EP0994886A1 - Composes organometalliques, ligands et polymerisation d'olefines - Google Patents
Composes organometalliques, ligands et polymerisation d'olefinesInfo
- Publication number
- EP0994886A1 EP0994886A1 EP99924944A EP99924944A EP0994886A1 EP 0994886 A1 EP0994886 A1 EP 0994886A1 EP 99924944 A EP99924944 A EP 99924944A EP 99924944 A EP99924944 A EP 99924944A EP 0994886 A1 EP0994886 A1 EP 0994886A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- formula
- compound
- substituents
- metallocene
- group
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
- 239000003446 ligand Substances 0.000 title claims abstract description 38
- 238000006116 polymerization reaction Methods 0.000 title claims abstract description 36
- 150000001336 alkenes Chemical class 0.000 title claims abstract description 25
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 title claims description 6
- 150000001875 compounds Chemical class 0.000 claims abstract description 98
- 125000001424 substituent group Chemical group 0.000 claims abstract description 54
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 claims abstract description 39
- 239000003054 catalyst Substances 0.000 claims abstract description 33
- 125000000623 heterocyclic group Chemical group 0.000 claims abstract description 16
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 14
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 11
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 7
- 150000003624 transition metals Chemical class 0.000 claims abstract description 7
- 239000001257 hydrogen Substances 0.000 claims abstract description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 4
- 229910052768 actinide Inorganic materials 0.000 claims abstract description 3
- 150000001255 actinides Chemical class 0.000 claims abstract description 3
- 229910052747 lanthanoid Inorganic materials 0.000 claims abstract description 3
- 150000002602 lanthanoids Chemical class 0.000 claims abstract description 3
- 230000000737 periodic effect Effects 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 43
- 238000002360 preparation method Methods 0.000 claims description 28
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 22
- 239000005977 Ethylene Substances 0.000 claims description 22
- -1 organometallic lithium salts Chemical class 0.000 claims description 22
- 229910052710 silicon Inorganic materials 0.000 claims description 21
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 20
- 229910052757 nitrogen Inorganic materials 0.000 claims description 15
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 claims description 14
- 150000001450 anions Chemical class 0.000 claims description 13
- 125000006736 (C6-C20) aryl group Chemical group 0.000 claims description 12
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 11
- 125000005843 halogen group Chemical group 0.000 claims description 11
- 125000003358 C2-C20 alkenyl group Chemical group 0.000 claims description 10
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical group [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 claims description 10
- 125000005842 heteroatom Chemical group 0.000 claims description 10
- 239000010703 silicon Substances 0.000 claims description 10
- 229910052726 zirconium Inorganic materials 0.000 claims description 10
- 229910052799 carbon Inorganic materials 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 229910052732 germanium Inorganic materials 0.000 claims description 8
- 239000002585 base Substances 0.000 claims description 7
- 229910052736 halogen Inorganic materials 0.000 claims description 7
- 239000000178 monomer Substances 0.000 claims description 6
- 229920006395 saturated elastomer Polymers 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 5
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 5
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 5
- 229910052783 alkali metal Inorganic materials 0.000 claims description 5
- 125000004429 atom Chemical group 0.000 claims description 5
- 150000002367 halogens Chemical class 0.000 claims description 5
- 150000004678 hydrides Chemical class 0.000 claims description 5
- 150000004679 hydroxides Chemical class 0.000 claims description 5
- 229910052698 phosphorus Inorganic materials 0.000 claims description 5
- 229910052700 potassium Inorganic materials 0.000 claims description 5
- 239000011591 potassium Substances 0.000 claims description 5
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 5
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 5
- 229910052708 sodium Inorganic materials 0.000 claims description 5
- 239000011734 sodium Substances 0.000 claims description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 230000003197 catalytic effect Effects 0.000 claims description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- IPZJQDSFZGZEOY-UHFFFAOYSA-N dimethylmethylene Chemical compound C[C]C IPZJQDSFZGZEOY-UHFFFAOYSA-N 0.000 claims description 3
- PDPJQWYGJJBYLF-UHFFFAOYSA-J hafnium tetrachloride Chemical compound Cl[Hf](Cl)(Cl)Cl PDPJQWYGJJBYLF-UHFFFAOYSA-J 0.000 claims description 3
- 229910003002 lithium salt Inorganic materials 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 claims description 3
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical group [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- 239000004411 aluminium Substances 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- 150000001768 cations Chemical class 0.000 claims description 2
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 2
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 2
- 229910052735 hafnium Inorganic materials 0.000 claims description 2
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 claims description 2
- 230000003647 oxidation Effects 0.000 claims description 2
- 238000007254 oxidation reaction Methods 0.000 claims description 2
- 239000000758 substrate Substances 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 239000010936 titanium Substances 0.000 claims description 2
- 125000002827 triflate group Chemical group FC(S(=O)(=O)O*)(F)F 0.000 claims description 2
- 150000002899 organoaluminium compounds Chemical class 0.000 claims 2
- ZMZGFLUUZLELNE-UHFFFAOYSA-N 2,3,5-triiodobenzoic acid Chemical compound OC(=O)C1=CC(I)=CC(I)=C1I ZMZGFLUUZLELNE-UHFFFAOYSA-N 0.000 claims 1
- 239000007848 Bronsted acid Substances 0.000 claims 1
- 125000002877 alkyl aryl group Chemical group 0.000 claims 1
- 229910052801 chlorine Inorganic materials 0.000 claims 1
- 229930195733 hydrocarbon Natural products 0.000 abstract description 4
- 150000002430 hydrocarbons Chemical group 0.000 abstract description 4
- 239000004215 Carbon black (E152) Substances 0.000 abstract description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 2
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 41
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 28
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 18
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 18
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 18
- 239000000243 solution Substances 0.000 description 18
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 16
- 239000002904 solvent Substances 0.000 description 13
- WRCCQWJRVXGOOO-UHFFFAOYSA-N 2h-azadiphosphole Chemical compound C=1C=PPN=1 WRCCQWJRVXGOOO-UHFFFAOYSA-N 0.000 description 12
- AQZWEFBJYQSQEH-UHFFFAOYSA-N 2-methyloxaluminane Chemical compound C[Al]1CCCCO1 AQZWEFBJYQSQEH-UHFFFAOYSA-N 0.000 description 11
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 11
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 10
- VPGLGRNSAYHXPY-UHFFFAOYSA-L zirconium(2+);dichloride Chemical compound Cl[Zr]Cl VPGLGRNSAYHXPY-UHFFFAOYSA-L 0.000 description 10
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 9
- ZSWFCLXCOIISFI-UHFFFAOYSA-N endo-cyclopentadiene Natural products C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 7
- 239000002798 polar solvent Substances 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 6
- 229910007928 ZrCl2 Inorganic materials 0.000 description 6
- 125000003118 aryl group Chemical group 0.000 description 6
- 238000001704 evaporation Methods 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- 239000004711 α-olefin Substances 0.000 description 6
- DFZWURXRBNWZPX-UHFFFAOYSA-N azasiline Chemical compound C1=CC=[SiH]N=C1 DFZWURXRBNWZPX-UHFFFAOYSA-N 0.000 description 5
- 229920001577 copolymer Polymers 0.000 description 5
- 239000000523 sample Substances 0.000 description 5
- 238000005160 1H NMR spectroscopy Methods 0.000 description 4
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 4
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 4
- 125000004122 cyclic group Chemical group 0.000 description 4
- 239000003921 oil Substances 0.000 description 4
- 235000019198 oils Nutrition 0.000 description 4
- 239000005022 packaging material Substances 0.000 description 4
- 150000004291 polyenes Chemical class 0.000 description 4
- 229920000098 polyolefin Polymers 0.000 description 4
- 150000003254 radicals Chemical class 0.000 description 4
- PRBHEGAFLDMLAL-GQCTYLIASA-N (4e)-hexa-1,4-diene Chemical compound C\C=C\CC=C PRBHEGAFLDMLAL-GQCTYLIASA-N 0.000 description 3
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Natural products C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 description 3
- CMYHCDYRVCUFPC-UHFFFAOYSA-N N-[dimethyl-(1-methylcyclopenta-2,4-dien-1-yl)silyl]-2-methylpropan-2-amine Chemical compound CC1(C=CC=C1)[Si](C)(C)NC(C)(C)C CMYHCDYRVCUFPC-UHFFFAOYSA-N 0.000 description 3
- 150000001399 aluminium compounds Chemical class 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 238000007334 copolymerization reaction Methods 0.000 description 3
- 150000001993 dienes Chemical class 0.000 description 3
- LIKFHECYJZWXFJ-UHFFFAOYSA-N dimethyldichlorosilane Chemical compound C[Si](C)(Cl)Cl LIKFHECYJZWXFJ-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229920001198 elastomeric copolymer Polymers 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 125000003454 indenyl group Chemical group C1(C=CC2=CC=CC=C12)* 0.000 description 3
- 239000000543 intermediate Substances 0.000 description 3
- 125000000654 isopropylidene group Chemical group C(C)(C)=* 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- CXWXQJXEFPUFDZ-UHFFFAOYSA-N tetralin Chemical compound C1=CC=C2CCCCC2=C1 CXWXQJXEFPUFDZ-UHFFFAOYSA-N 0.000 description 3
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 description 3
- PRBHEGAFLDMLAL-UHFFFAOYSA-N 1,5-Hexadiene Natural products CC=CCC=C PRBHEGAFLDMLAL-UHFFFAOYSA-N 0.000 description 2
- CRSBERNSMYQZNG-UHFFFAOYSA-N 1-dodecene Chemical compound CCCCCCCCCCC=C CRSBERNSMYQZNG-UHFFFAOYSA-N 0.000 description 2
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 2
- HFDVRLIODXPAHB-UHFFFAOYSA-N 1-tetradecene Chemical compound CCCCCCCCCCCCC=C HFDVRLIODXPAHB-UHFFFAOYSA-N 0.000 description 2
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 2
- SLQMKNPIYMOEGB-UHFFFAOYSA-N 2-methylhexa-1,5-diene Chemical compound CC(=C)CCC=C SLQMKNPIYMOEGB-UHFFFAOYSA-N 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- JAHUCWAAGICQQB-UHFFFAOYSA-N N-[cyclopenta-2,4-dien-1-yl(dimethyl)silyl]-2-methylpropan-2-amine Chemical compound CC(C)(C)N[Si](C)(C)C1C=CC=C1 JAHUCWAAGICQQB-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- 235000019502 Orange oil Nutrition 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 125000000129 anionic group Chemical group 0.000 description 2
- 229940077746 antacid containing aluminium compound Drugs 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 150000001923 cyclic compounds Chemical class 0.000 description 2
- 150000001925 cycloalkenes Chemical class 0.000 description 2
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 description 2
- QRUYYSPCOGSZGQ-UHFFFAOYSA-L cyclopentane;dichlorozirconium Chemical compound Cl[Zr]Cl.[CH]1[CH][CH][CH][CH]1.[CH]1[CH][CH][CH][CH]1 QRUYYSPCOGSZGQ-UHFFFAOYSA-L 0.000 description 2
- LPIQUOYDBNQMRZ-UHFFFAOYSA-N cyclopentene Chemical compound C1CC=CC1 LPIQUOYDBNQMRZ-UHFFFAOYSA-N 0.000 description 2
- 238000007872 degassing Methods 0.000 description 2
- YMWUJEATGCHHMB-DICFDUPASA-N dichloromethane-d2 Chemical compound [2H]C([2H])(Cl)Cl YMWUJEATGCHHMB-DICFDUPASA-N 0.000 description 2
- 229960004132 diethyl ether Drugs 0.000 description 2
- 230000008020 evaporation Effects 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
- GEAWFZNTIFJMHR-UHFFFAOYSA-N hepta-1,6-diene Chemical compound C=CCCCC=C GEAWFZNTIFJMHR-UHFFFAOYSA-N 0.000 description 2
- PYGSKMBEVAICCR-UHFFFAOYSA-N hexa-1,5-diene Chemical compound C=CCCC=C PYGSKMBEVAICCR-UHFFFAOYSA-N 0.000 description 2
- 229920001903 high density polyethylene Polymers 0.000 description 2
- 239000004700 high-density polyethylene Substances 0.000 description 2
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 2
- 229920000092 linear low density polyethylene Polymers 0.000 description 2
- 239000004707 linear low-density polyethylene Substances 0.000 description 2
- 150000002642 lithium compounds Chemical class 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- DVSDBMFJEQPWNO-UHFFFAOYSA-N methyllithium Chemical compound C[Li] DVSDBMFJEQPWNO-UHFFFAOYSA-N 0.000 description 2
- VAMFXQBUQXONLZ-UHFFFAOYSA-N n-alpha-eicosene Natural products CCCCCCCCCCCCCCCCCCC=C VAMFXQBUQXONLZ-UHFFFAOYSA-N 0.000 description 2
- 125000006574 non-aromatic ring group Chemical group 0.000 description 2
- 239000012454 non-polar solvent Substances 0.000 description 2
- JFNLZVQOOSMTJK-KNVOCYPGSA-N norbornene Chemical compound C1[C@@H]2CC[C@H]1C=C2 JFNLZVQOOSMTJK-KNVOCYPGSA-N 0.000 description 2
- CCCMONHAUSKTEQ-UHFFFAOYSA-N octadec-1-ene Chemical compound CCCCCCCCCCCCCCCCC=C CCCMONHAUSKTEQ-UHFFFAOYSA-N 0.000 description 2
- 239000010502 orange oil Substances 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 2
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 description 2
- TZZOMQMRUILQEH-UHFFFAOYSA-N (1-methylcyclopenta-2,4-dien-1-yl)silane Chemical compound CC1([SiH3])C=CC=C1 TZZOMQMRUILQEH-UHFFFAOYSA-N 0.000 description 1
- DMGCMUYMJFRQSK-AEJSXWLSSA-N (1s,4s,5r)-5-prop-1-en-2-ylbicyclo[2.2.1]hept-2-ene Chemical compound C1[C@@H]2[C@H](C(=C)C)C[C@H]1C=C2 DMGCMUYMJFRQSK-AEJSXWLSSA-N 0.000 description 1
- GDDAJHJRAKOILH-QFXXITGJSA-N (2e,5e)-octa-2,5-diene Chemical compound CC\C=C\C\C=C\C GDDAJHJRAKOILH-QFXXITGJSA-N 0.000 description 1
- OGQVROWWFUXRST-FNORWQNLSA-N (3e)-hepta-1,3-diene Chemical compound CCC\C=C\C=C OGQVROWWFUXRST-FNORWQNLSA-N 0.000 description 1
- QVLAWKAXOMEXPM-DICFDUPASA-N 1,1,1,2-tetrachloro-2,2-dideuterioethane Chemical compound [2H]C([2H])(Cl)C(Cl)(Cl)Cl QVLAWKAXOMEXPM-DICFDUPASA-N 0.000 description 1
- PAAZPARNPHGIKF-UHFFFAOYSA-N 1,2-dibromoethane Chemical compound BrCCBr PAAZPARNPHGIKF-UHFFFAOYSA-N 0.000 description 1
- KNKRKFALVUDBJE-UHFFFAOYSA-N 1,2-dichloropropane Chemical compound CC(Cl)CCl KNKRKFALVUDBJE-UHFFFAOYSA-N 0.000 description 1
- KPZGRMZPZLOPBS-UHFFFAOYSA-N 1,3-dichloro-2,2-bis(chloromethyl)propane Chemical compound ClCC(CCl)(CCl)CCl KPZGRMZPZLOPBS-UHFFFAOYSA-N 0.000 description 1
- 229940106006 1-eicosene Drugs 0.000 description 1
- FIKTURVKRGQNQD-UHFFFAOYSA-N 1-eicosene Natural products CCCCCCCCCCCCCCCCCC=CC(O)=O FIKTURVKRGQNQD-UHFFFAOYSA-N 0.000 description 1
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 1
- XIIJLUZCNRNFRT-UHFFFAOYSA-N 1H-azaphosphasilole Chemical compound N1P=[SiH]C=C1 XIIJLUZCNRNFRT-UHFFFAOYSA-N 0.000 description 1
- PAPNRQCYSFBWDI-UHFFFAOYSA-N 2,5-Dimethyl-1H-pyrrole Chemical compound CC1=CC=C(C)N1 PAPNRQCYSFBWDI-UHFFFAOYSA-N 0.000 description 1
- USVQDQRLYYGLPV-UHFFFAOYSA-N 2-(2,4,4-trimethylpentyl)oxaluminane Chemical compound CC(C)(C)CC(C)C[Al]1CCCCO1 USVQDQRLYYGLPV-UHFFFAOYSA-N 0.000 description 1
- NMXLXQGHBSPIDR-UHFFFAOYSA-N 2-(2-methylpropyl)oxaluminane Chemical compound CC(C)C[Al]1CCCCO1 NMXLXQGHBSPIDR-UHFFFAOYSA-N 0.000 description 1
- MWOKYBPYFUJFBK-UHFFFAOYSA-N 2-tert-butyl-1,1-dimethyl-4,7a-dihydro-3h-cyclopenta[c]azasiline;zirconium Chemical compound [Zr].C[Si]1(C)N(C(C)(C)C)CCC2=CC=CC21 MWOKYBPYFUJFBK-UHFFFAOYSA-N 0.000 description 1
- UFERIGCCDYCZLN-UHFFFAOYSA-N 3a,4,7,7a-tetrahydro-1h-indene Chemical compound C1C=CCC2CC=CC21 UFERIGCCDYCZLN-UHFFFAOYSA-N 0.000 description 1
- FSWNZCWHTXTQBY-UHFFFAOYSA-N 4,6-dimethylhept-1-ene Chemical compound CC(C)CC(C)CC=C FSWNZCWHTXTQBY-UHFFFAOYSA-N 0.000 description 1
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 1
- OJOWICOBYCXEKR-UHFFFAOYSA-N 5-ethylidenebicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(=CC)CC1C=C2 OJOWICOBYCXEKR-UHFFFAOYSA-N 0.000 description 1
- 229910018516 Al—O Inorganic materials 0.000 description 1
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 1
- 229910007932 ZrCl4 Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 125000005234 alkyl aluminium group Chemical group 0.000 description 1
- 150000004791 alkyl magnesium halides Chemical class 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 150000001449 anionic compounds Chemical class 0.000 description 1
- 150000005840 aryl radicals Chemical class 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 239000013256 coordination polymer Substances 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- QSDQMOYYLXMEPS-UHFFFAOYSA-N dialuminium Chemical compound [Al]#[Al] QSDQMOYYLXMEPS-UHFFFAOYSA-N 0.000 description 1
- YQECBLVSMFAWIZ-UHFFFAOYSA-N dichloro(dimethyl)germane Chemical compound C[Ge](C)(Cl)Cl YQECBLVSMFAWIZ-UHFFFAOYSA-N 0.000 description 1
- OSXYHAQZDCICNX-UHFFFAOYSA-N dichloro(diphenyl)silane Chemical compound C=1C=CC=CC=1[Si](Cl)(Cl)C1=CC=CC=C1 OSXYHAQZDCICNX-UHFFFAOYSA-N 0.000 description 1
- IMDXZWRLUZPMDH-UHFFFAOYSA-N dichlorophenylphosphine Chemical compound ClP(Cl)C1=CC=CC=C1 IMDXZWRLUZPMDH-UHFFFAOYSA-N 0.000 description 1
- VIMUQFAJSXTQEH-UHFFFAOYSA-L dichlorozirconium;trimethyl-(3-trimethylsilylcyclopentyl)silane Chemical compound C1=CC([Si](C)(C)C)=CC1([Si](C)(C)C)[Zr](Cl)(Cl)C1([Si](C)(C)C)C=C([Si](C)(C)C)C=C1 VIMUQFAJSXTQEH-UHFFFAOYSA-L 0.000 description 1
- YNLAOSYQHBDIKW-UHFFFAOYSA-M diethylaluminium chloride Chemical compound CC[Al](Cl)CC YNLAOSYQHBDIKW-UHFFFAOYSA-M 0.000 description 1
- 238000000113 differential scanning calorimetry Methods 0.000 description 1
- 229940069096 dodecene Drugs 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- UAIZDWNSWGTKFZ-UHFFFAOYSA-L ethylaluminum(2+);dichloride Chemical compound CC[Al](Cl)Cl UAIZDWNSWGTKFZ-UHFFFAOYSA-L 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 150000004795 grignard reagents Chemical class 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000001282 iso-butane Substances 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
- 125000004491 isohexyl group Chemical group C(CCC(C)C)* 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 235000019988 mead Nutrition 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- AFFLGGQVNFXPEV-UHFFFAOYSA-N n-decene Natural products CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 1
- 150000002848 norbornenes Chemical class 0.000 description 1
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 1
- 125000000538 pentafluorophenyl group Chemical group FC1=C(F)C(F)=C(*)C(F)=C1F 0.000 description 1
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- JUJWROOIHBZHMG-UHFFFAOYSA-N pyridine Substances C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 238000000646 scanning calorimetry Methods 0.000 description 1
- 150000003376 silicon Chemical class 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 1
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- XZIKSWMNFLIAQP-UHFFFAOYSA-N tris(2,4,4-trimethylpentyl)alumane Chemical compound CC(C)(C)CC(C)C[Al](CC(C)CC(C)(C)C)CC(C)CC(C)(C)C XZIKSWMNFLIAQP-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F17/00—Metallocenes
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
- C07F5/02—Boron compounds
- C07F5/027—Organoboranes and organoborohydrides
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/0803—Compounds with Si-C or Si-Si linkages
- C07F7/081—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te
- C07F7/0812—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te comprising a heterocyclic ring
- C07F7/0816—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te comprising a heterocyclic ring said ring comprising Si as a ring atom
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/30—Germanium compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/6596—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having atoms other than oxygen, sulfur, selenium, tellurium, nitrogen or phosphorus as ring hetero atoms
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F10/02—Ethene
-
- 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
- C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F110/02—Ethene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/62—Refractory metals or compounds thereof
- C08F4/64—Titanium, zirconium, hafnium or compounds thereof
- C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
- C08F4/65908—Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with an ionising compound other than alumoxane, e.g. (C6F5)4B-X+
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/62—Refractory metals or compounds thereof
- C08F4/64—Titanium, zirconium, hafnium or compounds thereof
- C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
- C08F4/65912—Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with an organoaluminium compound
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/62—Refractory metals or compounds thereof
- C08F4/64—Titanium, zirconium, hafnium or compounds thereof
- C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
- C08F4/6592—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring
- C08F4/65922—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring containing at least two cyclopentadienyl rings, fused or not
- C08F4/65925—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 non-bridged
Definitions
- the present invention relates to a new class of metallocene compounds, to a catalyst for the
- the invention also relates to the corresponding ligands useful as
- Metallocene compounds with two cyclopendadienyl groups are known as catalyst components
- European Patent 0 129 368 describes a catalyst system for the polymerization of
- olefins comprising (a) a bis-cyclopentadienyl coordination complex with a transition metal and
- European Patent Application EP 0 185 918 describes the use of
- US Patent 5 489 659 relates to a class of silicon-containing metallocene compounds for the
- EP 0 590 486 describes metallocene compounds containing a
- polyolefins The only illustrative examples are bis(l-phospha-2,3,4,5-
- metallocenes are useful for the polymerization of olefins.
- a novel class of metallocene compounds having a particular cyclopentadienyl ligand system having a particular cyclopentadienyl ligand system
- the present invention provides a metallocene compound of formula
- R- is a structural bridge
- Cp is a heterocyclic cyclopentadienyl group of formula (II):
- substituents R 1 and R 2 are hydrogen atoms, C,-C 20 alkyl, C 3 -C 20
- substituents R 1 and R 2 can contain silicon or germanium atoms
- Z is NR 3 or O, R 3 being defined as substituents R 1 and R 2 ;
- X and Y are selected from (CR 4 2 ) r , BR 4 2 , PR 4 , SiR 4 2 or GeR 4 2 ; and
- substituents R 4 are hydrogen atoms, C,-C 20 alkyl, C 3 -C 20 cycloalkyl, C 2 -C 20
- R 4 can contain hetero atoms such as nitrogen, phosphor, oxygen, silicon or germanium atoms,
- A is a group selected from substituted or unsubstituted cyclopentadienyls, which may carry one
- M is a transition metal selected from those belonging to group 3, 4, 5 or 6 or to the lanthanides
- the substituent L is a monoanionic ligand, selected from the group
- substituents R 6 same or different, are linear or branched, saturated or unsaturated C,-C 20
- alkyl C 3 -C 20 cycloalkyl, C 2 -C 20 alkenyl, C 6 -C 20 aryl, C 7 -C 20 alkylaryl, or C 7 -C 20 arylalkyl
- radicals optionally containing silicon or germanium atoms
- p is an integer from 0 to 3, p being equal to the oxidation state of the metal M minus two;
- n is an integer ranging from 0 to 4.
- r is an integer ranging from 1 to 4.
- R, n, Cp, A have the meanings as reported above and q is 0 when n is 0 and is 1 when
- n 1 to 4, particularly useful as intermediates in the preparation of the metallocene compounds
- a further aspect of the present invention is a process for the preparation of ligands R réelle(Cp)(A) q
- a still further aspect of the present invention is a process for the preparation of the metallocene
- Another aspect of the present invention is a catalyst for the polymerization of olefins
- formula (II) may be linked to an identical cyclopentadienyl group, to a cyclopentadienyl
- cyclopentadienyls which may carry one or more aromatic or non-aromatic condensed cycles
- the divalent group (QR 7 m ) n is selected from the group consisting of
- CR 7 2 , SiR 7 2 , GeR 7 2 , NR 7 , PR 7 and (CR 7 2 ) 2 and the R 7 groups, equal or different, are linear or branched, saturated or unsaturated C,-C 20 alkyl, C 3 -C 20 cycloalkyl, C 2 -C 20 alkenyl, C 6 -C 20 aryl,
- substituents R 7 can form a cycle comprising from 3 to 8 atoms. More preferably, said divalent
- n is 1 or 2, being 1 when Q is N or P, and being 2 when Q is C, Si or Ge; n ranges from 0 to 6
- the atoms Q can be the same or different, such as, for example, in the bridges
- the transition metal is preferably titanium, zirconium and hafnium, more preferably it is
- the substituents R 1 and R 2 are preferably hydrogen atoms.
- the substituents L are preferably halogen atoms or R 6 groups, R 6 being defined as reported
- cyclopentadienyl moieties of the metallocene compound of the invention are identical.
- Non limitative examples of said metallocenes are:
- azadisilolejzirconium dichloride or dimethyl isopropylidenebis ⁇ 2-(tert-butyl)-l,l,3,3,5-pentamethyl-l,2,3,3a-tetrahydrocyclopenta[c][l,2,5] azadisilole ⁇ zirconium dichloride or dimethyl;
- Non limiting examples of said class are:
- R is a structural bridge
- Cp is a heterocyclic cyclopentadienyl group of formula (IV):
- R, R 1 , R 2 , X, Y and Z, n and q have the meaning as reported,
- A is a group selected
- the two double bonds of the cyclopentadienyl ring of the ligands of formula (IV) can be in any
- cyclopentadienyls which may carry one or more aromatic or non-aromatic condensed cycles
- Non-limiting examples of this class of ligands according to the invention are:
- a further interesting class of ligands according to the present invention corresponds to formula
- Non limiting examples of said ligands are:
- n is an integer from 1 to 4 and q is 1, i.e. the two groups Cp and A' are linked by a
- A' is a group selected from substituted or unsubstituted cyclopentadienyls
- Non-limiting examples of bases used to form the above compounds of formula (VI) are
- organometallic lithium compounds Preferably, methyllithium or n-butyllithium is used.
- Non-limiting examples of compounds able to form the anionic compounds of formula (VII) are
- organometallic lithium compounds Preferably, methyllithium or n-butyllithium is used.
- the synthesis of the above bridged ligands is preferably carried out by adding a solution of an
- bridged ligand can be finally separated by conventional general known procedures.
- apolar solvents suitable for the above process are pentane, hexane and benzene.
- the temperature is preferably kept between -180°C and 80°C, and
- a still further aspect of the present invention is a process for the preparation of the metallocene
- the compound able to form said dianion is selected from the group consisting of hydroxides
- organometallic lithium salts and preferably said anion is n-butyllithium.
- Non-limiting examples of compounds of formula ML' p+2 are titanium tetrachloride, zirconium
- cyclopentadienyl derivate can be prepared by first reacting the bridged ligands of formula (III),
- titanium tetrachloride zirconium tetrachloride and hafnium tetrachloride.
- bridged ligands are dissolved in an aprotic polar solvent and to the
- anionic form is separated, dissolved in an aprotic polar solvent and thereafter
- the temperature is preferably kept between -180°C and 80°C, and
- formula (II) can be prepared by reacting the anions of the formula (VII) with a tetrahalide of
- the metallocenes can be reacted with alkylmagnesium halides (Grignard reagents) or with
- the temperature is preferably kept between -180°C and 80°C, and
- heterocyclic metallocene compounds of the present invention can conveniently be used as
- the alumoxane used as component (B) can be obtained by reacting water with an organo-
- reaction the molar ratio of Al/water is comprised between 1 : 1 and 100: 1.
- the molar ratio between aluminium and the metal of the metallocene is comprised between
- alumoxanes used in the catalyst according to the invention are considered to be linear,
- R 9 substituents same or different, are hydrogen atoms, C,-C 20 -alkyl, C 3 -C 20 -
- germanium atoms or are a -O-Al(R 9 ) 2 group and, if appropriate, some R 9 substituents can be
- n is 0 or an integer from 1 to 40 and the
- R 9 substituents are defined as above, or alumoxanes of the formula:
- n is an integer from 2 to 40 and the R 9
- alumoxanes suitable for use according to the present invention are
- MAO methylalumoxane
- TIBAO isobutylalumoxane
- both the heterocyclic metallocene compound of the formula (I) and the alumoxane can be
- halogen atoms C,-C 20 -alkyl, C 3 -C 20 -cyclalkyl, C 6 -C 20 -aryl, C 7 -C 20 -alkylaryl or C 7 -C 20 -arylalkyl,
- Non-limiting examples of aluminium compounds of the formula A1R 8 3 or A1 2 R 8 6 are: Al(Me) 3 ,
- TMA trimethylaluminium
- TIBAL triisobutylaluminium
- TIOA tris(2,4,4-trimethyl-pentyl)aluminium
- Non limitative examples of compounds able to form a metallocene alkyl cation are compounds
- TJD a Broensted acid, able to give a proton and to react irreversibly
- the anion D " comprises one or more boron atoms. More
- the anion D " is an anion of the formula BAr' " ⁇ , wherein substituents Ar, the same or
- aryl radicals such as phenyl, pentafluorophenyl,
- the catalysts used in the process of the present invention can be also used on inert supports.
- silica such as for example silica, alumina, styrene-divinylbenzene copolymers, polyethylene or
- Catalysts of the present invention are useful in the homo- and copolymerization reaction of
- a still further object of the present invention is a process for the polymerization of
- olefins comprising the polymerization reaction of at least an olefinic monomer in the presence
- the catalysts of the present invention can be used in the homo-polymerisation reaction of
- olefins preferably of ethylene for the preparation of HDPE, or of a-olefins, such as propylene
- heterocyclic metallocenes of the invention show
- R 10 is an alkyl radical having from 1 to 10 carbon atoms, and cycloolefins.
- these olefins are propylene, 1-butene, 1-pentene, 4-methyl-l-pentene, 1-hexene, 1-octene, 1-
- decene 1-dodecene, 1-tetradecene, 1-esadecene, 1-octadecene, 1-eicosene, allylcyclohexene,
- the copolymers may also contain small proportions of units deriving from polyenes, in
- isoprene 1,3-butadiene, 1,5-hexadiene and 1 ,6-heptadiene.
- polienes are present in the copolymers preferably in amounts ranging from 1% to 20% by
- the saturated elastomeric copolymers can contain ethylene units and ⁇ -olefins and/or non
- the unsaturated elastomeric copolymers can be any unsaturated elastomeric copolymer.
- the content of unsaturated units is preferably comprised between 0 and 5% by
- Non limitative examples of suitable ⁇ -olefins comprise propylene, 1-butene and 4-methyl-l-
- Suitable non conjugated diolefms able to cyclopolymerise comprise 1,5-hexadiene,
- Non limitative examples of suitable polyenes are:
- bicyclic diolefms such as 4,5,8,9-tetrahydroindene and 6 and 7-methyl-4,5,8,9-
- alkenyl or alkyliden norbornenes such as 5-ethyliden-2-norbornene, 5-isopropyliden-
- polycyclic diolefms such as dicyclopentadiene, tricyclo-[6.2.1.0 27 ]4,9-undecadiene
- non-conjugated diolefms able to cyclopolymerise such as 1.5-hexadiene, 1 ,6-
- conjugated dienes such as butadiene and isoprene.
- Another object of the present invention is a process for the polymerisation of propylene carried
- Monocychc and polycyclic olefin monomers can be either
- aromatic such as toluene
- aliphatic such as propane, hexane, heptane, isobutane
- the polymerisation temperature is preferably ranging from about 0°C to about 250°C.
- the elastomeric copolymers it is preferably comprised between 0°C and 200°C
- the polymerization pressure is ranging from 0,5 to 100 bar, preferably from 2 to 50 bar, and
- the molecular weight of the polymers can be also varied merely by varying the polymerization
- weight regulators such as, for example, hydrogen.
- the molecular weight distribution can be varied by using mixtures of different metallocenes, or
- the polymerization yields depend on the purity of the metallocene component of the catalyst.
- metallocenes are generally used
- the components of the catalyst can be brought into contact before the polymerization.
- contact concentrations are generally between 1 and 10 "8 mol/1 for the metallocene component
- the pre-contact time is generally comprised between 1 minute and 24
- Solvents were distilled from blue Na-benzophenone ketyl (Et 2 O), CaH 2 (CH 2 C1 2 ) or Al Bu 3
- the melting point Tm (°C) and ⁇ H (J/g) of the polymers were measured by Differential
- the density (g/ml) was determined by immersion of a sample of extruded copolymer in a
- r is the relative reactivity of the alpha-comonomer versus ethylene and r 2 that of
- Butylhthium (4.0 mmol of a 2.5 M sol. in hexanes) was added slowly to a solution of 1,1,3,3-
- the catalyst system was prepared separately in 10 mL of hexane by
- polymer was washed with acidic methanol, methanol, and dried in an oven at 60 °C under
- the catalyst system was prepared separately in 10 mL
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Abstract
On décrit une classe de composés organométalliques représentés par la formule (I), dans laquelle Rn représente un pont structurel; Cp représente un groupe cyclopentadiényle hétérocyclique de formule (II) dans laquelle R1 et R2 représentent des groupes hydrogène ou hydrocarbure, M représente un métal de transition du groupe 3,4,5 ou 6 ou faisant partie des lanthanides ou des actinides du tableau périodique des éléments (nouvelle version UICPA). L représente un ligand monoanionique; Z représente NR3 ou O; X et Y sont sélectionnés parmi (CR42)n, BR42, PR4, SiR42 ou GeR42; et les substituants R4 sont des atomes d'hydrogène ou des radicaux hydrocarbure, à condition que X et Y ne puissent être tous les deux ensembles des atomes de carbone au même moment; A représente un groupe sélectionné entre des cyclopentanediényles substitués ou non substitués, qui peuvent supporter un ou plusieurs cycles condensés, des groupes =NR5, -O-, -S- et =PR5, R5 étant défini comme les substituants R1 et R2, et des groupes correspondant à la formule (II); p représente un entier compris entre 0 et 3. Ces composés organométalliques sont utiles en tant qu'éléments catalyseurs employés pour polymériser des oléfines.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP99924944A EP0994886A1 (fr) | 1998-05-08 | 1999-05-07 | Composes organometalliques, ligands et polymerisation d'olefines |
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP98201501 | 1998-05-08 | ||
EP98201501 | 1998-05-08 | ||
PCT/EP1999/003247 WO1999058539A1 (fr) | 1998-05-08 | 1999-05-07 | Composes organometalliques, ligands et polymerisation d'olefines |
EP99924944A EP0994886A1 (fr) | 1998-05-08 | 1999-05-07 | Composes organometalliques, ligands et polymerisation d'olefines |
Publications (1)
Publication Number | Publication Date |
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EP0994886A1 true EP0994886A1 (fr) | 2000-04-26 |
Family
ID=8233694
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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EP99924944A Withdrawn EP0994886A1 (fr) | 1998-05-08 | 1999-05-07 | Composes organometalliques, ligands et polymerisation d'olefines |
Country Status (7)
Country | Link |
---|---|
EP (1) | EP0994886A1 (fr) |
JP (1) | JP2002513428A (fr) |
KR (1) | KR20010021604A (fr) |
CN (1) | CN1268951A (fr) |
AU (1) | AU4141999A (fr) |
CA (1) | CA2294608A1 (fr) |
WO (1) | WO1999058539A1 (fr) |
Families Citing this family (17)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR20010112459A (ko) | 2000-02-24 | 2001-12-20 | 간디 지오프레이 에이치. | 올레핀 중합용 조촉매로서 유용한 유기금속 화합물 |
JP2004516365A (ja) | 2000-12-22 | 2004-06-03 | バセル ポリオレフィン イタリア エス.ピー.エー. | 多孔性ポリマーの製造方法およびそれから得られるポリマー |
US6703458B2 (en) | 2000-12-22 | 2004-03-09 | Basell Polyolefine Gmbh | Catalyst components for the polymerization of olefins |
KR100422940B1 (ko) * | 2000-12-23 | 2004-03-12 | 주식회사 엘지화학 | 하프 메탈로센 촉매 및 이를 이용한 입체규칙성을 가진비닐 방향족 중합체의 제조방법 |
DE60202524T2 (de) | 2001-05-21 | 2005-06-30 | Basell Polyolefine Gmbh | Katalysatorsystem für die polymerisierung von olefinen |
EP1448624A1 (fr) | 2001-11-27 | 2004-08-25 | Basell Polyolefine GmbH | Procede de traitement de compositions polymeres |
KR100497172B1 (ko) * | 2002-11-11 | 2005-06-28 | 주식회사 엘지화학 | 양쪽 메탈로센 유도체 화합물을 리간드로 가진 다중핵반쪽 메탈로센 촉매 및 이를 이용한 스티렌 중합체의제조방법 |
BRPI0409738B1 (pt) | 2003-04-17 | 2014-01-21 | Processo contínuo para a polimerização de olefinas em um reator de leito fluidizado | |
US7122606B2 (en) | 2003-07-04 | 2006-10-17 | Basell Polyolefine Gmbh | Olefin polymerization process |
EP1735355B1 (fr) | 2004-03-12 | 2010-09-29 | Basell Polyolefine GmbH | Procede de polymerisation de 1-hexene ou d'alpha-olefines superieures |
BRPI0508155A (pt) | 2004-03-12 | 2007-08-07 | Basell Polyolefine Gmbh | sistema catalìtico para a polimerização de olefinas |
US7943716B2 (en) | 2004-03-12 | 2011-05-17 | Basell Polyolefine Gmbh | Process for polymerizing 1-hexene or higher alpha-olefins |
EP1655314A1 (fr) | 2004-11-09 | 2006-05-10 | Basell Polyolefine GmbH | Procede de ppolymerisation du 1-butene avec le propene |
KR20070093058A (ko) | 2004-11-22 | 2007-09-17 | 바젤 폴리올레핀 게엠베하 | 프로필렌 기재 삼중합체 |
WO2009077185A1 (fr) | 2007-12-18 | 2009-06-25 | Basell Polyolefine Gmbh | Processus en phase gazeuse pour la polymérisation des alpha-oléfines |
CN104558058B (zh) * | 2013-10-12 | 2017-08-08 | 中国科学院长春应用化学研究所 | 茂金属配合物及其制备方法、催化剂组合物 |
EP3694811B1 (fr) | 2017-10-11 | 2024-04-03 | Basell Polyolefine GmbH | Système de catalyseur supporté |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0590486A3 (en) * | 1992-09-24 | 1994-08-24 | Idemitsu Kosan Co | Polymerization catalysts and process for producing polymers |
-
1999
- 1999-05-07 AU AU41419/99A patent/AU4141999A/en not_active Abandoned
- 1999-05-07 CN CN99800705A patent/CN1268951A/zh active Pending
- 1999-05-07 CA CA002294608A patent/CA2294608A1/fr not_active Abandoned
- 1999-05-07 KR KR1020007000162A patent/KR20010021604A/ko not_active Application Discontinuation
- 1999-05-07 WO PCT/EP1999/003247 patent/WO1999058539A1/fr not_active Application Discontinuation
- 1999-05-07 JP JP55623599A patent/JP2002513428A/ja active Pending
- 1999-05-07 EP EP99924944A patent/EP0994886A1/fr not_active Withdrawn
Non-Patent Citations (1)
Title |
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See references of WO9958539A1 * |
Also Published As
Publication number | Publication date |
---|---|
AU4141999A (en) | 1999-11-29 |
JP2002513428A (ja) | 2002-05-08 |
CN1268951A (zh) | 2000-10-04 |
CA2294608A1 (fr) | 1999-11-18 |
KR20010021604A (ko) | 2001-03-15 |
WO1999058539A1 (fr) | 1999-11-18 |
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