WO2003004506A1 - Non-metallocene, verfahren zur herstellung von diesen und deren verwendung zur polymerisation von olefinen - Google Patents
Non-metallocene, verfahren zur herstellung von diesen und deren verwendung zur polymerisation von olefinen Download PDFInfo
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- WO2003004506A1 WO2003004506A1 PCT/EP2002/006772 EP0206772W WO03004506A1 WO 2003004506 A1 WO2003004506 A1 WO 2003004506A1 EP 0206772 W EP0206772 W EP 0206772W WO 03004506 A1 WO03004506 A1 WO 03004506A1
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- alkylaryl
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- 238000006116 polymerization reaction Methods 0.000 title claims abstract description 20
- 150000001336 alkenes Chemical class 0.000 title claims abstract description 16
- 238000000034 method Methods 0.000 title claims description 9
- 238000004519 manufacturing process Methods 0.000 title description 3
- 239000003054 catalyst Substances 0.000 claims abstract description 38
- 229910052757 nitrogen Inorganic materials 0.000 claims description 57
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 46
- -1 C 2 -C 2 o-alkenyl Chemical group 0.000 claims description 41
- 125000000217 alkyl group Chemical group 0.000 claims description 41
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 33
- 125000002877 alkyl aryl group Chemical group 0.000 claims description 29
- 150000001875 compounds Chemical class 0.000 claims description 25
- 125000006736 (C6-C20) aryl group Chemical group 0.000 claims description 24
- 125000003358 C2-C20 alkenyl group Chemical group 0.000 claims description 24
- 125000006649 (C2-C20) alkynyl group Chemical group 0.000 claims description 22
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 21
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 20
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 20
- 229910052736 halogen Inorganic materials 0.000 claims description 19
- 150000002367 halogens Chemical class 0.000 claims description 19
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 18
- 125000005842 heteroatom Chemical group 0.000 claims description 18
- 125000002950 monocyclic group Chemical group 0.000 claims description 18
- 229910052760 oxygen Inorganic materials 0.000 claims description 18
- 230000000737 periodic effect Effects 0.000 claims description 18
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 18
- 125000004429 atom Chemical group 0.000 claims description 15
- 125000000304 alkynyl group Chemical group 0.000 claims description 14
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 14
- 125000002183 isoquinolinyl group Chemical group C1(=NC=CC2=CC=CC=C12)* 0.000 claims description 13
- 125000004076 pyridyl group Chemical group 0.000 claims description 13
- 125000002943 quinolinyl group Chemical group N1=C(C=CC2=CC=CC=C12)* 0.000 claims description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- 229910052698 phosphorus Inorganic materials 0.000 claims description 12
- 229910052717 sulfur Inorganic materials 0.000 claims description 12
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 12
- 229910052739 hydrogen Inorganic materials 0.000 claims description 11
- 125000001981 tert-butyldimethylsilyl group Chemical group [H]C([H])([H])[Si]([H])(C([H])([H])[H])[*]C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 11
- JUJWROOIHBZHMG-UHFFFAOYSA-N pyridine Substances C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 10
- 125000004432 carbon atom Chemical group C* 0.000 claims description 9
- 239000001257 hydrogen Substances 0.000 claims description 9
- 125000005843 halogen group Chemical group 0.000 claims description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 8
- 229910052719 titanium Inorganic materials 0.000 claims description 8
- 229910052735 hafnium Inorganic materials 0.000 claims description 7
- 229910052742 iron Inorganic materials 0.000 claims description 7
- 229910052759 nickel Inorganic materials 0.000 claims description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 6
- 229910052785 arsenic Inorganic materials 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 6
- 229910052763 palladium Inorganic materials 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 6
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 6
- 229910052711 selenium Inorganic materials 0.000 claims description 6
- 229910052714 tellurium Inorganic materials 0.000 claims description 6
- 229910052726 zirconium Inorganic materials 0.000 claims description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 5
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 5
- 239000001301 oxygen Substances 0.000 claims description 5
- 125000003837 (C1-C20) alkyl group Chemical group 0.000 claims description 4
- VEUMANXWQDHAJV-UHFFFAOYSA-N 2-[2-[(2-hydroxyphenyl)methylideneamino]ethyliminomethyl]phenol Chemical class OC1=CC=CC=C1C=NCCN=CC1=CC=CC=C1O VEUMANXWQDHAJV-UHFFFAOYSA-N 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 229910052804 chromium Inorganic materials 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 4
- 229910052748 manganese Inorganic materials 0.000 claims description 4
- 229910052703 rhodium Inorganic materials 0.000 claims description 4
- 229910052707 ruthenium Inorganic materials 0.000 claims description 4
- 229910052706 scandium Inorganic materials 0.000 claims description 4
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims description 4
- 229910052727 yttrium Inorganic materials 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- 125000004122 cyclic group Chemical group 0.000 claims description 3
- 229910052746 lanthanum Inorganic materials 0.000 claims description 3
- 229910052750 molybdenum Inorganic materials 0.000 claims description 3
- 229910052720 vanadium Inorganic materials 0.000 claims description 3
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 claims description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 claims description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052794 bromium Inorganic materials 0.000 claims description 2
- 239000000460 chlorine Substances 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- 229910052731 fluorine Inorganic materials 0.000 claims description 2
- 239000011737 fluorine Substances 0.000 claims description 2
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 claims description 2
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 claims description 2
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims description 2
- 150000003222 pyridines Chemical class 0.000 claims description 2
- 125000001889 triflyl group Chemical group FC(F)(F)S(*)(=O)=O 0.000 claims description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 2
- 125000003367 polycyclic group Chemical group 0.000 claims 2
- 150000003623 transition metal compounds Chemical class 0.000 abstract description 20
- 239000002904 solvent Substances 0.000 description 46
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 42
- 150000003254 radicals Chemical class 0.000 description 31
- 239000000243 solution Substances 0.000 description 29
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 28
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 24
- 125000003118 aryl group Chemical group 0.000 description 20
- 239000000047 product Substances 0.000 description 19
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 18
- 239000000203 mixture Substances 0.000 description 18
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 15
- 238000001914 filtration Methods 0.000 description 14
- 239000007787 solid Substances 0.000 description 13
- 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 12
- QQONPFPTGQHPMA-UHFFFAOYSA-N Propene Chemical compound CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 11
- 125000003342 alkenyl group Chemical group 0.000 description 11
- 239000012876 carrier material Substances 0.000 description 11
- 238000003756 stirring Methods 0.000 description 11
- 229910052723 transition metal Inorganic materials 0.000 description 11
- 229910052782 aluminium Inorganic materials 0.000 description 10
- 239000000843 powder Substances 0.000 description 10
- 238000002360 preparation method Methods 0.000 description 10
- 150000003624 transition metals Chemical class 0.000 description 10
- LWNGJAHMBMVCJR-UHFFFAOYSA-N (2,3,4,5,6-pentafluorophenoxy)boronic acid Chemical compound OB(O)OC1=C(F)C(F)=C(F)C(F)=C1F LWNGJAHMBMVCJR-UHFFFAOYSA-N 0.000 description 9
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 9
- 238000001035 drying Methods 0.000 description 9
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 9
- OSCBARYHPZZEIS-UHFFFAOYSA-N phenoxyboronic acid Chemical compound OB(O)OC1=CC=CC=C1 OSCBARYHPZZEIS-UHFFFAOYSA-N 0.000 description 9
- 238000005160 1H NMR spectroscopy Methods 0.000 description 8
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 8
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 8
- 239000011148 porous material Substances 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- 229910021577 Iron(II) chloride Inorganic materials 0.000 description 6
- 229910021585 Nickel(II) bromide Inorganic materials 0.000 description 6
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- UORVGPXVDQYIDP-UHFFFAOYSA-N borane Chemical compound B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 description 6
- 238000006297 dehydration reaction Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 239000003446 ligand Substances 0.000 description 6
- 239000003921 oil Substances 0.000 description 6
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 6
- 229920000098 polyolefin Polymers 0.000 description 6
- 125000006374 C2-C10 alkenyl group Chemical group 0.000 description 5
- 239000002841 Lewis acid Substances 0.000 description 5
- 150000004645 aluminates Chemical class 0.000 description 5
- 150000002430 hydrocarbons Chemical group 0.000 description 5
- 150000007517 lewis acids Chemical class 0.000 description 5
- 239000000178 monomer Substances 0.000 description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 5
- 150000002902 organometallic compounds Chemical class 0.000 description 5
- 125000000538 pentafluorophenyl group Chemical group FC1=C(F)C(F)=C(*)C(F)=C1F 0.000 description 5
- 239000010936 titanium Substances 0.000 description 5
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 5
- IMFACGCPASFAPR-UHFFFAOYSA-O tributylazanium Chemical compound CCCC[NH+](CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-O 0.000 description 5
- 0 ***c1c(C=*=C)cccc1 Chemical compound ***c1c(C=*=C)cccc1 0.000 description 4
- GXUQLHCFCIJSFE-UHFFFAOYSA-N 2-(dipyridin-2-ylmethylideneamino)cyclohexan-1-amine Chemical compound NC1CCCCC1N=C(C1=NC=CC=C1)C1=NC=CC=C1 GXUQLHCFCIJSFE-UHFFFAOYSA-N 0.000 description 4
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 125000000041 C6-C10 aryl group Chemical group 0.000 description 4
- 239000004215 Carbon black (E152) Substances 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 4
- 150000001555 benzenes Chemical group 0.000 description 4
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- 239000000969 carrier Substances 0.000 description 4
- 230000018044 dehydration Effects 0.000 description 4
- JLTDJTHDQAWBAV-UHFFFAOYSA-O dimethyl(phenyl)azanium Chemical compound C[NH+](C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-O 0.000 description 4
- 229930195733 hydrocarbon Natural products 0.000 description 4
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 4
- 239000011777 magnesium Substances 0.000 description 4
- 229910052749 magnesium Inorganic materials 0.000 description 4
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 4
- 235000019341 magnesium sulphate Nutrition 0.000 description 4
- IPLJNQFXJUCRNH-UHFFFAOYSA-L nickel(2+);dibromide Chemical compound [Ni+2].[Br-].[Br-] IPLJNQFXJUCRNH-UHFFFAOYSA-L 0.000 description 4
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 4
- 239000012074 organic phase Substances 0.000 description 4
- OLFPYUPGPBITMH-UHFFFAOYSA-N tritylium Chemical compound C1=CC=CC=C1[C+](C=1C=CC=CC=1)C1=CC=CC=C1 OLFPYUPGPBITMH-UHFFFAOYSA-N 0.000 description 4
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 3
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 3
- IBOFVQJTBBUKMU-UHFFFAOYSA-N 4,4'-methylene-bis-(2-chloroaniline) Chemical compound C1=C(Cl)C(N)=CC=C1CC1=CC=C(N)C(Cl)=C1 IBOFVQJTBBUKMU-UHFFFAOYSA-N 0.000 description 3
- FOJJREBLHNCKQL-UHFFFAOYSA-N BBBBBCBBB Chemical compound BBBBBCBBB FOJJREBLHNCKQL-UHFFFAOYSA-N 0.000 description 3
- 125000005865 C2-C10alkynyl group Chemical group 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 229910000085 borane Inorganic materials 0.000 description 3
- 229910052796 boron Inorganic materials 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- TUTOKIOKAWTABR-UHFFFAOYSA-N dimethylalumane Chemical compound C[AlH]C TUTOKIOKAWTABR-UHFFFAOYSA-N 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 239000011261 inert gas Substances 0.000 description 3
- 229910052809 inorganic oxide Inorganic materials 0.000 description 3
- 150000008040 ionic compounds Chemical class 0.000 description 3
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 3
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- 239000013557 residual solvent Substances 0.000 description 3
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 3
- 229910000033 sodium borohydride Inorganic materials 0.000 description 3
- 239000012279 sodium borohydride Substances 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 3
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 description 3
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 3
- HTGQCLJTWPSFNL-UHFFFAOYSA-N (2-methylphenoxy)boronic acid Chemical compound CC1=CC=CC=C1OB(O)O HTGQCLJTWPSFNL-UHFFFAOYSA-N 0.000 description 2
- PRBHEGAFLDMLAL-GQCTYLIASA-N (4e)-hexa-1,4-diene Chemical compound C\C=C\CC=C PRBHEGAFLDMLAL-GQCTYLIASA-N 0.000 description 2
- KVNYFPKFSJIPBJ-UHFFFAOYSA-N 1,2-diethylbenzene Chemical compound CCC1=CC=CC=C1CC KVNYFPKFSJIPBJ-UHFFFAOYSA-N 0.000 description 2
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 2
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical group [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- RGSFGYAAUTVSQA-UHFFFAOYSA-N Cyclopentane Chemical compound C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 2
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 2
- AFBPFSWMIHJQDM-UHFFFAOYSA-N N-methylaniline Chemical compound CNC1=CC=CC=C1 AFBPFSWMIHJQDM-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 125000002091 cationic group Chemical group 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 150000004696 coordination complex Chemical class 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
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- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 1
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- 150000002576 ketones Chemical class 0.000 description 1
- 150000007527 lewis bases Chemical class 0.000 description 1
- KJJBSBKRXUVBMX-UHFFFAOYSA-N magnesium;butane Chemical compound [Mg+2].CCC[CH2-].CCC[CH2-] KJJBSBKRXUVBMX-UHFFFAOYSA-N 0.000 description 1
- QSLMQGXOMLSFAW-UHFFFAOYSA-N methanidylbenzene;zirconium(4+) Chemical compound [Zr+4].[CH2-]C1=CC=CC=C1.[CH2-]C1=CC=CC=C1.[CH2-]C1=CC=CC=C1.[CH2-]C1=CC=CC=C1 QSLMQGXOMLSFAW-UHFFFAOYSA-N 0.000 description 1
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- NEMUVWSQFWIZKP-UHFFFAOYSA-N n-methyl-n-trichlorosilylmethanamine Chemical compound CN(C)[Si](Cl)(Cl)Cl NEMUVWSQFWIZKP-UHFFFAOYSA-N 0.000 description 1
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- GNWXVOQHLPBSSR-UHFFFAOYSA-N oxolane;toluene Chemical compound C1CCOC1.CC1=CC=CC=C1 GNWXVOQHLPBSSR-UHFFFAOYSA-N 0.000 description 1
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- 229920000573 polyethylene Polymers 0.000 description 1
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- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 1
- 125000002568 propynyl group Chemical group [*]C#CC([H])([H])[H] 0.000 description 1
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- JQJOGAGLBDBMLU-UHFFFAOYSA-N pyridine-2-sulfonyl chloride Chemical compound ClS(=O)(=O)C1=CC=CC=N1 JQJOGAGLBDBMLU-UHFFFAOYSA-N 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 150000004756 silanes Chemical class 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000005049 silicon tetrachloride Substances 0.000 description 1
- 239000011877 solvent mixture Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000375 suspending agent Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
- XBFJAVXCNXDMBH-UHFFFAOYSA-N tetracyclo[6.2.1.1(3,6).0(2,7)]dodec-4-ene Chemical compound C1C(C23)C=CC1C3C1CC2CC1 XBFJAVXCNXDMBH-UHFFFAOYSA-N 0.000 description 1
- RAOIDOHSFRTOEL-UHFFFAOYSA-N tetrahydrothiophene Chemical compound C1CCSC1 RAOIDOHSFRTOEL-UHFFFAOYSA-N 0.000 description 1
- MNWRORMXBIWXCI-UHFFFAOYSA-N tetrakis(dimethylamido)titanium Chemical compound CN(C)[Ti](N(C)C)(N(C)C)N(C)C MNWRORMXBIWXCI-UHFFFAOYSA-N 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- ZMANZCXQSJIPKH-UHFFFAOYSA-O triethylammonium ion Chemical compound CC[NH+](CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-O 0.000 description 1
- LALRXNPLTWZJIJ-UHFFFAOYSA-N triethylborane Chemical compound CCB(CC)CC LALRXNPLTWZJIJ-UHFFFAOYSA-N 0.000 description 1
- RXJKFRMDXUJTEX-UHFFFAOYSA-O triethylphosphanium Chemical compound CC[PH+](CC)CC RXJKFRMDXUJTEX-UHFFFAOYSA-O 0.000 description 1
- RXJKFRMDXUJTEX-UHFFFAOYSA-N triethylphosphine Chemical compound CCP(CC)CC RXJKFRMDXUJTEX-UHFFFAOYSA-N 0.000 description 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 1
- ORYGRKHDLWYTKX-UHFFFAOYSA-N trihexylalumane Chemical compound CCCCCC[Al](CCCCCC)CCCCCC ORYGRKHDLWYTKX-UHFFFAOYSA-N 0.000 description 1
- LFXVBWRMVZPLFK-UHFFFAOYSA-N trioctylalumane Chemical compound CCCCCCCC[Al](CCCCCCCC)CCCCCCCC LFXVBWRMVZPLFK-UHFFFAOYSA-N 0.000 description 1
- MXSVLWZRHLXFKH-UHFFFAOYSA-N triphenylborane Chemical compound C1=CC=CC=C1B(C=1C=CC=CC=1)C1=CC=CC=C1 MXSVLWZRHLXFKH-UHFFFAOYSA-N 0.000 description 1
- RIOQSEWOXXDEQQ-UHFFFAOYSA-O triphenylphosphanium Chemical compound C1=CC=CC=C1[PH+](C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-O 0.000 description 1
- LKNHGIFPRLUGEG-UHFFFAOYSA-N tris(3,4,5-trifluorophenyl)borane Chemical compound FC1=C(F)C(F)=CC(B(C=2C=C(F)C(F)=C(F)C=2)C=2C=C(F)C(F)=C(F)C=2)=C1 LKNHGIFPRLUGEG-UHFFFAOYSA-N 0.000 description 1
- YPVVTWIAXFPZLS-UHFFFAOYSA-N tris(4-fluorophenyl)borane Chemical compound C1=CC(F)=CC=C1B(C=1C=CC(F)=CC=1)C1=CC=C(F)C=C1 YPVVTWIAXFPZLS-UHFFFAOYSA-N 0.000 description 1
- OSMBUUFIZBTSNO-UHFFFAOYSA-N tris[4-(fluoromethyl)phenyl]borane Chemical compound C1=CC(CF)=CC=C1B(C=1C=CC(CF)=CC=1)C1=CC=C(CF)C=C1 OSMBUUFIZBTSNO-UHFFFAOYSA-N 0.000 description 1
- 238000004018 waxing Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 229910052845 zircon Inorganic materials 0.000 description 1
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 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
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
- C07F15/04—Nickel compounds
- C07F15/045—Nickel compounds without a metal-carbon linkage
-
- 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
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
- C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group
- C07F15/006—Palladium compounds
- C07F15/0066—Palladium compounds without a metal-carbon linkage
-
- 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
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
- C07F15/02—Iron compounds
- C07F15/025—Iron compounds without a metal-carbon linkage
-
- 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
- C07F7/003—Compounds containing elements of Groups 4 or 14 of the Periodic Table without C-Metal linkages
Definitions
- Non-metallocenes processes for their preparation and their use in the polymerization of olefins
- the present invention relates to a process for the preparation of special transition metal compounds, new transition metal compounds and their use for the polymerization of olefins
- Metallocenes are used to generate polyolefins with special properties that cannot be achieved with conventional Ziegler catalysts. Metallocenes, optionally in combination with one or more cocatalysts, can be used as a catalyst component for the polymerization and copolymerization of olefins. In particular, as
- Halogen-containing metallocenes are used as catalyst precursors, which can be converted, for example, by an aluminoxane into a polymerization-active cationic metallocene complex.
- non-metallocenes are described in the literature, for example in EP 874 005, which are notable for advantages in the representability and the cost of the educts. The high activities of these complexes represent a further cost-saving factor.
- numerous compounds known from the literature such as e.g. in J. Organomet. Chem. 1999, 587, 58-66 and Organometallics 2001, 20, 408-
- Ligands with transition metal compounds provide chiral transition metal complexes that are capable of stereospecifically polymerizing propene. This type of representation represents universal access to these new types of connection. The object underlying the invention is thus achieved by these connections.
- the present invention relates to compounds of the formula I.
- M 1 is a metal of III. to XII.
- Group of the Periodic Table of the Elements in particular Sc, Y, La, Ti, Zr, Hf, V, Cr, Mo, Mn, Fe, Ru, Co, Rh, Ni, Pd or Cu and D 1 is the same or different and a donor atom of the XV and XVI.
- Group of the Periodic Table of the Elements in particular N, P, As, O, S, Se and Te and D 2 is the same or different and a donor atom of XV and XVI.
- N is a bridging structural element between the two donor atoms D 1 and X is the same or different and a hydrogen atom, a C C ⁇ o-
- Hydrocarbon group such as C ⁇ -C ⁇ o-alkyl, C 6 -C ⁇ o-aryl, C 7 -C 2 o-alkylaryl, C 7 - C 20 arylalkyl, C 2 -C 2 o-alkenyl, C 2 -C 2 o-alkynyl or a halogen atom, or OR 6 , SR 6 , OS0 2 R 6 , OSi (R 6 ) 3 , Si (R 6 ) 3 , P (R 6 ) 2 , P (R 6 ) 3 , NCR 6 , N (R 6 ) 3 , B (R 6 ) 4 , substituted or unsubstituted pyridine or N (R 6 ) 2 , and R 1 is the same or different and are a hydrogen atom, a C ⁇ -C 2 o alkyl group, a C 6 -C 2 n-aryl group, a C -C 2 o-alkylaryl group, a C
- radicals R 1 with one or more radicals R 2 can form a mono- or polycyclic ring system, such as pyridinyl, quinolinyl or isoquinolinyl , which in turn can be substituted by one or more radicals R 6 , and
- R 2 is the same or different and a hydrogen atom, a -C 20 alkyl group, a C 6 -C 20 aryl group, a C -C 20 alkylaryl group, a C -C 3 o-arylalkyl group, a C 2 -C 2 o-alkenyl group, a C 2 -C 2 r j: j alkynyl group or a halogen-containing C 1 -C 20 alkyl group, C 6 -C 2 o aryl group, C 7 -C 2 o alkylaryl group, C 7 -C 30 arylalkyl group, C 2 -C 20 alkenyl group, C 2 -C 20 -
- Alkynyl group or a heteroatom-containing CC 2 o -alkyl group, C 6 -C 20 aryl group, C 7 -C 20 alkylaryl group, C 7 -C 30 arylalkyl group, C 2 -C 20 alkenyl group, C 2 -C 20 alkynyl group or Si (R 6 ) 3 means, where one or more radicals R 2 with one or more radicals R 1 and / or R 3 is a mono- or polycyclic ring system, such as pyridinyl, quinolinyl or
- Isoquinolinyl may form which may itself be substituted by one or more radicals R 6, and R 3 are identical or different and are a hydrogen atom, a C ⁇ -C 2 o alkyl group, a C 6 -C 2 o-aryl group, a C 7 -C 20 alkylaryl group, a C 7 -C 30 - aralkyl group, a C 2 -C 20 alkenyl group, a C 2 -C 20 alkynyl group or a halogen-containing C 1 -C 20 alkyl, C 6 -C 20 - Aryl group, C 7 -C 2 o -alkylaryl group, C 7 -C 30 arylalkyl group, C 2 -C 2 o-alkenyl group, C 2 -C 20 alkynyl group or a heteroatom-containing C 1 -C 20 alkyl group, C 6 - C 20 - ar l group, C 7 -C 20 alkyla
- R 4 is the same or different and is a hydrogen atom, a C 1 -C 20 -alkyl group, a C 6 -C 2 o-aryl group, a C 7 -C 20 alkylaryl group, a C 7 -C 30 arylalkyl group, a C 2 -C 20 alkenyl group, a C 2 -C 2 o-alkynyl group or a halogen-containing -C-C 20 alkyl group, C 6 -C 20 aryl group, C -C 2 o- alkylaryl group, C -C 3 o-arylalkyl group, C 2 -C 20 alkenyl group, C 2 -C 20 -
- Alkynyl group or a heteroatom-containing C- ⁇ -C 2 o alkyl group Ce-C 2 o aryl, C 7 -C 20 -alkylaryl, C 7 -C 30 arylalkyl group, C 2 -C 20 - alkenyl or C 2 -C 20 alkynyl group, and R 5 are identical or different and are a hydrogen atom, a C ⁇ -C 2 o alkyl group, a C 6 -C 2 o-aryl group, a C 7 -C 20 alkylaryl group, a C 7 -C 30 -
- Arylalkyl group a C 2 -C 20 alkenyl group, a C 2 -C 20 alkynyl group or a halogen-containing C ⁇ -C 20 alkyl, C 6 -C 20 aryl group, C7-C 20 - alkylaryl, C 7 -C 30 - Arylalkyl group, C 2 -C 20 alkenyl group, C 2 -C 20 alkynyl group or a heteroatom-containing C 1 -C 2 rj alkyl group, C6-C20 aryl group, C 7 -C 20 alkylaryl group, C 7 -C 30 arylalkyl group, C2-C 2 0-
- D 1 -Z 1 (R 5 ) fD 1 are:
- Transition metal compounds of the formula I in which are preferred are preferred
- M 1 is a metal of III. to XII.
- Group of the Periodic Table of the Elements is, in particular Sc, Y, Ti, Zr, Hf, Cr, Mn, Fe., Ru, Co, Rh, Ni, Pd or Cu and D 1 is the same or different and a donor atom of XV. and XVI.
- Periodic table of the elements in particular N, P, O and S, and D 2 is identical or different and a donor atom of XV. and XVI.
- Group of the Periodic Table of the Elements, in particular N, P, O and S, and Z is a bridging structural element between the two donor atoms D 1 , in particular formula !!
- X is the same or different and is a C ⁇ -C ⁇ 0 -hydrocarbon group such as C-Cs alkyl, C 6 -C 10 aryl, CrCu-alkylaryl, C7-Cn aralkyl, C 2 -C ⁇ 0 - Alkenyl, C 2 -C ⁇ 0 - alkynyl or a halogen atom, or OR 6 , SR 6 , OS0 2 R 6 , OSi (R 6 ) 3 , Si (R ⁇ ) 3 , P (R 6 ) 2 , P (R 6 ) 3, NCR 6 , N (R 6 ) 3 , B (R 6 ) 4 , substituted or unsubstituted.es
- R 1 is identical or different and is a hydrogen atom, a C 10 -C 10 alkyl group, a C 6 -C 10 aryl group, a C 7 -C 8 alkylaryl group, a C -Cn- Ar lalkyl group, a C 2 -C ⁇ 0 alkenyl group, a C 2 -C ⁇ o alkynyl group or a halogen-containing C ⁇ -C ⁇ 0 alkyl group, C 6 -C 10 aryl group, C 7 -Cn-
- Arylalkyl group a C 2 -C ⁇ 0 alkenyl group, a C 2 -C 10 alkynyl group or a halogen-containing CrCio alkyl group, C 6 -C ⁇ 0 aryl group, C 7 -C ⁇ r alkylaryl group, C 7 -Cn arylalkyl group, C 2 - C 10 alkenyl group, C 2 -C 10 alkynyl group or a hetero atom-containing CrC 10 alkyl group, C 6 -C 10 aryl group, C 7 -Cn alkylaryl group, C 7 -Cn arylalkyl group, C 2 -C ⁇ o-
- Aryl group, C 7 -C ⁇ -alkylaryl, C7-Cn arylalkyl group, C 2 -C 10 - alkenyl or C 2 -C ⁇ 0 alkynyl group, and R 5 are identical or different and are a hydrogen atom, a G 1 -C 1 1 -
- Alkylaryl group C -C 30 arylalkyl group, C 2 -C 2 o-alkenyl group, C 2 -C 20 -
- Alkynyl group or a hetero atom-containing C 20 alkyl group C 6 -C 20 -
- Aryl group, C 7 -C 2 o-alkylaryl group, C 7 -C 30 arylalkyl group, C 2 -C 2 o-alkenyl group, C 2 -C 20 alkynyl group, and a are each the same or different and an integer of 1 to 4 and b are each the same or different and are an integer from 0 to 2 and c are each the same or different and are an integer from 0 to 2 and d are each the same or different and an integer from 0 to 2 and e are the same or different and are an integer from 0 to 2 and f are each the same or different and are an integer from 2 to 20 and g are each the same or different and 1 or 2 and h are each the same or are different and are an integer from 1 to 4 and i are each the same or different and are an integer from 0 to 24 and j are each the same or different and are an integer from 0 to 10,
- Periodic table of the elements, in particular N, P, O and S, and D 2 is identical or different and a donor atom of XV. and XVI.
- Periodic table of the elements is, in particular N, P, O and S, and Z corresponds to the formulas II d, II j, II o, II r or II s and X is the same or different and chloride, bromide, iodide, methyl, ethyl Propyl
- R 1 is the same or different and represents a hydrogen atom, methyl, ethyl, propyl, i-
- a radical R 1 with a radical R 2 forms a mono- or polycyclic ring system, preferably pyridinyl, quinolinyl or isoquinolinyl, which in turn is represented by one or more radicals R. 6 can be substituted, and R 2 is the same or different and represents a hydrogen atom, methyl, ethyl, propyl, i-
- a radical R 2 with a radical R 1 forms a mono- or polycyclic ring system, preferably pyridinyl, quinolinyl or isoquinolinyl, which in turn is represented by one or more radicals R. 6 can be substituted, and R 3 is the same or different and represents a hydrogen atom, methyl, ethyl, propyl, i-
- R 4 is the same or different and is a hydrogen atom, methyl, ethyl, propyl, i-
- R 5 is the same or different and is a hydrogen atom, methyl, ethyl, propyl, i-
- R 5 can form a mono- or polycyclic ring system with one another, and R s is identical or different and is a hydrogen atom, fluorine, chlorine, bromine, iodine,
- the ligands with bisimine structure can be obtained by condensing bisamines with aldehydes or ketones.
- the bisamine ligands are obtained by reducing the corresponding bisimines or by alkylating bisamines with common alkylation reagents, e.g. Arylalkyl halides, prepared with the addition of bases in a solvent.
- the reaction of bisimines with transition metal salts e.g. with iron (II) chloride, nickel (II) bromide * DME, cobalt (II) chloride or bisacetonitrile palladium dichloride in a solvent, e.g. Tetrahydrofuran or dichloromethane, provides the corresponding
- Transition metal complexes The reaction of ligands with a bisamine structure with transition metal compounds, such as, for example, tetrabenzylzircon, tetrakis (dimethylamido) zircon, tetrabenzyltitanium, tetrakis (dimethylamido) titanium, Tetrabenzylhafnium or tetrakis (dimethylamido) hafnium, in a solvent such as benzene, toluene or tetrahydrofuran provides the corresponding transition metal complexes.
- complexes of this type can be obtained by deprotonation of the bisamine ligand with a base in a solvent, such as toluene or THF, or solvent mixtures, followed by the conversion with
- Transition metal halide dides such as e.g. Zirconium tetrachloride, titanium tetrachloride, or hafnium tetrachloride can be obtained.
- the present invention also relates to a catalyst system which contains the chemical compound of the formula I according to the invention.
- the metal complexes of the formula I according to the invention are particularly suitable as a constituent of catalyst systems for the preparation of polyolefins by polymerizing at least one olefin in the presence of a catalyst which contains at least one cocatalyst and at least one metal complex of the formula I.
- the cocatalyst which, together with a transition metal complex of the formula I according to the invention, forms the catalyst system, contains at least one compound of the type of an aluminoxane or a Lewis acid or an ionic compound which, by reaction with a metal complex, converts the latter into a cationic compound.
- a compound of the general formula (III) is preferred as the aluminoxane
- aluminoxanes can e.g. cyclic as in formula (IV)
- the radicals R in the formulas (III), (IV), (V) and (VI) can be the same or different and a Ci ⁇ rj hydrocarbon group such as a C-
- the radicals R are preferably the same and are methyl, isobutyl, n-butyl, phenyl or benzyl, particularly preferably methyl.
- radicals R are different, they are preferably methyl and hydrogen, methyl and isobutyl or methyl and n-butyl, where hydrogen or isobutyl or n-
- Butyl preferably 0.01 to 40% (number of radicals R) are contained.
- the aluminoxane can be prepared in various ways by known methods.
- One of the methods is, for example, that an aluminum hydrocarbon compound and / or a hydridoaluminium hydrocarbon compound with water (gaseous, solid, liquid or bound - for example as water of crystallization) in an inert solvent (such as toluene).
- the C j ⁇ n-carbonaceous groups such as branched or unbranched alkyl or haloalkyl, such as methyl, propyl, isopropyl, isobutyl or trifluoromethyl, unsaturated groups, such as aryl or haloaryl such as phenyl, tolyl, benzyl groups, p-fluorophenyl, 3,5-difluorophenyl, pentachlorophenyl, pentafluorophenyl, 3,4,5 trifluorophenyl and 3,5 di (trifluoromethyl) phenyl.
- the C j ⁇ n-carbonaceous groups such as branched or unbranched alkyl or haloalkyl, such as methyl, propyl, isopropyl, isobutyl or trifluoromethyl
- unsaturated groups such as aryl or haloaryl such as phenyl, tolyl, benzyl groups, p
- Lewis acids are trimethyl aluminum, triethyl aluminum,
- Compounds which contain a non-coordinating anion such as, for example, tetrakis (pentafluorophenyl) borates, tetraphenylborates, SbF 6 ⁇ , CF3SO3- or CIO4-, are preferably used as ionic cocatalysts.
- Protonated Lewis bases such as methylamine, aniline, N, N-dimethylbenzylamine and derivatives, N, N-dimethylcyclohexylamine and derivatives, dimethylamine, diethylamine, N-methylaniline, diphenylamine, N, N- are used as cationic counterions.
- Trimethylammonium tetra (tolyl) borate Trimethylammonium tetra (tolyl) borate, tributylammonium tetra (tolyl) borate,
- Triphenylcarbenium tetrakis (phenyl) aluminate Triphenylcarbenium tetrakis (phenyl) aluminate
- Ferrocenium (pentafluorophenyl) aluminate
- Mixtures of at least one Lewis acid and at least one ionic compound can also be used.
- Borane or carborane compounds such as e.g.
- Combinations of at least one of the amines mentioned above and a support with organic compounds as described in patent WO 99/40129 are also important as cocatalyst systems.
- P 7 is a hydrogen atom, a halogen atom, a C- ⁇ -C o-koh! Enstoffha! Tige
- R 17 can also be a -OSiR 18 3 group, in which R 18 are identical or different and have the same meaning as R 17 .
- cocatalysts are generally compounds which are formed by the reaction of at least one compound of the formula (C) and / or (D) and / or (E) with at least one compound of the formula (F).
- R 80 is a hydrogen atom or a boron-free C ⁇ -C 40 -group such as C ⁇ -C 20 alkyl, C 6 -C 20 aryl, C 7 -C 40 -Arylalky, C -C 40 -alkylaryl may be, and wherein
- R1 has the same meaning as above,
- X 1 is an element of VI.
- Main group of the Periodic Table of the Elements or an NR group in which R is a hydrogen atom or a C 1 -C 2 -hydrocarbon radical such as C 1 -C 20 alkyl or C 1 -C 20 aryl, D is an element of VI.
- Main group of the Periodic Table of the Elements or an NR group in which R is a hydrogen atom or a CrC 2 o hydrocarbon radical such as -CC 20 alkyl or C 1 -C 20 aryl, v is an integer from 0 to 3, s is a is an integer from 0 to 3, h is an integer from 1 to 10,
- B is boron
- AI is aluminum.
- the elemental organic compounds are combined with an organometallic compound of the formula III to V and or VII [M ⁇ 0R ⁇ , where M ⁇ 0 is an element of I., II. And III. Main group of the Periodic Table of the Elements is, R19 is the same or different and is a hydrogen atom, a halogen atom, a C-
- Examples of the cocatalytically active compounds of the formulas A and B are H 3 OC-
- the organometallic compounds of the formula VII are preferably neutral Lewis acids in which M ⁇ O is lithium, magnesium and / or aluminum, in particular aluminum.
- Examples of the preferred organometallic compounds of the formula XII are trimethylaluminium, triethylaluminium, triisopropylaluminum, trihexylaluminium, trioctylaluminium, tri-n-butylaluminium, trin-propylaluminium, triisoprenaluminium, dimethylaluminium monochloride, diethylaluminiumaluminiumchloromethylaluminium chloride, diethylaluminiumaluminium chloride, , Dimethylaluminiumhydrid, Diethylaluminiumhydrid, Diisopropylaluminiumhydrid, Dimethylaluminium (trimethylsiloxid), Dimethylaluminium (triethylsiloxid), Phenylalan, Pentafluorphen
- the carrier component of the catalyst system according to the invention can be any organic or inorganic, inert solid, in particular a porous carrier such as talc, inorganic oxides and finely divided polymer powders (e.g.
- Suitable inorganic oxides can be found in the II-VI main group of the periodic table and the III-IV sub-group in the periodic table of the elements.
- oxides preferred as carriers include silicon dioxide, aluminum oxide, and mixed oxides of the elements calcium, aluminum, silicon, magnesium, titanium and corresponding oxide mixtures, and hydrotalcites.
- Other inorganic oxides that can be used alone or in combination with the last-mentioned preferred oxide carriers are, for example, MgO, ZrO 2 , Ti0 2 or B 2 0 3 , to name just a few.
- the carrier materials used have a specific surface area in the range from 10 to 1000 m 2 / g, a pore volume in the range from 0.1 to 5 ml / g and an average particle size from 1 to 500 ⁇ m. Carriers with a specific surface area in the range from 50 to 500 ⁇ m, a pore volume in the range between 0.5 and 3.5 ml / g and an average particle size in the range from 5 to 350 ⁇ m are preferred. Carriers with a specific surface area in the range from 200 to 400 m 2 / g, a pore volume in the range between 0.8 to 3.0 ml / g and an average particle size of 10 to 200 ⁇ m are particularly preferred.
- the carrier material used has a naturally low moisture content or residual solvent content, dehydration or drying can be avoided before use. If this is not the case, as with the use of silica gel as a carrier material, dehydration or drying is recommended.
- the thermal dehydration or drying of the carrier material can be carried out under vacuum and at the same time with an inert gas blanket (eg nitrogen). The drying temperature is between 100 and
- the pressure parameter is not critical.
- the drying process can take between 1 and 24 hours. Shorter or longer drying times are possible, provided that under the chosen conditions the equilibrium can be established with the hydroxyl groups on the support surface, which normally requires between 4 and 8 hours.
- Suitable inerting agents are, for example, silicon halides and silanes, such as silicon tetrachloride, chlorotrimethylsilane, dimethylaminotrichlorosilane, or organometallic compounds of aluminum, boron and magnesium, such as trimethyl aluminum, triethyl aluminum, triisobutyl aluminum, triethyl borane and dibutyl magnesium.
- the chemical dehydration or inertization of the carrier material takes place, for example, by suspending the carrier material in a suitable manner with the exclusion of air and moisture Solvent with the inerting reagent in pure form or dissolved in a suitable solvent to react.
- suitable solvents are, for example, aliphatic or aromatic hydrocarbons such as pentane, hexane, heptane, toluene or xylene.
- the inerting takes place at temperatures between 25 ° C and 120 ° C, preferably between 50 and 70 ° C. Higher and lower temperatures are possible.
- the duration of the reaction is between 30 minutes and 20 hours, preferably 1 to 5 hours.
- the support material is isolated by filtration under inert conditions, washed one or more times with suitable inert solvents as described above and then in an inert gas stream or on
- Organic carrier materials such as finely divided polyolefin powders (e.g. polyethylene, polypropylene or polystyrene) can also be used and should also be freed of adhering moisture, solvent residues or other contaminants by appropriate cleaning and drying operations before use.
- polyolefin powders e.g. polyethylene, polypropylene or polystyrene
- At least one of the transition metal compounds of the formula I described above is brought into contact with at least one cocatalyst component in a suitable solvent, a soluble reaction product, an adduct or a mixture preferably being obtained.
- the preparation so obtained is then mixed with the dehydrated or rendered inert support material, the solvent removed and the resulting supported transition metal compound catalyst system dried to ensure that all or most of the solvent is removed from the pores of the support material.
- the supported catalyst is obtained as a free flowing powder.
- a process for the preparation of a free-flowing and optionally prepolymerized transition metal compound catalyst system comprises the following steps: a) preparation of a transition metal compound / cocatalyst mixture in a suitable solvent or suspension medium, the transition metal compound component having one of the structures described above, b) application of the Transition metal compound / cocatalyst mixture on a porous, preferably inorganic, dehydrated support c) removing the majority of the solvent from the resulting mixture d) isolating the supported catalyst system e) optionally prepolymerizing the resulting supported catalyst system with one or more olefinic monomer (s) to obtain a prepolymerized supported catalyst system.
- Preferred solvents for the preparation of the transition metal compound / cocatalyst mixture are hydrocarbons and hydrocarbon mixtures which are liquid at the selected reaction temperature and in which the individual components preferably dissolve.
- the solubility of the individual components is not a prerequisite if it is ensured that the reaction product of transition metal compound and cocatalyst components is soluble in the solvent selected.
- suitable solvents include alkanes such as pentane, isopentane, hexane, heptane, octane, and nonane; Cycloalkanes such as cyclopentane and cyclohexane; and aromatics such as benzene, toluene. Ethylbenzene and diethylbenzene.
- Toluene is very particularly preferred.
- the amounts of aluminoxane and transition metal compound used in the preparation of the supported catalyst system can be varied over a wide range.
- a molar ratio of aluminum to the transition metal in the transition metal compounds of 10: 1 to 1000: 1 is preferably set, very particularly preferably a ratio of 50: 1 to 500: 1.
- 30% toluene solutions are preferably used; the use of 10% solutions is also possible.
- the transition metal compound is dissolved in the form of a solid in a solution of the aluminoxane in a suitable solvent. It is also possible to dissolve the transition metal compound separately in a suitable solvent and then to combine this solution with the aluminoxane solution. Toluene is preferably used.
- the preactivation time is 1 minute to 200 hours.
- the preactivation can take place at room temperature (25 ° C). In individual cases, the use of higher temperatures can shorten the time required for preactivation and cause an additional increase in activity. In this case, a higher temperature means a range between 50 and 100 ° C.
- the preactivated solution or the transition metal compound / cocatalyst mixture is then combined with an inert support material, usually silica gel, which is in the form of a dry powder or as a suspension in one of the abovementioned solvents.
- the carrier material is preferably used as a powder. The order of addition is arbitrary.
- Transition metal compound-cocatalyst solution or the transition metal compound-cocatalyst mixture can be metered into the support material provided, or the support material can be introduced into the solution presented.
- Cocatalyst mixture can 100% of the total pore volume of the used
- Contact can vary between 0 and 100 ° C. However, lower or higher temperatures are also possible.
- the solvent is then completely or largely removed from the supported catalyst system, and the mixture can be stirred and optionally also heated. Both the visible portion of the solvent and the portion in the pores of the carrier material are preferably removed.
- the solvent can be removed in a conventional manner using vacuum and / or purging with inert gas. During the drying process, the mixture can be heated until the free solvent has been removed, which usually requires 1 to 3 hours at a preferably selected temperature between 30 and 60 ° C.
- the free solvent is the visible proportion of solvent in the mixture. Residual solvent is the proportion that is enclosed in the pores.
- the supported catalyst system can also be dried only to a certain residual solvent content, the free solvent having been removed completely.
- the supported catalyst system can then be washed with a low-boiling hydrocarbon such as pentane or hexane and dried again.
- a low-boiling hydrocarbon such as pentane or hexane
- the supported catalyst system shown according to the invention can either be used directly for the polymerization of olefins or prepolymerized with one or more olefinic monomers before it is used in a polymerization process.
- the prepolymerization of supported catalyst systems is described, for example, in WO 94/28034.
- an olefin preferably an olefin (for example vinylcyclohexane, styrene or phenyldimethylvinylsilane) can be added as a modifying component or an antistatic (as described in US Serial No. 08/365280) during or after the preparation of the supported catalyst system.
- an olefin for example vinylcyclohexane, styrene or phenyldimethylvinylsilane
- an antistatic as described in US Serial No. 08/365280
- Metallocene component compound I is preferably between 1: 1000 to 1000: 1, very particularly preferably 1:20 to 20: 1.
- the present invention also relates to a process for the preparation of a polyolefin by polymerization of one or more olefins in the presence of the catalyst system according to the invention, comprising at least one transition metal component of the formula VII.
- polymerization is understood to mean homopolymerization and also copolymerization.
- Examples of such olefins are 1-olefins with 2 - 20, preferably 2 to 10 C -
- Atoms such as ethene, propene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene or 1-octene, styrene, dienes such as 1, 3-butadiene, 1, 4-hexadiene, vinyl norbornene, norbornadiene , Ethyl norbornadiene and cyclic olefins such as norbornene, tetracyclododecene or methyl norbornene.
- Ethene or propene are preferably homopolymerized in the process according to the invention, or propene with ethene and / or with one or more 1-olefins having 4 to 20 carbon atoms, such as butene, hexene, styrene or vinylcyclohexane, and / or one or more dienes 4 to 20 carbon atoms, such as 1, 4-butadiene, norbomadiene, ethylidene norbones or ethyl norbornadiene, copolymerized.
- 1-olefins having 4 to 20 carbon atoms, such as butene, hexene, styrene or vinylcyclohexane
- dienes 4 to 20 carbon atoms such as 1, 4-butadiene, norbomadiene, ethylidene norbones or ethyl norbornadiene, copolymerized.
- copolymers examples include ethene / propene copolymers, ethene / norbornene, ethene / styrene or ethene / propene / 1,4-hexadiene terpolymers.
- the polymerization is carried out at a temperature of 0 to 300 ° C., preferably 50 to 200 ° C., very particularly preferably 50 to 80 ° C.
- the pressure is 0.5 to 2000 bar, preferably 5 to 64 bar.
- the polymerization can be carried out in solution, in bulk, in suspension or in the gas phase, continuously or batchwise, in one or more stages.
- the catalyst system shown according to the invention can be used as the only catalyst component for the polymerization of olefins having 2 to 20 carbon atoms, or preferably in combination with at least one
- Alkyl compound of the elements from I. to III. Main group of the periodic table, e.g. an aluminum, magnesium or lithium alkyl or an aluminoxane can be used.
- the alkyl compound is added to the monomer or suspending agent and is used to purify the monomer from substances which can impair the catalyst activity. The amount of the alkyl compound added depends on the quality of the monomers used. If necessary, hydrogen is added as a molecular weight regulator and / or to increase the activity.
- the catalyst system can be fed to the polymerization system neat or for better dosing with inert components such as paraffins, oils or
- an antistatic can also be metered into the polymerization system together with or separately from the catalyst system used.
- the polymers represented by the catalyst system according to the invention have a uniform grain morphology and have no fine grain proportions.
- Polymerization with the catalyst system according to the invention does not result in deposits or caking.
- Reaction mixture refluxed for one hour. After cooling 30 ml of water are added to room temperature and the product is extracted with 3 ⁇ 100 ml of dichloromethane. The combined organic phases are dried over magnesium sulfate and that
- Phases are dried over magnesium sulfate, and the solvent is in
- a solution of 3.30 g (5.0 mmol) of fraA7s-N, N'-bis- (2-diphenylphosphanyl-benzylidene) -cyclohexane-1,2-diamine in 60 ml of methanol is mixed with 1.14 g (30 mmol) of sodium borohydride in portions.
- the solution is refluxed for 24 h and after cooling to room temperature with 20 ml of water are added.
- the organic phase is extracted 3 times with 50 ml of dichloromethane and the combined organic phases are extracted 2 times with 30 ml of 10% ammonium chloride.
- Example 12 (N'-P dimethylamino-methylenaminoJ-II 'jbinaphthalenyl ⁇ -yl] - N, N-dimethyl-formamidino) palladium (II) chloride
- Example 17 (N 2 , N 2 '-Bis-dimethylaminomethyl- [1,1 , ] binaphthalenyl-2,2'-diamido) -dibenzylzircon
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- Chemical & Material Sciences (AREA)
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- Pyridine Compounds (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
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Claims
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JP2003510673A JP2004533487A (ja) | 2001-06-22 | 2002-06-19 | 非メタロセン類、それらの製造方法およびそれらのオレフィン類の重合のための使用 |
US10/481,440 US7148174B2 (en) | 2001-06-22 | 2002-06-19 | Non-metallocene catalyst system |
EP02751045A EP1401848A1 (de) | 2001-06-22 | 2002-06-19 | Non-metallocene, deren herstellung und verwendung zur polymerisation von olefinen |
US11/326,863 US20060135352A1 (en) | 2001-06-22 | 2006-01-06 | Process for polymerizing olefins with non-metallocene catalysts |
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DE10130229A DE10130229A1 (de) | 2001-06-22 | 2001-06-22 | Non-Metallocene, Verfahren zur Herstellung von diesen und deren Verwendung zur Polymerisation von Olefinen |
DE10130229.0 | 2001-06-22 |
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EP (1) | EP1401848A1 (de) |
JP (1) | JP2004533487A (de) |
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Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2003076481A1 (en) * | 2002-03-04 | 2003-09-18 | Equistar Chemicals, Lp | Late transition metal polymerization catalysts |
EP1982975A1 (de) * | 2007-04-17 | 2008-10-22 | Total Petrochemicals Research Feluy | Polymerisation von Ethylen und Alpha-Olefinen mit Katalysatorsystemen auf Basis von BINAM-abgeleiteten Liganden |
Families Citing this family (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US7304172B2 (en) * | 2004-10-08 | 2007-12-04 | Cornell Research Foundation, Inc. | Polycarbonates made using highly selective catalysts |
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KR101205474B1 (ko) | 2008-10-01 | 2012-11-27 | 주식회사 엘지화학 | 금속 화합물 및 이를 이용한 올레핀 중합체의 제조방법 |
US8673998B2 (en) | 2010-09-22 | 2014-03-18 | Bridgestone Corporation | Polymer compositions with improved cold flow |
WO2012139994A1 (de) | 2011-04-13 | 2012-10-18 | Basf Se | Verfahren zur kupplung von epoxiden und kohlendioxid |
CN102952021B (zh) * | 2011-08-31 | 2014-04-16 | 云南大学 | 一种3,4-二甲基苯胺的合成方法 |
CN105143281B (zh) * | 2013-03-15 | 2018-06-01 | 尤尼威蒂恩技术有限责任公司 | 用于烯烃聚合催化剂的三齿氮类配体 |
BR112018068879B1 (pt) * | 2016-03-31 | 2022-11-16 | Dow Global Technologies Llc | Sistema catalisador de polimerização de olefina e polímero à base de olefina |
US10919995B2 (en) * | 2016-03-31 | 2021-02-16 | Dow Global Technologies Llc | Olefin polymerization catalyst systems and methods of use thereof |
ES2848316T3 (es) * | 2016-09-30 | 2021-08-06 | Dow Global Technologies Llc | Catalizadores de metales de transición del grupo IV y tioguanidina, y sistemas de polimerización |
WO2018063799A1 (en) * | 2016-09-30 | 2018-04-05 | Dow Global Technologies Llc | Thiourea group iv transition metal catalysts and polymerization systems |
CN108359035B (zh) * | 2017-01-26 | 2020-07-24 | 中国石油化工股份有限公司 | 一种乙烯与端烯基硅烷/硅氧烷的共聚方法 |
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Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0874005A1 (de) * | 1997-04-25 | 1998-10-28 | Mitsui Chemicals, Inc. | Olefinpolymerisationskatalysatoren, Übergangsmetallverbindungen, Verfahren zur Polymerisation von Olefinen, und alpha-olefin/conjugiertes Dien Copolymeren |
Family Cites Families (25)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4465630A (en) * | 1981-08-24 | 1984-08-14 | Asahi Kasei Kogyo Kabushiki Kaisha | Tetraazaannulene cobalt complex compounds and method for preparation therefor |
ES2144461T3 (es) * | 1990-05-02 | 2000-06-16 | Grace W R & Co | Composiciones polimeras que contienen compuestos captadores de oxigeno. |
US5200539A (en) * | 1990-08-27 | 1993-04-06 | Louisiana State University Board Of Supervisors, A Governing Body Of Louisiana State University Agricultural And Mechanical College | Homogeneous bimetallic hydroformylation catalysts, and processes utilizing these catalysts for conducting hydroformylation reactions |
US5449650A (en) | 1992-12-08 | 1995-09-12 | Mitsubishi Petrochemical Company Limited | Catalyst components for polymerization of olefins and use thereof |
KR100314971B1 (ko) | 1993-05-25 | 2002-07-03 | 엑손모빌 케미칼 패턴츠 인코포레이티드 | 올레핀중합을위한지지된메탈로센촉매시스템,그의제조방법및용도 |
US6211107B1 (en) * | 1994-02-04 | 2001-04-03 | Smithkline Beecham P.L.C. | Process for expoxidizing prochiral olefins and a catalyst therefor and intermediates for making the catalyst |
US6271164B1 (en) * | 1995-09-28 | 2001-08-07 | Cornelia Fritze | Supported catalyst system, process for its production and its use in polymerizing olefins |
DE19606167A1 (de) * | 1996-02-20 | 1997-08-21 | Basf Ag | Geträgerte Katalysatorsysteme |
DE19622207A1 (de) | 1996-06-03 | 1997-12-04 | Hoechst Ag | Chemische Verbindung |
EP0824112B1 (de) | 1996-08-13 | 2006-05-10 | Basell Polyolefine GmbH | Geträgerte chemische Verbindung |
ES2160289T3 (es) | 1996-08-13 | 2001-11-01 | Basell Polyolefine Gmbh | Sistema catalizador soportado, un procedimiento para su obtencion y su empleo para la polimerizacion de olefinas. |
US5744620A (en) * | 1997-07-10 | 1998-04-28 | Bayer Corporation | Catalytic oxidation of cyclic olefins |
US5981424A (en) * | 1997-07-31 | 1999-11-09 | Sunoco, Inc. (R&M) | Catalysts for hydroxylation and ammination of aromatics using molecular oxygen as the terminal oxidant without coreductant |
DE69823969T2 (de) | 1997-12-22 | 2005-05-12 | Mitsui Chemicals, Inc. | Katalysatorbestandteil, Katalysator und Verfahren zur Polymerisation von äthylenisch ungesättigten Monomeren |
DE19804970A1 (de) * | 1998-02-07 | 1999-08-12 | Aventis Res & Tech Gmbh & Co | Katalysatorsystem |
TW541318B (en) * | 2000-07-04 | 2003-07-11 | Mitsui Chemicals Inc | Process for producing polar olefin copolymer and polar olefin copolymer obtained thereby |
US6686490B1 (en) * | 2000-11-06 | 2004-02-03 | Ramot University Authority For Applied Research & Industrial Development Ltd. | Active non-metallocene pre-catalyst and method for tactic catalytic polymerization of alpha-olefin monomers |
KR100342659B1 (en) * | 2000-12-15 | 2002-07-04 | Rstech Co Ltd | Chiral polymer salene catalyst and process for preparing chiral compounds from racemic epoxide using the same |
JP3968076B2 (ja) * | 2001-06-27 | 2007-08-29 | アールエス テック コーポレイション | 新しいキラルサレン化合物、キラルサレン触媒及びこれを利用したラセミックエポキシ化合物からキラル化合物を製造する方法 |
US6809058B2 (en) * | 2001-08-28 | 2004-10-26 | Exxonmobil Research And Engineering Company | Multi-dentate late transition metal catalyst complexes and polymerization methods using those complexes |
US6730757B2 (en) * | 2002-03-08 | 2004-05-04 | Exxonmobil Research And Engineering Company | Sulfur-containing and sulfur-nitrogen-containing catalysts for polymerization of olefins and polar monomers |
US7091292B2 (en) * | 2002-04-24 | 2006-08-15 | Symyx Technologies, Inc. | Bridged bi-aromatic catalysts, complexes, and methods of using the same |
JP4371305B2 (ja) * | 2002-04-24 | 2009-11-25 | シミックス・ソルーションズ・インコーポレーテッド | 架橋ビス芳香族リガンド、錯体、触媒、または、重合方法およびそれにより得られるポリマー |
US6781006B2 (en) * | 2002-09-17 | 2004-08-24 | Rhodia Pharma Solutions Inc. | Active catalysts for stereoselective ring-opening reactions |
US7304172B2 (en) * | 2004-10-08 | 2007-12-04 | Cornell Research Foundation, Inc. | Polycarbonates made using highly selective catalysts |
-
2001
- 2001-06-22 DE DE10130229A patent/DE10130229A1/de not_active Withdrawn
-
2002
- 2002-06-19 JP JP2003510673A patent/JP2004533487A/ja active Pending
- 2002-06-19 EP EP02751045A patent/EP1401848A1/de not_active Withdrawn
- 2002-06-19 US US10/481,440 patent/US7148174B2/en not_active Expired - Lifetime
- 2002-06-19 WO PCT/EP2002/006772 patent/WO2003004506A1/de not_active Application Discontinuation
- 2002-06-19 CN CNB028125770A patent/CN100432084C/zh not_active Expired - Lifetime
-
2006
- 2006-01-06 US US11/326,863 patent/US20060135352A1/en not_active Abandoned
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0874005A1 (de) * | 1997-04-25 | 1998-10-28 | Mitsui Chemicals, Inc. | Olefinpolymerisationskatalysatoren, Übergangsmetallverbindungen, Verfahren zur Polymerisation von Olefinen, und alpha-olefin/conjugiertes Dien Copolymeren |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2003076481A1 (en) * | 2002-03-04 | 2003-09-18 | Equistar Chemicals, Lp | Late transition metal polymerization catalysts |
EP1982975A1 (de) * | 2007-04-17 | 2008-10-22 | Total Petrochemicals Research Feluy | Polymerisation von Ethylen und Alpha-Olefinen mit Katalysatorsystemen auf Basis von BINAM-abgeleiteten Liganden |
WO2008125548A1 (en) * | 2007-04-17 | 2008-10-23 | Total Petrochemicals Research Feluy | Polymerisation of ethylene and alpha-olefins with catalyst systems based on binam derived ligands |
US8420756B2 (en) | 2007-04-17 | 2013-04-16 | Total Petrochemicals Research Feluy | Polymerisation of ethylene and alpha-olefins with catalyst systems based on binam derived ligands |
Also Published As
Publication number | Publication date |
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JP2004533487A (ja) | 2004-11-04 |
US7148174B2 (en) | 2006-12-12 |
US20060135352A1 (en) | 2006-06-22 |
US20050037918A1 (en) | 2005-02-17 |
CN100432084C (zh) | 2008-11-12 |
DE10130229A1 (de) | 2003-01-02 |
EP1401848A1 (de) | 2004-03-31 |
CN1518556A (zh) | 2004-08-04 |
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