbers 1, 2 or 3, and the sum k + m + p amounts to 1 to 5 depending on the degree of oxidation of M, n means a number from 1 to 10, by reaction of a transition metal compound of the formula (lia) or (Ilb)
A ^ -Xs (Ha) mXs nM (Hb)
wherein A, X, L, M, m, s and n have the meaning indicated above and s means 2, 3, 4, 5 or 6 and s > p, with a fulvene compound of the formula (III)
(III), wherein R1, R2, R3, R4, R5 and R6 have the meaning indicated above, in the presence of a reducing agent. The preparation of fulvene metal complexes of the formula () is explained by means of the following reaction scheme:
Agen-be reductor Metallic complex of fulvene (I)
The reaction can be carried out in a single reaction step, that is to say in a reaction in a single vessel, the order of the addition of the individual components of the reaction not being predetermined. The reaction can also be carried out in separate reaction steps, for example, the transition metal compounds of the formula (Ha) or (Hb) can first be contacted with a reducing agent and reacted in one step of separate reaction, with fulvene compounds of the formula (III). further, preferably, the transition metal compound (lia) or (Hb) will be added first to the fulvene (III) compound, and then the reducing agent will be added. Suitable reducing agents are, for example, alkali metals, alkaline earth metals, aluminum, zinc, alkali metal alloys, such as, for example, sodium-potassium alloy or sodium amalgam, alkaline earth metal alloys, as well as metal hydrides. Examples of metal hydrides are lithium hydride, sodium hydride, magnesium hydride, aluminum hydride, lithium aluminum hydride and sodium borohydride. Special examples of reducing agents are sodium naphthalenide, potassium graphite, lithium alkyls, magnesium butadiene, magnesium anthracene, trialkylaluminium compounds and Grignard reagents. Preferred reducing agents are the alkali metals or the alkaline earth metals, the alkyl lithiums with 1 to 6 carbon atoms, the tri-alkylaluminum compounds with the carbon atoms and the Grignard reagents. Preferred reducing agents are lithium, magnesium, n-butyllithium, as well as triethylaluminum and triisobutylaluminum. Instead of the mentioned reducing agents, an electrochemical reduction can also be carried out. The process for obtaining the fulvene metal complexes of the formula (I) is carried out in a suitable reaction medium at temperatures from -100 to + 250 ° C, preferably from -78 to + 130 ° C, especially preferred from -10 to + 120 ° C. Suitable reaction media are, for example, aliphatic or aromatic hydrocarbons, halogenated hydrocarbons, ethers and cyclic ethers. Examples in this regard are unbranched aliphatic hydrocarbons, such as butane, pentane, hexane, heptane, octane, branched aliphatic hydrocarbons, such as isobutane, isopentane, isohexane, cyclic aliphatic hydrocarbons such as cyclohexane, methylocyclohexane, aromatic hydrocarbons, such as benzene , toluene, xylene, and ethers, such as dialkyl ethers, dimethoxyethane and tetrahydrofuran. Mixtures of various solvents are also suitable. The preparation and handling of the fulvene metal complexes of the formula (I) is carried out with the exclusion of air and water under inert gas conditions (protective gas technique). Examples of inert gases are nitrogen or argon. As a protective gas technique, for example, the Schlenk technique, which is generally used for organometallic substances, is suitable. The metal complexes of fulvene of the formula (I) can be isolated or used directly for other reactions. When isolation is required, the secondary products formed according to the usual methods of purification may be separated, for example by filtration. Alternatively, the desired products can also be extracted with a solvent. If necessary, a purification operation, for example recrystallization, can be carried out. Examples of transition metal complexes of the formula (Ha) or (Hb) are those in which M means a metal from the group consisting of titanium, zirconium, hafnium, vanadium, niobium, tantalum and chromium, A means a pyrazolate of the formula N2C3R 3- where
R8 means hydrogen or an alkyl group with 1 to
carbon atoms, or an aryl group with 6 to 10 carbon atoms, a pyrazolylborate of the formula R7B (N2C3R83), an alcoholate or phenolate of the formula OR7, a siloxane of the formula 0SiR73, a thiolate of the formula SR7, an acetylacetonate of the formula (R7CO) 2CR7, a diimine of the formula (R7N = CR7) 2-an amidinate of the formula R7C (NR72) 2-a cyclooctatetraenyl of the formula C8HqR78-q where q means 0, 1, 2, 3, 4, 5, 6, or 7, a cyclopentadienyl of the formula C5HqR75-q where q means 0, 1, 2, 3, 4, 5, an indenyl of the formula C9H7-rR7r where r means
0, 1, 2, 3, 4, 5, 6, 7, a fluorenyl of the formula C? 3H9-sR7s where s means
0, 1, 2, 3, 4, 5, 6, 7, 8, 9 as well as an alkyl moiety with 1 to 30 carbon atoms, an aryl moiety with 6 to 10 carbon atoms, as well as an alkylaryl moiety having 7 to 10 carbon atoms. up to 40 carbon atoms, L, X, R7, m, syn have the meaning indicated above. Very particular preference is given to complexes of the transition metals of the formula (la) or (Hb), in which M means titanium, zirconium or hafbio, A means bis (trimethylsilyl) amide, dimethylamide, diethylamide, diisopropylamide, 2,6 -di-terc. -butyl-4-ethylphenolate, cyclooctatetraenyl, cyclopentadienyl, methylcyclopentadienyl, benzylcyclopentadienyl, n-propylcyclopentadienyl, n-butylcyclopentadienyl, iso-butylcyclopentadienyl, t-butylcyclopentadienyl, cyclopentylcyclopentadienyl, octadecylcyclopentadienyl,
1,2-dimethylcyclopentadienyl, 1,3-dimethyl-cyclopentadienyl, 1,3-di-isopropylcyclopentadienyl, 1,3-di-t-butylcyclopentadienyl, l-ethyl-2-methylcyclopentadienyl, 1-isopropyl-3-methylcyclopentadienyl, 1- (n-butyl) -3-methylcyclopentadienyl, 1- (t-butyl) -3-methylcyclopentadienyl, pentamethylcyclopentadienyl, 1,2,3,4-tetramethyl-cyclopentadienyl, 1,2,4-trimethyl-cyclopentadienyl, 1,2, 4-triisopropyl-cyclopentadienyl, 1, 2, -tri (t-butyl) -cyclopentadienyl, indenyl, tetrahydroindenyl, 2-methylindenyl, 4,7-dimethylindenyl, 2-methyl-4,5-benzoindenyl, 2-methyl-4- phenylindenyl, fluorenyl or
9-methyl-fluorenyl. X means fluorine or chlorine L, m, s and n have the meaning indicated above. Suitable fulvene compounds are those of the formula
(III) in which R1 to R6 mean an alkyl group with 1 to 30 carbon atoms, an aryl group with 6 to 10 carbon atoms, an alkylaryl group with 7 to
40 carbon atoms, especially hydrogen, methyl, trifluoromethyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, phenyl, pentafluorophenyl, methylphenyl, cyclohexyl or benzyl. The preferred compounds of the formula
(III) are fulvene compounds of the formula (IV)
(IV), or fulvene compounds of the formula (V)
where RX, R2, R3 and R4 have the meaning indicated above. Particularly preferred compounds of the formula (III) are 6-cyclohexylfulvene, 6-isopropylfulvene, 6-tert.-butylfulvene,
6-Phenylfulvene, 6- (dimethylamino) -fulvene, 6,6-bis (dimethylamino) fulvene, 6,6-dimethyl fulvene, 6,6-bis (trifluoromethyl) fulvene, 6,6-diphenyl fulvene, 6,6-bis (pentafluorophenyl) fulvene, 6,6-penta-methylene fulvene, 6,6-tetramethoxy fulvene, 6,6-trimethylene fulvene, 2- (2, -cyclopentadien-1-ylidene) -1, 3-dithiolane, 5-benzylidene 1,2,3-triphenyl-1,3-cyclopentadiene, 1,2,3,4-tetramethylfulvene,
1,2,3, 4-tetraphenyl fulvene, 2,3-dimethylfulvene,
2, 3-diisopropylfulvene, 2,3-diphenylfulvene,
1,4-dimethyl-2,3-diphenylfulvene and 1,4-diethyl-2,3-diphenylfuvene. The synthesis of the fulvene compounds of the formula (III), (IV) and (V) can be carried out, for example, according to J. Org. Chem. Vo. 49, No. 11 (1984), 1849. The formula (I) indicated for fulvene metal complexes should be considered as a formal representation of bonding relationships. The binding ratios in the metal complexes depend, among other things, on the central atom, the oxidation level as well as the substituents of the fulvene ligand.
Detailed Description of the Figures
Figure 1 shows the constitution of a fulvene metal complex obtainable according to the invention, in perspective representation as obtained by means of X-ray structural analysis. As an example of the compound (6-tert.-butylfuvinyl) chloride ( pentamethylcyclopentadienyl) -titanium. The process according to the invention offers an access to new metal complexes of fulvene of the formula (I), which, for example, can not be formed by thermolysis. Another object of the present invention are therefore fulvene metal complexes of the formula (I), in which M means a metal from the group consisting of titanium, zirconium, hafnium, vanadium, niobium, tantalum and chromium, k means 1, A, X,, p, R1, R2, R3, R4, R5 and R6 have the meaning indicated above, with the exception of the compounds of the formula (I), in which R1 and R2 mean hydrogen and, simultaneously, R3 ,
R4, R5 and R6 mean a methyl group and simultaneously A means a pentamethylcyclopentadienyl group or a 'carborandiyl group of the formula C2B9HH. Another object of the present invention is a catalytic system, consisting of a) a metal complex of fulvene of the formula (I), prepared according to the process of the invention, wherein M means a metal from the group consisting of titanium, zirconium, hafnium, vanadium, niobium, tantalum and chromium, k means 1, A, X, m, p, R1, R2, R3, R4, R5 and R6 have the meaning indicated above.
b) a co-catalyst suitable for the activation of the metal complex a) the molar ratio between component a) and component b) being in the range of 1: 0.1 to 1: 10,000, preferably 1: 1 to 1 : 1,000 Suitable co-catalysts are co-catalysts known in the field of metallocene catalysis, such as polymeric aluminoxanes or oligomers, Lewis acids as well as aluminates and borates. In this context, reference will be made especially to the Macromol publication. Symp. Vol. 97, July 1995, pages 1-246 (for alumoxanes) as well as EP 277 003, EP 277 004, Organometallics 1997, 16, 842-857 (for borates), and EP 573 403 (for aluminates). Especially suitable are co-catalysts methylaluminoxane, methylalumoxane modified with triisobutylaluminum as well as diisobutylalumoxane, trialkylaluminum compounds, such as trimethylaluminum, triethylaluminum, triisobutylaluminum, triisooctylaluminum, in addition dialkylaluminum compounds such as diisobutylaluminum hydride, diisobutylaluminum fluoride and diethylaluminum chloride, of substituted triarylaluminum, such as tris (pen-tafluorophenyl) aluminum, as well as ionic compounds, which contain tetrakis (pentafluorophenyl) aluminium anion, such as triphenylmethyl-tetrakis (penta-fluorophenyl) aluminate, as well as tetrakis- (pentafluorophenyl) N, N-dimethyl anilinium aluminate, substituted triarylboron compounds, such as tris- (pentafluorophenyl) boron as well as ionic compounds, containing as tetrakis- (pentafluorophenyl) borate anion, such as triphenylmethyl-tetrakis (pentafluorophenyl) borate , as well as tetraqu is (pentafluorophenyl) 'borate of N, N-dimethylanilinium. Mixtures of various co-catalysts for the activation of the fulvene metal complexes of the formula (I) are also suitable. Another object of the present invention is the use of this new catalytic system for the polymerization of unsaturated compounds, especially olefins and dienes. As polymerization, it will be understood in this case both the homopolymerization and the copolymerization of the mentioned unsaturated compounds. In the polymerization of alkenes with 2 to 10 carbon atoms, such as ethylene, propylene, butene-1, pentene-1, and hexene-1, octene-1, isobutylene and arylalkenes, such as styrene, will be used in particular. As dienes will be used especially: conjugated dienes, such as 1,3-butadiene, isoprene, 1,3-pentadiene, and non-conjugated dienes, such as 1,4-hexadiene, 1,5-heptadiene, 5,7-dimethyl-1,6-octadiene, 4-vinyl-1-cyclohexene, 5- ethylidene-2-norbornene, 5-vinyl-2-norbornene and dicyclopentadiene. The catalysts according to the invention are suitable for obtaining rubbers based on copolymers of ethylene with one or more of the a-olefins mentioned and the aforementioned diene. Furthermore, the catalyst system according to the invention is suitable for the polymerization of cyclo-olefins such as norbornene, cyclopentene, cyclohexene, cyclooctane and for the copolymerization of cycloolefins with ethylene or with α-olefins. The polymerization can be carried out in the liquid phase, in the presence or absence of an inert solvent, or in the gas phase. Suitable solvents are aromatic hydrocarbons such as benzene and / or toluene, or aliphatic hydrocarbons, such as propane, hexane, heptane, octane, isobutane, cyclohexane or mixtures of various hydrocarbons. It is possible to use the catalytic system according to the invention arranged on a support. Suitable support materials include, for example, inorganic or organic polymeric supports, such as silica gel, zeolites, soot, activated carbons, aluminum oxide, polystyrene and polypropylene. In this case, the catalyst system according to the invention can be arranged in a conventional manner on the carrier materials. The methods for the support of the catalyst systems have been described, for example, in US 4 808 561, 4 912 075, 5 008 228 and 4 914 253. The polymerization is carried out, in general, at pressures of 1 to 1,000, preferably from 1 to 100 bar, preferably from 1 to 1,000 bar, and at temperatures from -100 to + 250 ° C, preferably from 0 to + 150 ° C. The polymerization can be carried out in conventional reactors, continuously or discontinuously.
The invention is explained in more detail by means of the following examples. General indications: Obtaining and handling organometallic compounds was carried out with the exclusion of air and humidity under argon protection (Schlenk technique). All necessary solvents were made absolute before use by boiling for several hours on a suitable drying agent and subsequent distillation under argon. The compounds were characterized by means of spectroscopy of
1 H-NMR, 13 C-NMR and mass. Abbreviations: Cp: Cyclopentadienyl Cp *: Pentamethylcyclopentadienyl 'HV: High vacuum RT: Ambient temperature THF: Tetrahydrofuran MS: Mass spectrum EA: Elemental analysis Tg: Vitreous transition temperature (measured DSC) of: Excess diastereomer.
Synthesis of the compounds of the formula (I).
Example 1. Synthesis of fulvene complex by reaction of 6,6-dimethylfulvene with Cp * TiCl 3 in the presence of magnesium [(C5 (CH3) 5) (C5H4) C (CH3) 2TiCl].
Cp * TiCl3 (0.610 g, 2.11 mmol) and 1.05 equivalents of magnesium (0.054 g, 2.21 mmol) were placed in 25 mL of THF. 1.05 equivalents of 6,6-dimethyl fulvene (0.227 g, 2.14 mmol) were added dropwise at room temperature. It was allowed to stir overnight at RT, so that all the Mg was consumed. The solvent in HV was removed and the green residue was taken up in hexane. The solid product was separated by filtration and the solution was concentrated by evaporation to the middle, whereupon bright green platelets precipitated. For crystallization separation, the charge was cooled to -20 ° C. The olive green crystals were isolated and dried in HV. We obtained 0.429 g (59%) of
[(C5 (CH3) 5) (C5H4) C (CH3) 2TiCl]. XH-NMR: (C6D6, 300 MHZ): d = 1.16 (s, 3H, C (CH3) 2), 1.70 (s, 15H, C5 (CH3) 5), 1.75 (s, 3H , C (CH3) 2), 3.43, 4.65, 6.03, 6.70 (m, lH, C5H4) ppm. 13 C-NMR: (C6D6, 75 MHZ): 5 = 12, 82 (C5 (CH3) 5) • 22.76, 24.50 (C (CH3) 2), 108, 10 (C (CH3) 2) 117 , 23, 117.46,
120.04, 124, 09 (C4H4), 122, 55 (C5 (CH3) 5), 132.16 (ipso-C5H4) ppm. MS (70eV) m / e / (%): 324 (4 O) [M +], 288 (40) [M + -HC1], 135 (5) [Cp *], 106 (100) [dimethylfulvene].
Example 2. Synthesis of fulvene complex by the reaction of 6,6-dimethyl fulvene with Cp * TiCl 3 in the presence of butyl-lithium, [(Cp *). 400 mg (1.38 mmol) of Cp * TiCl3, 154 mg (1.45 mmol) of 6,6-dimethylfulvene and 1.11 ml (2.76 mmol) of n-butyl lithium in 25 ml were combined. of THF at a temperature of -78 ° C in a Schlenk vessel. It was allowed to slowly warm to 0 ° C and was stirred until the reaction was complete for another 2 hours at this temperature. The solvent was then removed in HV and the green residue was taken up in n-hexane. The solid product was separated by filtration and the solution was concentrated halfway, whereupon green crystals precipitated. 290 mg (65%) of [(C5 (CH3) s) (C5H4) C (CH3) z ~
TiCl]. 1H-NMR: (C6D6, 300 MHZ): 5 = 1.16 (s, 3H, C (CH3) 2), 1.70 (s, 15H, C5 (CH3) 5), 1.75 (s, 3H , C (CH3) 2), 3.43 / 4.65
/ 6.03 / 6.70 (s, lH, C5H4). 13 C-NMR: (C6D6, 75 MHz): d = 12, 82 (C5 (CH3) 5), 22.76 / 24.50 (C (CH3) 2), 108, 10 (C (CH3) 2) 117 , 23 / 117.46 / 120.04 / 124.09 (C4H4), 122, 55 (C5 (CH3) 5), 132, 16 (ipso-C).
Example 3: Synthesis of fulvene complex by reaction of 6,6-dimethylfulvene with Cp * ZrCl 3 in the presence of magnesium [(Cs (CH 3) 5) (C 5 H) C (CH 3) 2 ZrCl]. CP * ZrCl3 (0.380 g, 1.14 mmol) and 1.1 equivalents of magnesium, 0.031 g, 1.26 mmol) were placed in 10 mL of THF. To this solution were added, dropwise, 1.1 equivalents of 6,6-dimethyl fulvene (0.134 g, 126 mmol). After 5 minutes, a turbidity of the reaction solution occurred. It was stirred overnight to completely dissolve the magnesium. It was concentrated by evaporation in HV to dryness, taken up in 10 ml of hexane and the formed precipitate was filtered off. From the filtrate, 197 mg (47%) of [(C5 (CH3) 5) (C5H4) C (CH3) 2ZrCl] was isolated as a reddish brown solid product. XH-NMR: (C6D6, 300 MHZ): d = 1.77 (s, 15H, C5 (CH3) 5), 1, 98, 1, 99 (s, 3H, C (CH3) 2), 5.40 (dd, 1H, 3 J (H, H) = 2, 69, 3.02 Hz, C5H4), 5.58 (dd, ÍH, 3J (H, H) = 2, 69, 2, 68 Hz, C5H4), 5.85 ( dd, 1H, 3J (H, H) = 2.68, 3.02 Hz, C5H4), 5.92 (dd, 1H, 3J = 2.69, 2.68 Hz, C5H4) ppm. 13 C-NMR: (C6D6, 75 MHz): d = 10.98 (C5 (CH3) 5), 21.35, 21.90 (C (CH3) 2), 109.78 (C (CH3) 2), 107.75, 110.68, 113.88, 118.11 (C5 (H4), 115.69 (ipso-C5H4),
122, 35 (C (CH3) 5) ppm. MS (70eV) m / e (%): 366 (10) [M +], 330 (5) [M + -HC1], 259 (2), 135 (5) [Cp *], 106 (100) [dimet ilf ulveno].
Example 4. Synthesis of bis (α6,6,6-diphenyl fulvene) titanium by reaction of 6,6-diphenyl fulvene with titanium tetrachloride in the presence of magnesium. 610 mg (1.83 mmol) of TiCl4 (THF), 89 mg (3.65 mmol) of magnesium filings and 841 mg (3.65 mmol) of 6,6-diphenylfulvene in a Schlenk vessel were combined in a Schlenk vessel. ml of THF as reaction medium. To complete the reaction, it was stirred for 12 hours until complete consumption of the magnesium filings. Concentration by evaporation of the reaction solution to dryness gave a green solid product which could be separated from the magnesium chloride formed by collecting n-hexane and filtration. By stepped evaporation and cooling the filtrate, 640 mg (70%) of bis (? 6-6,6-diphenylthiovan) titanium was obtained.
Use 5. Synthesis of the fulvene complex by reaction of 6,6-dimethyl ulvene with CpTiCl 3, in the presence of magnesium [(C5H5) (C5H4) C (CH3) 2TiCl]. They were placed in 20 ml of THF, CpTiCl3 (0.410 g, 1.87 mmol) and 1.05 equivalents of magnesium (0.048 g, 1.96 mmol). To this yellow solution were added dropwise at RT 1.03 equivalents of 6,6-dimethyl fulvene (0.204 g, 1.92 mmol) and stirred until the magnesium used had been consumed. It was then concentrated by evaporation in HV and the resulting green solid product was taken up in 20 ml of hexane. After separation by filtration of the solid product, the solution, dark green in color, was evaporated to one half in HV. By crystallization at -20 ° C, 0.2 g (42%) of [(C5H5) (C5H4) C (CH3) 2TiCl] was obtained as a dark green solid product. 1H-NMR: (C6D6, 300 MHz): d = 0.94, 1.64 (s, 3H, C (CH3) 2) •
3.66 (m, 1H, C5H4), 4.76 (m, 1H, C5H4), 5.80 s, 5H,
CSH5), 6.23 (m, 1H, C5H4), 6.66 (m, 1H, C5H4) ppm 13C-NMR: (C6D6, 75 MHz): d = 10.98 (C5 (CH3) 5), 21 , 35
21.90 (C (CH3) 2), 109.78 (C (CH3) 2), 107.75, 110.68, 113.88, 118.11 (C5H4), 115.69 (ipso-C5H4), 122.35 (C5 (CH3) 5) ppm
Example 6 Synthesis of fulvene complex by reaction of 6,6-diphenyl ulvene with CP * TiCl 3 in the presence of magnesium [(C5 (CH3) 5) (C5H4) C (C6H5) 2TiCl]. Cp * TiCl3 (0.690 g, 2.38 mmol) and 1.1 equivalents of magnesium (0.064 g, 2.62 mmol) were placed in 20 mL of THF. To this solution were added, drop by drop, at RT, 1.1 equivalents of 6,6-diphenyl fulvene (0.604 g, 2.62 mmol). It was stirred overnight at RT in such a manner that all the magnesium was consumed. The solvent in HV was removed and the green residue was taken up in hexane. The precipitate was separated by filtration and the solution was concentrated by evaporation to half. For the separation by crystallization, the charge was cooled to -20 ° C, whereby 0.29 g (27%) of [(C5 (CH3) 5 (C5H4) C (C6H5) 2TiCl] as a solid product was obtained green, 1H-NMR: (C6D6, 300 MHz): d = 1.55 (s, 15 H, C5 (CH3) 5), 4.20, 4.55, 5.89, 6.37 (m, 1H) , C5H4), 6.89-7.41 (m, 10H, C6H5) ppm 13C-NMR: (C6D6, 75 MHz): d = 12.38 (C5 (CH3) 5), 116.29, 117, 24, 118.22, 121.82 (C4H4), 124.04 (C5 (CH3) 5), 125.61 (ipso-C5H4), 126.50, 126.84, 127.26, 128.07, 128 , 83, 129.81 (C6H5), 130.72 (-C -CβHj-)), 141.93, 144.23 (ipso-C6H5) ppm. MS (70eV) m / e (%): 448 (5) [M +], 413 (2) [M + -HC1], 230 (100) [6,6-diphenylfulvene], 135 (15) [Cp *], 78 (12) [Ph].
Example 7. Synthesis of the fulvene complex by reaction of 6,6-diphenyl fulvene with CP * ZrCl 3 in the presence of magnesium [(C 5 (CH 3) 5) (C 5 H 4) C (C 6 H 5) 2 ZrCl].
C? * ZrCl3 (0.310 g, 093 mmol and 1.05 equivalents of magnesium (0.024 g, 0.98 mmol) in 10 ml of THF was added to this solution, 1.05 equivalents of 6 were added dropwise, 6-diphenylfulvene (0.225 g, 0.98 mmol), stirred overnight to completely convert magnesium, concentrated by evaporation in HV to dryness, it was taken up in 20 ml of toluene and the insoluble precipitate was filtered off. After coating with hexane at -20 ° C, 178 mg (39%) of [(C5 (CH3) 5) (C5H4) C (C6H5) 2ZrCl] was obtained as a red solid product. ^ • H-NMR: (C6D6, 300 MHZ): d = 1.63 (s, 15 H, C5 (CH3) 5), 4.65, 5.20, 5.22, 6.06 (m, 1H) , C5H4), 6.98-7.16 (m, 8H, C6 (H5), 7.26-7.49 (m, 2H, C6H5) ppm 13C-NMR: (C6D6, 75 MHz): d = 11.66 (C5 (CH3) 5), 104.67, 111.14, 113.62, 117.52 (C4H4), 120, 82 { C5 (CH3) 5),. 125, 61 (ipso-C5H), 126.50, 126.84, 127.26, 128.07, 128 83, 129.81 (C6H5), 130.72 (-C (C6H5)), 141.93, 144.23 (ipso-C6H5) ppm. MS (70eV) m / e (%): 448 (5) [M +], 413 (2) [M + -HC1], 230 (100) [6,6-difenilfulvene], 135 (15) [Cp *], 78 (12) [Ph].
Example 8. Synthesis of the fulvene complex by reaction of 2, 3, 4, 5-tetramethylfulvene with CP * TiCl3 in the presence of magnesium [(C5 (CH3) 5) (C5 (CH3) 4) CH2TiCl]. Cp * TiCl3 (0.370 g,
1. 28 mmoles) and 1.05 equivalents of magnesium (0.033 g, 1.35 mmoles) in 25 ml of THF. To this red solution was added, dropwise, at room temperature, 1.05 equivalents of 2,3,4,5 tetramethylfulvene (0.185 g, 1.35 mmol). It was stirred overnight at RT so that all the magnesium was consumed. The solvent was removed in HV and then the green residue in hexane was collected. The solid product was separated by filtration and the solution was concentrated by evaporation to half. For the separation by crystallization, the charge was cooled to -20 ° C, whereby 0.23 g (52%) of [(C5 (CH3) 5) (C5 (CH3) 4) CH2TiCl] as product was obtained solid green. XH-NMR: (C6D6, 300 MHz): d = 1.21, 1.47, 1.70 (s, 3H,
C5 (CH3) 4 = CH2), 1.79 (s, 3H, C5 (CH3) 5), 2.07 (s, 3H,
C5 (CH3) 4 = CH2), 1.43 (d, ÍH, 2J (H, H) = 3.66
Hz, C5 (CH3) 4 = CHH), 2.54 (d, ÍH, 2J (H, H), 3.66 Hz, C5 (CH3) 4 = CHH) ppm.
13 C-NMR: (C6D6, 75 MHz): d * = 9.82, 10.22 (C5 (CH3) 4 = CH2), 11.13 (C5 (CH3) 5). 11.85 14.00 (C5 (CH3) 4 = CH2), 77.65 (C5 (CH3) 4 = CH2), 120.08 (C5 (CH3) 5), 120.32, 124.43
124.73, 128.61, 135.17 (C5 (CH3) 4 = CH2) 4 = CH2) ppm.
Example 9 Synthesis of the fulvene complex by reaction of 2,3,4,5-tetramethylfulvene with CpTiCl 3 in the presence of magnesium [(C5H5) (C5 (CH3) 4) CH2TiCl]. They were placed in 20 ml of THF, CpTiCl3
(0.350 g, 1.60 mmol) and 1.05 equivalents of magnesium (0.041 g, 1.67 mmol). To this solution, 1.1 equivalents of 2, 3, 4, 5-tetramethylfulvene (0.260 g, 1.67 mmol) were added dropwise at room temperature and stirred until the magnesium used was consumed. It was then concentrated by evaporation in HV and the resulting green solid product was taken up in 20 ml of hexane. After separation by filtration of the solid product, the dark green solution was concentrated by evaporation to half in HV. Crystallization at -20 ° C yielded 0.3 g (67%) of [(C5H5) (C5 (CH3) 4) CH2TiCl] solid product of dark green color.
1H-NMR: (C6D6, 300 MHZ): d = 0.82, 1.27, 1.74 (s, 3H, C5 (CH3) 4 = CH2), 1.99 (d, 1H, 2J (H, H) = 3.7 Hz,
C5 (CH3) 4 = CHH), 2.05 (s, 3H, C5 (CH3) 4 = CH2), 2.56 (d, ÍH, 2J (H, H) = 3.7 Hz, C5 (CH3) 4 = CHH), 5.77 (s, 5H, C5H5) ppm.
13 C-NMR: (C6D6, 75 MHZ): d = 9.47, 10.35, 12.01.1 12.95
(C5 (CH3) 4 = CH2), 74.47 (C5 (CH3) 4 = CH2), 110.80 (C5H5),
119.92, 124.60, 127.82, 129.43, 134.80
(C5 (CH3) 4 = CH2) ppm. MS (70eV) m / e (%): 283 (10) [M +], 247 (15) [M + -HC1], 134 (50) [2, 3, 4, 5-tetramethylfulvene], 119 (100)
[2, 3, 4, 5-tetramethylfulvene-CH4], 65 (30) [Cp].
Example 10. Synthesis of the fulvene complex by reaction of 1,2,3,4,6-pentamethylfulvene with CpTiCl 3 in the presence of magnesium [(C 5 H 5) (C 5 (CH 3) 4) C (H) (CH 3) TiCl].
CpTiCl3 (0.450 g, 2.05 mmol) and 1.05 equivalents of magnesium (0.054 g, 2.15 mmol) were placed in 20 ml of THF. To this solution, 1.03 equivalents of 1, 2, 3, 4, 6-pentamethylfulvene (0.320 g, 2.15 mmol) were added dropwise at RT and stirred until the magnesium used had been consumed. It was then concentrated by evaporation in HV and the resulting green solid product was taken up in 20 ml of hexane. After evaporation by filtration of the solid product, the solution, dark green in color, was evaporated to one half in HV. Crystallization at -20 ° C gave 0.17 g (28%) of [(C5H5) (C5 (CH3) 4) C (H) (CH3) TiCl] as a dark green solid product. XH-NMR: (C6D6, 300 MHz): d = 0.73, 1.12 (s, 3H, C5 (CH3) 4 = C (CH3) (H), 1.64 (d, 3H, 3J (H , H) = 7.25 Hz, C5 (CH3) 4 = C (CH3) (H)), 1.71 (s, 3H, C5 (CH3) 4 = C (CH3) (H)), 2.29 (q, ÍH, 3J (H, H) = 7.25 Hz, C5 (CH3) 4 = C (CH3) (H)), 2.55 (s, 3H, C5 (CH3) 4 = C (CH3) (H)), 5.79 (s, 5H, C5H5) ppm 13C-NMR: (C6D6,) 75 MHz): d = 10.87, 13.35, 16.19, 16.97 (C5 (CH3 ) 4 = C (CH3) (H)), 37.62 (C5 (CH3) 4 C (CH3) (H)), 94.39 (C5 (CH3) 4 = C (CH3) (H)), 112 , 02 (C5H5), 121.46, 125.56, 130.91, 131.46, 136.90 (C5 (CH3) 4 = C (CH3) (H)) ppm.
Example 11. Synthesis of the fulvene complex by reaction of
6-tert-butylfulvene with Cp * TiCl3 in the presence of magnesium [C5 (CH3) 5) (C5H4) C (H) (C (CH3) 3) TiCl]. Cp * TiCl3 (0.450 g, 1.55 mmol) and 1.05 equivalents of magnesium (0.039 g, 1.63 mmol) were placed in 15 mL of THF. To this solution, 1.05 equivalents of tert-butylfulvene (0.249 g, 1.63 mmol) were added dropwise at RT. It was stirred overnight at RT so that all the magnesium was consumed. The solvent was removed in HV and the green residue was taken up in hexane. The solid product was separated by filtration and the solution was concentrated by evaporation to half. For the recrystallization separation, the charge was cooled to -20 ° C, whereby 0.35 g (64%) of [(C5 (CH3) 5) (C5H4) C (H) (C (CH3) was obtained. 3) TiCl] in the form of green crystals. An analysis of the structure was carried out by means of X-rays (figure 1). from: > 98% lH-NMR: (C6D6, 300 MHz): d = 1.16 (s, 9H, C5H4 = C (H) (C (CH3) 3)). 1.68 (s, 1H, C5H4 = C (H) (C (CH3) 3)), 1.70 (s, 15H, C5 (CH3) 5), 3.15, 4.74, 5.97, 6.63 (m, 1H, C 5 H 4 = C (H) (C (CH 3) 3)) ppm. 13C-NMR: (C6D6,) 75 MHz): d = 11.69 (C5 (CH3) 5), 32.30 (C5H4 = C (H) C (CH3) 3)), 34.28) (C5H4 = C (H) (C (CH3) 3)), 114.31 (C5H4 = C (H) (C (CH3) 3)), 117.83, 118.31, 118.77 (C5H4) = C (H ) (C (CH3) 3)), 120.46 C5 (CH3) 5), 124.72, 128.23 (C5H4 = C (H) C (CH3) 3)) ppm. MS (70eV) m / e (%): 353 (12) [M +], 316 (5) [M + -HC1], 270 (18), 235 (8), 135 (100) [Cp *], 119 ( 35), 80 (85), 57 (90) [C (CH3) 3].
Example 12 Synthesis of the fulvene complex by reaction of 6-tert-butylfulvene with CpTiCl3 in the presence of magnesium [(C5H5) (C5H4) C (H) (C (CH3) 3) TiCl]. They were placed in 120 ml of THF, CpTiCl3
(0.420 g, 1.91 mmol) and 1.05 equivalents of magnesium, (0.048 g, 2.01 mmol). To this solution, 1.03 equivalents of tert-butylfulvene (0.295, 1.91 mmol) were added dropwise at RT and stirred until the magnesium used had been consumed. It was then concentrated by evaporation in HV and the resulting green solid product was taken up in 20 ml of hexane. After separation by filtration of the solid product, the dark green solution was evaporated by half evaporation in HV. By crystallization at -20 ° C 0.23 g (44%) of ((C5H5) (C5H4) C (H) (C (CH3) 3) TiCl] were obtained as dark green crystals.
of > 98%. - H-NMR: (C6D6, 300 MHz): d = 1.05 (s, 9H, C5H4 - =
C (H) (C (CH3) 5)), 2.05 (s, ÍH, C5H4 = C (H) (C (CH3) 3)),
3.28, 4.83 (m, ÍH, C5H4 = C (H) (C (CH3) 3)),),
.85 (s, 5H, C5H5), 6.17, 6.59 (m, ÍH, C5H4
C (H) (C (CH3) 3)) ppm. 13C-NMR: (C6D6, 75 MHz): d = 32.84 (C5H4
C (H) (C (CH3) 3)), 35.76 (C5H4 = C (H) (C (CH3) 3)), 111.23
(C5H5), 111.63 (C5H4 = C (H) (C (CH3) 3)). 116, 62, 117.41,
121.63, 127.65, 127.50 (C5H4 = C (H) (C (CH3) 3)), ppm. MS (70eV) m / e (%): 282 (5) [M +], 246 (45) [M + -HC1],
228 (15), 135 (10) [Cp *], 119 (35).
Examples of polymerization. Example 13. Obtaining the catalyst solution. 8.3 mg (22.6 μmol) of [(CP *) (C5H4 = C (CH3) 2) ZrCl of example 3 was dissolved in 11.3 ml of toluene.
Polymerization of ethylene. 100 ml of toluene were placed in a 250 ml glass reactor, 1 ml of a 0.1 molar solution of triisobutylaluminium in toluene and 0.5 ml of the catalyst solution were added. The ethylene was then introduced into the solution with a tube for the introduction of gases, continuously, at a pressure of 1.1 bar Polymerization was initiated by the addition of 1 ml of a 0.001 molar solution of tetrakis (pentafluorophenyl) ) N, N-dimethyl anilinium borate in toluene After a polymerization time of 5 minutes at a temperature of 40 ° C and an ethylene pressure of 1.1 bar, the reaction was stopped by the addition of 10 ml. of methanol, the formed polymer was separated by filtration, washed with acetone and dried in the vacuum drying cabinet, 1.61 g of polyethylene was obtained.
Example 14. Copolymerization of ethylene and propylene. 500 ml of toluene and 5 ml of a 10% solution of MAO in toluene were placed in a 1.4 liter steel autoclave, which was equipped with a mechanical stirrer, pressure gauge, temperature sensor, a device for control of the temperature, a lock for the catalyst and a dosing device of the monomers for ethylene and propylene and were stirred for 10 minutes. Then, 52 g of propylene were metered in. The internal temperature was adjusted to 40 ° C with a thermostat. Ethylene was then metered in until the internal pressure of the reactor was 6 bar. By addition of 5 ml of the catalyst solution of example 5 the polymerization was started and ethylene was dosed continuously so that the internal pressure, at 40 ° C, was kept constant at 6 bar. After 1 hour of polymerization time, the polymerization was stopped with a 1% solution of HCl in methanol, stirred for 10 minutes and then the polymer was precipitated in methanol. The polymer, obtained in this way, was washed with methanol, isolated and dried for 20 hours at 60 ° C under vacuum, whereby 48 g of copolymer was obtained. The determination by IR spectroscopy of the composition of the copolymer gave a constitution of 82.9% ethylene and 17.1% propylene. A Tg of -24 ° C was determined with the DSC method.
Example 15. Obtaining the catalyst 73.9 mg (0.221 mmol) of TiCl4 (THF) 2 were dissolved in 3 ml of THF. Then, 5.4 mg (0.22 mmol) of magnesium and 51 mg (0.221 mmol) of 6,6-diphenylfulvene were added. After 20 hours of stirring at 20 ° C a dark green solution was obtained. The solution was concentrated by evaporation to dryness, the formed residue was dried for 2 hours in HV and then combined with 22 ml of toluene, whereby a dark green suspension was formed. In this case 1 ml of the catalyst suspension contained 0.012 mmole of titanium.
Polymerization of ethylene. 90 ml of toluene and 5 ml of an MAO solution (10% in toluene) were placed in a 250 ml glass reactor and stirred for 5 minutes. Then 5 ml of the catalyst suspension was added and stirred for 10 minutes at 40 ° C. It was then introduced, continuously, into the ethylene solution with a tube for the introduction of gases. After 10 minutes of polymerization time at a temperature of 40 ° C and an ethylene pressure of 1.1 bar, the reaction was stopped by the addition of 10 ml of a 10% solution of HCl in methanol, the polymer formed it was separated by filtration, washed with methanol and dried in the vacuum drying cabinet. 8.9 g of polyethylene were obtained.
It is noted that in relation to this date, the best method known to the applicant to carry out the aforementioned invention, is that which is clear from the present description of the invention.
Having described the invention as above, property is claimed as contained in the following:
Claims (8)
1. - Procedure for obtaining fulvene metal complexes of the formula (la) XpM (the). or of the formula (Ib) ApXpU (Ib). characterized in that M means a metal of the groups IHb, IVb, Vb, VIb or of the lanthanides or of the actinides of the Periodic Table of the Elements according to IUPAC, A means an anionic ligand where one or several times bridged, X means hydrogen is an alkyl group with 1 to 10 carbon atoms, an alkoxy group with 1 to 10 carbon atoms, an aryl group with 6 to 10 carbon atoms, an aryloxy group with 6 to 10 carbon atoms, an alkenyl group with 2 to 10 carbon atoms, an arylalkyl group with 7 to 40 carbon atoms, an alkylaryl group with 7 to 40 carbon atoms, an arylalkenyl group with 8 to 40 carbon atoms, a silyl group substituted by a hydrocarbon radical having 1 to 10 carbon atoms, a halogen atom or an amide of the formula NR72, L means a neutral ligand, R1, R2, R3 R4, R5, R6 are the same or different and mean hydrogen, halogen, a cyano group, an alkyl group with 1 to 20 carbon atoms, a group fluoroalkyl with 1 to 6 carbon atoms, a fluoroaryl group with 6 to 10 carbon atoms, an alkoxy group with 1 to 10 carbon atoms, an aryl group with 6 to 20 carbon atoms, an aryloxy group with 6 to 10 atoms of carbon, an alkenyl group with 2 to 10 carbon atoms, an arylalkyl group with 7 to 40 carbon atoms, an alkylaryl group with 7 to 40 carbon atoms, an arylalkenyl group with 8 to 40 carbon atoms, an alkynyl group with 2 to 10 atoms carbon atoms, a silyl group substituted by hydrocarbon radicals with 1 to 10 carbon atoms, an amino group optionally substituted by hydrocarbon radicals with 1 to 20 carbon atoms, or R 1, R 2, R 3, R 4, R 5, R 6 respectively, together with the atoms with which they are linked, one or more aliphatic or aromatic ring systems, which may contain one or more heteroatoms (O, N, S) and having from 5 to 10 carbon atoms, R7 means hydrogen, alkyl group with 1 to 20 carbon atoms, an aryl group with 6 to 20 carbon atoms, an arylalkyl group with 7 to 40 carbon atoms, an alkylaryl group with 7 to 40 carbon atoms, a silyl group substituted for hydrocarbon radicals with 1 to 10 carbon atoms, an amino group optionally substituted by hydrocarbon radicals having 1 to 20 carbon atoms, m, p means the numbers 0, 1, 2, 3 or 4, which are produced by the valency and by the state of linked to M, as well as k means the numbers 1, 2 or 3, and the sum k + m + p amounts to 1 to 5 as a function of the degree of oxidation of M, n means a number from 1 to 10, characterized in that it comprises the reaction of a transition metal compound of the formula (Ha) or (Hb) AmXsM (lia) AmXsLnM (I Ib) wherein A, X, L, M, m, s and n have the meaning indicated above and s means 2, 3, 4, 5 or 6 and s > p, with a fulvene compound of the formula (III) wherein R1, R2, R3, R4, R5 and R6 have the meaning indicated above, in the presence of a reducing agent.
2. - Process according to claim 1, characterized in that the reaction is carried out in a suitable reaction medium at temperatures of -100 to + 250 ° C.
3. Process according to claim 1, characterized in that alkali metals, alkaline earth metals or lithium alkyls are used as reducing agents.
4. Process according to claim 1, characterized in that the reaction is carried out in a solvent.
5. Process according to claim 4, characterized in that the reaction is carried out in an ether.
6.- Metallic complexes of fulvene of the formula (la) or (Ib), characterized in that M means a metal of the group formed by titanium, zirconium, hafnium, vanadium, niobium, tantalum and chromium, k means 1, A, X, L, m, n, p, R1, R2, R3, R4, R5 and R6 have the meaning indicated above, with the exception of the compounds of the formula (la) or (Ib), in which R1 and R2 mean hydrogen and , simultaneously, R3, R ^ R-R * means a methyl group simultaneously A means a pentamethylcyclopentadienyl group or a carbohydrate group of the formula C2B9Hn.
7. Catalytic system, consisting of a) a fulvene metallic complex of the formula (la) or (Ib), prepared according to the process of the invention, wherein M means a metal from the group consisting of titanium, zirconium, hafnium, vanadium, niobium , tantalum and chromium, k means 1, A, X, L, m, n, p, Rx. R2, R3, R4, R5 and R6 have the meaning indicated above and b) a co-catalyst suitable for the activation of the metal complex a) the molar ratio between component a) and component b) being in the range of 1: 0 , 1 to 1: 10,000.
8. Use of the catalytic system according to claim 7 for the polymerization of olefins and / or dienes.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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DE19749293.2 | 1997-11-07 | ||
DE19756742.8 | 1997-12-19 |
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