WO2011119116A1 - Self-assembled multi-nuclear catalyst for olefin polymerization - Google Patents
Self-assembled multi-nuclear catalyst for olefin polymerization Download PDFInfo
- Publication number
- WO2011119116A1 WO2011119116A1 PCT/SG2011/000123 SG2011000123W WO2011119116A1 WO 2011119116 A1 WO2011119116 A1 WO 2011119116A1 SG 2011000123 W SG2011000123 W SG 2011000123W WO 2011119116 A1 WO2011119116 A1 WO 2011119116A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- group
- optionally substituted
- self
- olefin polymerization
- polymerization catalyst
- Prior art date
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- 150000001336 alkenes Chemical class 0.000 title claims abstract description 85
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 title claims abstract description 66
- 239000003054 catalyst Substances 0.000 title claims description 199
- 238000006116 polymerization reaction Methods 0.000 title claims description 32
- 239000003446 ligand Substances 0.000 claims abstract description 100
- 239000002685 polymerization catalyst Substances 0.000 claims abstract description 64
- 150000003624 transition metals Chemical class 0.000 claims abstract description 42
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 39
- 125000006736 (C6-C20) aryl group Chemical group 0.000 claims abstract description 21
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 21
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 18
- 150000002367 halogens Chemical class 0.000 claims abstract description 18
- 230000000737 periodic effect Effects 0.000 claims abstract description 9
- 125000003837 (C1-C20) alkyl group Chemical group 0.000 claims abstract description 7
- -1 organo aluminum Chemical compound 0.000 claims description 76
- 238000000034 method Methods 0.000 claims description 47
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 claims description 37
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 37
- 239000005977 Ethylene Substances 0.000 claims description 37
- 229910052751 metal Inorganic materials 0.000 claims description 37
- 239000002184 metal Substances 0.000 claims description 37
- 239000000203 mixture Substances 0.000 claims description 33
- 230000008569 process Effects 0.000 claims description 32
- 239000002253 acid Substances 0.000 claims description 28
- 125000004432 carbon atom Chemical group C* 0.000 claims description 23
- 150000002430 hydrocarbons Chemical class 0.000 claims description 22
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 20
- 229910052719 titanium Inorganic materials 0.000 claims description 18
- 125000003118 aryl group Chemical group 0.000 claims description 17
- 229920000098 polyolefin Polymers 0.000 claims description 17
- 239000007787 solid Substances 0.000 claims description 17
- 125000006850 spacer group Chemical group 0.000 claims description 17
- 150000003839 salts Chemical class 0.000 claims description 15
- 229910052721 tungsten Inorganic materials 0.000 claims description 15
- 229910052726 zirconium Inorganic materials 0.000 claims description 15
- 238000007334 copolymerization reaction Methods 0.000 claims description 14
- 229910052727 yttrium Inorganic materials 0.000 claims description 14
- 229930195733 hydrocarbon Natural products 0.000 claims description 13
- 229910052757 nitrogen Inorganic materials 0.000 claims description 13
- 239000004215 Carbon black (E152) Substances 0.000 claims description 12
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 12
- 150000001993 dienes Chemical class 0.000 claims description 12
- 125000003358 C2-C20 alkenyl group Chemical group 0.000 claims description 11
- 125000005234 alkyl aluminium group Chemical group 0.000 claims description 11
- 125000000217 alkyl group Chemical group 0.000 claims description 11
- 239000003426 co-catalyst Substances 0.000 claims description 10
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 10
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical compound C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 claims description 10
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 10
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 10
- 150000002902 organometallic compounds Chemical class 0.000 claims description 9
- 239000000377 silicon dioxide Substances 0.000 claims description 9
- 125000006738 (C6-C20) heteroaryl group Chemical group 0.000 claims description 8
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- 229910052731 fluorine Inorganic materials 0.000 claims description 8
- 150000008040 ionic compounds Chemical class 0.000 claims description 8
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 6
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 6
- 229910010272 inorganic material Inorganic materials 0.000 claims description 6
- 229910052758 niobium Inorganic materials 0.000 claims description 6
- 229910052720 vanadium Inorganic materials 0.000 claims description 6
- 229910052769 Ytterbium Inorganic materials 0.000 claims description 5
- 150000007513 acids Chemical class 0.000 claims description 5
- 229910052735 hafnium Inorganic materials 0.000 claims description 5
- 125000001072 heteroaryl group Chemical group 0.000 claims description 5
- 229910052698 phosphorus Inorganic materials 0.000 claims description 5
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 4
- 125000002723 alicyclic group Chemical group 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 4
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 4
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 4
- 229910052725 zinc Inorganic materials 0.000 claims description 4
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical group [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims description 3
- 229910052794 bromium Inorganic materials 0.000 claims description 3
- 150000001925 cycloalkenes Chemical class 0.000 claims description 3
- 125000002534 ethynyl group Chemical class [H]C#C* 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 3
- 229910052750 molybdenum Inorganic materials 0.000 claims description 3
- 230000007935 neutral effect Effects 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 125000002524 organometallic group Chemical group 0.000 claims description 3
- 229910052763 palladium Inorganic materials 0.000 claims description 3
- 125000004437 phosphorous atom Chemical group 0.000 claims description 3
- 229910052703 rhodium Inorganic materials 0.000 claims description 3
- 229910052706 scandium Inorganic materials 0.000 claims description 3
- 229910052711 selenium Inorganic materials 0.000 claims description 3
- 125000000304 alkynyl group Chemical group 0.000 claims description 2
- 229910052804 chromium Inorganic materials 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 239000010949 copper Substances 0.000 claims description 2
- 125000002147 dimethylamino group Chemical group [H]C([H])([H])N(*)C([H])([H])[H] 0.000 claims description 2
- 229910052740 iodine Inorganic materials 0.000 claims description 2
- 229910052741 iridium Inorganic materials 0.000 claims description 2
- 229910052746 lanthanum Inorganic materials 0.000 claims description 2
- 229910052748 manganese Inorganic materials 0.000 claims description 2
- HZVOZRGWRWCICA-UHFFFAOYSA-N methanediyl Chemical compound [CH2] HZVOZRGWRWCICA-UHFFFAOYSA-N 0.000 claims description 2
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims description 2
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- 229910052713 technetium Inorganic materials 0.000 claims description 2
- 239000011147 inorganic material Substances 0.000 claims 2
- 239000002638 heterogeneous catalyst Substances 0.000 claims 1
- 239000002815 homogeneous catalyst Substances 0.000 claims 1
- 239000011368 organic material Substances 0.000 claims 1
- 125000003860 C1-C20 alkoxy group Chemical group 0.000 abstract description 2
- 239000010936 titanium Substances 0.000 description 69
- 150000001875 compounds Chemical class 0.000 description 53
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- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 45
- 125000004429 atom Chemical group 0.000 description 36
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 36
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 30
- 239000000243 solution Substances 0.000 description 30
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 28
- 239000004698 Polyethylene Substances 0.000 description 28
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 27
- 229920000573 polyethylene Polymers 0.000 description 27
- 230000000694 effects Effects 0.000 description 26
- 238000002360 preparation method Methods 0.000 description 25
- 239000000460 chlorine Substances 0.000 description 20
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 18
- 229910052796 boron Inorganic materials 0.000 description 18
- 229920000642 polymer Polymers 0.000 description 18
- 239000013557 residual solvent Substances 0.000 description 17
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 15
- 238000006243 chemical reaction Methods 0.000 description 15
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 14
- AQZWEFBJYQSQEH-UHFFFAOYSA-N 2-methyloxaluminane Chemical compound C[Al]1CCCCO1 AQZWEFBJYQSQEH-UHFFFAOYSA-N 0.000 description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 12
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 11
- 239000001257 hydrogen Substances 0.000 description 11
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 10
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- 239000010955 niobium Substances 0.000 description 6
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- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 5
- ROILLNJICXGZQQ-UHFFFAOYSA-N 3-tert-butyl-2-hydroxybenzaldehyde Chemical compound CC(C)(C)C1=CC=CC(C=O)=C1O ROILLNJICXGZQQ-UHFFFAOYSA-N 0.000 description 5
- 229910010068 TiCl2 Inorganic materials 0.000 description 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 5
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 5
- 150000001299 aldehydes Chemical class 0.000 description 5
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- LWLPYZUDBNFNAH-UHFFFAOYSA-M magnesium;butane;bromide Chemical compound [Mg+2].[Br-].CCC[CH2-] LWLPYZUDBNFNAH-UHFFFAOYSA-M 0.000 description 1
- QUXHCILOWRXCEO-UHFFFAOYSA-M magnesium;butane;chloride Chemical compound [Mg+2].[Cl-].CCC[CH2-] QUXHCILOWRXCEO-UHFFFAOYSA-M 0.000 description 1
- YHNWUQFTJNJVNU-UHFFFAOYSA-N magnesium;butane;ethane Chemical compound [Mg+2].[CH2-]C.CCC[CH2-] YHNWUQFTJNJVNU-UHFFFAOYSA-N 0.000 description 1
- NXPHGHWWQRMDIA-UHFFFAOYSA-M magnesium;carbanide;bromide Chemical compound [CH3-].[Mg+2].[Br-] NXPHGHWWQRMDIA-UHFFFAOYSA-M 0.000 description 1
- CCERQOYLJJULMD-UHFFFAOYSA-M magnesium;carbanide;chloride Chemical compound [CH3-].[Mg+2].[Cl-] CCERQOYLJJULMD-UHFFFAOYSA-M 0.000 description 1
- DLPASUVGCQPFFO-UHFFFAOYSA-N magnesium;ethane Chemical compound [Mg+2].[CH2-]C.[CH2-]C DLPASUVGCQPFFO-UHFFFAOYSA-N 0.000 description 1
- FRIJBUGBVQZNTB-UHFFFAOYSA-M magnesium;ethane;bromide Chemical compound [Mg+2].[Br-].[CH2-]C FRIJBUGBVQZNTB-UHFFFAOYSA-M 0.000 description 1
- YCCXQARVHOPWFJ-UHFFFAOYSA-M magnesium;ethane;chloride Chemical compound [Mg+2].[Cl-].[CH2-]C YCCXQARVHOPWFJ-UHFFFAOYSA-M 0.000 description 1
- UGVPKMAWLOMPRS-UHFFFAOYSA-M magnesium;propane;bromide Chemical compound [Mg+2].[Br-].CC[CH2-] UGVPKMAWLOMPRS-UHFFFAOYSA-M 0.000 description 1
- RYEXTBOQKFUPOE-UHFFFAOYSA-M magnesium;propane;chloride Chemical compound [Mg+2].[Cl-].CC[CH2-] RYEXTBOQKFUPOE-UHFFFAOYSA-M 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- LBSANEJBGMCTBH-UHFFFAOYSA-N manganate Chemical compound [O-][Mn]([O-])(=O)=O LBSANEJBGMCTBH-UHFFFAOYSA-N 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000012968 metallocene catalyst Substances 0.000 description 1
- NEMYBHYAISOMTI-UHFFFAOYSA-N methanolate;2-methylpropylaluminum(2+) Chemical compound [O-]C.[O-]C.CC(C)C[Al+2] NEMYBHYAISOMTI-UHFFFAOYSA-N 0.000 description 1
- BQBCXNQILNPAPX-UHFFFAOYSA-N methoxy(dimethyl)alumane Chemical compound [O-]C.C[Al+]C BQBCXNQILNPAPX-UHFFFAOYSA-N 0.000 description 1
- MPHUYCIKFIKENX-UHFFFAOYSA-N methyl 2-ethenylbenzoate Chemical compound COC(=O)C1=CC=CC=C1C=C MPHUYCIKFIKENX-UHFFFAOYSA-N 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- DVSDBMFJEQPWNO-UHFFFAOYSA-N methyllithium Chemical compound C[Li] DVSDBMFJEQPWNO-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- JESXATFQYMPTNL-UHFFFAOYSA-N mono-hydroxyphenyl-ethylene Natural products OC1=CC=CC=C1C=C JESXATFQYMPTNL-UHFFFAOYSA-N 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000003136 n-heptyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 150000002790 naphthalenes Chemical class 0.000 description 1
- LKNLEKUNTUVOML-UHFFFAOYSA-L nickel(2+);sulfate;hydrate Chemical compound O.[Ni+2].[O-]S([O-])(=O)=O LKNLEKUNTUVOML-UHFFFAOYSA-L 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- 125000006574 non-aromatic ring group Chemical group 0.000 description 1
- JFNLZVQOOSMTJK-KNVOCYPGSA-N norbornene Chemical compound C1[C@@H]2CC[C@H]1C=C2 JFNLZVQOOSMTJK-KNVOCYPGSA-N 0.000 description 1
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N o-biphenylenemethane Natural products C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 description 1
- QTYUSOHYEPOHLV-UHFFFAOYSA-N octa-1,3-diene Chemical compound CCCCC=CC=C QTYUSOHYEPOHLV-UHFFFAOYSA-N 0.000 description 1
- 229940038384 octadecane Drugs 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 230000008520 organization Effects 0.000 description 1
- 150000002900 organolithium compounds Chemical class 0.000 description 1
- WCPAKWJPBJAGKN-UHFFFAOYSA-N oxadiazole Chemical compound C1=CON=N1 WCPAKWJPBJAGKN-UHFFFAOYSA-N 0.000 description 1
- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical compound C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- HFPZCAJZSCWRBC-UHFFFAOYSA-N p-cymene Chemical compound CC(C)C1=CC=C(C)C=C1 HFPZCAJZSCWRBC-UHFFFAOYSA-N 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- WXHIJDCHNDBCNY-UHFFFAOYSA-N palladium dihydride Chemical compound [PdH2] WXHIJDCHNDBCNY-UHFFFAOYSA-N 0.000 description 1
- NRNCYVBFPDDJNE-UHFFFAOYSA-N pemoline Chemical compound O1C(N)=NC(=O)C1C1=CC=CC=C1 NRNCYVBFPDDJNE-UHFFFAOYSA-N 0.000 description 1
- 229960000761 pemoline Drugs 0.000 description 1
- SLIUAWYAILUBJU-UHFFFAOYSA-N pentacene Chemical compound C1=CC=CC2=CC3=CC4=CC5=CC=CC=C5C=C4C=C3C=C21 SLIUAWYAILUBJU-UHFFFAOYSA-N 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- DHRLEVQXOMLTIM-UHFFFAOYSA-N phosphoric acid;trioxomolybdenum Chemical compound O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.OP(O)(O)=O DHRLEVQXOMLTIM-UHFFFAOYSA-N 0.000 description 1
- IYDGMDWEHDFVQI-UHFFFAOYSA-N phosphoric acid;trioxotungsten Chemical compound O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.OP(O)(O)=O IYDGMDWEHDFVQI-UHFFFAOYSA-N 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- LFSXCDWNBUNEEM-UHFFFAOYSA-N phthalazine Chemical compound C1=NN=CC2=CC=CC=C21 LFSXCDWNBUNEEM-UHFFFAOYSA-N 0.000 description 1
- 229960005235 piperonyl butoxide Drugs 0.000 description 1
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920001470 polyketone Polymers 0.000 description 1
- 230000037048 polymerization activity Effects 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Inorganic materials [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical group C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- BOQSSGDQNWEFSX-UHFFFAOYSA-N propan-2-yl 2-methylprop-2-enoate Chemical compound CC(C)OC(=O)C(C)=C BOQSSGDQNWEFSX-UHFFFAOYSA-N 0.000 description 1
- LYBIZMNPXTXVMV-UHFFFAOYSA-N propan-2-yl prop-2-enoate Chemical compound CC(C)OC(=O)C=C LYBIZMNPXTXVMV-UHFFFAOYSA-N 0.000 description 1
- QIPHSSYCQCBJAX-UHFFFAOYSA-N propan-2-ylboronic acid Chemical compound CC(C)B(O)O QIPHSSYCQCBJAX-UHFFFAOYSA-N 0.000 description 1
- 125000004368 propenyl group Chemical group C(=CC)* 0.000 description 1
- NHARPDSAXCBDDR-UHFFFAOYSA-N propyl 2-methylprop-2-enoate Chemical compound CCCOC(=O)C(C)=C NHARPDSAXCBDDR-UHFFFAOYSA-N 0.000 description 1
- PNXMTCDJUBJHQJ-UHFFFAOYSA-N propyl prop-2-enoate Chemical compound CCCOC(=O)C=C PNXMTCDJUBJHQJ-UHFFFAOYSA-N 0.000 description 1
- OBRKWFIGZSMARO-UHFFFAOYSA-N propylalumane Chemical compound [AlH2]CCC OBRKWFIGZSMARO-UHFFFAOYSA-N 0.000 description 1
- JAQOMSTTXPGKTN-UHFFFAOYSA-N propylboronic acid Chemical compound CCCB(O)O JAQOMSTTXPGKTN-UHFFFAOYSA-N 0.000 description 1
- 125000002568 propynyl group Chemical group [*]C#CC([H])([H])[H] 0.000 description 1
- CPNGPNLZQNNVQM-UHFFFAOYSA-N pteridine Chemical compound N1=CN=CC2=NC=CN=C21 CPNGPNLZQNNVQM-UHFFFAOYSA-N 0.000 description 1
- PBMFSQRYOILNGV-UHFFFAOYSA-N pyridazine Chemical compound C1=CC=NN=C1 PBMFSQRYOILNGV-UHFFFAOYSA-N 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 125000004076 pyridyl group Chemical group 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000011514 reflex Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 229910002028 silica xerogel Inorganic materials 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 229910000104 sodium hydride Inorganic materials 0.000 description 1
- 239000012312 sodium hydride Substances 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 150000003440 styrenes Chemical class 0.000 description 1
- 125000003107 substituted aryl group Chemical group 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- ISXSCDLOGDJUNJ-UHFFFAOYSA-N tert-butyl prop-2-enoate Chemical compound CC(C)(C)OC(=O)C=C ISXSCDLOGDJUNJ-UHFFFAOYSA-N 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
- 125000005329 tetralinyl group Chemical group C1(CCCC2=CC=CC=C12)* 0.000 description 1
- 150000003536 tetrazoles Chemical class 0.000 description 1
- 229930192474 thiophene Natural products 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 150000003608 titanium Chemical class 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 150000003623 transition metal compounds Chemical class 0.000 description 1
- NDUUEFPGQBSFPV-UHFFFAOYSA-N tri(butan-2-yl)alumane Chemical compound CCC(C)[Al](C(C)CC)C(C)CC NDUUEFPGQBSFPV-UHFFFAOYSA-N 0.000 description 1
- URNNTTSIHDDFIB-UHFFFAOYSA-N tri(cyclooctyl)alumane Chemical compound C1CCCCCCC1[Al](C1CCCCCCC1)C1CCCCCCC1 URNNTTSIHDDFIB-UHFFFAOYSA-N 0.000 description 1
- 150000003852 triazoles Chemical class 0.000 description 1
- SQBBHCOIQXKPHL-UHFFFAOYSA-N tributylalumane Chemical compound CCCC[Al](CCCC)CCCC SQBBHCOIQXKPHL-UHFFFAOYSA-N 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 1
- ZIYNWDQDHKSRCE-UHFFFAOYSA-N tricyclohexylalumane Chemical compound C1CCCCC1[Al](C1CCCCC1)C1CCCCC1 ZIYNWDQDHKSRCE-UHFFFAOYSA-N 0.000 description 1
- ZMANZCXQSJIPKH-UHFFFAOYSA-O triethylammonium ion Chemical compound CC[NH+](CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-O 0.000 description 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 1
- UORVGPXVDQYIDP-UHFFFAOYSA-N trihydridoboron Substances B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 description 1
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 description 1
- GETQZCLCWQTVFV-UHFFFAOYSA-O trimethylammonium Chemical compound C[NH+](C)C GETQZCLCWQTVFV-UHFFFAOYSA-O 0.000 description 1
- JOJQVUCWSDRWJE-UHFFFAOYSA-N tripentylalumane Chemical compound CCCCC[Al](CCCCC)CCCCC JOJQVUCWSDRWJE-UHFFFAOYSA-N 0.000 description 1
- JQPMDTQDAXRDGS-UHFFFAOYSA-N triphenylalumane Chemical compound C1=CC=CC=C1[Al](C=1C=CC=CC=1)C1=CC=CC=C1 JQPMDTQDAXRDGS-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
- 125000005580 triphenylene group Chemical group 0.000 description 1
- CNWZYDSEVLFSMS-UHFFFAOYSA-N tripropylalumane Chemical compound CCC[Al](CCC)CCC CNWZYDSEVLFSMS-UHFFFAOYSA-N 0.000 description 1
- GIIXTFIYICRGMZ-UHFFFAOYSA-N tris(2,3-dimethylphenyl)phosphane Chemical compound CC1=CC=CC(P(C=2C(=C(C)C=CC=2)C)C=2C(=C(C)C=CC=2)C)=C1C GIIXTFIYICRGMZ-UHFFFAOYSA-N 0.000 description 1
- YFDAMRSZJLWUSQ-UHFFFAOYSA-N tris(2-methylphenyl)borane Chemical compound CC1=CC=CC=C1B(C=1C(=CC=CC=1)C)C1=CC=CC=C1C YFDAMRSZJLWUSQ-UHFFFAOYSA-N 0.000 description 1
- COIOYMYWGDAQPM-UHFFFAOYSA-N tris(2-methylphenyl)phosphane Chemical compound CC1=CC=CC=C1P(C=1C(=CC=CC=1)C)C1=CC=CC=C1C COIOYMYWGDAQPM-UHFFFAOYSA-N 0.000 description 1
- AGOOAFIKKUZTEB-UHFFFAOYSA-N tris(3,5-difluorophenyl)borane Chemical compound FC1=CC(F)=CC(B(C=2C=C(F)C=C(F)C=2)C=2C=C(F)C=C(F)C=2)=C1 AGOOAFIKKUZTEB-UHFFFAOYSA-N 0.000 description 1
- OHSAEOPCBBOWPU-UHFFFAOYSA-N tris(3,5-dimethylphenyl)borane Chemical compound CC1=CC(C)=CC(B(C=2C=C(C)C=C(C)C=2)C=2C=C(C)C=C(C)C=2)=C1 OHSAEOPCBBOWPU-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
- LEIHCYASDULBKZ-UHFFFAOYSA-N tris(4-methylphenyl)borane Chemical compound C1=CC(C)=CC=C1B(C=1C=CC(C)=CC=1)C1=CC=C(C)C=C1 LEIHCYASDULBKZ-UHFFFAOYSA-N 0.000 description 1
- OBAJXDYVZBHCGT-UHFFFAOYSA-N tris(pentafluorophenyl)borane Chemical compound FC1=C(F)C(F)=C(F)C(F)=C1B(C=1C(=C(F)C(F)=C(F)C=1F)F)C1=C(F)C(F)=C(F)C(F)=C1F OBAJXDYVZBHCGT-UHFFFAOYSA-N 0.000 description 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
- RTAKQLTYPVIOBZ-UHFFFAOYSA-N tritert-butylalumane Chemical compound CC(C)(C)[Al](C(C)(C)C)C(C)(C)C RTAKQLTYPVIOBZ-UHFFFAOYSA-N 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- PXXNTAGJWPJAGM-UHFFFAOYSA-N vertaline Natural products C1C2C=3C=C(OC)C(OC)=CC=3OC(C=C3)=CC=C3CCC(=O)OC1CC1N2CCCC1 PXXNTAGJWPJAGM-UHFFFAOYSA-N 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Classifications
-
- 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
-
- 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
-
- 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
- C08F2410/00—Features related to the catalyst preparation, the catalyst use or to the deactivation of the catalyst
- C08F2410/03—Multinuclear procatalyst, i.e. containing two or more metals, being different or not
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2410/00—Features related to the catalyst preparation, the catalyst use or to the deactivation of the catalyst
- C08F2410/04—Dual catalyst, i.e. use of two different catalysts, where none of the catalysts is a metallocene
Definitions
- the present invention relates to a self-assembled olefin polymerization catalyst, to a process for the polymerization of olefins and to the polyolefins obtained therefrom.
- Polyolefins are raw materials used in a wide range of industries, including packaging, automotives and construction. Therefore, the production of polyolefins is a very important branch of industry.
- the catalysts for olefin polymerization play a key role in the production process, which has led to much work in this area of research.
- phenoxy-imine-based Group 4 metal catalysts have received much attention in both academia and industry because they intrinsically have high activities that compare favorably with that of commercial metallocene or half-sandwich Group 4 metal catalysts.
- this kind of phenoxy-imine-based catalysts has poor stability resulting in limited lifetimes, primarily because of the transfer of supporting ligand to aluminum in the co-catalyst mixture especially under elevated temperatures used in industry.
- the catalysts decay quickly within a matter of minutes. Consequently, these catalysts are usually studied at low temperature and/or short reaction time. This greatly hinders the application of this kind of catalysts in industry.
- the present invention refers to a self-assembled polymerization catalyst comprising a transition metal complex according to formula (I)
- each M is independently a transition metal selected from the group consisting Group 3-11 of the periodic table;
- each X is independently selected from the group consisting of H, halogen, CN, optionally substituted N(R a ) 2 , OH, optionally substituted Ci-C 20 alkyl, optionally substituted Ci-C 20 alkoxy, wherein R a is independently selected from the group consisting of optionally substituted Ci-C 20 alkyl, optionally substituted C 6 -C 20 aryl and halogen;
- A is nothing, ⁇ ⁇ tile) 8 ⁇ ⁇ - , or MX n ⁇ ⁇ ⁇ ) ⁇ ⁇ ⁇ , -;
- A' is nothing, - ⁇ ⁇ ⁇ ) 8 ⁇ ⁇ , or - L'(MX n ) g, ;
- B is nothing, -L 2 (MX n ) h or -L 2 (MX n ) h MX n ; g is 0 or an integer of at least 1 ;
- h is 0 or an integer of at least 1 ;
- p is 0 or an integer of at least 1 ;
- q is 0 or an integer of at least 1 ;
- r is 0 or an integer of at least 1 ;
- t is 0 or an integer of at least 1 ;
- u is 0 or an integer of at least 1 ;
- v is 0 or an integer of at least 1 ;
- w is an integer of at least 1 ;
- y is an integer of at least 1 ;
- z is an integer of at least 1 ;
- n is an integer selected from 0-6, wherein n is selected depending on the valency of M such that the net charge of each M nucleus is zero or all ligand binding positions of M are occupied;
- L 1 and L 2 are independently selected ligands, wherein L 1 and L 2 are different,
- each of L and L having at least two linked coordination units, wherein each coordination unit binds to a different transition metal atom.
- the present invention provides a process for polymerization or copolymerization of an olefin or a mixture of olefins in the presence of the self-assembled olefin polymerization catalyst described in the present invention.
- the present invention provides polyolefins obtainable according to the process of the present invention.
- Fig. 1 illustrates a reaction scheme to produce a mono-nuclear Ti (FI-Ti) and a mono-nuclear Zr (Fl-Zr) catalyst from a phenoxy-imine ligand (FI).
- the mono-nuclear catalysts shown are representative titanium and zirconium catalysts of the prior art based on phenoxy-imine ligand bearing coordination model- 1 as shown in Fig. 2.
- Fig. 1 illustrates a reaction scheme to produce a mono-nuclear Ti (FI-Ti) and a mono-nuclear Zr (Fl-Zr) catalyst from a phenoxy-imine ligand (FI).
- the mono-nuclear catalysts shown are representative titanium and zirconium catalysts of the prior art based on phenoxy-imine ligand bearing coordination model- 1 as shown in Fig. 2.
- Fig. 1 illustrates a reaction scheme to produce a mono-nuclear Ti (FI-Ti) and
- model- 1 mono-nuclear Fl-catalyst
- model-2 mono-nuclear tetradentate-ligand catalyst
- model-3 multi-nuclear catalyst
- FIG. 3 illustrates a tetradentate ligand (II) forming model-2 type catalyst as shown in Fig. 2, as well as further tetradentate ligands (III-XVII) forming model-2 type catalyst as shown in Fig. 2.
- Fig. 4 illustrates a state of the art self-assembling strategy in order to synthesize olefin polymerization catalysts.
- Fig. 5A illustrates a self-assembling strategy in order to synthesize olefin polymerization catalysts according to an embodiment of the present invention, which is carried out in two steps.
- a bis-ligand bis- ligand- 1 is added to two different metal atoms in a first step to form a bi-nuclear species.
- the bi-nuclear species react with a second bis-ligand (bis-ligand-2) to form a multi-nuclear self-assembled olefin polymerization catalyst (multi- nuclear catalyst).
- Fig. 5B illustrates a self-assembling strategy in order to synthesize olefin polymerization catalysts according to another embodiment of the present invention, which is carried out in a single step.
- a bis-ligand (bis-ligand- 1) and a second bis-ligand (bis-ligand-2) are added to two different metal atoms in one single step to form a multi-nuclear self- assembled olefin polymerization catalyst (multi-nuclear catalyst).
- Fig. 5C illustrates a self- assembling strategy in order to synthesize olefin polymerization catalysts according to a further embodiment of the present invention, which is carried out in one step.
- the multi-nuclear self-assembled olefin polymerization catalyst may have a disordered arrangement of the two bis-ligands (bis-ligand- 1 and bis-ligand-2), which may be in an alternate or random fashion.
- Fig. 6 illustrates the molecular structure of a bis-phenoxy-imine ligand (BFI-3) obtained by single crystal X-ray diffraction.
- BFI-3 bis-phenoxy-imine ligand
- Fig. 7 illustrates the molecular structure of a bis-phenoxy-imine ligand (BFI-4) obtained by single crystal X-Ray diffraction.
- BFI-4 bis-phenoxy-imine ligand
- Fig. 8 illustrates the synthesis of self-assembled catalysts MNTi-3 and MNZr-3 using two different bis-phenoxy-imine ligands BFI-1 and BFI-2 in a two step process.
- Bis- phenoxy-imine ligand BFI-1 is added to two different metal atoms M in a first step to form a bi-nuclear species.
- the bi-nuclear species react with a second bis-phenoxy-imine ligand BFI- 2 to form a multi-nuclear self-assembled olefin polymerization catalyst MNTi-3 or MNZr-3 (wavy lines indicate that the depicted structure can be part of a bigger molecule that contains further repeating units. Alternatively, the wavy lines may represent the remaining, non- depicted part of the respective ligand, with or without a metal atom bound).
- Fig. 9 illustrates the synthesis of self-assembled catalysts MNTi-4 and MNTi-5 using two different bis-phenoxy-imine ligands BFI-3 and BPI-1, and BFI-4 and BPI-1 respectively in a two step process.
- bis-phenoxy-imine ligand BFI-3 is added to two different metal atoms M in a first step to form a bi-nuclear species.
- the bi-nuclear species react with a second bis-phenoxy-imine ligand BPI-1 to form a multi-nuclear self-assembled olefin polymerization catalyst MNTi-4 (wavy lines indicate that the depicted structure can be part of a bigger molecule that contains further repeating units. Alternatively, the wavy lines may represent the remaining, non-depicted part of the respective ligand, with or without a metal atom bound).
- Fig. 10 illustrates the synthesis of self-assembled catalysts MNTi-6 and MNZr-6 using two different bis-phenoxy-imine ligands BFI-1 and BFI-2 in a one step process.
- Fig. 11 illustrates the synthesis of bis-phenoxy-imine ligand BFI-1 and the corresponding self-assembled catalysts MNTi-1 and MNZr-1.
- Fig. 12 illustrates the synthesis of bis-phenoxy-imine ligand BFI-2 and the corresponding self-assembled catalysts MNTi-2 and MNZr-2.
- Fig. 13 is a table (Table 1) summarizing the performance of ethylene polymerization obtained using self-assembled polymerization catalysts (MNTi-3 and MNTi-6) according to embodiments of the present invention, and state of the art catalysts (MNTi-1, MNTi-2, and FI-Ti).
- the polymerization reaction was carried out in a 300 mL stainless steel autoclave, using 100 mL hexane, 5.5 bar of ethylene pressure, 2.0 mmol of methyl aluminoxane (MAO), catalyst loading of 0.9 ⁇ ⁇ metal.
- Activity of the catalyst is expressed in terms of kgp E moljvf 1 h "1 bar "1 .
- Table 14 is a table (Table 2) summarizing the performance of ethylene polymerization obtained using self-assembled polymerization catalysts (MNZr-3 and MNZr- 6) according to embodiments of the present invention, and state of the art catalysts (MNZr-1, MNZr-2, and Fl-Zr).
- the polymerization reaction was carried out in a 300 mL stainless steel autoclave, using 100 mL hexane, 5.5 bar of ethylene pressure, 2.0 mmol of methyl aluminoxane (MAO), catalyst loading of 0.09 ⁇ ⁇ metal.
- Activity of the catalyst is expressed in terms of kgPEmolivf 1 h "1 bar "1 .
- Fig. 15 is a graph comparing the amount of polyethylene obtained (PE, g) with time ("productivity comparison") for MNTi-3 and MNTi-6, and state of the art catalysts MNTi- 1 , MNTi-2, and FI-Ti.
- Fig. 16 is a graph comparing the amount of polyethylene obtained (PE, g) with time ("productivity comparison") for MNZr-3 and MNZr-6, and state of the art catalysts MNZr-1, MNZr-2, and Fl-Zr.
- Fig. 17 illustrates the amounts of polymer produced after several reaction times of (i) 30 minutes, (ii) 60 minutes and (iii) 120 minutes using (A) MNTi-3, (B) MNTi-6 and (C) state of the art catalyst FI-Ti. It is shown that for both MNTi-3 and MNTi-6, the amount of polyethylene (PE) increased quickly with an increase in reaction time while for FI-Ti, the amount of polyethylene obtained increased very slowly.
- PE polyethylene
- Fig. 18 illustrates the amounts of polymer produced after several reaction times of (i) 5 minutes, (ii) 15 minutes, (iii) 30 minutes, (iv) 60 minutes and (v) 120 minutes using (A)
- MNZr-3, B) MNZr-6 and (C) state of the art catalyst Fl-Zr It is shown that for both MNZr-3 and MNZr-6, the amount of polyethylene (PE) increased quickly with an increase in reaction time while for Fl-Zr, the amount of polyethylene obtained increased very slowly.
- Fig. 19 is a table (Table 3) summarizing the FTIR readings of MNTi-3 and MNZr- 3, and state of the art catalysts MNTi-1, MNTi-2, FI-Ti, MNZr-1, MNZr-2, and Fl-Zr.
- Fig. 20 is a table (Table 4) summarizing the Laser Raman readings of MNTi-3, and state of the art catalysts MNTi-1, MNTi-2, and FI-Ti.
- Fig. 21 is a table (Table 5) summarizing the performance of co-polymerization of ethylene and 1 -hexene using self-assembled polymerization catalysts (MNTi-4, MNTi-5) according to embodiments of the present invention.
- the co-polymerization reaction was carried out in a 1 L stainless steel autoclave, using 600 mL of pentane, 6.0 bar of ethylene pressure, varying amounts of 1-hexene and/or hydrogen gas, catalyst loading of 6.0 ⁇ ⁇ ⁇ metal and 6.0 mmol of MAO.
- Activity of the catalyst is expressed in terms of kgPE molM -1 h "1 bar "1 .
- the present invention refers to a self-assembled olefin polymerization catalyst comprising a transition metal complex according to formula (I) wherein
- each M is independently a transition metal selected from the group consisting of Group 3-11 of the periodic table;
- each X is independently selected from the group consisting of H, halogen, CN, optionally substituted N(R a ) 2 , OH, optionally substituted Ci-C 20 alkyl, optionally substituted C 1 -C 2 0 alkoxy, wherein R a is independently selected from the group consisting of optionally substituted Ci-C 20 alkyl, optionally substituted C 6 -C 20 aryl and halogen;
- A is nothing, L'(MX n ) g MX n - , or MX n L 1 (MX n ) g MX n ,-;
- A' is nothing, - L'(MX transit) g MX n , or - ⁇ ( ⁇ ) & ;
- B is nothing, -L 2 (MX n ) h or -L 2 (MX n ) h MX n ;
- g is 0 or an integer of at least 1 ;
- h is 0 or an integer of at least 1 ;
- p is 0 or an integer of at least 1 ;
- q is 0 or an integer of at least 1 ;
- r is 0 or an integer of at least 1 ;
- t is 0 or an integer of at least 1 ;
- u is 0 or an integer of at least 1 ;
- v is 0 or an integer of at least 1 ;
- w is an integer of at least 1 ;
- y is an integer of at least 1 ;
- z is an integer of at least 1 ;
- n is an integer selected from 0-6, wherein n is selected depending on the valency of M such that the net charge of each M nucleus is zero or all ligand binding positions of M are occupied;
- L and L are independently selected ligands, wherein L and L are different, each of L 1 and L 2 having at least two linked coordination units, wherein each coordination unit binds to a different transition metal atom.
- SA self-assembly
- the transition metal M is selected from the group consisting of Group 3-11 of the periodic table.
- the transition metal M may be, but is not limited to, Sc, Y, La, Ti, Zr, Hf, V, Nb, Ta, Sm, Yb, Cr, Mo, W, Mn, Tc, Re, Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt, Cu, Zn, or mixtures thereof.
- M may be Sc, Ti, Zr, Hf, V, Nb, Ta, Sm, Yb, Fe, Co, Rh, Ni or Pd, for example Ti, Zr, Hf, V, Nb, Ta, Sm, Yb, or mixtures thereof.
- M may be Ti, Zr, or mixtures thereof. In exemplary embodiments of the present invention, M is Ti or Zr.
- the selection of the respective transition metal atom may depend on the reaction conditions and/or the olefin which should be polymerized.
- the transition metal M may be in the oxidation state (0).
- the oxidation state of the transition metal may be between (I) and (VI) depending on the further type and number of the ligands L and L .
- M may represent a transition metal atom including, but not limited to, Sc(III), Ti(III), Ti(IV), Zr(III), Zr(IV), Hf(IV), V(III), V(IV), V(V), Nb(V), Ta(V), Fe(II), Fe(III), Co(II), Co(III), Rh(II), Rh(III), Rh(IV), Cr(III), Ni(II), and Pd(II).
- M may be Ti(IV), Zr(IV), Hf(IV), V(III), V(IV), V(V), Nb(V), and Ta(V); such as Ti(IV), Zr(IV), and Hf(IV). This may mean that M is positively charged and thus is a metal ion.
- the polymerization catalyst will depend on the number of the ligands L and L which are present in the self-assembled catalyst.
- the number of atoms of the transition metal M may be in the range of about 1 or about 2 to about 1000, for example about 1 to about 100 or about 200 or 300.
- the number of atoms of the transition metal M may also be any other integer being useful in the present invention.
- X is a group which is coordinated to the transition metal atom.
- X may be, but is not limited to, hydrogen, halogen, CN, optionally substituted N(R a ) 2 , OH, optionally substituted Ci-C 2 o alkyl, or optionally substituted Ci-C 20 alkoxy, wherein R a is independently selected from the group consisting of optionally substituted Ci-C 20 alkyl, optionally substituted C 6 -C 20 aryl and halogen.
- X may be H, F, CI, Br, CN, N(CH 3 ) 2 , N(CH 2 CH 3 ) 2 , CH 3 , CH 2 CH 3 , OCH 3 , OCH 2 CH 3 , OCH(CH 3 ) 3 , OC(CH 3 ) 3 , or OC 6 H 6 , and the like. In case multiple X moieties are present, X may be the same or different.
- n in formula (I) represents an integer selected from 0-6, wherein n is selected depending on the valency of the transition metal M such that the net charge of each M nucleus is zero or all ligand binding positions of M are occupied.
- n may be an integer from about 0-5, such as about 0-4 or about 0-3.
- n may be 1 or 2.
- n is 2 to form an octahedral metal configuration together with the two WY units of each of the ligands L 1 and lA Further metal configurations may be possible depending on n.
- L and L are independently selected ligands, wherein L and L 2 are different i.e. L 1 is not the same ligand as L 2 .
- Each of ligands L 1 and L 2 have at least two coordination units which are linked via a spacer Z such that each coordination unit can only bind to a different transition metal atom. This means that, for example, a ligand L 1 having two separate coordination units cannot bind to the same transition metal atom with both coordination units. Instead, each coordination unit may bind to a different transition metal atom only.
- g, h, p, q, r, t, u, and v may independently be 0 or may be an integer of at least 1.
- the values of g, h, p, q, r, t, u, and v may depend on the number of transition metal atoms in the self-assembled catalyst as well as the number of coordination units present in each of the ligands L 1 and L 2 .
- g, h, p, q, r, t, u, and v may independently be in the range from about 0 to about 1000, for example about 0 to about 500, about 0 to about 200, or about 0 to about 100.
- each g, h, p, q, r, t, u, and v can independently be selected from 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10.
- each g, h, p, q, r, t, u, and v may also be any other integer being useful in the present invention.
- w, y and z may independently be an integer of at least 1. The values of w, y and z may depend on the number of transition metal atoms in the self- assembled catalyst and the amount of ligands L 1 and L 2 present.
- w, y and z may independently be in the range from about 0 to about 1000, for example about 0 to about 500, about 0 to about 200, or about 0 to about 100.
- w, y and z are independently 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 15, 20, 25, 30, 35, 40, 45, or 50.
- w, y and z may also be any other integer being useful in the present invention.
- A, A' and B are end groups of the complex.
- A may be nothing, L ⁇ MX ⁇ g MXn- , or MX n L ⁇ MX ⁇ g MX,,,-.
- A' may be nothing, - L'(MXn) g MX n , or - L 1 (MXn) g ,.
- B may be nothing, -L 2 (MX repeat) h or -L 2 (MX n ) h MX n .
- L 1 and L 2 may independently be a ligand according to formula (II)
- each WY unit forms a coordination unit
- n is an integer of at least 2;
- Z is a bridging spacer selected from the group consisting of optionally substituted hydrocarbons having about 2 to about 100 carbon atoms and optionally substituted hetero- hydrocarbons having about 2 to about 100 carbon atoms, wherein Z has a size, length and angle so that each coordination unit WY binds to a different transition metal atom;
- each W and Y is independently a metal-coordinating moiety selected from the group consisting of a carbene, an optionally substituted C 5 -C 2 o aryl, and metal-coordinating groups comprising an oxygen atom, a sulphur atom, a selenium atom, a nitrogen atom, or a phosphorus atom in neutral or charged form;
- the semi-circle in the WY unit represents an optionally substituted hydrocarbon, hetero-hydrocarbon or Si-containing backbone to which the metal-coordinating moieties W and Y are bonded.
- the metal-coordinating group is one of an oxygen atom, a sulphur atom, a selenium atom, a nitrogen atom, or a phosphorus atom, preferably in negatively charged form.
- the afore-mentioned atoms can be part of a larger group or can be bound to another atom or group, including, but not limited to hydrogen
- Each of the ligands L 1 and L 2 may be prepared according to the process described below.
- n may be 2, 3, 4, 5 or 6 or an integer > 6.
- each of the li ands L and L may independently
- Each unit WY forms a coordination unit, i.e. one transition metal atom is coordinated to both W and Y of the same WY coordination unit.
- the semi-circle in the WY coordination unit represents the hydrocarbon backbone to which the metal-coordinating moiety W and Y are bonded.
- In neutral or charged form means that both W and Y may have, for example, the charge state 0 or -1 or any other charge state which contributes to a stable molecule.
- the hydrocarbon, hetero-hydrocarbon or Si-containing backbone to which the metal-coordinating moieties W and Y are bonded may be, for example, any organic compound which is capable of linking W and Y to form the coordination unit.
- the hydrocarbon backbone may be an optionally substituted hydrocarbon, hetero-hydrocarbon or Si-containing backbone to which the metal-coordinating moieties W and Y are bonded.
- the hydrocarbon backbone may be, but is not limited to, an optionally substituted C 6 -C 20 aryl group, an optionally substituted C 6 -C 20 heteroaryl group or an optionally substituted Si group.
- W and Y may be linked to an aromatic hydrocarbon (aryl), to a Si-chain or the like.
- the WY coordination unit may
- Z is a spacer molecule, wherein the term "spacer molecule" refers to an atom or group of atoms that separate two or more groups from one another by a desired number of atoms. Any group of atoms may be used to separate those groups by the desired number of atoms. In some embodiments, spacers are optionally substituted.
- the spacer Z has a size, length and angle so that the at least two coordination sites WY of each of the ligands L 1 and L 2 can only bind to two different transition metal atoms and not to the same transition metal atom.
- hydrocarbons having about 2 to about 100 carbon atoms refer to all possible sorts of organic compounds consisting of hydrogen and carbon, e.g. aromatic hydrocarbons (aryl), alkanes, alkenes and alkyne-based compounds, but not limited to.
- Z may be, but is not limited to, an optionally substituted C3-C10 alicyclic group, an optionally substituted C 6 -C 20 aryl group, an optionally substituted C 6 -C 20 heteroaryl group, a system of condensed nucleus of fused two, three, four or five membered rings (which can optionally have heteroatoms in the ring system, such as naphthalene derivatives, anthracene derivates, quinoline, isoquinoline, quinazoline, acridinine, phenanthrene, naphthacene, chrysene, pyrene, or triphenylene, to name only a few illustrative examples), or a system of two, three or four C 6 -C 20 aryl groups being connected via a N-atom, a Si-atom, an C 1 -C 20 alkyl group, an C 2 -C 20 alkenyl group or an C 6 -C
- the above terms may encompass compounds such as biphenyl, terphenyl or [(R n R 12 R 13 R 14 )C 6 -(CH 2 ) k -C 6 (R 15 R 16 R 17 R 18 )], wherein k is an integer from 1 to 10, and the like. All these compounds may be optionally substituted.
- hetero-hydrocarbons having about 2 to about 100 carbon atoms refer to all sort of organic compounds consisting of hydrogen, carbon and at least one heteroatom selected from for example N, S, O, Si or P, but not limited to.
- this term may encompass compounds according to the formula [(R n R I2 R 13 R 14 )C6-(V) d -C 6 (R 15 R 16 R 17 R 18 )], wherein V is Si or S and d is an integer from about 1 to about 6. All these compounds may be optionally substituted.
- examples of the spacer Z include, but are not limited to, the following benzyl, pyridyl, napthtyl, biphenyl, terphenyl, anthacenyl, phenanthrenyl, or benzyl groups being connected via a N-atom, a Si-atom, or an C1-C20 alkyl group, an C 2 -C 20 alkenyl group or an C 6 -C 20 aryl group,
- s may be selected from 1 , 2, 3, 4, 5 or 6.
- the star indicates the point of attachment to the WY unit.
- Z is a tri-linker. This means that three of the WY coordination units may be bonded to the same spacer. Examples of the such spacer Z may be, but are not limited to,
- Z is a tetrakis-linker. This means that four of the WY coordination units may be bonded to the same spacer. Examples of such spacer Z may be, but are not limited to,
- Z may also be a multi-linker having five or more than five linking sites, i.e. m in formula (II) may be 5 or 6 or even more.
- Z may also be a polymeric backbone having a plurality of linking sites forming a macro polymeric multi- linker.
- the polymeric backbone may be, for example, polyethylene, polypropylene, and the like.
- R and R 1 to R 20 in the above or below formulas may be the same or different and are each selected from the group consisting of H, optionally substituted straight- chain or branched Ci-C 2 o alkyl, optionally substituted straight-chain or branched C 2 -C 20 alkenyl, optionally substituted straight-chain or branched C 2 -C 20 alkynyl, optionally substituted C 6 -C 2 o aryl, optionally substituted C 6 -C 20 heteroaryl, halogen, OH, N0 2 , and CN, wherein two or more of R to R may be bonded to each other to form a ring.
- Ci-Qo alkyl represented by R 1 to R 20 refers to a fully saturated aliphatic hydrocarbon. Whenever it appears here, a numerical range, such as 1 to 20 or Ci-C 20 refers to each integer in the given range, e.g. it means that an alkyl group comprises only 1 carbon atom, 2 carbon atoms, 3 carbon atoms etc. up to and including 20 carbon atoms.
- alky groups may be, but are not limited to, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s-butyl, t-butyl, tert.- amyl. pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl or n-decyl and the like.
- alkenyl refers to an aliphatic hydrocarbon having one or more carbon-carbon double bonds.
- alkenyl groups may be, but are not limited to, ethenyl, propenyl, allyl or 1,4-butadienyl and the like.
- alkynyl refers to an aliphatic hydrocarbon having one or more carbon-carbon triple bonds.
- alkynyl groups may be, but are not limited to, ethynyl, propynyl, butynyl, and the like.
- Ci-C 20 alkoxy refers to a group of formula -OR, wherein R is a Ci-C 20 alkyl group.
- alkoxy groups may be, but are not limited to, methoxy, ethoxy, propoxy, and the like.
- C 3 -Cio alicyclic group refers to a group comprising a non-aromatic ring, wherein each of the atoms forming the ring is a carbon atom. Such rings may be formed by 3 to 10 carbon atoms.
- Examples of alicyclic groups may be, but are not limited to, cyclopropane, cyclobutane, cyclopentane, cyclopentene, cyclopentadiene, cyclohexane, cyclohexene, cycloheptane, cycloheptene and the like.
- C 6 -C 20 aryl refers to an aromatic ring, wherein each of the atoms forming the ring is a carbon atom.
- Aromatic in this context means a group comprising a covalently closed planar ring having a delocalized 7r-electron system comprising 4b+2 7r-electrons, wherein b is an integer of at least 1 , for example 1 , 2, 3 or 4.
- Examples of aryl groups may be, but are not limited to, phenyl, napthalenyl, phenanthrenyl, anthracenyl, tetralinyl, fluorenyl, indenyl, and indanyl, and the like.
- heteroaryl refers to an aromatic heterocycle. Heteroaryls may comprise at least one or more oxygen atoms or at least one or more sulphur atoms or one to four nitrogen atoms or a combination thereof.
- heteroaryl groups may be, but are not limited to, furan, benzofuran, thiophene, benzothiophene, pyrrole, pyridine, indole, oxazole, benzoxazole, isoxazole, benzisoxazole, thiazole, benzothiazole, imidazole, benzimidazole, pyrazole, indazole, tetrazole, quinoline, isoquinoline, pyridazine, purine, pyrazine, furazan, triazole, benzotriazole, pteridine, phenoxazole, oxadiazole, benzopyrazole, quinolizine, cinnoline, phthalazine, quinazoline or quinoxaline, and the like.
- halogen refers to fluorine, chlorine, bromine or iodine.
- Si group refers to a group containing 1 to 5 silicon atoms which are substituted by hydrogen or an alkyl group or an aryl group.
- Examples of a Si group may be, but are not limited to, monosilane, methylsilyl, dimethylsilyl, ethylsilyl, diethylsilyl, phenylsilyl, methylphenylsilyl, and the like.
- a system of condensed nucleus refers to compounds having at least two aromatic or non-aromatic condensed ring systems.
- condensed nucleus may be, but are not limited to, decalin, hydrindane, napthalene, anthracene, phenanthrene, naphthacene, pentacene, hexacene, pyrene, indene, fluorene, and the like.
- a system of two, three or four optionally substituted C 6 -C 20 aryl groups being connected via a N-atom, a Si-atom, an C 1 -C 20 alkyl group, an C 2 -C 20 alkenyl group or an C 6 -C 20 aryl group refers to compounds having a N-atom, a Si-atom, an alkyl group, an alkenyl group or an aryl group as a central bonding unit to which two, three or four aryl groups are bonded.
- the term “optionally substituted,” refers to a group in which none, one, or more than one of the hydrogen atoms has been replaced with one or more group(s) independently selected from the group consisting of alkyl, aryl, heteroaryl, hydroxy, alkoxy, halogen, carbonyl, C-amido, N-amido, isocyanato, thiocyanato, isothiocyanato, nitro, silyl, and amino, including mono- and di-substituted amino groups, and the protected derivatives of amino groups.
- the substituent groups may be linked to form a ring.
- the term "linked to form a ring” refers to the circumstance where two atoms that are bound either to a single atom or to atoms that are themselves ultimately bound, are each bound to a linking group, such that the resulting structure forms a ring.
- the resulting ring comprises the two atoms, the atom (or atoms) that previously linked those atoms, and the inker.
- R 1 to R 4 are as described above.
- R 1 , R 2 , R 3 and R 4 may be the same or different, wherein R 1 is selected from the group consisting of H, CH 3 and tert-butyl; R 2 is selected from the group consisting of H and tert-butyl; R 3 is selected from the group consisting of H, CH 3 , CH 2 CH 3 , and CH(CH 3 ) 2 ; and R 4 is selected from the group consisting of H, F and CH 3 .
- the ligand L and L may be any suitable ligand L and L.
- the molar ratio of the coordination unit WY to the transition metal may be in the range of about 0.5: 1 to about 6:1, for example about 1 :1 to about 3:1.
- the ligand compounds L and L may be prepared via a Schiff-Base condensation of the respective aldehyde or ketone and the amino substituted spacer molecule.
- the spacer molecule may have more than one amino substituent in order to react with more than one aldehyde and/or ketone.
- the ligand compounds may be prepared by a Schiff-Base condensation between an aldehyde or ketone with a di-aniline, tri-aniline or tetrakis-aniline.
- the aldehyde or ketone may include, but is not limited to,
- the di-aniline, tri-aniline or tetrakis- aniline may include, but is not limited to,
- the ligand compounds L and L may also be prepared by a Schiff-Base condensation between an aniline and a di-aldehyde/di-ketone, tri- aldehyde/tri-ketone or tetrakis-aldehyde/tetrakis-ketone.
- the aniline may include, but is not limited to,
- R to R 5 are as described above.
- the di-aldehyde/di-ketone, tri-aldehyde/tri-ketone or tetrakis- aldehyde/tetrakis-ketone may include is not limited
- the Schiff-Base condensation may be promoted by an acid catalyst or a solid catalyst.
- the acid catalyst may include, but is not limited to, formic acid, acetic acid, p-toluenesulfonic acid or a Lewis acid and the like.
- the formed ligand compound for example, L 1 may be reacted with the respective metal compound, followed by addition of a second ligand compound, for example, L to form the catalyst of the present invention.
- a second ligand compound for example, L to form the catalyst of the present invention.
- both L 1 and L 2 may be mixed together prior to addition of the metal compound to form the catalyst of the present invention.
- the self-assembly process to form the catalyst may be carried out at any temperature, such as about -100 °C to about 50 °C, about -75 °C or about 25 °C.
- the strategy of the present invention is that the specific coordination geometry of the ligands L 1 and L2 does not allow the at least two WY coordination units of each of L 1 and L 2 to coordinate with one and the same transition metal atom to form a mono-nuclear complex because of the spacer's size, length and angle, hence the at least two WY units of each ligand have to coordinate with two or more different transition metal atoms, thus forming self-assembled multi-nuclear catalysts.
- This concept can be exemplarily taken from Fig. 5, which shows each coordination site of the linked bis-ligands coordinates to one metal atom such that self-assembling starts to achieve long-lived highly efficient polymerization catalyst.
- Fig. 5 shows each coordination site of the linked bis-ligands coordinates to one metal atom such that self-assembling starts to achieve long-lived highly efficient polymerization catalyst.
- different bis-ligand combinations can be obtained, which can form a wide range of multinuclear catalysts.
- the self-assembling structure may be linear, i.e. the ligands L and L may form a long chain of bis-ligand combinations with the transition metal atoms.
- the self-assembling structure may also be macrocyclic i.e. the long chain of bis-ligand combinations formed may be linked to form a ring.
- the kind of structure of the self- assembled catalyst will depend on the geometry of the used spacer Z and the kind and number of the substituents of the ligands L 1 and L 2 .
- the self-assembled catalyst of the present invention may form, for example, a 3-dimensional framework.
- the self-assembled olefin polymerization catalyst may comprise the unit
- bridging spacer is and M is Ti or Zr.
- Pr means phenyl and "t-Bu” means tert-butyl.
- the number of units may be 1 to 1000.
- the self-assembled olefin polymerization catalyst may comprise the unit
- the number of units may be 1 to 1000.
- the self-assembled olefin polymerization catalyst of the present invention may be used together with at least one co-catalyst.
- a catalytic system for olefin polymerization or copolymerization is formed, which may be used as such or which may be used in connection with other catalyst compounds or components necessary in the polymerization process.
- the at least one co-catalyst of the present invention may be, but is not limited to, an organometallic compound, an organoaluminum oxy-compound, or an ionizing ionic compound, and the like.
- the co-catalyst may be selected from organometallic compounds, wherein the organometallic compound may be, but is not limited to, an organometallic compound of metals of Group 1, Group 2, Group 12 and Group 13 of the Periodic Table.
- the compounds may be represented by the general Formula:
- organoaluminum compound may include the following compounds, but are not limited to, organoaluminum compounds represented by the general formula
- R a e Al(OR b ) 3-f wherein R a and R b , which may be the same or different, may be a hydrocarbon group of 1 to 15, for example 1 to 4 carbon atoms; and e may be a number satisfying the condition of 1.5 ⁇ e ⁇ 3.
- R a e AlX 3- wherein R a is a hydrocarbon group of 1 to 15, for example 1 to 4 carbon atoms; X is a halogen atom; and e may be an integer satisfying the condition of 0 ⁇ e ⁇ 3.
- R a e AlH 3-e wherein R a is a hydrocarbon group of 1 to 15, for example 1 to 4 carbon atoms; and e may be an integer satisfying the condition of 2 ⁇ e ⁇ 3.
- organo aluminum compounds may include, but are not limited to, tri-n-alkylaluminums, such as trimethylaluminum, triethylaluminum, tri-n- butylaluminum, tripropylaluminum, tripentylaluminum, trihexylaluminum, trioctylaluminum and tridecylaluminum; branched-chain trialkylaluminums, such as triisopropylaluminum, triisobutylaluminum, tri-sec-butylaluminum, tri-t -butylaluminum, tri-2- methylbutylaluminum, tri-3-methylbutylaluminum, tri-2-methylpentylaluminum, tri-3- methylpentylaluminum, tri-4-methylpentylaluminum, tri-2-methylhexylaluminum, tri-3- methylhexylaluminum and tri-2-ethy
- organo aluminum compounds wherein two or more aluminum compounds are combined through a nitrogen atom, such as (C 2 H5) 2 A1N(C 2 H 5 )A1(C 2 H 5 ) 2 .
- the above organometallic compound may be a compound of a Group 1 metal of the Periodic Table and aluminum represented by the general formula
- M 2 AlR a 4 wherein M 2 is Li, Na or K; and R a is a hydrocarbon group of 1 to 15, for example 1 to 4 carbon atoms.
- organo aluminum compounds include, but are not limited to, LiAl(C 2 H 5 ) 4 and LiAl(C 7 H 15 ) 4 , and the like.
- the above organometallic compound may be a compound of a Group 2 Metal or a Group 12 Metal of the Periodic Table represented by the general formula
- R a R b M 3 wherein R a and R b , which may be the same or different, may be a hydrocarbon group of 1 to 15, preferably 1 to 4 carbon atoms; and M 3 is Mg, Zn or Cd.
- methyllithium, ethyllithium, propyllithium, butyllithium, methylmagnesium bromide, methylmagnesium chloride, ethylmagnesium bromide, ethylmagnesium chloride, propylmagnesium bromide, propylmagnesium chloride, butylmagnesium bromide, butylmagnesium chloride, dimethylmagnesium, diethylmagnesium, dibutylmagnesium and butylethylmagnesium may also be employable as the above organometallic compound.
- combinations of compounds capable of forming the aforesaid organoaluminum compounds in the polymerization system e.g., a combination of halogenated aluminum and alkyllithium and a combination of halogenated aluminum and alkylmagnesium, are also employable.
- the above organometallic compounds may be used singly or in combination.
- the organoaluminum oxy-compound may be conventional aluminoxane or a benzene-insoluble organoaluminum oxy-compound as exemplified in JP-A-2(1990)/78687.
- the conventional aluminoxane can be prepared by, for example, the following processes, and is usually obtained as a hydrocarbon solvent solution:
- a compound containing absorbed water or a salt containing water of crystallization such as magnesium chloride hydrate, copper sulfate hydrate, aluminum sulfate hydrate, nickel sulfate hydrate or cerous chloride hydrate
- the aluminoxane may contain a small amount of an organometallic component.
- the solvent or the unreacted organoaluminum compound is distilled off from the recovered solution of aluminoxane and the remainder may be redissolved in a solvent or suspended in a poor solvent of aluminoxane.
- the organoaluminum compound used for preparing the aluminoxane include the same organoaluminum compounds as described above.
- the organoaluminum compounds can be used singly or in combination.
- Examples of the solvent used in preparing the aluminoxane include aromatic hydrocarbons, such as benzene, toluene, xylene, cumene and cymene; aliphatic hydrocarbons, such as pentane, hexane, heptane, octane, decane, dodecane, hexadecane and octadecane; alicyclic hydrocarbons, such as cyclopentane, cyclohexane, cyclooctane and methylcyclopentane; petroleum fractions, such as gasoline, kerosine and gas oil; and halides of these aromatic, aliphatic and alicyclic hydrocarbons, particularly chlorides and bromides thereof. Also employable are ethers such as ethyl ether and tetrahydrofuran. Of the solvents, particularly preferable are aromatic hydrocarbons and aliphatic hydrocarbons.
- the benzene- insoluble organoaluminum oxy-compound used in the invention preferably has a content of Al component which is soluble in benzene at about 60°C of usually not more than about 10%, for example not more than about 5%, such as not more than about 2%, in terms of Al atom. That is, the benzene- insoluble organoaluminum oxy- compound is preferably insoluble or hardly soluble in benzene.
- the organoaluminum oxy-compound employable in the invention is, for example, an organoaluminum oxy-compound containing boron, which is represented by the following formula (XX)
- R 8 R 8 wherein R 7 is a hydrocarbon group of 1 to 10 carbon atoms; and the groups R 8 , which may be the same or different, may be a hydrogen atom, a halogen atom or a hydrocarbon group of 1 to 10 carbon atoms.
- the organoaluminum oxy-compound containing boron that is represented by the formula (XX) can be prepared by reacting an alkylboronic acid represented by the following formula (XXI) with an organoaluminum compound in an inert solvent under an inert gas atmosphere at a temperature of about -80°C to room temperature for about 1 minute to about 24 hours:
- alkylboronic acid represented by the formula (XXI) include methylboronic acid, ethylboronic acid, isopropylboronic acid, n-propylboronic acid, n-butylboronic acid, isobutylboronic acid, n-hexylboronic acid, cyclohexylboronic acid, phenylboronic acid, 3,5-difluoroboronic acid, pentafluorophenylboronic acid and 3,5-bis (trifluoromethyl)phenylboronic acid.
- methylboronic acid n-butylboronic acid, isobutylboronic acid, 3,5- difluorophenylboronic acid and pentafluorophenylboronic acid.
- alkylboronic acids are used singly or in combination.
- organoaluminum compound to be reacted with the alkylboronic acid include the same organoaluminum compounds as described for the organoaluminum compounds above. These organoaluminum compounds can be used singly or in combination.
- the co-catalyst may be selected from organoaluminium compounds, wherein the organo aluminium compound may be, but is not limited to, trialkylaluminum such as trimethylaluminum, triethylaluminum, triisobutylalurninum, trihexylaluminum, trioctylaluminum, and tridecylaluminum; alkylaluminum halides such as diethylaluminum monochloride, diisobutylaluminum monochloride, ethylaluminum sesquichloride, and ethylaluminum dichloride; alkylaluminum hydrides such as diethylaluminum hydride, and diisobutylaluminum hydride.
- the co-catalyst may be a methyl aluminoxane (MAO) and/or a modified methyl aluminoxane
- the compound that reacts with the transition metal compound to form an ion pair may include, but is not limited to, Lewis acids, ionic compounds, borane compounds and carborane compounds as described in JP-A- 1(1989)/501950, JP-A-l(1989)/502036, JP-A-3(1991 )/l 79005, JP-A-3(1991)/179006, JP-A- 3(1991)/207703 and JP-A-3(1991)/207704, and U.S. Pat. No. 5,321,106. Examples further include heteropoly compounds and isopoly compounds.
- Lewis acids examples include compounds represented by BR 3 (wherein R is a phenyl group which may have a substituent group such as fluorine, methyl or trifluoromethyl, or a fluorine atom), such as, but are not limited to, trifluoroboron, triphenylboron, tris(4-fluorophenyl)boron, tris(3,5-difluorophenyl)boron, tris(4- fluoromethylphenyl)boron, tris(pentafluorophenyl)boron, tris(p-tolyl)boron, tris(o-tolyl)boron and tris(3,5-dimethylphenyl)boron.
- R is a phenyl group which may have a substituent group such as fluorine, methyl or trifluoromethyl, or a fluorine atom
- Examples of the ionic compounds include compounds represented by the following formula (XXII) R 9® R 10_ B Q_ R 12 (XXII) R 13
- R 9 may be H + , carbonium cation, oxonium cation, ammonium cation, phosphonium cation, cycloheptyltrienyl cation, ferrocenium cation having a transition metal, or the like.
- R 10 to R 13 which may be the same or different, are each an organic group, preferably an aryl group or a substituted aryl group.
- Examples of the carbonium cation include tri-substituted carbonium cations, such as triphenylcarbonium cation, tri(methylphenyl) carbonium cation and tri(dimethylphenyl)carbonium cation.
- ammonium cation examples include trialkylammonium cations, such as trimethylammonium cation, triethylammonium cation, tripropylammonium cation, tributylammonium cation and tri(n- butyl)ammonium cation; ⁇ , ⁇ -dialkylanilinium cations, such as N,N-dimethylanilinium cation, ⁇ , ⁇ -diethylanilinium cation and N,N-2,4,6-pentamethylanilinium cation; and dialkylammonium cations, such as di(isopropyl)ammonium cation and dicyclohexylammonium cation.
- trialkylammonium cations such as trimethylammonium cation, triethylammonium cation, tripropylammonium cation, tributylammonium cation and tri(n- butyl)ammoni
- Examples - of the phosphonium cation include triarylphosphonium cations, such as triphenylphosphonium cation, tri(methylphenyl)phosphonium cation and tri(dimethylphenyl)phosphonium cation.
- R 9 is preferably carbonium cation or ammonium cation, particularly preferably triphenylcarbonium cation, ⁇ , ⁇ -dimethylanilinium cation or N,N-diethylanilinium cation.
- Examples of the ionic compounds further include trialkyl-substituted ammonium salts, ⁇ , ⁇ -dialkylanilinium salts, dialkylammonium salts and triarylphosphonium salts.
- Examples of the trialkyl-substituted ammonium salts include triethylammoniumtetra(phenyl)boron, tripropylammoniumtetra(phenyl)boron, tri(n- butyl)ammoniumtetra(phenyl)boron, trimethylammoniumtetra(p-tolyl)boron, trimethylammoniumtetra(o-tolyl)boron, tri(n-butyl)ammoniumtetra(pentafluorophenyl)boron, tripropylammoniumtetra-(o,p-dimethylphenyl)boron, tri(n-butyl)ammoniumtetra(m,m- dimethylphenyl)boron,
- Examples of the ⁇ , ⁇ -dialkylanilinium salts include N,N- dimethylaniliniumtetra(phenyl)boron, N,N-diethylaniliniumtetra(phenyl)boron and N,N- 2,4,6-pentamethylaniliniumtetra(phenyl)boron.
- dialkylammonium salts include di(l- propyl)ammoniumtetra(pentafluorophenyl)boron and dicyclohexylammoniumtetra(phenyl)boron.
- examples of the ionic compounds further include triphenylcarbeniumtetrakis(pentafluorophenyl)borate, N,N- dimethylaniliniumtetrakis(pentafluorophenyl)borate,
- borane compounds include, but are not limited to, decaborane; salts of anions, such as bis[tri(n-butyl)ammonium]nonaborate, bis[tri(n- butyl)ammonium]decaborate, bis[tri(n-butyl)ammonium]undecaborate, bis[tri(n- butyl)ammonium]dodecaborate, bis[tri(n-butyl)ammonium]decachlorodecaborate and bis[tri(n-butyl)ammonium]dodecachlorododecaborate; and salts of metallic borane anions, such as tri(n-butyl)ammoniumbis(dodecahydridododecaborato) cobaltate(III) and bis[tri(n- butyl)ammonium]bis(dodecahydridododecaborato) nickelate(III).
- anions such as bis[tri(n
- Examples of the carborane compounds may include, but are not limited to, salts of anions, such as 4-carbanonaborane, 1,3-dicarbanonaborane, 6,9-dicarbadecaborane, dodecahydrido- 1 -phenyl- 1 ,3 -dicarbanonaborane, dodecahydrido- 1 -methyl- 1,3- dicarbanonaborane, undecahydrido-l,3-dimethyl-l,3-dicarbanonaborane, 7,8- dicarbaundecaborane, 2,7-dicarbaundecaborane, undecahydrido-7,8-dimefhyl-7,8- dicarbaundecaborane, dodecahydrido-1 l -methyl-2,7-dicarbaundecaborane, tri(n- butyl)ammonium- 1 -carbadecaborate, tri(n-butyl)ammonium- 1
- the heteropoly compounds comprise an atom selected from silicon, phosphorus, titanium, germanium, arsenic and tin, and at least one atom selected from vanadium, niobium, molybdenum and tungsten.
- the heteropoly compounds include without limiting thereto phosphovanadic acid, germanovanadic acid, arsenovanadic acid, phosphoniobic acid, germanoniobic acid, siliconomolybdic acid, phosphomolybdic acid, titanomolybdic acid, germanomolybdic acid, arsenomolybdic acid, stannnomolybdic acid, phosphotungstic acid, germanotungstic acid, stannotungstic acid, phosphomolybdovanadic acid, phosphotungstovanadic acid, germanotungstovanadic acid, phosphomolybdotungstovanadic acid, germanomolybdotungstovanadic acid, phosphomolybdotungstic acid and
- the co-catalyst may be a conventional methyl aluminoxane (MAO), a modified methyl aluminoxane (MMAO), a metal salt of (C 6 F 5 ) 4 B " or a combination of an alkyl aluminium compound with MgCl 2 .
- MAO methyl aluminoxane
- MMAO modified methyl aluminoxane
- metal salt of (C 6 F 5 ) 4 B " or a combination of an alkyl aluminium compound with MgCl 2 .
- the ionizing ionic compounds mentioned above can be used singly or in combination.
- the catalystico-catalyst ratio may be about in the range of about 1 :1 to about 1 :5000, for example in the range of about 1 : 10 to about 1 :2000.
- the self-assembled olefin polymerization catalyst of the present invention may be supported by an inorganic or organic carrier material.
- the inorganic compound for the carrier may include, but is not limited to, inorganic oxides, inorganic chlorides, and other inorganic salts such as sulfates, carbonates, phosphates, nitrates, silicates, and the like.
- the inorganic compounds for the carrier may be inorganic oxides such as silica, titania, alumina, zirconia, chromia, magnesia, boron oxide, calcium oxide, zinc oxide, barium oxide, silica xerogel, silica aerogel, and mixtures thereof such as silica/chromia, silica/chromia/titania, silica/alumina, silica/titania, silica/magnesia, silica/magnesia/titania, aluminum phosphate gel.
- inorganic oxides such as silica, titania, alumina, zirconia, chromia, magnesia, boron oxide, calcium oxide, zinc oxide, barium oxide, silica xerogel, silica aerogel, and mixtures thereof such as silica/chromia, silica/chromia/titania, silica/alumina, silica/tit
- the inorganic oxide may contain a carbonate salt, a nitrate salt, a sulphate salt, an oxide, including Na 2 C0 3 , K 2 C0 3 , CaC0 3 , MgC0 3 , Na 2 S0 4 , A1 2 (S0 4 ) 3 , BaS0 4 , KN0 3 , Mg(N0 3 ) 2 , A1(N0 3 ) 3 , Na 2 0, K 2 0, and Li 2 0.
- a carbonate salt including Na 2 C0 3 , K 2 C0 3 , CaC0 3 , MgC0 3 , Na 2 S0 4 , A1 2 (S0 4 ) 3 , BaS0 4 , KN0 3 , Mg(N0 3 ) 2 , A1(N0 3 ) 3 , Na 2 0, K 2 0, and Li 2 0.
- the inorganic compound used in the present invention may also include, but is not limited to, inorganic compound polymers such as carbosilo ane, phosphazyne, siloxane, and polymer/silica composites.
- the inorganic carrier material may be, but is not limited to, silica, alumina, titania, magnesium chloride, and mixtures thereof.
- the organic compound useful as the carrier may include, but is not limited to, polyethylene, ethylene/[a] -olefin copolymers, polypropylene, polystyrenes, functionalized polyethylenes, functionalized polypropylenes, functionalized polystyrenes, polyketones and polyesters.
- Another embodiment of the present invention is directed to a process for polymerization or copolymerization of an olefin or a mixture of olefins in the presence of the self-assembled olefin polymerization catalyst according to the invention and optionally in the presence of at least one of the above mentioned co-catalysts.
- the temperature of polymerization with the olefin polymerization catalyst is in the range usually from about -50 to about +200°C, such as from about -20°C to about 150°C. In another embodiment, the temperature is in the range of about 0°C to about 100°C. In another embodiment, the temperature may be in the range of about 40 to about 60°C.
- the polymerization pressure is in the range usually from atmospheric pressure (about 0.1 MPa) to about 10 MPa. For example, the pressure may be in the range of about 0.5 to about 1.0 MPa.
- the polymerization may be conducted by any of a batch system, a semicontinuous system, and a continuous system or the like. The polymerization can be conducted in two or more steps under different reaction conditions.
- the molecular weight of the produced olefin polymer may be controlled, for example, by presence of hydrogen in the polymerization system or the change of polymerization temperature or pressure.
- polymers having a number molecular weight from about 3.000 to about 3.000.000 can be obtained. It is very useful that the catalysts of the present invention can produce low molecular weight polyolefins as well as ultra high molecular weight polyolefins of more than one million with narrow molecular weight distribution.
- the molecular weight may depend on several factors.
- the substituents of the catalyst system may influence the molecular weight, for example bulkier substituents (in particular adjacent to the WY coordination unit) may give higher molecular weight.
- a higher ethylene pressure may also contribute to a higher molecular weight.
- a higher hydrogen pressure may lead to a lower molecular weight.
- the kind of metal atom in the catalyst plays also a decisive role.
- the use of titanium may give higher molecular weight than the use of zirconium.
- the present invention also revealed that self- assembling increased molecular weight compared to corresponding mono-nuclear catalyst. In general it may be stated without being bound to any particular theory that higher molecular weight may give a higher melting point and better mechanical properties.
- the olefins which can be polymerized according to the present invention include linear or branched o «-olefins of 2-30, for example 2-20 carbon atoms.
- the olefins may be, but are not limited to, ethylene, propylene, 1 -butene, 2-butene, 1-pentene, 3- methyl- 1-butene, 1-hexene, 4-methyl- 1-pentene, 3 -methyl- 1-pentene, 1-octene, 1-decene, 1- dodecene, 1 -tetradecene, 1 -hexadecene, 1-octadecene, and 1-icosene; cycloolefins of 3-30, for example 3-20 carbon atoms such as, for example, cyclopentene, cycloheptene, norbornene, 5-methyl-2-norbornene, and tetracyclododecene; polar mono
- the diene and polyenes include cyclic or linear compounds having two or more double bonds having 4-30, such as 4- 20 carbon atoms, specifically including butadiene, isoprene, 4-methyl-l,3-pentadiene, 1,3- pentadiene, 1 ,4-pentadiene, 1 ,5-hexadiene, 1 ,4-hexadiene, 1,3-hexadiene, 1 ,3-octadiene, 1,4- octadiene, 1,5-octadiene, 1,6-octadiene, 1,7-octadiene, ethylidenenorbornene, vinylnorbornene, dicyclopentadiene, 7-methyl- 1,6-octadiene, 4-ethylidene-8-methyl-l,7- nonadiene, and 5,9-di
- aromatic vinyl compounds including mono- or polyalkylstyrenes such as styrene, o-methylstyrene, m-methylstyrene, p- methylstyrene, o,p-dimethylstyrene, o-ethylstyrene, m-ethylstyrene, p-ethylstyrene; functional group-containing styrene derivatives such as methoxystyrene, ethoxystyrene, vinylbenzoic acid, methyl vinylbenzoate, vinylbenzyl acetate, hydroxystyrene, o- chloro styrene, p-chlorostyrene, and divinylbenzene; 3-phenylpropylene, 4-phenylpropylene, and [alpha] -methylstyrene.
- mono- or polyalkylstyrenes such as styrene,
- the olefins may be, but are not limited to, C 2 -C 30 a-olefins, C 2 -C 30 functionalized alkenes, cycloalkenes, norborene and derivatives thereof, dienes, acetylenes, styrene, alkenols, alkenoic acids and derivatives or mixtures thereof.
- the olefins may be ethylene, propylene, butene, pentene, hexene, 4-methyl-l- pentene, octene, norborene or methacrylate.
- the olefin is ethylene or propylene.
- oolefins or functionalized alkenes may be used singly or in combination of two or more thereof.
- the olefins may be ethylene, C 6 alkenes, and their derivatives or mixtures thereof.
- the olefins may be ethylene and 1- hexene, their derivatives or mixtures thereof.
- the olefin polymerization catalyst of the present invention has a high polymerization activity, giving a polymer having a narrow molecular weight distribution, and giving an olefin copolymer having narrow composition distribution in copolymerization of two or more olefins.
- the olefin polymerization catalyst of the present invention may also be used for copolymerization of an Q!-olefin and a conjugated diene.
- the conjugated diene includes aliphatic conjugated dienes of 4-30, such as 4-20 carbon atoms.
- dienes may be, but are not limited to, 1,3 -butadiene, isoprene, chloroprene, 1,3-cyclo hexadiene, 1,3-pentadiene, 4-methyl-l,3-pentadiene, 1,3- hexadiene, and 1,3-octdiene.
- These conjugate dienes may be use singly or in combination of two or more thereof.
- a nonconjugated diene or a polyene may be additionally used.
- the nonconjugated diene and the polyene include, but is not limited to, 1,4-pentadiene, 1,5-hexadiene, 1 ,4-hexadiene, 1,4- octadiene, 1 ,5-octadiene, 1,6-octadiene, 1,7-octadiene, ethylidenenorbornene, vinylnorbornene, dicyclopentadiene, 7-methyl- 1,6-octadiene, 4-ethylidene-8-methyl-l,7- nonadiene, and 5,9-dimethyl-l,4,8-decatriene.
- the process for producing an olefin polymer of the present invention gives the olefin polymer having a narrow molecular weight distribution at a high yield by polymerization in the presence of the above olefin polymerization catalyst.
- the present invention provides polyolefins obtainable according to the process of the present invention.
- the polyolefins obtained may have a molecular weight in the range from low molecular weight polyolefins to ultra high molecular weight polyolefins.
- High temperature GPC analyses of polyethylene were performed on a Polymer Labs GPC-220 with a refractive index detector.
- Typical operating conditions for analyzing polyethylene are: two PLgel 10 ⁇ Mixed B columns (300*7.5 mm) and one PLgel 10 ⁇ guard column (50*7.5 mm) at 160 °C using 1 ,2,4-trichlorobenzene stabilized with 0.0125 wt. % BHT as the eluent.
- Polymer samples were prepared at a concentration of 1 mg/mL using a Polymer Labs SP260 sample preparation system at 150 °C until dissolved (typically about 4 to 6 hours), followed by filtration where necessary.
- FT-IR spectra were recorded on a Bruker Vertex 70 spectrometer.
- Laser Raman spectra were recorded on an InVia Reflex instrument (Renishaw) equipped with a near infrared enhanced deep-depleted thermo electrically Peltier cooled CCD array detector (576 x 384 pixels) and a high grade Leica microscope. The methyl branching of the copolymers was measured with FT-IR by comparison against standard samples.
- the ligand BFI-2 was synthesized via the same procedure as ligand BFI-1 using aniline (1.01 g, 10.86 mmol) and 5,5-methylene-di-3-tert-butyl-salicylaldehyde (2.00 g, 5.43 mmol) in anhydrous methanol (80 mL). After reaction, the yellow slurry was concentrated to about 10 mL. The product was filtered, washed with methanol (2> 5mL) and dried in vacuo to obtain 2.56 g of a yellow powder (91% yield).
- the ligand BFI-3 was synthesized via the same procedure as ligand BFI-1 using benzidine (1.06 g, 5.74 mmol) and 3-tert-butyl-2-hydroxy-benzaldehyde (2.09 g, 11.49 mmol) in anhydrous methanol (30 mL). The product was obtained as a yellow powder in 99% yield (2.80 g).
- 1H-NMR (CDC1 3 , 400MHz, ⁇ ): 1.51 (s, 18H, -C(CH 3 ) 3 ), 6.90-7.71 (m, 14H, aromatic-H), 8.71 (s, 2H, -CH N-), 13.96 (s, 2H, -OH).
- Second batch product (0.76 g) was obtained by further concentrating the residual solution to about 5 mL and repeating the crystallization process.
- Product obtained was 2.76 g (61 % yield).
- 1H-NMR (CDC1 3 , 400MHz, ⁇ ): 1.49 (s, 18H, -C(CH 3 ) 3 ), 6.94-7.53 (m, 6 ⁇ , aromatic-H), 8.92 (s, 2 ⁇ , - CH N-), 12.92 (s, 2 ⁇ , - ⁇ ).
- Single crystal was crystallized from toluene solution (see Fig. 7 for the crystal structure of BFI-4).
- the title catalyst MNZr-3 was synthesized via the same procedure as MNTi-3 using BFI-1 (0.50g, 0.96 mmol), BFI-2 (0.50g, 0.96 mmol) and ZrCLt (0.4474g, 1.92 mmol).
- the catalyst MNZr-3 was obtained as a pale yellow solid with a repeating unit of C 35 H 36 Cl 2 N 2 0 2 Zr. The Zr% was found to be 12.09%. Calculated against the theoretical Zr% of 13.44% in C 35 H 36 Cl 2 N 2 0 2 Zr, the residual solvent was found to be 10.04%.
- the catalyst yield was 1.41g (97%).
- Example 7 Preparation of catalysts MNTi-4 and MNTi-5
- Catalyst MNTi-4 was synthesized via the same procedure as MNTi-3 using BFI-3 (0.50g, 0.99 mmol), BPI-1 (349 mg, 0.99 mmol) and TiC (1.98 mmol).
- Catalyst MNTi-5 was synthesized via the same procedure as MNTi-3 using BFI-4 (0.50g, 0.77 mmol), BPI-1 (272 mg, 0.77 mmol) and T1CI4 (1.54 mmol).
- BFI-4 0.50g, 0.77 mmol
- BPI-1 272 mg, 0.77 mmol
- T1CI4 1.54 mmol
- Example 8 Preparation of catalyst MNTi-6 and MNZr-6 (One pot mixing) [00177] Catalysts MNTi-6 and MNZr-6 were synthesized according to the reaction scheme shown in Fig. 10.
- the catalyst has a repeating unit of C3 5 H 3 Cl 2 N 2 0 2 Ti with residual solvents which are mainly THF and a trace of DCM.
- the Ti% was found to be 6.59% by ICP. Calculated against the theoretical Ti% of 7.53% in C 35 H 3 Cl 2 N 2 0 2 Ti, the residual solvent was found to be 12.48% by weight.
- the catalyst yield was 1.36 g (97%).
- the title catalyst MNZr-6 was synthesized via the same procedure as MNTi-6 using ligand BFI-1 (0.5 g) and BFI-2 (0.5 g) (totally 1.0 g, 1.93 mmol) and equimolar ZrC -
- the multi-nuclear Zr catalyst was obtained as pale yellow solid with a repeating unit of C 35 H 36 Cl 2 N 2 0 2 Zr.
- the Zr% was found to be 12.18% by ICP.
- the catalyst yield was 1.40 g (97%).
- Catalysts MNTi-1 and MNZr-1 were synthesized according to the reaction scheme shown in Fig. 11.
- Example 9a Preparation of catalyst MNTi-1 (Comparative Example 1)
- the catalyst has a repeating unit of C 35 H 36 Cl 2 N 2 0 2 Ti with residual solvent being THF and a trace of DCM.
- the Ti% was found to be 6.52% by ICP. Calculated against the theoretical Ti% of 7.53% in C 35 H 3 Cl 2 N 2 0 2 Ti, the residual solvent was found to be 13.41% by weight.
- the catalyst yield was 1.35 g (95%).
- Example 9b Preparation of catalyst MNZr-1 (Comparative Example 2)
- Catalyst MNZr-1 was synthesized via the same procedure as MNTi-1 using ligand BFI-1 (1.00 g, 1.93 mmol) and equimolar ZrC -
- the multi-nuclear Zr catalyst was obtained as pale yellow solid with a repeating unit of C 35 H36Cl 2 N 2 0 2 Zr.
- the Zr% was found to be 12.15%.
- the catalyst yield was 1.42 g (98%).
- Catalysts MNTi-2 and MNZr-2 were synthesized according to the reaction scheme shown in Fig. 12.
- Example 10a Synthesis of catalysts MNTi-2 (Comparative Example 3)
- Catalyst MNTi-2 was synthesized via the same procedure as MNTi-1 using ligand BFI-2 (0.60 g, 1.16 mmol) in 20 mL THF and equimolar TiC in 15 mL THF.
- the multi- nuclear catalyst MNTi-2 was obtained as a deep reddish-brown solid with a repeating unit of C 35 H 36 Cl 2 N 2 0 2 Ti. The Ti% was found to be 6.58%. Calculated against the theoretical Ti% of 7.53%i in C 3 5H 36 Cl 2 N 02Ti, the residual solvent was found to be 12.62% 0 .
- the catalyst yield was 0.81g (96%).
- Example 10b Synthesis of catalyst MNZr-2 (Comparative Example 4)
- Catalyst MNZr-2 was synthesized via the same procedure as MNTi-1 using ligand BFI-4 (0.60 g, 1.16 mmol) in 20 mL THF and equimolar TiC in 15 mL THF.
- the multi- nuclear catalyst MNZr-2 was obtained as a pale yellow solid with a repeating unit of C 35 H 36 Cl 2 N 2 0 2 Zr. The Zr% was found to be 12.13%. Calculated against the theoretical Zr% of 13.44% in C 35 H 36 Cl 2 N 2 0 2 Zr, the residual solvent was found to be 9.75%.
- the catalyst yield was 0.87g (100%).
- Example 11 Preparation of mono-nuclear Ti catalyst (FI-Ti) (Comparative Example 5)
- Catalyst FI-Ti was synthesized via the same procedure as MNTi-1 using ligand (FI) (1.00 g, 3.95 mmol) and half an equivalent of TiC -
- the catalyst was obtained as a deep reddish-brown solid bearing a general formula of C 34 H 36 Cl 2 N 2 0 2 Ti with residual solvent being THF and traces of DCM.
- the Ti% was found to be 6.69%.
- Calculated against the theoretical Ti% of 7.68% in C 34 H 36 Cl 2 N 2 0 2 Ti the residual solvent was found to be 12.89%.
- the catalyst yield was 1.34 g (95%).
- Example 12 Preparation of mono-nuclear Zr catalyst (Fl-Zr) (Comparative Example 6)
- Catalyst Fl-Zr was synthesized via the same procedure as MNTi-1 using ligand (FI) (1.00 g, 3.95 mmol) and half an equivalent of ZrCU.
- the catalyst was obtained as a pale yellow solid bearing a general formula of C 34 H 36 Cl 2 N 2 0 2 Zr with residual solvent being THF and traces of DCM. The Zr% was found to be 12.18%). Calculated against the theoretical Zr% of 13.68% in C 34 H 36 Cl 2 N 2 0 2 Zr, the residual solvent was found to be 10.96%.
- the catalyst yield was 1.40 g (95%).
- FT-IR (cm "1 ): cm “1 , ⁇ ⁇ - N 330 cm “1 .
- Example 13 Catalyst Evaluation - General procedure for ethylene homo- polymerization in 300 mL reactor
- Fig. 13 is a table (Table 1) summarizing the performance of ethylene polymerization obtained using self-assembled polymerization catalysts (MNTi-3 and MNTi-6) according to embodiments of the present invention, and state of the art catalysts (MNTi-1, MNTi-2, and FI-Ti).
- Fig. 14 is a table (Table 2) summarizing the performance of ethylene polymerization obtained using self-assembled polymerization catalysts (MNZr-3 and MNZr- 6) according to embodiments of the present invention, and state of the art catalysts (MNZr-1, MNZr-2, and Fl-Zr).
- Example 14 Catalyst Evaluation - General procedure for copolymerization of ethylene and 1-hexene in 1-L reactor
- Copolymerization of ethylene and 1-hexene was carried out in a 1 L stainless steel autoclave, which was heated by recycling hot oil.
- the reactor was equipped with a small burette (10 mL) and a big burette (150 mL) connected in series for hydrogen and 1 -hexene addition, respectively. The big one was fixed directly above the reactor.
- the autoclave was dried under vacuum at 100 °C for 4 hours during which period the autoclave was swept with dry argon at least three times.
- pentane 600 mL
- the reactor was heated to 60 °C and desired amount of MAO was pressurized with Ar as well.
- the Ar pressure was controlled to about 5.0 bar at a stirring rate of 500 RPM. Varying amounts of hydrogen and 1-hexene were pressurized with ethylene, followed by the introduction of catalyst (6.0 /xmol) solution in DCM (3 mL) with Ar pressure. Then ethylene was quickly pressurized into the autoclave until the total ethylene pressure reached 6.0 bar. During the polymerization process, the ethylene pressure was maintained at 6.0 bar via mass flow controller. After the polymerization was run for 2 h, the pressure was vented quickly and the reaction was quenched with 12 mL ethanol. The produced copolymer was collected by filtration, washed with ethanol and hexane and dried in vacuo at 50 °C.
- Fig. 21 is a table (Table 5) summarizing the performance of co- polymerization of ethylene and 1-hexene using self-assembled polymerization catalysts (MNTi-4 and MNTi-5) according to embodiments of the present invention.
- Example 15 Catalyst Evaluation - Catalytic activity and stability
- the multi-nuclear catalysts were evaluated for ethylene polymerization for different reaction times (see Table 1 in Fig. 13 and Table 2 in Fig. 14). From the figures, it can be seen that the multi-nuclear catalysts (MNTi-1 to MNTi-6 and MNZr-1 to MNZr-6) displayed higher activity and better stability than the corresponding mono-nuclear catalysts (FI-Ti and Fl-Zr).
- both MNTi-3 and MNTi-6 according to embodiments of the present invention displayed 1.7 and 2.0 times higher activity, respectively, compared to that of the mono-nuclear FI-Ti catalyst at a run time of 120 minutes.
- MNTi-6 displayed a much higher activity of 1300 kg PE moi M 1 h "1 bar "1 compared to that of the mononuclear FI-Ti catalyst with an activity of 660 kgP E mol M -1 h "1 bar "1 for a 120 minutes run.
- MNZr-3 according to an embodiment of the present invention displayed a 2.2, 3.3, 4.4, 5.4, and 6.4 times higher activity at a run time of 5, 15, 30, 60 and 120 min respectively compared to that of mono-nuclear Fl-Zr catalyst.
- MNZr-3 displayed the highest activity among the four multi-nuclear catalysts MNZr-6, MNZr-1, MNZr-2 and MNZr-3.
- the cumulative activity of MNZr-3 was 1.5 and 1.7 times higher than for MNZr-1 and MNZr-2.
- MNZr-3 displayed an extremely high activity up to 12600 kgPE mo 1M "1 h "1 bar "1 .
- Fig. 15 are photographs showing the amounts of polymer produced after several reaction times of (i) 30 minutes, (ii) 60 minutes and (iii) 120 minutes using (A) MNTi-3, (B) MNTi-6 and (C) state of the art catalyst FI-Ti. From these figures, it can be seen that for both MNTi-3 and MNTi-6, the amount of polyethylene (PE) increased quickly with an increase in reaction time while for FI-Ti, the amount of polyethylene produced increased very slowly.
- Fig. 16 is a corresponding graph comparing the amount of polyethylene obtained (PE, g) with time ("productivity comparison") for MNZr-3 and MNZr-6 and state of the art catalysts MNZr-1 , MNZr-2, and Fl-Zr.
- Fig. 18 are photographs showing the amounts of polymer produced after several reaction times of (i) 5 minutes, (ii) 15 minutes, (iii) 30 minutes, (iv) 60 minutes and (v) 120 minutes using (A) MNZr-3, (B) MNZr-6 and (C) state of the art catalyst Fl-Zr. From the figures, it can be seen that the amount of polyethylene (PE) produced increased quickly with an increase in reaction time for both MNZr-3 and MNZr-6, while for Fl-Zr, the amount of polyethylene obtained increased very slowly.
- Example 16 Catalyst Evaluation - Molecular weight (MW)
- the obtained M n for the catalyst MNTi-3 are 492 x l O 3 , 903 x l O 3 and 984 x lO 3 at run times of 30 min, 60 min and 120 min respectively, all of which are higher than the corresponding values of 329 x l O 3 , 385 l O 3 and 493 x lO 3 for FI-Ti.
- the obtained M n for the catalyst MNZr-3 are 1 1.0 x l O 3 , 22.6 x l O 3 , 16.7 x lO 3 , 35.6 x l O 3 and 35.3 x l O 3 at run times of 5 min, 15 min, 30 min, 60 min and 120 min respectively, all of which are higher the corresponding values of 3.43 *10 , 3.63 lO 3 , 4.29 x l O 3 , 4.56 x l O 3 and 5.10 x l O 3 for Fl-Zr.
- Example 17 Catalyst Evaluation - Comparison of metal coordination surroundings
- Catalysts MNTi- 1 to MNTi-3 and MNZr- 1 to MNZr-3 were characterized with FT- IR and Laser-Raman, and compared with FI-Ti and Fl-Zr.
- Fig. 19 is a table (Table 3) summarizing the FTIR readings of MNTi-3 and MNZr-3, and state of the art catalysts MNTi- 1, MNTi-2, FI-Ti, MNZr-1, MNZr-2, and Fl-Zr.
- Fig. 20 is a table (Table 4) summarizing the Laser Raman readings of MNTi-3, and state of the art catalysts MNTi-1, MNTi-2, and FI-Ti.
- Example 18 Catalyst Evaluation - Multi-nuclear catalysts with hetero coordination units
- the phenoxy-imine based catalysts including various multi-nuclear catalysts and mono-nuclear catalysts, are not able to copolymerize ethylene with 1-hexene very well.
- a second ligand the bis-pyrrolide-imine ligand was used to replace the bis-phenoxy-imine in the second self-assembly step, hence forming a multi-nuclear FIPI catalyst.
- Bis-pyrrolide-imine is a smaller ligand as compared to bis-phenoxy-imine. Therefore the obtained catalyst may still have sufficient space to allow 1 -hexene to approach the central metal, thus offering the opportunity for 1-hexene to be incorporated into the polyethylene backbone.
- the experimental results showed that the multinuclear catalyst MNTi-4 produced a copolymer of ethylene and 1 -hexene with 1.6% branching.
- the fluorine-containing multinuclear catalyst MNTi-5 can increase the branching to 5.0% under identical conditions.
- the branching was further increased to 7.5% (see Table 5 of Fig. 21).
- MNTi-5 also has good hydrogen response.
- the Mn decreased gradually with the increase of the amount of hydrogen. This provides an easy way to regulate the molecular weight for practical applications.
- Example 19 Direct Use of Catalyst After Synthesized
- Catalyst purifications via re-crystallization or wash with solvents generally lose much catalyst resulting in low yields and high operation cost in catalyst production.
- all the bis-ligands and metals employed should be used in the catalyst.
- all the catalysts were used directly after synthesized without further purification. Ti% can be found by ICP to calculate the catalyst loading.
- Solvent residue (THF) in the catalyst can be removed by excess Al(III) in MAO, because Al(III) in MAO is a stronger Lewis acid than Ti(IV) in the catalyst.
- THF Solvent residue
- the catalyst can fully display its catalytic capabilities for olefin polymerization.
- the examples show that all the invention multinuclear catalysts demonstrated high activities, producing polyethylene with high molecular weight.
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Abstract
A self-assembled olefin polymerization catalyst comprising a transition metal complex according to formula (I) A-[(L2(MXn)p(MXn-L1(MXn)q-MXn-B)r-MXn)y-(L1(MXn)t(MXn-L2(MXn)u-MXn-A')vMXn)w]z-B (I) wherein each M is independently a transition metal selected from the group consisting of Group 3-11 of the periodic table; each X is independently selected from the group consisting of H, halogen, CN, optionally substituted N(Ra)2, OH, optionally substituted C1-C20 alkyl, optionally substituted C1-C20 alkoxy, wherein Ra is independently selected from the group consisting of optionally substituted C1-C20 alkyl, optionally substituted C6-C20 aryl and halogen; A is nothing, L1(MXn)g MXn-, or MXn L1(MXn)g MXn,-; A' is nothing, - L1(MXn)g MXn, or - L1(MXn)g,; B is nothing, -L2(MXn)h or -L2(MXn)h MXn; g is 0 or an integer of at least 1; h is 0 or an integer of at least 1; p is 0 or an integer of at least 1; q is 0 or an integer of at least 1; r is 0 or an integer of at least 1; t is 0 or an integer of at least 1; u is 0 or an integer of at least 1; v is 0 or an integer of at least 1; w is an integer of at least 1; y is an integer of at least 1; z is an integer of at least 1; n is an integer selected from 0-6, wherein n is selected depending on the valency of M such that the net charge of each M nucleus is zero or all ligand binding positions of M are occupied; L1 and L2 are independently selected ligands, wherein L1 and L2 are different, each of L1 and L2 having at least two linked coordination units, wherein each coordination unit binds to a different transition metal atom.
Description
SELF-ASSEMBLED MULTI-NUCLEAR CATALYST
FOR OLEFIN POLYMERIZATION
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This application claims the benefit of priority of US provisional application No. 61/317,470, filed March 25, 2010, the contents of it being hereby incorporated by reference in its entirety for all purposes.
FIELD OF THE INVENTION
[0002] The present invention relates to a self-assembled olefin polymerization catalyst, to a process for the polymerization of olefins and to the polyolefins obtained therefrom.
BACKGROUND OF THE INVENTION
[0003] Polyolefins are raw materials used in a wide range of industries, including packaging, automotives and construction. Therefore, the production of polyolefins is a very important branch of industry. The catalysts for olefin polymerization play a key role in the production process, which has led to much work in this area of research.
[0004] Amongst the catalysts studied, phenoxy-imine-based Group 4 metal catalysts (see Fig.l and Model- 1 shown in Fig. 2) have received much attention in both academia and industry because they intrinsically have high activities that compare favorably with that of commercial metallocene or half-sandwich Group 4 metal catalysts. However, this kind of phenoxy-imine-based catalysts has poor stability resulting in limited lifetimes, primarily because of the transfer of supporting ligand to aluminum in the co-catalyst mixture especially under elevated temperatures used in industry. In some cases, the catalysts decay quickly within a matter of minutes. Consequently, these catalysts are usually studied at low temperature and/or short reaction time. This greatly hinders the application of this kind of catalysts in industry. In light of the above, there is substantial incentive to develop robust phenoxy-imine catalysts with high activity and minimal catalyst decay.
[0005] As titanium and zirconium catalysts based on phenoxy-imine ligand have limited lifetime, much effort has been made to solve this problem using tetradentate ligands, which were expected to form more stable mono-nuclear catalysts of coordination model-2 (see Model-2 shown in Fig. 2). Studies have shown that the tetradentate ligands of Cn-chain-
bridged phenoxy-imine units (see II of Fig. 3, n = 2-6) form mono-nuclear catalysts. From the results obtained, it can be seen that the ligands of longer bridge (n = 5 or 6) displayed high activity for five minutes run, while the ligands of shorter bridge (n = 2 to 4) displayed low activity, and the issue of catalyst rapid deactivation was not addressed.
[0006] Some research groups believe that the tetradentate ligands incorporating titanium and zirconium may form more stable catalysts bearing the coordination model-2 (see Model- 2 in Fig. 2) with two imine-N linked. However, experimental results demonstrated that the tetradentate ligands III and XII (see Fig. 3) did not afford olefin polymerization catalysts, principally because of a destructive 1 ,2-migratory insertion of a metal-bound alkyl/polymeryl chain into the imine C=N unit. It was found subsequently that introducing an alkyl group at the position R4 (see ligand XI shown in Fig. 3) of a zirconium salicylaldiminato complex leads to a long-lived catalyst (1 hour test in toluene) for ethylene polymerization because of steric blocking of an intramolecular 1 ,2-migratory insertion. However, this steric blocking promotes a new radical catalyst decomposition mechanism in certain instances, thus resulting in far lower activities compared to the corresponding catalyst based on the FI ligand. In addition, all the zirconium complexes of ligands IV-X shown in Fig. 3 have no activity probably due to the lack of steric bulk in the phenolate 2-position.
[0007] Further studies on other types of tetradentate ligands were conducted (see XIII- XVII shown in Fig. 3). For titanium complexes, [(XIII)TiCl2] had no activity for ethylene polymerization when treated with MAO because the two chloride ligands are in trans- arrangement. The cz's-complex [(XIV)TiCl2] was also unproductive, which could be due to enhanced imine reactivity brought on by ring-strain in the diamine backbone. Complex [(XV)TiCl2] produced only a trace of polymer. Although complexes [(XVI)TiCl2] and [(XVII)TiCl2] demonstrated improved activity at 25 °C (in excess of 2 x 10 KgPE moU' h" W for a one hour test), the overall productivities are much lower at 50 °C resulting from a more rapid catalyst decomposition.
[0008] For zirconium complexes, complex [(XV)ZrCl2] produced only a trace of polymer. The complexes [(XVI)ZrCl2] and [(XVII)ZrCl2] demonstrated only low activities. Similarly, introducing a methyl group at the phenolate 5-position of the simple phenoxy-imine ligand may block the intramolecular 1 ,2-migratory insertion, however this steric blocking failed to improve the catalytic lifetime.
[0009] A family of multi-nuclear catalysts produced using the process protocol illustrated in Fig. 4 has been developed. A higher activity, better stability and improved lifetime compared to corresponding mono-nuclear catalysts have been demonstrated for this family of multi-nuclear catalysts. For example, good catalytic activities for ethylene homopolymerization to prepare high quality HDPE (High Density Polyethylene) and UHMWPE (Ultra High Molecular Weight Polyethylene), as well as co-polymerization of ethylene with small co-monomers such as propylene have been demonstrated. However, this family of catalysts does not exhibit good performance when they are used to co-polymerize ethylene with higher 1-alkenes such as 1-hexene, thereby limiting their application.
[0010] In view of the above, there remains a need for an improved catalyst which has an increased lifetime, a higher activity and which allows polymers with higher molecular weight to be obtained. In particular, there remains a need for an improved catalyst which can be used to co-polymerize ethylene with higher 1-alkenes such as 1 -hexene, while exhibiting increased lifetime and a higher activity.
SUMMARY OF THE INVENTION
[0011] In a first aspect the present invention refers to a self-assembled polymerization catalyst comprising a transition metal complex according to formula (I)
A-[(L2(MXn)p(MXn-L1(MXn)q-MXn-B)rMXn)y-(L^MXn)t(MXn-L2(MXn)u-MXn-A')vMXn)w]z-B
(I) wherein
each M is independently a transition metal selected from the group consisting Group 3-11 of the periodic table;
each X is independently selected from the group consisting of H, halogen, CN, optionally substituted N(Ra)2, OH, optionally substituted Ci-C20 alkyl, optionally substituted Ci-C20 alkoxy, wherein Ra is independently selected from the group consisting of optionally substituted Ci-C20 alkyl, optionally substituted C6-C20 aryl and halogen;
A is nothing, ΐ ΜΧ„)8ΜΧη- , or MXn ΐ ΜΧη)§ ΜΧη,-;
A' is nothing, - ΐ ΜΧη)8ΜΧη, or - L'(MXn)g,;
B is nothing, -L2(MXn)h or -L2(MXn)h MXn;
g is 0 or an integer of at least 1 ;
h is 0 or an integer of at least 1 ;
p is 0 or an integer of at least 1 ;
q is 0 or an integer of at least 1 ;
r is 0 or an integer of at least 1 ;
t is 0 or an integer of at least 1 ;
u is 0 or an integer of at least 1 ;
v is 0 or an integer of at least 1 ;
w is an integer of at least 1 ;
y is an integer of at least 1 ;
z is an integer of at least 1 ;
n is an integer selected from 0-6, wherein n is selected depending on the valency of M such that the net charge of each M nucleus is zero or all ligand binding positions of M are occupied;
L1 and L2 are independently selected ligands, wherein L1 and L2 are different,
1 2
each of L and L having at least two linked coordination units, wherein each coordination unit binds to a different transition metal atom.
[0012] In a second aspect, the present invention provides a process for polymerization or copolymerization of an olefin or a mixture of olefins in the presence of the self-assembled olefin polymerization catalyst described in the present invention.
[0013] In a third aspect, the present invention provides polyolefins obtainable according to the process of the present invention.
BRIEF DESCRIPTION OF THE DRAWINGS
[0014] The invention will be better understood with reference to the detailed description when considered in conjunction with the non-limiting examples and the accompanying drawings, in which:
[0015] Fig. 1 illustrates a reaction scheme to produce a mono-nuclear Ti (FI-Ti) and a mono-nuclear Zr (Fl-Zr) catalyst from a phenoxy-imine ligand (FI). The mono-nuclear catalysts shown are representative titanium and zirconium catalysts of the prior art based on phenoxy-imine ligand bearing coordination model- 1 as shown in Fig. 2.
[0016] Fig. 2 illustrates a comparison of three possible coordination models for a catalyst, wherein model- 1 (mono-nuclear Fl-catalyst) and model-2 (mono-nuclear tetradentate-ligand catalyst) are state of the art and model-3 (multi-nuclear catalyst) illustrates one of the possible coordination models of the present invention.
[0017] Fig. 3 illustrates a tetradentate ligand (II) forming model-2 type catalyst as shown in Fig. 2, as well as further tetradentate ligands (III-XVII) forming model-2 type catalyst as shown in Fig. 2.
[0018] Fig. 4 illustrates a state of the art self-assembling strategy in order to synthesize olefin polymerization catalysts.
[0019] Fig. 5A illustrates a self-assembling strategy in order to synthesize olefin polymerization catalysts according to an embodiment of the present invention, which is carried out in two steps. A bis-ligand (bis- ligand- 1) is added to two different metal atoms in a first step to form a bi-nuclear species. The bi-nuclear species react with a second bis-ligand (bis-ligand-2) to form a multi-nuclear self-assembled olefin polymerization catalyst (multi- nuclear catalyst). Fig. 5B illustrates a self-assembling strategy in order to synthesize olefin polymerization catalysts according to another embodiment of the present invention, which is carried out in a single step. A bis-ligand (bis-ligand- 1) and a second bis-ligand (bis-ligand-2) are added to two different metal atoms in one single step to form a multi-nuclear self- assembled olefin polymerization catalyst (multi-nuclear catalyst). Fig. 5C illustrates a self- assembling strategy in order to synthesize olefin polymerization catalysts according to a further embodiment of the present invention, which is carried out in one step. As shown, the multi-nuclear self-assembled olefin polymerization catalyst may have a disordered arrangement of the two bis-ligands (bis-ligand- 1 and bis-ligand-2), which may be in an alternate or random fashion.
[0020] Fig. 6 illustrates the molecular structure of a bis-phenoxy-imine ligand (BFI-3) obtained by single crystal X-ray diffraction. This X-ray structure clearly shows that the distance between the two coordination sites is too long for coordination of one and the same metal atom, therefore the second NO unit will coordinate with a second metal atom to form the self-assembled catalyst.
[0021] Fig. 7 illustrates the molecular structure of a bis-phenoxy-imine ligand (BFI-4) obtained by single crystal X-Ray diffraction. As in the case for BFI-3 shown in Fig. 6, this X- ray structure clearly shows that the distance between the two coordination sites is too long for
coordination of one and the same metal atom, therefore the second NO unit will coordinate with a second metal atom to form the self-assembled catalyst.
[0022] Fig. 8 illustrates the synthesis of self-assembled catalysts MNTi-3 and MNZr-3 using two different bis-phenoxy-imine ligands BFI-1 and BFI-2 in a two step process. Bis- phenoxy-imine ligand BFI-1 is added to two different metal atoms M in a first step to form a bi-nuclear species. The bi-nuclear species react with a second bis-phenoxy-imine ligand BFI- 2 to form a multi-nuclear self-assembled olefin polymerization catalyst MNTi-3 or MNZr-3 (wavy lines indicate that the depicted structure can be part of a bigger molecule that contains further repeating units. Alternatively, the wavy lines may represent the remaining, non- depicted part of the respective ligand, with or without a metal atom bound).
[0023] Fig. 9 illustrates the synthesis of self-assembled catalysts MNTi-4 and MNTi-5 using two different bis-phenoxy-imine ligands BFI-3 and BPI-1, and BFI-4 and BPI-1 respectively in a two step process. For example, in the case of MNTi-4, bis-phenoxy-imine ligand BFI-3 is added to two different metal atoms M in a first step to form a bi-nuclear species. The bi-nuclear species react with a second bis-phenoxy-imine ligand BPI-1 to form a multi-nuclear self-assembled olefin polymerization catalyst MNTi-4 (wavy lines indicate that the depicted structure can be part of a bigger molecule that contains further repeating units. Alternatively, the wavy lines may represent the remaining, non-depicted part of the respective ligand, with or without a metal atom bound).
[0024] Fig. 10 illustrates the synthesis of self-assembled catalysts MNTi-6 and MNZr-6 using two different bis-phenoxy-imine ligands BFI-1 and BFI-2 in a one step process.
[0025] Fig. 11 illustrates the synthesis of bis-phenoxy-imine ligand BFI-1 and the corresponding self-assembled catalysts MNTi-1 and MNZr-1.
[0026] Fig. 12 illustrates the synthesis of bis-phenoxy-imine ligand BFI-2 and the corresponding self-assembled catalysts MNTi-2 and MNZr-2.
[0027] Fig. 13 is a table (Table 1) summarizing the performance of ethylene polymerization obtained using self-assembled polymerization catalysts (MNTi-3 and MNTi-6) according to embodiments of the present invention, and state of the art catalysts (MNTi-1, MNTi-2, and FI-Ti). The polymerization reaction was carried out in a 300 mL stainless steel autoclave, using 100 mL hexane, 5.5 bar of ethylene pressure, 2.0 mmol of methyl aluminoxane (MAO), catalyst loading of 0.9 μη οΐ metal. Activity of the catalyst is expressed in terms of kgpEmoljvf1 h"1 bar"1.
[0028] Fig. 14 is a table (Table 2) summarizing the performance of ethylene polymerization obtained using self-assembled polymerization catalysts (MNZr-3 and MNZr- 6) according to embodiments of the present invention, and state of the art catalysts (MNZr-1, MNZr-2, and Fl-Zr). The polymerization reaction was carried out in a 300 mL stainless steel autoclave, using 100 mL hexane, 5.5 bar of ethylene pressure, 2.0 mmol of methyl aluminoxane (MAO), catalyst loading of 0.09 μη οΐ metal. Activity of the catalyst is expressed in terms of kgPEmolivf 1 h"1 bar"1.
[0029] Fig. 15 is a graph comparing the amount of polyethylene obtained (PE, g) with time ("productivity comparison") for MNTi-3 and MNTi-6, and state of the art catalysts MNTi- 1 , MNTi-2, and FI-Ti.
[0030] Fig. 16 is a graph comparing the amount of polyethylene obtained (PE, g) with time ("productivity comparison") for MNZr-3 and MNZr-6, and state of the art catalysts MNZr-1, MNZr-2, and Fl-Zr.
[0031] Fig. 17 illustrates the amounts of polymer produced after several reaction times of (i) 30 minutes, (ii) 60 minutes and (iii) 120 minutes using (A) MNTi-3, (B) MNTi-6 and (C) state of the art catalyst FI-Ti. It is shown that for both MNTi-3 and MNTi-6, the amount of polyethylene (PE) increased quickly with an increase in reaction time while for FI-Ti, the amount of polyethylene obtained increased very slowly.
[0032] Fig. 18 illustrates the amounts of polymer produced after several reaction times of (i) 5 minutes, (ii) 15 minutes, (iii) 30 minutes, (iv) 60 minutes and (v) 120 minutes using (A)
MNZr-3, (B) MNZr-6 and (C) state of the art catalyst Fl-Zr. It is shown that for both MNZr-3 and MNZr-6, the amount of polyethylene (PE) increased quickly with an increase in reaction time while for Fl-Zr, the amount of polyethylene obtained increased very slowly.
[0033] Fig. 19 is a table (Table 3) summarizing the FTIR readings of MNTi-3 and MNZr- 3, and state of the art catalysts MNTi-1, MNTi-2, FI-Ti, MNZr-1, MNZr-2, and Fl-Zr.
[0034] Fig. 20 is a table (Table 4) summarizing the Laser Raman readings of MNTi-3, and state of the art catalysts MNTi-1, MNTi-2, and FI-Ti.
[0035] Fig. 21 is a table (Table 5) summarizing the performance of co-polymerization of ethylene and 1 -hexene using self-assembled polymerization catalysts (MNTi-4, MNTi-5) according to embodiments of the present invention. The co-polymerization reaction was carried out in a 1 L stainless steel autoclave, using 600 mL of pentane, 6.0 bar of ethylene pressure, varying amounts of 1-hexene and/or hydrogen gas, catalyst loading of 6.0 μτηο\
metal and 6.0 mmol of MAO. Activity of the catalyst is expressed in terms of kgPE molM-1 h"1 bar"1.
DETAILED DESCRIPTION OF THE PRESENT INVENTION
[0036] In the following description non-limiting embodiments of the process of the invention will be explained.
[0037] In a first aspect the present invention refers to a self-assembled olefin polymerization catalyst comprising a transition metal complex according to formula (I)
wherein
each M is independently a transition metal selected from the group consisting of Group 3-11 of the periodic table;
each X is independently selected from the group consisting of H, halogen, CN, optionally substituted N(Ra)2, OH, optionally substituted Ci-C20 alkyl, optionally substituted C1-C20 alkoxy, wherein Ra is independently selected from the group consisting of optionally substituted Ci-C20 alkyl, optionally substituted C6-C20 aryl and halogen;
A is nothing, L'(MXn)g MXn- , or MXn L1(MXn)g MXn,-;
A' is nothing, - L'(MX„)g MXn, or - ΐ (ΜΧη)&;
B is nothing, -L2(MXn)h or -L2(MXn)h MXn;
g is 0 or an integer of at least 1 ;
h is 0 or an integer of at least 1 ;
p is 0 or an integer of at least 1 ;
q is 0 or an integer of at least 1 ;
r is 0 or an integer of at least 1 ;
t is 0 or an integer of at least 1 ;
u is 0 or an integer of at least 1 ;
v is 0 or an integer of at least 1 ;
w is an integer of at least 1 ;
y is an integer of at least 1 ;
z is an integer of at least 1 ;
n is an integer selected from 0-6, wherein n is selected depending on the valency of M such that the net charge of each M nucleus is zero or all ligand binding positions of M are occupied;
1 2 1 2 L and L are independently selected ligands, wherein L and L are different, each of L1 and L2 having at least two linked coordination units, wherein each coordination unit binds to a different transition metal atom.
[0038] The term "self-assembly" (SA) as used herein refers to processes in which a disordered system of pre-existing components forms an organized structure or pattern as a consequence of specific, local interactions among the components themselves, without external direction. It can be defined as the spontaneous and reversible organization of molecular units into ordered structures by non-covalent interactions.
[0039] The transition metal M is selected from the group consisting of Group 3-11 of the periodic table. The transition metal M may be, but is not limited to, Sc, Y, La, Ti, Zr, Hf, V, Nb, Ta, Sm, Yb, Cr, Mo, W, Mn, Tc, Re, Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt, Cu, Zn, or mixtures thereof. In one embodiment of the present invention, M may be Sc, Ti, Zr, Hf, V, Nb, Ta, Sm, Yb, Fe, Co, Rh, Ni or Pd, for example Ti, Zr, Hf, V, Nb, Ta, Sm, Yb, or mixtures thereof. In further embodiments of the present invention, M may be Ti, Zr, or mixtures thereof. In exemplary embodiments of the present invention, M is Ti or Zr. The selection of the respective transition metal atom may depend on the reaction conditions and/or the olefin which should be polymerized.
[0040] The transition metal M may be in the oxidation state (0). Alternatively, in another embodiment the oxidation state of the transition metal may be between (I) and (VI) depending on the further type and number of the ligands L and L . For example, M may represent a transition metal atom including, but not limited to, Sc(III), Ti(III), Ti(IV), Zr(III), Zr(IV), Hf(IV), V(III), V(IV), V(V), Nb(V), Ta(V), Fe(II), Fe(III), Co(II), Co(III), Rh(II), Rh(III), Rh(IV), Cr(III), Ni(II), and Pd(II). For example, M may be Ti(IV), Zr(IV), Hf(IV), V(III), V(IV), V(V), Nb(V), and Ta(V); such as Ti(IV), Zr(IV), and Hf(IV). This may mean that M is positively charged and thus is a metal ion.
[0041 ] The number of atoms of the transition metal M present in the self-assembled olefin
1 2 ■
polymerization catalyst will depend on the number of the ligands L and L which are present in the self-assembled catalyst. Thus, the number of atoms of the transition metal M may be in
the range of about 1 or about 2 to about 1000, for example about 1 to about 100 or about 200 or 300. However, the number of atoms of the transition metal M may also be any other integer being useful in the present invention.
[0042] X is a group which is coordinated to the transition metal atom. X may be, but is not limited to, hydrogen, halogen, CN, optionally substituted N(Ra)2, OH, optionally substituted Ci-C2o alkyl, or optionally substituted Ci-C20 alkoxy, wherein Ra is independently selected from the group consisting of optionally substituted Ci-C20 alkyl, optionally substituted C6-C20 aryl and halogen. In some embodiments, X may be H, F, CI, Br, CN, N(CH3)2, N(CH2CH3)2, CH3, CH2CH3, OCH3, OCH2CH3, OCH(CH3)3, OC(CH3)3, or OC6H6, and the like. In case multiple X moieties are present, X may be the same or different.
[0043] The symbol n in formula (I) represents an integer selected from 0-6, wherein n is selected depending on the valency of the transition metal M such that the net charge of each M nucleus is zero or all ligand binding positions of M are occupied. For example, n may be an integer from about 0-5, such as about 0-4 or about 0-3. Also, n may be 1 or 2. In one embodiment, n is 2 to form an octahedral metal configuration together with the two WY units of each of the ligands L1 and lA Further metal configurations may be possible depending on n.
1 2 1
[0044] In the above formula (I), L and L are independently selected ligands, wherein L and L2 are different i.e. L1 is not the same ligand as L2. Each of ligands L1 and L2 have at least two coordination units which are linked via a spacer Z such that each coordination unit can only bind to a different transition metal atom. This means that, for example, a ligand L1 having two separate coordination units cannot bind to the same transition metal atom with both coordination units. Instead, each coordination unit may bind to a different transition metal atom only.
[0045] In the above formula (I), g, h, p, q, r, t, u, and v may independently be 0 or may be an integer of at least 1. The values of g, h, p, q, r, t, u, and v may depend on the number of transition metal atoms in the self-assembled catalyst as well as the number of coordination units present in each of the ligands L1 and L2. For example, g, h, p, q, r, t, u, and v may independently be in the range from about 0 to about 1000, for example about 0 to about 500, about 0 to about 200, or about 0 to about 100. In various embodiments, each g, h, p, q, r, t, u, and v can independently be selected from 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10. However, each g, h, p, q, r, t, u, and v may also be any other integer being useful in the present invention.
[0046] In the above formula (I), w, y and z may independently be an integer of at least 1. The values of w, y and z may depend on the number of transition metal atoms in the self- assembled catalyst and the amount of ligands L1 and L2 present. For example, w, y and z may independently be in the range from about 0 to about 1000, for example about 0 to about 500, about 0 to about 200, or about 0 to about 100. In various embodiments, w, y and z are independently 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 15, 20, 25, 30, 35, 40, 45, or 50. However, w, y and z may also be any other integer being useful in the present invention.
[0047] In the above formula (I), A, A' and B are end groups of the complex. A may be nothing, L^MX^g MXn- , or MXn L^MX^g MX,,,-. A' may be nothing, - L'(MXn)g MXn, or - L1 (MXn)g,. B may be nothing, -L2(MX„)h or -L2(MXn)h MXn.
[0048] L1 and L2 may independently be a ligand according to formula (II)
each WY unit forms a coordination unit;
m is an integer of at least 2;
Z is a bridging spacer selected from the group consisting of optionally substituted hydrocarbons having about 2 to about 100 carbon atoms and optionally substituted hetero- hydrocarbons having about 2 to about 100 carbon atoms, wherein Z has a size, length and angle so that each coordination unit WY binds to a different transition metal atom;
each W and Y is independently a metal-coordinating moiety selected from the group consisting of a carbene, an optionally substituted C5-C2o aryl, and metal-coordinating groups comprising an oxygen atom, a sulphur atom, a selenium atom, a nitrogen atom, or a phosphorus atom in neutral or charged form;
wherein the semi-circle in the WY unit represents an optionally substituted hydrocarbon, hetero-hydrocarbon or Si-containing backbone to which the metal-coordinating moieties W and Y are bonded.
[0049] In various embodiments, the metal-coordinating group is one of an oxygen atom, a sulphur atom, a selenium atom, a nitrogen atom, or a phosphorus atom, preferably in
negatively charged form. The afore-mentioned atoms can be part of a larger group or can be bound to another atom or group, including, but not limited to hydrogen
[0050] Each of the ligands L1 and L2 may be prepared according to the process described below.
[0051] In the above formula II), m may be 2, 3, 4, 5 or 6 or an integer > 6. In case of m
1 2
case of m = 3 each of the li ands L and L may independently
[0052] Each unit WY forms a coordination unit, i.e. one transition metal atom is coordinated to both W and Y of the same WY coordination unit. The semi-circle in the WY coordination unit represents the hydrocarbon backbone to which the metal-coordinating moiety W and Y are bonded. In neutral or charged form means that both W and Y may have, for example, the charge state 0 or -1 or any other charge state which contributes to a stable molecule.
[0053] The hydrocarbon, hetero-hydrocarbon or Si-containing backbone to which the metal-coordinating moieties W and Y are bonded may be, for example, any organic compound which is capable of linking W and Y to form the coordination unit. Generally, the hydrocarbon backbone may be an optionally substituted hydrocarbon, hetero-hydrocarbon or Si-containing backbone to which the metal-coordinating moieties W and Y are bonded. In one embodiment, the hydrocarbon backbone may be, but is not limited to, an optionally substituted C6-C20 aryl group, an optionally substituted C6-C20 heteroaryl group or an optionally substituted Si group. For example, W and Y may be linked to an aromatic hydrocarbon (aryl), to a Si-chain or the like.
[0055] In the above formulae, the star indicates the bond/attachment to Z.
[0056] Also encompassed by the present invention are groups of the above formulae, wherein the coordinating atom is not negatively charged but substituted by a hydrogen atom. Coordination may then occur via the free electron pair of the heteroatom, for example.
[0057] In the above formula (II), Z is a spacer molecule, wherein the term "spacer molecule" refers to an atom or group of atoms that separate two or more groups from one another by a desired number of atoms. Any group of atoms may be used to separate those groups by the desired number of atoms. In some embodiments, spacers are optionally substituted. The spacer Z has a size, length and angle so that the at least two coordination sites WY of each of the ligands L1 and L2 can only bind to two different transition metal atoms and not to the same transition metal atom. In other words, this means that it is not possible that every coordination site of the same ligand L1, for example, may bind to one and the same transition metal atom as described in the prior art. This may require that Z is structurally constrained such that the WY units are spatially arranged such that they cannot bind to the same metal atom/ion.
[0058] In this respect, the term "hydrocarbons having about 2 to about 100 carbon atoms" refer to all possible sorts of organic compounds consisting of hydrogen and carbon, e.g. aromatic hydrocarbons (aryl), alkanes, alkenes and alkyne-based compounds, but not limited to. In one embodiment of the present invention, Z may be, but is not limited to, an optionally substituted C3-C10 alicyclic group, an optionally substituted C6-C20 aryl group, an optionally
substituted C6-C20 heteroaryl group, a system of condensed nucleus of fused two, three, four or five membered rings (which can optionally have heteroatoms in the ring system, such as naphthalene derivatives, anthracene derivates, quinoline, isoquinoline, quinazoline, acridinine, phenanthrene, naphthacene, chrysene, pyrene, or triphenylene, to name only a few illustrative examples), or a system of two, three or four C6-C20 aryl groups being connected via a N-atom, a Si-atom, an C1-C20 alkyl group, an C2-C20 alkenyl group or an C6-C20 aryl group. For example, the above terms may encompass compounds such as biphenyl, terphenyl or [(RnR12R13R14)C6-(CH2)k-C6(R15R16R17R18)], wherein k is an integer from 1 to 10, and the like. All these compounds may be optionally substituted.
[0059] The term hetero-hydrocarbons having about 2 to about 100 carbon atoms refer to all sort of organic compounds consisting of hydrogen, carbon and at least one heteroatom selected from for example N, S, O, Si or P, but not limited to. For example, this term may encompass compounds according to the formula [(RnRI2R13R14)C6-(V)d-C6(R15R16R17R18)], wherein V is Si or S and d is an integer from about 1 to about 6. All these compounds may be optionally substituted.
[0060] In case of m = 2 in formula (II), examples of the spacer Z include, but are not limited to, the following benzyl, pyridyl, napthtyl, biphenyl, terphenyl, anthacenyl, phenanthrenyl, or benzyl groups being connected via a N-atom, a Si-atom, or an C1-C20 alkyl group, an C2-C20 alkenyl group or an C6-C20 aryl group,
20, for example from 1 to about 10. In one embodiment, s may be selected from 1 , 2, 3, 4, 5 or 6. In these formulae, the star indicates the point of attachment to the WY unit.
[0061] In case of m = 3 in formula (II), Z is a tri-linker. This means that three of the WY coordination units may be bonded to the same spacer. Examples of the such spacer Z may be, but are not limited to,
[0062] In case of m = 4 in formula (II), Z is a tetrakis-linker. This means that four of the WY coordination units may be bonded to the same spacer. Examples of such spacer Z may be, but are not limited to,
star indicates the attachment to the WY unit.
[0063] Besides the above examples, Z may also be a multi-linker having five or more than five linking sites, i.e. m in formula (II) may be 5 or 6 or even more. In addition, Z may also be a polymeric backbone having a plurality of linking sites forming a macro polymeric multi- linker. The polymeric backbone may be, for example, polyethylene, polypropylene, and the like.
[0064] R and R1 to R20 in the above or below formulas may be the same or different and are each selected from the group consisting of H, optionally substituted straight- chain or branched Ci-C2o alkyl, optionally substituted straight-chain or branched C2-C20 alkenyl, optionally substituted straight-chain or branched C2-C20 alkynyl, optionally substituted C6-C2o
aryl, optionally substituted C6-C20 heteroaryl, halogen, OH, N02, and CN, wherein two or more of R to R may be bonded to each other to form a ring.
[0065] The term "optionally substituted straight-chain or branched Ci-Qo alkyl" represented by R1 to R20 refers to a fully saturated aliphatic hydrocarbon. Whenever it appears here, a numerical range, such as 1 to 20 or Ci-C20 refers to each integer in the given range, e.g. it means that an alkyl group comprises only 1 carbon atom, 2 carbon atoms, 3 carbon atoms etc. up to and including 20 carbon atoms. Examples of alky groups may be, but are not limited to, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s-butyl, t-butyl, tert.- amyl. pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl or n-decyl and the like.
[0066] The term "optionally substituted straight-chain or branched C2-C20 alkenyl" refers to an aliphatic hydrocarbon having one or more carbon-carbon double bonds. Examples of alkenyl groups may be, but are not limited to, ethenyl, propenyl, allyl or 1,4-butadienyl and the like.
[0067] The term "optionally substituted straight-chain or branched C2-C20 alkynyl" refers to an aliphatic hydrocarbon having one or more carbon-carbon triple bonds. Examples of alkynyl groups may be, but are not limited to, ethynyl, propynyl, butynyl, and the like.
[0068] The term "optionally substituted Ci-C20 alkoxy" refers to a group of formula -OR, wherein R is a Ci-C20 alkyl group. Examples of alkoxy groups may be, but are not limited to, methoxy, ethoxy, propoxy, and the like.
[0069] The term "optionally substituted C3-Cio alicyclic group" refers to a group comprising a non-aromatic ring, wherein each of the atoms forming the ring is a carbon atom. Such rings may be formed by 3 to 10 carbon atoms. Examples of alicyclic groups may be, but are not limited to, cyclopropane, cyclobutane, cyclopentane, cyclopentene, cyclopentadiene, cyclohexane, cyclohexene, cycloheptane, cycloheptene and the like.
[0070] The term "optionally substituted C6-C20 aryl" refers to an aromatic ring, wherein each of the atoms forming the ring is a carbon atom. Aromatic in this context means a group comprising a covalently closed planar ring having a delocalized 7r-electron system comprising 4b+2 7r-electrons, wherein b is an integer of at least 1 , for example 1 , 2, 3 or 4. Examples of aryl groups may be, but are not limited to, phenyl, napthalenyl, phenanthrenyl, anthracenyl, tetralinyl, fluorenyl, indenyl, and indanyl, and the like.
[0071 ] The term "optionally substituted C6-C20 heteroaryl" refers to an aromatic heterocycle. Heteroaryls may comprise at least one or more oxygen atoms or at least one or
more sulphur atoms or one to four nitrogen atoms or a combination thereof. Examples of heteroaryl groups may be, but are not limited to, furan, benzofuran, thiophene, benzothiophene, pyrrole, pyridine, indole, oxazole, benzoxazole, isoxazole, benzisoxazole, thiazole, benzothiazole, imidazole, benzimidazole, pyrazole, indazole, tetrazole, quinoline, isoquinoline, pyridazine, purine, pyrazine, furazan, triazole, benzotriazole, pteridine, phenoxazole, oxadiazole, benzopyrazole, quinolizine, cinnoline, phthalazine, quinazoline or quinoxaline, and the like.
[0072] The term "halogen" refers to fluorine, chlorine, bromine or iodine.
[0073] The term "optionally substituted Si group" refers to a group containing 1 to 5 silicon atoms which are substituted by hydrogen or an alkyl group or an aryl group. Examples of a Si group may be, but are not limited to, monosilane, methylsilyl, dimethylsilyl, ethylsilyl, diethylsilyl, phenylsilyl, methylphenylsilyl, and the like.
[0074] The term "a system of condensed nucleus" refers to compounds having at least two aromatic or non-aromatic condensed ring systems. Examples of condensed nucleus may be, but are not limited to, decalin, hydrindane, napthalene, anthracene, phenanthrene, naphthacene, pentacene, hexacene, pyrene, indene, fluorene, and the like.
[0075] The term "a system of two, three or four optionally substituted C6-C20 aryl groups being connected via a N-atom, a Si-atom, an C1-C20 alkyl group, an C2-C20 alkenyl group or an C6-C20 aryl group" refers to compounds having a N-atom, a Si-atom, an alkyl group, an alkenyl group or an aryl group as a central bonding unit to which two, three or four aryl groups are bonded.
[0076] Unless otherwise indicated, the term "optionally substituted," refers to a group in which none, one, or more than one of the hydrogen atoms has been replaced with one or more group(s) independently selected from the group consisting of alkyl, aryl, heteroaryl, hydroxy, alkoxy, halogen, carbonyl, C-amido, N-amido, isocyanato, thiocyanato, isothiocyanato, nitro, silyl, and amino, including mono- and di-substituted amino groups, and the protected derivatives of amino groups. In embodiments in which two or more hydrogen atoms have been substituted, the substituent groups may be linked to form a ring.
[0077] The term "linked to form a ring" refers to the circumstance where two atoms that are bound either to a single atom or to atoms that are themselves ultimately bound, are each bound to a linking group, such that the resulting structure forms a ring. The resulting ring comprises the two atoms, the atom (or atoms) that previously linked those atoms, and the
inker.
and the like, wherein R1 to R4 are as described above. In further embodiments of the present invention, R1, R2, R3 and R4 may be the same or different, wherein R1 is selected from the group consisting of H, CH3 and tert-butyl; R2 is selected from the group consisting of H and tert-butyl; R3 is selected from the group consisting of H, CH3, CH2CH3, and CH(CH3)2; and R4 is selected from the group consisting of H, F and CH3.
I 2
[0082] The molar ratio of the coordination unit WY to the transition metal may be in the range of about 0.5: 1 to about 6:1, for example about 1 :1 to about 3:1.
1 2
[0083] In general, the ligand compounds L and L may be prepared via a Schiff-Base condensation of the respective aldehyde or ketone and the amino substituted spacer molecule. Depending on the desired geometry of the ligand, the spacer molecule may have more than one amino substituent in order to react with more than one aldehyde and/or ketone. For example, the ligand compounds may be prepared by a Schiff-Base condensation between an aldehyde or ketone with a di-aniline, tri-aniline or tetrakis-aniline. For example, the aldehyde or ketone may include, but is not limited to,
and the like, wherein R1 to R6 are as described above. The di-aniline, tri-aniline or tetrakis- aniline may include, but is not limited to,
NH2
I
H2N— Z— NH2 H2N— Z— NH2 H N_ ;_NH
I NH2 I
N 1 H, , and the like wherein Z is as described above.
1 2
[0084] In an alternative embodiment, the ligand compounds L and L may also be prepared by a Schiff-Base condensation between an aniline and a di-aldehyde/di-ketone, tri- aldehyde/tri-ketone or tetrakis-aldehyde/tetrakis-ketone. The aniline may include, but is not limited to,
wherein R to R5 are as described above. The di-aldehyde/di-ketone, tri-aldehyde/tri-ketone or tetrakis- aldehyde/tetrakis-ketone may inclu is not limited
Z are as described above.
[0085] It will be understood that any other combination of aldehydes or ketones with the respective aniline compounds will be possible in the present invention to prepare the ligand compounds described above.
1 2
[0086] In the above described process for preparing the ligand compounds L and L the Schiff-Base condensation may be promoted by an acid catalyst or a solid catalyst. The acid catalyst may include, but is not limited to, formic acid, acetic acid, p-toluenesulfonic acid or a
Lewis acid and the like.
[0087] Following reaction with an organolithium compound or sodium hydride ( aH), the formed ligand compound, for example, L1 may be reacted with the respective metal compound, followed by addition of a second ligand compound, for example, L to form the catalyst of the present invention. In some embodiments, such as that shown in Example 8, both L1 and L2 may be mixed together prior to addition of the metal compound to form the catalyst of the present invention. The self-assembly process to form the catalyst may be carried out at any temperature, such as about -100 °C to about 50 °C, about -75 °C or about 25 °C.
[0088] The strategy of the present invention is that the specific coordination geometry of the ligands L 1 and L2 does not allow the at least two WY coordination units of each of L 1 and L2 to coordinate with one and the same transition metal atom to form a mono-nuclear complex because of the spacer's size, length and angle, hence the at least two WY units of each ligand have to coordinate with two or more different transition metal atoms, thus forming self-assembled multi-nuclear catalysts. This concept can be exemplarily taken from Fig. 5, which shows each coordination site of the linked bis-ligands coordinates to one metal atom such that self-assembling starts to achieve long-lived highly efficient polymerization catalyst. Depending on the way in which the bis-ligands self-assemble, different bis-ligand combinations can be obtained, which can form a wide range of multinuclear catalysts.
1 2
[0089] The self-assembling structure may be linear, i.e. the ligands L and L may form a long chain of bis-ligand combinations with the transition metal atoms. The self-assembling structure may also be macrocyclic i.e. the long chain of bis-ligand combinations formed may be linked to form a ring. The kind of structure of the self- assembled catalyst will depend on the geometry of the used spacer Z and the kind and number of the substituents of the ligands L1 and L2. Depending on the number of the linking sites on the spacer Z, the self-assembled catalyst of the present invention may form, for example, a 3-dimensional framework.
[0090] Referring to formula (I), when g = h = p = q = r = t = u = v = 0, w = y = z= 1, and A = A' = B = nothing, the catalyst may have the formula (III)
L2MXn L'MXn (III).
[0091] In some embodiments, the self-assembled olefin polymerization catalyst may comprise the unit
wherein the bridging spacer is
and M is Ti or Zr. In this structure "Ph" means phenyl and "t-Bu" means tert-butyl. In a catalyst of the invention the number of units may be 1 to 1000.
[0092] In some embodiments, the self-assembled olefin polymerization catalyst may comprise the unit
[0093] The self-assembled olefin polymerization catalyst of the present invention may be
used together with at least one co-catalyst. In this case a catalytic system for olefin polymerization or copolymerization is formed, which may be used as such or which may be used in connection with other catalyst compounds or components necessary in the polymerization process. The at least one co-catalyst of the present invention may be, but is not limited to, an organometallic compound, an organoaluminum oxy-compound, or an ionizing ionic compound, and the like.
[0094] In one embodiment, the co-catalyst may be selected from organometallic compounds, wherein the organometallic compound may be, but is not limited to, an organometallic compound of metals of Group 1, Group 2, Group 12 and Group 13 of the Periodic Table. For example, in case of Al compounds, the compounds may be represented by the general Formula:
Ra eAl(ORb)fHiXj wherein Ra and Rb, which may be the same or different, may be a hydrocarbon group of 1 to 15, for example 1 to 4 carbon atoms; X may be a halogen atom; and e, f, i and j are integers satisfying the conditions of 0 < e≤3, 0 <f < 3, 0 <i < 3, 0 <j < 3 and e + f + i + j = 3.
[0095] Examples of the above organoaluminum compound may include the following compounds, but are not limited to, organoaluminum compounds represented by the general formula
Ra eAl(ORb)3-f, wherein Ra and Rb, which may be the same or different, may be a hydrocarbon group of 1 to 15, for example 1 to 4 carbon atoms; and e may be a number satisfying the condition of 1.5≤ e <3.
[0096] Further exemplary compounds are represented by the general formula
Ra eAlX3- wherein Ra is a hydrocarbon group of 1 to 15, for example 1 to 4 carbon atoms; X is a halogen atom; and e may be an integer satisfying the condition of 0 < e < 3.
[0097] Further exemplary compounds are represented by the general formula
Ra eAlH3-e wherein Ra is a hydrocarbon group of 1 to 15, for example 1 to 4 carbon atoms; and e may be an integer satisfying the condition of 2 <e < 3.
[0098] Further exemplary compounds are represented by the general formula
Ra eAl(ORb)fXj wherein Ra and Rb, which may be the same or different, may be a hydrocarbon group of 1 to 15, for example 1 to 4 carbon atoms; X may be a halogen atom; and e, f and j are integers satisfying the conditions of 0 < e <3, 0 < f <3, 0 <j < 3 and e + f + j = 3.
[0099] Specific examples of the above organo aluminum compounds may include, but are not limited to, tri-n-alkylaluminums, such as trimethylaluminum, triethylaluminum, tri-n- butylaluminum, tripropylaluminum, tripentylaluminum, trihexylaluminum, trioctylaluminum and tridecylaluminum; branched-chain trialkylaluminums, such as triisopropylaluminum, triisobutylaluminum, tri-sec-butylaluminum, tri-t -butylaluminum, tri-2- methylbutylaluminum, tri-3-methylbutylaluminum, tri-2-methylpentylaluminum, tri-3- methylpentylaluminum, tri-4-methylpentylaluminum, tri-2-methylhexylaluminum, tri-3- methylhexylaluminum and tri-2-ethylhexylaluminum; tricyclo alkylaluminums, such as tricyclohexylaluminum and tricyclooctylaluminum; triarylaluminums, such as triphenylaluminum and tritolylaluminum; dialkylaluminum hydrides, such as diisobutylaluminum hydride; trialkenylaluminums represented by the formula (i- C4H9)xAly(C5Hio)z (wherein x, y and z are positive numbers, and z > 2x), such as triisoprenylaluminum; alkylaluminum alkoxides, such as isobutylaluminum methoxide, isobutylaluminum ethoxide and isobutylaluminum isopropoxide; dialkylaluminum alkoxides, such as dimethylaluminum methoxide, diethylaluminum ethoxide and dibutylaluminum butoxide; alkylaluminum sesquialkoxides, such as ethylaluminum sesquiethoxide and butylaluminum sesquibutoxide; partially alkoxylated alkylaluminums having an average composition, represented by Ra 2 5Al(ORb)o.5; dialkylaluminum aryloxides, such as diethylaluminum phenoxide, diethylaluminum(2,6-di-t-butyl-4-methylphenoxide), ethylaluminum bis-(2,6-di-t-butyl-4-methylphenoxide), diisobutylalumium(2,6-di-t-butyl-4-
methylphenoxide) and isobutylaluminum bis(2,6-di-t-butyl-4-methylphenoxide); dialkylaluminum halides, such as dimethylaluminum chloride, diethylaluminum chloride, dibutylaluminum chloride, diethylaluminum bromide and diisobutylaluminum chloride; alkylaluminum sesquihalides, such as ethylaluminum sesquichloride, butylaluminum sesquichloride and ethylaluminum sesquibromide, partially halogenated alkylaluminums, such as alkylaluminum dihalides, e.g., ethylaluminum dichloride, propylaluminum dichloride and butylaluminum dibromide; dialkylaluminum hydrides, such as diethylaluminum hydride and dibutylaluminum hydride; partially hydrogenated alkylaluminums, such as alkylaluminum dihydrides, e.g., ethylaluminum dihydride and propylaluminum dihydride; and partially alkoxylated and halogenated alkylaluminums, such as ethylaluminum ethoxychloride, butylaluminum butoxychloride and ethylaluminum ethoxybromide.
[00100] Also employable are compounds analogous to the above organo aluminum compounds. For example, there can be mentioned organo aluminum compounds wherein two or more aluminum compounds are combined through a nitrogen atom, such as (C2H5)2A1N(C2H5)A1(C2H5)2.
[00101] In one embodiment, the above organometallic compound may be a compound of a Group 1 metal of the Periodic Table and aluminum represented by the general formula
M2AlRa4 wherein M2 is Li, Na or K; and Ra is a hydrocarbon group of 1 to 15, for example 1 to 4 carbon atoms. Examples of these organo aluminum compounds include, but are not limited to, LiAl(C2H5)4 and LiAl(C7H15)4, and the like.
[00102] In a further embodiment, the above organometallic compound may be a compound of a Group 2 Metal or a Group 12 Metal of the Periodic Table represented by the general formula
RaRbM3 wherein Ra and Rb, which may be the same or different, may be a hydrocarbon group of 1 to 15, preferably 1 to 4 carbon atoms; and M3 is Mg, Zn or Cd.
[00103] Further, other compounds such as methyllithium, ethyllithium, propyllithium,
butyllithium, methylmagnesium bromide, methylmagnesium chloride, ethylmagnesium bromide, ethylmagnesium chloride, propylmagnesium bromide, propylmagnesium chloride, butylmagnesium bromide, butylmagnesium chloride, dimethylmagnesium, diethylmagnesium, dibutylmagnesium and butylethylmagnesium may also be employable as the above organometallic compound. Furthermore, combinations of compounds capable of forming the aforesaid organoaluminum compounds in the polymerization system, e.g., a combination of halogenated aluminum and alkyllithium and a combination of halogenated aluminum and alkylmagnesium, are also employable. The above organometallic compounds may be used singly or in combination.
[00104] The organoaluminum oxy-compound may be conventional aluminoxane or a benzene-insoluble organoaluminum oxy-compound as exemplified in JP-A-2(1990)/78687. The conventional aluminoxane can be prepared by, for example, the following processes, and is usually obtained as a hydrocarbon solvent solution:
(1) A process wherein such an organoaluminum compound as trialkylaluminum is added to a hydrocarbon medium suspension of a compound containing absorbed water or a salt containing water of crystallization, such as magnesium chloride hydrate, copper sulfate hydrate, aluminum sulfate hydrate, nickel sulfate hydrate or cerous chloride hydrate, to react the absorbed water or the water of crystallization with the organoaluminum compound.
(2) A process wherein water, ice or water vapor is allowed to act directly on such an organoaluminum compound as trialkylaluminum in a medium, such as benzene, toluene, ethyl ether or tetrahydrofuran.
(3) A process wherein an organotin oxide, such as dimethyltin-oxide or dibutyltin oxide, is allowed to react with such an organoaluminum compound as trialkylaluminum in a medium, such as decane, benzene or toluene.
[00105] The aluminoxane may contain a small amount of an organometallic component. The solvent or the unreacted organoaluminum compound is distilled off from the recovered solution of aluminoxane and the remainder may be redissolved in a solvent or suspended in a poor solvent of aluminoxane. Examples of the organoaluminum compound used for preparing the aluminoxane include the same organoaluminum compounds as described above. The organoaluminum compounds can be used singly or in combination.
[00106] Examples of the solvent used in preparing the aluminoxane include aromatic hydrocarbons, such as benzene, toluene, xylene, cumene and cymene; aliphatic hydrocarbons,
such as pentane, hexane, heptane, octane, decane, dodecane, hexadecane and octadecane; alicyclic hydrocarbons, such as cyclopentane, cyclohexane, cyclooctane and methylcyclopentane; petroleum fractions, such as gasoline, kerosine and gas oil; and halides of these aromatic, aliphatic and alicyclic hydrocarbons, particularly chlorides and bromides thereof. Also employable are ethers such as ethyl ether and tetrahydrofuran. Of the solvents, particularly preferable are aromatic hydrocarbons and aliphatic hydrocarbons.
[00107] The benzene- insoluble organoaluminum oxy-compound used in the invention preferably has a content of Al component which is soluble in benzene at about 60°C of usually not more than about 10%, for example not more than about 5%, such as not more than about 2%, in terms of Al atom. That is, the benzene- insoluble organoaluminum oxy- compound is preferably insoluble or hardly soluble in benzene.
[00108] The organoaluminum oxy-compound employable in the invention is, for example, an organoaluminum oxy-compound containing boron, which is represented by the following formula (XX)
R8 R7 ^R8
Al O B O— Al (XX)
/ \
R8 R8 wherein R7 is a hydrocarbon group of 1 to 10 carbon atoms; and the groups R8, which may be the same or different, may be a hydrogen atom, a halogen atom or a hydrocarbon group of 1 to 10 carbon atoms.
[00109] The organoaluminum oxy-compound containing boron that is represented by the formula (XX) can be prepared by reacting an alkylboronic acid represented by the following formula (XXI) with an organoaluminum compound in an inert solvent under an inert gas atmosphere at a temperature of about -80°C to room temperature for about 1 minute to about 24 hours:
R7-B-(OH)2 (XXI) wherein R7 is the same as mentioned above. Examples of the alkylboronic acid represented by the formula (XXI) include methylboronic acid, ethylboronic acid, isopropylboronic acid, n-propylboronic acid, n-butylboronic acid, isobutylboronic acid, n-hexylboronic acid, cyclohexylboronic acid, phenylboronic acid, 3,5-difluoroboronic acid,
pentafluorophenylboronic acid and 3,5-bis (trifluoromethyl)phenylboronic acid. Of these, preferable are methylboronic acid, n-butylboronic acid, isobutylboronic acid, 3,5- difluorophenylboronic acid and pentafluorophenylboronic acid. These alkylboronic acids are used singly or in combination. Examples of the organoaluminum compound to be reacted with the alkylboronic acid include the same organoaluminum compounds as described for the organoaluminum compounds above. These organoaluminum compounds can be used singly or in combination.
[001 10] In one embodiment the co-catalyst may be selected from organoaluminium compounds, wherein the organo aluminium compound may be, but is not limited to, trialkylaluminum such as trimethylaluminum, triethylaluminum, triisobutylalurninum, trihexylaluminum, trioctylaluminum, and tridecylaluminum; alkylaluminum halides such as diethylaluminum monochloride, diisobutylaluminum monochloride, ethylaluminum sesquichloride, and ethylaluminum dichloride; alkylaluminum hydrides such as diethylaluminum hydride, and diisobutylaluminum hydride. In one embodiment of the present invention the co-catalyst may be a methyl aluminoxane (MAO) and/or a modified methyl aluminoxane (MM AO).
[001 1 1] The organoaluminum oxy-compounds mentioned above are used singly or in combination.
[001 12] The compound that reacts with the transition metal compound to form an ion pair (also referred to as ionizing ionic compound may include, but is not limited to, Lewis acids, ionic compounds, borane compounds and carborane compounds as described in JP-A- 1(1989)/501950, JP-A-l(1989)/502036, JP-A-3(1991 )/l 79005, JP-A-3(1991)/179006, JP-A- 3(1991)/207703 and JP-A-3(1991)/207704, and U.S. Pat. No. 5,321,106. Examples further include heteropoly compounds and isopoly compounds.
[001 13] Examples of the Lewis acids include compounds represented by BR3 (wherein R is a phenyl group which may have a substituent group such as fluorine, methyl or trifluoromethyl, or a fluorine atom), such as, but are not limited to, trifluoroboron, triphenylboron, tris(4-fluorophenyl)boron, tris(3,5-difluorophenyl)boron, tris(4- fluoromethylphenyl)boron, tris(pentafluorophenyl)boron, tris(p-tolyl)boron, tris(o-tolyl)boron and tris(3,5-dimethylphenyl)boron.
[001 14] Examples of the ionic compounds include compounds represented by the following formula (XXII)
R9® R10_BQ_R12 (XXII) R13
In the above formula, R9 may be H+, carbonium cation, oxonium cation, ammonium cation, phosphonium cation, cycloheptyltrienyl cation, ferrocenium cation having a transition metal, or the like. R10 to R13, which may be the same or different, are each an organic group, preferably an aryl group or a substituted aryl group. Examples of the carbonium cation include tri-substituted carbonium cations, such as triphenylcarbonium cation, tri(methylphenyl) carbonium cation and tri(dimethylphenyl)carbonium cation. Examples of the ammonium cation include trialkylammonium cations, such as trimethylammonium cation, triethylammonium cation, tripropylammonium cation, tributylammonium cation and tri(n- butyl)ammonium cation; Ν,Ν-dialkylanilinium cations, such as N,N-dimethylanilinium cation, Ν,Ν-diethylanilinium cation and N,N-2,4,6-pentamethylanilinium cation; and dialkylammonium cations, such as di(isopropyl)ammonium cation and dicyclohexylammonium cation. Examples - of the phosphonium cation include triarylphosphonium cations, such as triphenylphosphonium cation, tri(methylphenyl)phosphonium cation and tri(dimethylphenyl)phosphonium cation.
[00115] R9 is preferably carbonium cation or ammonium cation, particularly preferably triphenylcarbonium cation, Ν,Ν-dimethylanilinium cation or N,N-diethylanilinium cation.
[00116] Examples of the ionic compounds further include trialkyl-substituted ammonium salts, Ν,Ν-dialkylanilinium salts, dialkylammonium salts and triarylphosphonium salts. Examples of the trialkyl-substituted ammonium salts include triethylammoniumtetra(phenyl)boron, tripropylammoniumtetra(phenyl)boron, tri(n- butyl)ammoniumtetra(phenyl)boron, trimethylammoniumtetra(p-tolyl)boron, trimethylammoniumtetra(o-tolyl)boron, tri(n-butyl)ammoniumtetra(pentafluorophenyl)boron, tripropylammoniumtetra-(o,p-dimethylphenyl)boron, tri(n-butyl)ammoniumtetra(m,m- dimethylphenyl)boron, tri(n-butyl)ammoniumtetra(p-trifluoromethylphenyl)boron, tri(n- butyl)ammoniumtetra(3,5-ditrifluoromethylphenyl) boron and tri(n-butyl)ammoniumtetra(o- tolyl)boron.
[00117] Examples of the Ν,Ν-dialkylanilinium salts include N,N-
dimethylaniliniumtetra(phenyl)boron, N,N-diethylaniliniumtetra(phenyl)boron and N,N- 2,4,6-pentamethylaniliniumtetra(phenyl)boron.
[00118] Examples of the dialkylammonium salts include di(l- propyl)ammoniumtetra(pentafluorophenyl)boron and dicyclohexylammoniumtetra(phenyl)boron. Examples of the ionic compounds further include triphenylcarbeniumtetrakis(pentafluorophenyl)borate, N,N- dimethylaniliniumtetrakis(pentafluorophenyl)borate,
ferroceniumtetra(pentafluorophenyl)borate, triphenylcarbeniumpentaphenylcyclopentadienyl complex, N,N-diethylaniliniumpentaphenylcyclopentadienyl complex and boron compounds represented by the following formula (XXIII) or (XXIV)
(XXIII)
[00119] Examples of the borane compounds include, but are not limited to, decaborane; salts of anions, such as bis[tri(n-butyl)ammonium]nonaborate, bis[tri(n- butyl)ammonium]decaborate, bis[tri(n-butyl)ammonium]undecaborate, bis[tri(n- butyl)ammonium]dodecaborate, bis[tri(n-butyl)ammonium]decachlorodecaborate and bis[tri(n-butyl)ammonium]dodecachlorododecaborate; and salts of metallic borane anions, such as tri(n-butyl)ammoniumbis(dodecahydridododecaborato) cobaltate(III) and bis[tri(n- butyl)ammonium]bis(dodecahydridododecaborato) nickelate(III).
[00120] Examples of the carborane compounds may include, but are not limited to, salts of anions, such as 4-carbanonaborane, 1,3-dicarbanonaborane, 6,9-dicarbadecaborane, dodecahydrido- 1 -phenyl- 1 ,3 -dicarbanonaborane, dodecahydrido- 1 -methyl- 1,3-
dicarbanonaborane, undecahydrido-l,3-dimethyl-l,3-dicarbanonaborane, 7,8- dicarbaundecaborane, 2,7-dicarbaundecaborane, undecahydrido-7,8-dimefhyl-7,8- dicarbaundecaborane, dodecahydrido-1 l -methyl-2,7-dicarbaundecaborane, tri(n- butyl)ammonium- 1 -carbadecaborate, tri(n-butyl)ammonium- 1 -carbaundecaborate, tri(n- butyl)ammonium- 1 -carbadodecaborate, tri(n-butyl)ammonium- 1 -trimethylsilyl- 1 - carbadecaborate, tri(n-butyl)ammoniumbromo- 1 -carbadodecaborate, tri(n-butyl)ammonium- 6-carbadecaborate, tri(n-butyl)ammonium-6-carbadecaborate, tri(n-butyl)ammonium-7- carbaundecaborate, tri(n-butyl)ammonium-7,8-dicarbaundecaborate, tri(n-butyl)ammonium- 2,9-dicarbaundecaborate, tri(n-butyl)ammoniumdodecahydrido-8-methyl-7,9- dicarbaundecaborate, tri(n-butyl)ammoniumundecahydrido-8-ethyl-7,9-dicarbaundecaborate, tri(n-butyl)aninioniumundecahydrido-8-butyl-7,9-dicarbaundecaborate, tri(n- butyl)ammoniumundecahydrido-8-allyl-7,9-dicarbaundecaborate, tri(n- butyl)ammoniumundecahydrido-9-trimethylsilyl-7,8-dicarbaundecaborate and tri(n- butyl)ammoniumundecahydrido-4,6-dibromo-7-carbaundecaborate; and salts of metallic carborane anions, such as tri(n-butyl)ammoniumbis(nonahydrido-l,3-dicarbanonaborato) cobaltate(III), tri(n-butyl)ammoniumbis(undecahydrido-7,8-dicarbaundecaborato)ferrate(III), tri(n-butyl)ammoniumbis(undecahydrido-7,8-dicarbaundecaborato)cobaltate(III), tri(n- butyl)ammoniumbis(undecahydrido-7,8-dicarbaundecaborato)nickelate(III), tri(n- butyl)ammoniumbis(undecahydrido-7,8-dicarbaundecaborato)cuprate(III), tri(n- butyl)ammoniumbis(undecahydrido-7,8-dicarbaundecaborato)aurate(III), tri(n- butyl)ammoniumbis(nonahydrido-7,8-dimethyl-7,8-dicarbaundecaborato)ferrate(III), tri(n- butyl)ammoniumbis(nonahydrido-7,8-dimethyl-7,8-dicarbaundecaborato)chromate(III), tri(n- butyl)ammoniumbis(tribromooctahydrido-7,8-dicarbaundecaborato)cobaltate(III), tris[tri(n- butyl)ammonium]bis(undecahydrido-7-carbaundecaborato)chromate(III), bis[tri(n- butyl)ammonium]bis(undecahydrido-7-carbaundecaborato)manganate(IV), bis[tri(n- butyl)ammonium]bis(undecahydrido-7-carbaundecaborato)cobaltate(III) and bis[tri(n- butyl)ammonium]bis(undecahydrido-7-carbaundecaborato)nickelate(IV).
[00121] The heteropoly compounds comprise an atom selected from silicon, phosphorus, titanium, germanium, arsenic and tin, and at least one atom selected from vanadium, niobium, molybdenum and tungsten. Examples of the heteropoly compounds include without limiting thereto phosphovanadic acid, germanovanadic acid, arsenovanadic acid, phosphoniobic acid, germanoniobic acid, siliconomolybdic acid, phosphomolybdic acid, titanomolybdic acid,
germanomolybdic acid, arsenomolybdic acid, stannnomolybdic acid, phosphotungstic acid, germanotungstic acid, stannotungstic acid, phosphomolybdovanadic acid, phosphotungstovanadic acid, germanotungstovanadic acid, phosphomolybdotungstovanadic acid, germanomolybdotungstovanadic acid, phosphomolybdotungstic acid and phosphomolybdomobic acid, salts of these acids with a metal of Group 1 or Group 2 of the Periodic Table, such as lithium, sodium, potassium, rubidium, cesium, beryllium, magnesium, calcium, strontium or barium, and organic salts of these acids with a triphenylethyl salt.
[00122] In one embodiment of the present invention, the co-catalyst may be a conventional methyl aluminoxane (MAO), a modified methyl aluminoxane (MMAO), a metal salt of (C6F5)4B" or a combination of an alkyl aluminium compound with MgCl2.
[00123] The ionizing ionic compounds mentioned above can be used singly or in combination.
[00124] The catalystico-catalyst ratio may be about in the range of about 1 :1 to about 1 :5000, for example in the range of about 1 : 10 to about 1 :2000.
[00125] The self-assembled olefin polymerization catalyst of the present invention may be supported by an inorganic or organic carrier material. The inorganic compound for the carrier may include, but is not limited to, inorganic oxides, inorganic chlorides, and other inorganic salts such as sulfates, carbonates, phosphates, nitrates, silicates, and the like.
[00126] In one embodiment the inorganic compounds for the carrier may be inorganic oxides such as silica, titania, alumina, zirconia, chromia, magnesia, boron oxide, calcium oxide, zinc oxide, barium oxide, silica xerogel, silica aerogel, and mixtures thereof such as silica/chromia, silica/chromia/titania, silica/alumina, silica/titania, silica/magnesia, silica/magnesia/titania, aluminum phosphate gel. The inorganic oxide may contain a carbonate salt, a nitrate salt, a sulphate salt, an oxide, including Na2C03, K2C03, CaC03, MgC03, Na2S04, A12(S04)3, BaS04, KN03, Mg(N03)2, A1(N03)3, Na20, K20, and Li20.
[00127] The inorganic compound used in the present invention may also include, but is not limited to, inorganic compound polymers such as carbosilo ane, phosphazyne, siloxane, and polymer/silica composites.
[00128] In one embodiment of the present invention the inorganic carrier material may be, but is not limited to, silica, alumina, titania, magnesium chloride, and mixtures thereof.
[00129] In a further embodiment of the present invention, the organic compound useful as
the carrier may include, but is not limited to, polyethylene, ethylene/[a] -olefin copolymers, polypropylene, polystyrenes, functionalized polyethylenes, functionalized polypropylenes, functionalized polystyrenes, polyketones and polyesters.
[00130] Another embodiment of the present invention is directed to a process for polymerization or copolymerization of an olefin or a mixture of olefins in the presence of the self-assembled olefin polymerization catalyst according to the invention and optionally in the presence of at least one of the above mentioned co-catalysts.
[00131 ] The temperature of polymerization with the olefin polymerization catalyst is in the range usually from about -50 to about +200°C, such as from about -20°C to about 150°C. In another embodiment, the temperature is in the range of about 0°C to about 100°C. In another embodiment, the temperature may be in the range of about 40 to about 60°C. The polymerization pressure is in the range usually from atmospheric pressure (about 0.1 MPa) to about 10 MPa. For example, the pressure may be in the range of about 0.5 to about 1.0 MPa. The polymerization may be conducted by any of a batch system, a semicontinuous system, and a continuous system or the like. The polymerization can be conducted in two or more steps under different reaction conditions.
[00132] The molecular weight of the produced olefin polymer may be controlled, for example, by presence of hydrogen in the polymerization system or the change of polymerization temperature or pressure. With the catalyst of the present invention polymers having a number molecular weight from about 3.000 to about 3.000.000 can be obtained. It is very useful that the catalysts of the present invention can produce low molecular weight polyolefins as well as ultra high molecular weight polyolefins of more than one million with narrow molecular weight distribution.
[00133] The molecular weight may depend on several factors. For example, the substituents of the catalyst system may influence the molecular weight, for example bulkier substituents (in particular adjacent to the WY coordination unit) may give higher molecular weight. Further, a higher ethylene pressure may also contribute to a higher molecular weight. Also, a higher hydrogen pressure may lead to a lower molecular weight. The kind of metal atom in the catalyst plays also a decisive role. For example, the use of titanium may give higher molecular weight than the use of zirconium. The present invention also revealed that self- assembling increased molecular weight compared to corresponding mono-nuclear catalyst. In general it may be stated without being bound to any particular theory that higher molecular
weight may give a higher melting point and better mechanical properties.
[00134] The olefins which can be polymerized according to the present invention include linear or branched o«-olefins of 2-30, for example 2-20 carbon atoms. In one embodiment the olefins may be, but are not limited to, ethylene, propylene, 1 -butene, 2-butene, 1-pentene, 3- methyl- 1-butene, 1-hexene, 4-methyl- 1-pentene, 3 -methyl- 1-pentene, 1-octene, 1-decene, 1- dodecene, 1 -tetradecene, 1 -hexadecene, 1-octadecene, and 1-icosene; cycloolefins of 3-30, for example 3-20 carbon atoms such as, for example, cyclopentene, cycloheptene, norbornene, 5-methyl-2-norbornene, and tetracyclododecene; polar monomers: including ,β- unsaturated carboxylic acid such as acrylic acid, methacrylic acid, fumaric acid, maleic anhydride, itaconic acid, itaconic anhydride, and bicyclo[2.2.1]-5-heptene-2,3-dicarboxylic acid anhydride, and αι,/3-unsaturated carboxylic acid metal salts such as salts thereof of sodium, potassium, lithium, zinc, magnesium, and calcium; α,/3-unsaturated carboxylic acid esters such as methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, t-butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, and isobutyl methacrylate; vinyl esters such as vinyl acetate, vinyl propionate, vinyl caproate, vinyl caprylate, vinyl laureate, vinyl stearate, and vinyl trifluoroacetate; and unsaturated glycidyl esters such as glycidyl acrylate, glycidyl methacrylate, and monoglycidyl itaconate.
[00135] Vinylcyclohexane, dienes, and polyenes are also useful. The diene and polyenes include cyclic or linear compounds having two or more double bonds having 4-30, such as 4- 20 carbon atoms, specifically including butadiene, isoprene, 4-methyl-l,3-pentadiene, 1,3- pentadiene, 1 ,4-pentadiene, 1 ,5-hexadiene, 1 ,4-hexadiene, 1,3-hexadiene, 1 ,3-octadiene, 1,4- octadiene, 1,5-octadiene, 1,6-octadiene, 1,7-octadiene, ethylidenenorbornene, vinylnorbornene, dicyclopentadiene, 7-methyl- 1,6-octadiene, 4-ethylidene-8-methyl-l,7- nonadiene, and 5,9-dimethyl-l,4,8-decatriene. Further useful are aromatic vinyl compounds including mono- or polyalkylstyrenes such as styrene, o-methylstyrene, m-methylstyrene, p- methylstyrene, o,p-dimethylstyrene, o-ethylstyrene, m-ethylstyrene, p-ethylstyrene; functional group-containing styrene derivatives such as methoxystyrene, ethoxystyrene, vinylbenzoic acid, methyl vinylbenzoate, vinylbenzyl acetate, hydroxystyrene, o- chloro styrene, p-chlorostyrene, and divinylbenzene; 3-phenylpropylene, 4-phenylpropylene, and [alpha] -methylstyrene.
[00136] In one embodiment of the present invention the olefins may be, but are not limited to, C2-C30 a-olefins, C2-C30 functionalized alkenes, cycloalkenes, norborene and derivatives thereof, dienes, acetylenes, styrene, alkenols, alkenoic acids and derivatives or mixtures thereof. Thus, the olefins may be ethylene, propylene, butene, pentene, hexene, 4-methyl-l- pentene, octene, norborene or methacrylate. In one embodiment the olefin is ethylene or propylene. These oolefins or functionalized alkenes may be used singly or in combination of two or more thereof. In some embodiments, the olefins may be ethylene, C6 alkenes, and their derivatives or mixtures thereof. In further embodiments, the olefins may be ethylene and 1- hexene, their derivatives or mixtures thereof.
[00137] The olefin polymerization catalyst of the present invention has a high polymerization activity, giving a polymer having a narrow molecular weight distribution, and giving an olefin copolymer having narrow composition distribution in copolymerization of two or more olefins.
[00138] The olefin polymerization catalyst of the present invention may also be used for copolymerization of an Q!-olefin and a conjugated diene.
[00139] The conjugated diene includes aliphatic conjugated dienes of 4-30, such as 4-20 carbon atoms. Examples of such dienes may be, but are not limited to, 1,3 -butadiene, isoprene, chloroprene, 1,3-cyclo hexadiene, 1,3-pentadiene, 4-methyl-l,3-pentadiene, 1,3- hexadiene, and 1,3-octdiene. These conjugate dienes may be use singly or in combination of two or more thereof.
[00140] In the present invention, in copolymerization of an a-olefin and a conjugated diene, a nonconjugated diene or a polyene may be additionally used. The nonconjugated diene and the polyene include, but is not limited to, 1,4-pentadiene, 1,5-hexadiene, 1 ,4-hexadiene, 1,4- octadiene, 1 ,5-octadiene, 1,6-octadiene, 1,7-octadiene, ethylidenenorbornene, vinylnorbornene, dicyclopentadiene, 7-methyl- 1,6-octadiene, 4-ethylidene-8-methyl-l,7- nonadiene, and 5,9-dimethyl-l,4,8-decatriene.
[00141] The process for producing an olefin polymer of the present invention gives the olefin polymer having a narrow molecular weight distribution at a high yield by polymerization in the presence of the above olefin polymerization catalyst.
[00142] In a third aspect, the present invention provides polyolefins obtainable according to the process of the present invention. The polyolefins obtained may have a molecular weight
in the range from low molecular weight polyolefins to ultra high molecular weight polyolefins.
[00143] The invention illustratively described herein may suitably be practiced in the absence of any element or elements, limitation or limitations, not specifically disclosed herein. Thus, for example, the terms "comprising", "including", "containing", etc. shall be read expansively and without limitation. Additionally, the terms and expressions employed herein have been used as terms of description and not of limitation, and there is no intention in the use of such terms and expressions of excluding any equivalents of the features shown and described or portions thereof, but it is recognized that various modifications are possible within the scope of the invention claimed. Thus, it should be understood that although the present invention has been specifically disclosed by preferred embodiments and optional features, modification and variation of the inventions embodied therein herein disclosed may be resorted to by those skilled in the art, and that such modifications and variations are considered to be within the scope of this invention.
[00144] The invention has been described broadly and generically herein. Each of the narrower species and subgeneric groupings falling within the generic disclosure also form part of the invention. This includes the generic description of the invention with a proviso or negative limitation removing any subject matter from the genus, regardless of whether or not the excised material is specifically recited herein.
[00145] Other embodiments are within the following claims and -non- limiting examples. In addition, where features or aspects of the invention are described in terms of Markush groups, those skilled in the art will recognize that the invention is also thereby described in terms of any individual member or subgroup of members of the Markush group. EXAMPLES
[00146] General Consideration of Materials and Characterization
[00147] 4,4'-Diaminodiphenylmethane, benzidine, 4,4'-diaminooctafluorobiphenyl, 3-tert- butyl-2-hydroxy-benzaldehyde, pyrrole-2-carboxaldehyde and anhydrous hexane were purchased from Sigma-Aldrich and used without pre-treatment. 5,5-Methylene-di-3-tert- butyl-salicylaldehyde was prepared according to literature methods. Methyl aluminoxane solution (Al%: -5.2%) in toluene was purchased from Chemtura Organometallics GmbH and used directly without any pre-treatment. Methanol was dried over 4°A molecular sieves.
Dichloromethane (DCM) and tetrahydrofuran (THF) were purified using an MBRAUN-SPS solvent purification system. Experiments that involve air-sensitive materials were carried out by using standard Schlenk line techniques or in a glove box under an atmosphere of argon.
[00148] 1H-NMR and 13C-NMR were recorded in CDC13 on a BRUKER 400 spectrometer. HRMS(EI) was performed on a Thermo Finnigan MAT 95. HRMS(ESI) was performed on an Agilent LC-MS TOF. Elemental analysis was performed on a EuroEA3000 Series Elemental Analyzer. Metal content was tested with ICP.
[00149] High temperature GPC analyses of polyethylene were performed on a Polymer Labs GPC-220 with a refractive index detector. Typical operating conditions for analyzing polyethylene are: two PLgel 10 μιτι Mixed B columns (300*7.5 mm) and one PLgel 10 μπι guard column (50*7.5 mm) at 160 °C using 1 ,2,4-trichlorobenzene stabilized with 0.0125 wt. % BHT as the eluent. Polymer samples were prepared at a concentration of 1 mg/mL using a Polymer Labs SP260 sample preparation system at 150 °C until dissolved (typically about 4 to 6 hours), followed by filtration where necessary.
[00150] FT-IR spectra were recorded on a Bruker Vertex 70 spectrometer. Laser Raman spectra were recorded on an InVia Reflex instrument (Renishaw) equipped with a near infrared enhanced deep-depleted thermo electrically Peltier cooled CCD array detector (576 x 384 pixels) and a high grade Leica microscope. The methyl branching of the copolymers was measured with FT-IR by comparison against standard samples.
[00151] Example 1: Preparation of bis-phenoxy-imine ligand (BFI-1)
[00152] 4,4'-Diaminodiphenylmethane (1.34 g, 6.76 mmol) was dissolved in anhydrous methanol (25 mL). After stirring for several minutes, 3-tert-butyl-2-hydroxy-benzaldehyde (2.65 g, 14.87 mmol) was added, followed by several drops of formic acid. The resulting mixture was stirred for one hour at room temperature and then refluxed for one day under argon atmosphere. After cooling to room temperature, the product was isolated by filtration, washed with methanol (12 mL) and dried in vacuo, resulting in 3.45 g of a yellow powder, yield 98%. 1H-NMR (CDC13, 400MHz, δ): 1.50 (s, 18H, -C(CH3)3), 4.04 (s, 2H, -CH2-), 6.87-7.42 (m, 14H, aromatic-H), 8.63 (s, 2H, -CH=N-), 13.96 (s, 2H, -OH). 13C-NMR (CDC13, 100MHz, δ): 29.38, 34.93, 41.04, 118.34, 119.13, 121.37, 129.89, 130.30, 130.62, 137.67, 139.64, 146.66, 160.55, 162.90. Elemental analysis C35H38N202 (518.71): Calc: C 81.05%, H 7.38%, N 5.40%; Found: C 80.89%, H 7.41%, N 5.46%. HRMS (EI, m/z): Calculated 518.2933; Found 518.2903(M+).
[00153] Example 2: Preparation of bis-phenoxy-imine ligand (BFI-2)
[00154] The ligand BFI-2 was synthesized via the same procedure as ligand BFI-1 using aniline (1.01 g, 10.86 mmol) and 5,5-methylene-di-3-tert-butyl-salicylaldehyde (2.00 g, 5.43 mmol) in anhydrous methanol (80 mL). After reaction, the yellow slurry was concentrated to about 10 mL. The product was filtered, washed with methanol (2> 5mL) and dried in vacuo to obtain 2.56 g of a yellow powder (91% yield). Ή-NMR (CDC13, 400MHz, δ): 1.46 (s, 18H, - C(CH3)3), 3.92 (s, 2H, -CH2-), 7.00-7.42 (m, 14H, aromatic-H), 8.57 (s, 2H, -CH=N-), 13.79 (s, 2H, -OH). 13C-NMR (CDC13, 100MHz, δ): 29.41, 34.93, 40.41, 1 18.93, 121.18, 126.68, 129.36, 130.28, 130.70, 131.32, 137.76, 148.53, 158.94, 163.38. Elemental analysis C35H38N202 (518.71): Calc: C 81.05%, H 7.38%, N 5.40%; Found: C 81.09%, H 7.46%, N 5.47%. HRMS (ESI): Calculated for [M+H]+: 519.3006; Found 519.3004.
[00155] Example 3: Preparation of bis-phenoxy-imine ligand (BFI-3)
[00156] The ligand BFI-3 was synthesized via the same procedure as ligand BFI-1 using benzidine (1.06 g, 5.74 mmol) and 3-tert-butyl-2-hydroxy-benzaldehyde (2.09 g, 11.49 mmol) in anhydrous methanol (30 mL). The product was obtained as a yellow powder in 99% yield (2.80 g). 1H-NMR (CDC13, 400MHz, δ): 1.51 (s, 18H, -C(CH3)3), 6.90-7.71 (m, 14H, aromatic-H), 8.71 (s, 2H, -CH=N-), 13.96 (s, 2H, -OH). 13C-NMR (CDC13, 100MHz, δ): 29.36, 34.94, 118.41, 119.12, 121.74, 127.87, 130.48, 130.71, 137.72, 138.80, 147.64, 160.61, 163.1 1. Elemental analysis C34H36N202 (504.68): Calc. C 80.92%, H 7.19%, N 5.55%; Found C 80.98%, H 7.12%, N 5.62%. HRMS(EI, m/z): Calculated 504.2777; Found 504.2823(M+). Single crystal was crystallized from toluene solution (see Fig. 6 for the crystal structure of BFI-3).
[00157] Example 4: Preparation of bis-phenoxy-imine ligand (BFI-4)
[00158] 4,4'-diaminooctafluorobiphenyl (2.30 g, 7.0 mmol) and 3-tert-butyl-2-hydroxy- benzaldehyde (3.0 g, 16.8 mmol) were dissolved in anhydrous toluene (40 mL), followed by addition of 12 mg of para-toluenesulphonic acid. The resulting mixture was refluxed for 4 days. The solution was concentrated to about 10 mL and kept in fridge. Crystal was filtered, washed with cold toluene (2 mL) and dried in vacuo to give 2.0 g of product. Second batch product (0.76 g) was obtained by further concentrating the residual solution to about 5 mL and repeating the crystallization process. Product obtained was 2.76 g (61 % yield). 1H-NMR (CDC13, 400MHz, δ): 1.49 (s, 18H, -C(CH3)3), 6.94-7.53 (m, 6Η, aromatic-H), 8.92 (s, 2Η, - CH=N-), 12.92 (s, 2Η, -ΟΗ). Elemental analysis C34H28F8N202 (648.59): Calc. C 62.96%, H
4.35%, N 4.32%; Found C 63.08%, H 4.04%, N 4.32%. Single crystal was crystallized from toluene solution (see Fig. 7 for the crystal structure of BFI-4).
[00159] Example 5: Preparation of bis-pyrrolide-imine ligand (BPI-1V
[00160] 4,4'-Diaminodiphenylmethane (2.61 g, 13.2 mmol) and pyrrole-2-carboxaldehyde (2.51 g, 26.4 mmol) were dissolved in anhydrous methanol (60 mL). After adding several drops of formic acid, the resulting mixture was stirred at room temperature for 2 days. The light yellow powder was filtered, washed with methanol (10 mL) and dried in vacuo to obtain 3.56 g product (77% yield). Ή-NMR (DMSO, 400MHz, δ): 3.92 (s, 2H, -CH2-), 6.18-7.00 (m, 6H, pyrrole-H), 7.11 (d, 4H, J=8.3 Hz, Phenyl-H), 7.23 (d, 4H, J=8.3 Hz, Phenyl-H), 8.29 (s, 2H, -CH=N-), 11.70 (s, broad, 2H, -OH). 13C-NMR (DMSO, 100MHz, δ): 40.06, 109.65, 116.21, 120.77, 123.68, 129.41, 130.55, 138.17, 149.98.
[00161] Example 6: Preparation of catalysts MNTi-3 and MNZr-3
[00162] Catalysts MNTi-3 and MNZr-3 were synthesized according the reaction scheme shown in Fig. 8.
[00163] Example 6a: Preparation of catalyst MNTi-3
[00164] (i) Preparation of BFI-1 -(TiChT solution in THF
[00165] To a stirred solution of BFI-1 (0.50 g, 0.96 mmol) in THF (15 mL), a solution of n- butyllithium (1.6M, 1.2 mL, 1.92 mmol) in hexane was added dropwise over a period of 10 minutes at -78°C. Then the mixture was allowed to warm to room temperature and stirred for two hours. The resulting solution was added dropwise to a stirred solution of TiCL, (0.3642 g, 1.92 mmol) in THF (15 mL) at -78 °C via a cannula over a period of 20 minutes. The resulting mixture was again warmed to room temperature and stirred for 18 hours affording a solution of BFI-1 -(TiCl3)2 in THF.
[00166] fip Preparation of catalyst MNTi-3
[00167] To a stirred solution of BFI-2 (0.50 g, 0.96 mmol) in THF (15 mL), a solution of n- butyllithium (1.6M, 1.2 mL, 1.92 mmol) in hexane was added dropwise over a period of 10 minutes at -78°C. Then the mixture was allowed to warm to room temperature and stirred for two hours. The resulting solution was added dropwise to the solution of BFI-1 -(TiCl3)2 via a cannula over a period of 20 minutes at -78°C. The resulting mixture was warmed to room temperature and stirred for 18 hours. After removal of THF, the residue was extracted with DCM (40 mL) and filtered to give a clear solution. Removal of DCM gave a deep reddish- brown solid which is the multi-nuclear catalyst bearing a repeating unit of C35H36Cl2N202Ti
with residual solvent being THF and traces of DCM. The catalyst was ground to a powder and dried in vacuo at room temperature. The Ti% was found to be 6.55%. Calculated against the theoretical Ti% of 7.53% in C35H36Cl2N202Ti, the residual solvent was found to be 13.01 %. The catalyst yield was 1.38g (99%). FT-IR (cm"1): DC=N=1554 cm"1, un-o=498 cm"1, uTi-ci=458 cm"1, υτί-Ν=362 cm"1. Raman (cm"1): UC=N= 584 and 1541 cm"1,uTi-o=884, 866, 549 and 425 cm"1,
cm"1.
[00168] Example 6b: Preparation of catalyst MNZr-3
[00169] The title catalyst MNZr-3 was synthesized via the same procedure as MNTi-3 using BFI-1 (0.50g, 0.96 mmol), BFI-2 (0.50g, 0.96 mmol) and ZrCLt (0.4474g, 1.92 mmol). The catalyst MNZr-3 was obtained as a pale yellow solid with a repeating unit of C35H36Cl2N202Zr. The Zr% was found to be 12.09%. Calculated against the theoretical Zr% of 13.44% in C35H36Cl2N202Zr, the residual solvent was found to be 10.04%. The catalyst yield was 1.41g (97%). FT-IR (cm"1): uc=N=1553 cm"1, uZr-o=445 cm'1, uZr-Ci=370 cm"1, uZr- N=330 cm"1.
[00170] Example 7: Preparation of catalysts MNTi-4 and MNTi-5
[00171 ] Catalysts MNTi-4 and MNZr-4 were synthesized according to the reaction scheme shown in Fig. 9.
[00172] Example 7a: Preparation of catalyst MNTi-4
[00173] Catalyst MNTi-4 was synthesized via the same procedure as MNTi-3 using BFI-3 (0.50g, 0.99 mmol), BPI-1 (349 mg, 0.99 mmol) and TiC (1.98 mmol). The catalyst MNTi-
4 was obtained as a reddish-brown solid with a repeating unit of ½(C57H52Ci4N602Ti2). The Ti% was found to be 7.62%. Calculated against the theoretical Ti% of 8.78% in ½(C57H52Ci4N 02Ti2), the residual solvent was found to be 13.21 %. The catalyst yield was 1.12g (92%).
[00174] Example 7b: Preparation of catalyst MNTi-5
[00175] Catalyst MNTi-5 was synthesized via the same procedure as MNTi-3 using BFI-4 (0.50g, 0.77 mmol), BPI-1 (272 mg, 0.77 mmol) and T1CI4 (1.54 mmol). The catalyst MNTi-
5 was obtained as a reddish-brown solid with a repeating unit of ½(C57H44Ci4F8N602Ti2). The Ti% was found to be 6.81 %. Calculated against the theoretical Ti% of 1.15% in ½( C57H44Ci4F8N602Ti2), the residual solvent was found to be 12.12%. The catalyst yield was 1.03g (97%).
[00176] Example 8: Preparation of catalyst MNTi-6 and MNZr-6 (One pot mixing)
[00177] Catalysts MNTi-6 and MNZr-6 were synthesized according to the reaction scheme shown in Fig. 10.
[00178] Example 8a: Preparation of catalyst MNTi-6
[00179] To a stirred solution of BFI-1 (0.5 g) and BFI-2 (0.5 g) (totally 1.00 g, 1.93 mmol) in THF (20 mL), a solution of n-butyllithium (1.6 M, 2.4 mL, 3.86 mmol) in hexane was added dropwise over a period of 10 minutes at -78°C. Then the mixture was allowed to warm to room temperature and stirred for two hours. The resulting solution was added dropwise to a stirred solution of TiC (0.3657 g, 1.93 mmol) in THF (15 mL) at -78 °C via a cannula over a period of 20 minutes. The resulting mixture was again warmed to room temperature and stirred overnight for 18 hours. After removal of THF, the residual solid was extracted with 30 mL DCM and filtered to give a clear solution. Removal of DCM gave a deep reddish- brown solid which was ground to powder with a spatula and then dried in vacuo at room temperature. The catalyst has a repeating unit of C35H3 Cl2N202Ti with residual solvents which are mainly THF and a trace of DCM. The Ti% was found to be 6.59% by ICP. Calculated against the theoretical Ti% of 7.53% in C35H3 Cl2N202Ti, the residual solvent was found to be 12.48% by weight. The catalyst yield was 1.36 g (97%).
[00180] Example 8b: Preparation of catalyst MNZr-6
[00181] The title catalyst MNZr-6 was synthesized via the same procedure as MNTi-6 using ligand BFI-1 (0.5 g) and BFI-2 (0.5 g) (totally 1.0 g, 1.93 mmol) and equimolar ZrC - The multi-nuclear Zr catalyst was obtained as pale yellow solid with a repeating unit of C35H36Cl2N202Zr. The Zr% was found to be 12.18% by ICP. Calculated against the theoretical Zr% of 13.44% in C34H36Cl2N202Zr, the residual solvent was found to be 9.38%. The catalyst yield was 1.40 g (97%).
[00182] Example 9: Preparation of catalysts MNTi-1 and MNZr-1
[00183] Catalysts MNTi-1 and MNZr-1 were synthesized according to the reaction scheme shown in Fig. 11.
[00184] Example 9a: Preparation of catalyst MNTi-1 (Comparative Example 1)
[00185] To a stirred solution of BFI-1 (1.00 g, 1.93 mmol) in THF (20 mL), a solution of n- butyllithium (1.6M, 2.4 mL, 3.86 mmol) in hexane was added dropwise over a period of 10 minutes at -78°C. Then the mixture was allowed to warm to room temperature and stirred for two hours. The resulting solution was added dropwise to a stirred solution of TiC (0.3657 g, 1.93 mmol) in THF (15 mL) at -78 °C via a cannula over a period of 20 minutes. The
resulting mixture was again warmed to room temperature and stirred overnight for 18 hours. After removal of THF, the residual solid was extracted with 30 mL DCM and filtered to give a clear solution. Removal of DCM gave a deep reddish-brown solid which was ground to powder with a spatula and then dried in vacuo at room temperature. The catalyst has a repeating unit of C35H36Cl2N202Ti with residual solvent being THF and a trace of DCM. The Ti% was found to be 6.52% by ICP. Calculated against the theoretical Ti% of 7.53% in C35H3 Cl2N202Ti, the residual solvent was found to be 13.41% by weight. The catalyst yield was 1.35 g (95%). FT-IR (cm"1): UC=N=1554 cm"1, uri-o=498 cm"1, υ·π-α=460 cm"1, uTi-N=360 cm"1. Raman (cm"1):
υτ,. N=325 cm"1.
[00186] Example 9b: Preparation of catalyst MNZr-1 (Comparative Example 2)
[00187] Catalyst MNZr-1 was synthesized via the same procedure as MNTi-1 using ligand BFI-1 (1.00 g, 1.93 mmol) and equimolar ZrC - The multi-nuclear Zr catalyst was obtained as pale yellow solid with a repeating unit of C35H36Cl2N202Zr. The Zr% was found to be 12.15%. Calculated against the theoretical Zr% of 13.44% in C34H36Cl2N202Zr, the residual solvent was found to be 9.60%. The catalyst yield was 1.42 g (98%). FT-IR (cm"1): r>c=N=1553 cm"1, uzr-o=445 cm"1, uzr-ci=370 cm"1, uzR-N=330 cm"1.
[00188] Example 10: Preparation of catalysts MNTi-2 and MNZr-2
[00189] Catalysts MNTi-2 and MNZr-2 were synthesized according to the reaction scheme shown in Fig. 12.
[00190] Example 10a: Synthesis of catalysts MNTi-2 (Comparative Example 3)
[00191] Catalyst MNTi-2 was synthesized via the same procedure as MNTi-1 using ligand BFI-2 (0.60 g, 1.16 mmol) in 20 mL THF and equimolar TiC in 15 mL THF. The multi- nuclear catalyst MNTi-2 was obtained as a deep reddish-brown solid with a repeating unit of C35H36Cl2N202Ti. The Ti% was found to be 6.58%. Calculated against the theoretical Ti% of 7.53%i in C35H36Cl2N 02Ti, the residual solvent was found to be 12.62%0. The catalyst yield was 0.81g (96%). FT-IR (cm"1):
cm"1.
[00192] Example 10b: Synthesis of catalyst MNZr-2 (Comparative Example 4)
[00193] Catalyst MNZr-2 was synthesized via the same procedure as MNTi-1 using ligand BFI-4 (0.60 g, 1.16 mmol) in 20 mL THF and equimolar TiC in 15 mL THF. The multi- nuclear catalyst MNZr-2 was obtained as a pale yellow solid with a repeating unit of
C35H36Cl2N202Zr. The Zr% was found to be 12.13%. Calculated against the theoretical Zr% of 13.44% in C35H36Cl2N202Zr, the residual solvent was found to be 9.75%. The catalyst yield was 0.87g (100%). FT-IR (cm"1): DC=N=1551 cm"1, υΖΓ-Ν=330 cm"1.
[00194] Example 11: Preparation of mono-nuclear Ti catalyst (FI-Ti) (Comparative Example 5)
[00195] (i) Preparation of phenoxy-imine ligand (FI)
[00196] Aniline (1.44 g, 15.46 mmol) was dissolved into anhydrous methanol (25 mL) under stirring. Then 3-tert-butyl-2-hydroxy-benzaldehyde (2.5 g, 14.03 mmol) was added, followed by several drops of formic acid. The resulting mixture was stirred for one hour at room temperature and then refluxed for 8 h under argon atmosphere. After being cooled down to room temperature, methanol was removed under vacuum. The yellow liquid residue was purified by column chromatography eluted with hexane/ethyl acetate (10: 1) affording the product as 3.2 g of a pale yellow oil (90% yield). Ή-NMR (CDC13, 400MHz, δ): 1.54 (s, 9H, ferf-Butyl), 6.91 -7.48 (m, 8H, aromatic-H), 8.66 (s, 1H, -CH=N-), 13.97 (s, 1H, -OH). 13C- NMR (CDC13, 100MHz, δ): 29.39, 34.96, 1 18.37, 1 19.10, 121.23, 126.75, 129.41 , 130.39, 130.71 , 137.69, 148.51 , 160.58, 163.42.
[00197] (ii) Preparation of catalyst FI-Ti
[00198] Catalyst FI-Ti was synthesized via the same procedure as MNTi-1 using ligand (FI) (1.00 g, 3.95 mmol) and half an equivalent of TiC - The catalyst was obtained as a deep reddish-brown solid bearing a general formula of C34H36Cl2N202Ti with residual solvent being THF and traces of DCM. The Ti% was found to be 6.69%. Calculated against the theoretical Ti% of 7.68% in C34H36Cl2N202Ti, the residual solvent was found to be 12.89%. The catalyst yield was 1.34 g (95%). FT-IR (cm"1): DC=N=1554 cm"1, uTi-o=500 cm"1, υτί- ci=458 cm"1, υ·π-Ν=365 cm"1. Raman (cm"1): DC=N=1586 cm"1 and 1555 αη"',υ·π-ο=890 cm"1, 558 cm"1 and 446 cm"1, t)Ti-ci=363 cm"1, υτί-Ν=336 cm"1.
[00199] Example 12: Preparation of mono-nuclear Zr catalyst (Fl-Zr) (Comparative Example 6)
[00200] Catalyst Fl-Zr was synthesized via the same procedure as MNTi-1 using ligand (FI) (1.00 g, 3.95 mmol) and half an equivalent of ZrCU. The catalyst was obtained as a pale yellow solid bearing a general formula of C34H36Cl2N202Zr with residual solvent being THF and traces of DCM. The Zr% was found to be 12.18%). Calculated against the theoretical Zr% of 13.68% in C34H36Cl2N202Zr, the residual solvent was found to be 10.96%. The catalyst
yield was 1.40 g (95%). FT-IR (cm"1):
cm"1, υΖΓ- N=330 cm"1.
[00201] Example 13: Catalyst Evaluation - General procedure for ethylene homo- polymerization in 300 mL reactor
[00202] Polymerization was carried out in a 300 mL stainless steel autoclave equipped with a mechanical stirrer with adjustable stirring rate. The autoclave was heated by a heating mantle. Before reaction, the autoclave was dried under vacuum at 100 °C for 2 hours during which period the autoclave was swept with dry argon at least three times. Then the temperature was lowered to the reaction temperature (60 °C) and the reactor was evacuated and refilled with ethylene. Hexane (100 mL), methylalumoxane (MAO) (2.0 mmol) and catalyst solution in DCM were added consecutively via syringe under ethylene atmosphere (-10 PSI) at a stirring rate of 300 RPM. Then the autoclave was quickly pressurized to 80 PSI (5.5 bar) with ethylene and the stirring rate was adjusted to 500 RPM. After the polymerization was run for the required time, the ethylene pressure was vented quickly and the reaction was quenched with 2 mL ethanol. The produced polyethylene was collected by filtration, washed with ethanol and hexane and dried in vacuo at 50 °C. The obtained white polymer was weighed and analyzed with GPC. The activity was calculated in unit of KgPE mo 1M"1 h"1 bar"1.
[00203] Fig. 13 is a table (Table 1) summarizing the performance of ethylene polymerization obtained using self-assembled polymerization catalysts (MNTi-3 and MNTi-6) according to embodiments of the present invention, and state of the art catalysts (MNTi-1, MNTi-2, and FI-Ti). Fig. 14 is a table (Table 2) summarizing the performance of ethylene polymerization obtained using self-assembled polymerization catalysts (MNZr-3 and MNZr- 6) according to embodiments of the present invention, and state of the art catalysts (MNZr-1, MNZr-2, and Fl-Zr).
[00204] Example 14: Catalyst Evaluation - General procedure for copolymerization of ethylene and 1-hexene in 1-L reactor
[00205] Copolymerization of ethylene and 1-hexene was carried out in a 1 L stainless steel autoclave, which was heated by recycling hot oil. The reactor was equipped with a small burette (10 mL) and a big burette (150 mL) connected in series for hydrogen and 1 -hexene addition, respectively. The big one was fixed directly above the reactor. Before reaction, the autoclave was dried under vacuum at 100 °C for 4 hours during which period the autoclave
was swept with dry argon at least three times. After the reactor was cooled down to room temperature, pentane (600 mL) was pressurized with Ar. Then the reactor was heated to 60 °C and desired amount of MAO was pressurized with Ar as well. The Ar pressure was controlled to about 5.0 bar at a stirring rate of 500 RPM. Varying amounts of hydrogen and 1-hexene were pressurized with ethylene, followed by the introduction of catalyst (6.0 /xmol) solution in DCM (3 mL) with Ar pressure. Then ethylene was quickly pressurized into the autoclave until the total ethylene pressure reached 6.0 bar. During the polymerization process, the ethylene pressure was maintained at 6.0 bar via mass flow controller. After the polymerization was run for 2 h, the pressure was vented quickly and the reaction was quenched with 12 mL ethanol. The produced copolymer was collected by filtration, washed with ethanol and hexane and dried in vacuo at 50 °C. The obtained white polymer was weighed and analyzed with GPC. The activity was calculated against the total pressure in unit of KgpE mo 1M"1 h"1 bar"1. Fig. 21 is a table (Table 5) summarizing the performance of co- polymerization of ethylene and 1-hexene using self-assembled polymerization catalysts (MNTi-4 and MNTi-5) according to embodiments of the present invention.
[00206] Example 15: Catalyst Evaluation - Catalytic activity and stability
[00207] Upon activation with MAO, the multi-nuclear catalysts were evaluated for ethylene polymerization for different reaction times (see Table 1 in Fig. 13 and Table 2 in Fig. 14). From the figures, it can be seen that the multi-nuclear catalysts (MNTi-1 to MNTi-6 and MNZr-1 to MNZr-6) displayed higher activity and better stability than the corresponding mono-nuclear catalysts (FI-Ti and Fl-Zr).
[00208] Referring to Fig. 13, both MNTi-3 and MNTi-6 according to embodiments of the present invention displayed 1.7 and 2.0 times higher activity, respectively, compared to that of the mono-nuclear FI-Ti catalyst at a run time of 120 minutes. In particular, MNTi-6 displayed a much higher activity of 1300 kgPEmoiM 1 h"1 bar"1 compared to that of the mononuclear FI-Ti catalyst with an activity of 660 kgPE molM -1 h"1 bar"1 for a 120 minutes run.
[00209] Referring to Fig. 14, MNZr-3 according to an embodiment of the present invention displayed a 2.2, 3.3, 4.4, 5.4, and 6.4 times higher activity at a run time of 5, 15, 30, 60 and 120 min respectively compared to that of mono-nuclear Fl-Zr catalyst. MNZr-3 displayed the highest activity among the four multi-nuclear catalysts MNZr-6, MNZr-1, MNZr-2 and MNZr-3. For example, at a run time of 120 min, the cumulative activity of MNZr-3 was 1.5
and 1.7 times higher than for MNZr-1 and MNZr-2. At this run time, MNZr-3 displayed an extremely high activity up to 12600 kgPE mo 1M"1 h"1 bar"1.
[00210] The amount of polyethylene (PE, g) obtained using the self-assembled polymerization catalysts (MNTi-3 and MNTi-6) according to embodiments of the present invention, and state of the art catalysts (MNTi-1 , MNTi-2, and FI-Ti) are plotted with time and shown in Fig. 15. Fig. 17 are photographs showing the amounts of polymer produced after several reaction times of (i) 30 minutes, (ii) 60 minutes and (iii) 120 minutes using (A) MNTi-3, (B) MNTi-6 and (C) state of the art catalyst FI-Ti. From these figures, it can be seen that for both MNTi-3 and MNTi-6, the amount of polyethylene (PE) increased quickly with an increase in reaction time while for FI-Ti, the amount of polyethylene produced increased very slowly.
[00211] Fig. 16 is a corresponding graph comparing the amount of polyethylene obtained (PE, g) with time ("productivity comparison") for MNZr-3 and MNZr-6 and state of the art catalysts MNZr-1 , MNZr-2, and Fl-Zr. Fig. 18 are photographs showing the amounts of polymer produced after several reaction times of (i) 5 minutes, (ii) 15 minutes, (iii) 30 minutes, (iv) 60 minutes and (v) 120 minutes using (A) MNZr-3, (B) MNZr-6 and (C) state of the art catalyst Fl-Zr. From the figures, it can be seen that the amount of polyethylene (PE) produced increased quickly with an increase in reaction time for both MNZr-3 and MNZr-6, while for Fl-Zr, the amount of polyethylene obtained increased very slowly.
[00212] Example 16: Catalyst Evaluation - Molecular weight (MW)
[00213] Industry catalysts produce high molecular weight (MW) polymers that is used in making final products in the markets, such as films, packing materials and tubes etc.. For most of the non-metallocene single-site catalysts, one main problem is that the polymer produced has too low MW. It is useful that, besides being more active and stable, all the multi-nuclear catalysts produced polyethylene of higher MW compared to the mono-nuclear catalysts (see Table 1 in Fig. 13 and Table 2 in Fig. 14).
[00214] Referring to Fig. 13, the obtained Mn for the catalyst MNTi-3 are 492 x l O3, 903 x l O3 and 984 x lO3 at run times of 30 min, 60 min and 120 min respectively, all of which are higher than the corresponding values of 329 x l O3, 385 l O3 and 493 x lO3 for FI-Ti.
[00215] Referring to Fig. 14, the obtained Mn for the catalyst MNZr-3 are 1 1.0 x l O3, 22.6 x l O3, 16.7 x lO3, 35.6 x l O3 and 35.3 x l O3 at run times of 5 min, 15 min, 30 min, 60 min and
120 min respectively, all of which are higher the corresponding values of 3.43 *10 , 3.63 lO3, 4.29 x l O3, 4.56 x l O3 and 5.10 x l O3 for Fl-Zr.
[00216] Example 17; Catalyst Evaluation - Comparison of metal coordination surroundings
[00217] Catalysts MNTi- 1 to MNTi-3 and MNZr- 1 to MNZr-3 were characterized with FT- IR and Laser-Raman, and compared with FI-Ti and Fl-Zr. Fig. 19 is a table (Table 3) summarizing the FTIR readings of MNTi-3 and MNZr-3, and state of the art catalysts MNTi- 1, MNTi-2, FI-Ti, MNZr-1, MNZr-2, and Fl-Zr. Fig. 20 is a table (Table 4) summarizing the Laser Raman readings of MNTi-3, and state of the art catalysts MNTi-1, MNTi-2, and FI-Ti.
[00218] The results indicate that, compared to FI-Ti and Fl-Zr, the multi-nuclear catalysts (Ti or Zr) have similar active sites that displayed higher activity and longer lifetime because of the self-assembly strategy.
[00219] Example 18; Catalyst Evaluation - Multi-nuclear catalysts with hetero coordination units
[00220] The phenoxy-imine based catalysts, including various multi-nuclear catalysts and mono-nuclear catalysts, are not able to copolymerize ethylene with 1-hexene very well. To overcome this problem, a second ligand, the bis-pyrrolide-imine ligand was used to replace the bis-phenoxy-imine in the second self-assembly step, hence forming a multi-nuclear FIPI catalyst. Bis-pyrrolide-imine is a smaller ligand as compared to bis-phenoxy-imine. Therefore the obtained catalyst may still have sufficient space to allow 1 -hexene to approach the central metal, thus offering the opportunity for 1-hexene to be incorporated into the polyethylene backbone.
[00221] The experimental results showed that the multinuclear catalyst MNTi-4 produced a copolymer of ethylene and 1 -hexene with 1.6% branching. The fluorine-containing multinuclear catalyst MNTi-5 can increase the branching to 5.0% under identical conditions. When the amount of 1-hexene was increased from 60 mL to 120 mL, the branching was further increased to 7.5% (see Table 5 of Fig. 21). On the other hand, MNTi-5 also has good hydrogen response. For both the homopolymerization of ethylene and copolymerization of ethylene with 1-hexene, the Mn decreased gradually with the increase of the amount of hydrogen. This provides an easy way to regulate the molecular weight for practical applications.
[00222] Example 19; Direct Use of Catalyst After Synthesized
[00223] Catalyst purifications via re-crystallization or wash with solvents generally lose much catalyst resulting in low yields and high operation cost in catalyst production. For practical applications, all the bis-ligands and metals employed should be used in the catalyst. In the present invention, all the catalysts were used directly after synthesized without further purification. Ti% can be found by ICP to calculate the catalyst loading. Solvent residue (THF) in the catalyst can be removed by excess Al(III) in MAO, because Al(III) in MAO is a stronger Lewis acid than Ti(IV) in the catalyst. Hence the catalyst can fully display its catalytic capabilities for olefin polymerization. The examples show that all the invention multinuclear catalysts demonstrated high activities, producing polyethylene with high molecular weight.
[00224] The advantages exemplified in above can meet the requirements of industrial applications. Therefore this family of self-assembled catalysts demonstrates the potential to compete with multi-site Ziegler-Natta catalysts and Group-4 metal metallocene catalysts.
Claims
Claims
1. A self-assembled olefin polymerization catalyst comprising a transition metal complex according to formula (I)
(I) wherein
each M is independently a transition metal selected from the group consisting of Group 3-1 1 of the periodic table;
each X is independently selected from the group consisting of H, halogen, CN, optionally substituted N(Ra)2, OH, optionally substituted Ci-C20 alkyl, optionally substituted Ci-C20 alkoxy, wherein Ra is independently selected from the group consisting of optionally substituted C!-C20 alkyl, optionally substituted C6-C20 aryl and halogen;
A is nothing, L1(MXn)g MXn- , or MXn L'(MXn)g MX„,-;
B is nothing, -L2(MXn)h or -L2(MXn)h MX„;
g is 0 or an integer of at least 1 ;
h is 0 or an integer of at least 1 ;
p is 0 or an integer of at least 1 ;
q is 0 or an integer of at least 1 ;
r is 0 or an integer of at least 1 ;
t is 0 or an integer of at least 1 ;
u is 0 or an integer of at least 1 ;
v is 0 or an integer of at least 1 ;
w is an integer of at least 1 ;
y is an integer of at least 1 ;
z is an integer of at least 1 ;
n is an integer selected from 0-6, wherein n is selected depending on the valency of M such that the net charge of each M nucleus is zero or all ligand binding positions of M are occupied;
L1 and L2 are independently selected ligands, wherein L1 and L2 are different, each of L1 and L2 having at least two linked coordination units, wherein each coordination unit binds to a different transition metal atom.
The self-assembled olefin polymerization catalyst according to claim 1, wherein said L1 and L2 are independently selected ligands having the following formula (II)
each WY unit forms a coordination unit;
m is an integer of at least 2;
Z is a bridging spacer selected from the group consisting of hydrocarbons having about 2 to about 100 carbon atoms and hetero-hydrocarbons having about 2 to about 100 carbon atoms, wherein Z has a size, length and angle so that each coordination units WY binds to a different transition metal atom;
each W and Y is independently a metal-coordinating moiety selected from the group consisting of a carbene, an optionally substituted C5-C2o aryl, and metal- coordinating groups comprising an oxygen atom, a sulphur atom, a selenium atom, a nitrogen atom, or a phosphorus atom in neutral or charged form;
wherein the semi-circle in the WY unit represents an optionally substituted hydrocarbon, hetero-hydrocarbon or Si-containing backbone to which the metal- coordinating moieties W and Y are bonded.
The self-assembled olefin polymerization catalyst according to claim 2, wherein the optionally substituted hydrocarbon, hetero-hydrocarbon or Si-containing backbone to which the metal-coordinating moieties W and Y are bonded is selected from the group
consisting of an optionally substituted C6-C20 aryl group, an optionally substituted C6- C2o heteroaryl group and an optionally substituted Si group.
The self-assembled olefin polymerization catalyst according to claim 2 or 3, wherein said WY unit is selected from the group consisting of
wherein
R1, R2, R3, R4, R5, R6, and R7 may be the same or different and are each selected from the group consisting of H, optionally substituted straight-chain or branched Ci-C2o alkyl, optionally substituted straight-chain or branched C2-C20 alkenyl, optionally substituted straight-chain or branched C2-C20 alkynyl, optionally substituted C6-C20 aryl, optionally substituted C6-C20 heteroaryl, halogen, OH, N02, and CN, wherein two or more of R1 to R7 may be bonded to each other to form a ring.
The self-assembled olefin polymerization catalyst according to claims 2 to 4, wherein Z is selected from the group consisting of an optionally substituted C3-Cio alicyclic group, an optionally substituted C6-C20 aryl group, an optionally substituted C -C20 heteroaryl group, a system of condensed nucleus and a system of two, three or four optionally substituted C6-C20 aryl groups being connected via a N-atom, a Si-atom, an Q-Qo alkyl group, an C2-C20 alkenyl group or an C6-C20 aryl group.
The self-assembled olefin polymerization catalyst according to claim 5, wherein Z is a bis-linker selected from the group consisting of
wherein R to R may be the same or different and are each selected from the group consisting of H, optionally substituted straight-chain or branched C1-C20 alkyl, optionally substituted straight-chain or branched C2-C20 alkenyl, optionally substituted straight-chain or branched C2-C20 alkynyl, optionally substituted C6-C2o aryl, optionally substituted C6-C2o heteroaryl, halogen, OH, N02, and CN, wherein two or more of R! 1 to R20 may be bonded to each other to form a ring and s is an integer from 1 to 20.
The self-assembled olefin polymerization catalyst according to claim 5, wherein Z is a tri-linker selected from the group consisting of
wherein R -R may be the same or different and are each selected from the group consisting of H, optionally substituted straight-chain or branched C1-C20 alkyl, optionally substituted straight-chain or branched C2-C20 alkenyl, optionally substituted straight-chain or branched C2-C20 alkynyl, optionally substituted C6-C20 aryl, optionally substituted C6-C20 heteroaryl, halogen, OH, N02, and CN, wherein two or more of R8 to R12 may be bonded to each other to form a ring.
8. The self-assembled olefin polymerization catalyst according to claim 5, wherein Z is a tetrakis-linker selected from the group consisting of
wherein R8-R16 may be the same or different and are each selected from the group consisting of H, optionally substituted straight-chain or branched Ci-C20 alkyl, optionally substituted straight-chain or branched C2-C20 alkenyl, optionally substituted straight-chain or branched C2-C20 alkynyl, optionally substituted C6-C20 aryl, optionally substituted C6-C20 heteroaryl, halogen, OH, N02, and CN, wherein two or more of R8 to R16 may be bonded to each other to form a ring.
9. The self-assembled olefin polymerization catalyst according to claim 5, wherein Z is a multi-linker which linking sites are five or more than five.
10. The self-assembled olefin polymerization catalyst according to claims 2 to 9, wherein Z is a macro polymeric mult i- linker.
1 1. The self-assembled olefin polymerization catalyst according to any of the preceding claims, wherein each of the ligands L1 and L2 are independently selected from the group consisting of
group consisting of H, optionally substituted straight-chain or branched Ci-C20 alkyl,
optionally substituted straight-chain or branched C2-C20 alkenyl, optionally substituted straight-chain or branched C2-C2o alkynyl, optionally substituted C6-C20 aryl, optionally substituted C6-C20 heteroaryl, halogen, OH, N02, and CN, wherein two or more of R1 to R4 may be bonded to each other to form a ring.
12. The self-assembled olefin polymerization catalyst according to claim 11, wherein R1, R2, R3 and R4 may be the same or different, wherein R1 is selected from the group consisting of H, CH3 and tert-butyl; R2 is selected from the group consisting of H and tert-butyl; R3 is selected from the group consisting of H, CH3, CH2CH3, and CH(CH3)2; and R4 is selected from the group consisting of H, F and CH3.
13. The self-assembled olefin polymerization catalyst according to claims 2 to 12, wherein the molar ratio of coordination unit WY to metal is about 0.5: 1 to about 6: 1. 14. The self- assembled olefin polymerization catalyst according to claim 13, wherein the molar ratio of coordination unit WY to metal is about 1 :1 to about 3:1.
15. The self-assembled olefin polymerization catalyst according to any of the preceding claims, wherein the transition metals are selected from the group consisting of Sc, Y, La, Ti, Zr, Hf, V, Nb, Ta, Sm, Yb, Cr, Mo, W, Mn, Tc, Re, Fe, Ru, Os, Co, Rh, Ir, Ni,
Pd, Pt, Cu, Zn and mixtures thereof.
16. The self- assembled olefin polymerization catalyst according to claim 15, wherein the transition metals are selected from the group consisting of Ti, Zr, Hf, V, Nb, Ta, Sm, Yb and mixtures thereof.
17. The self-assembled olefin polymerization catalyst according to claim 16, wherein the transition metals are selected from the group consisting of Ti, Zr and mixtures thereof.
18. The self- assembled olefin polymerization catalyst according to any of the preceding claims, wherein X is selected from the group consisting of F, CI, Br, I, H, CH3,
CH2CH3, OCH3, OCH2CH3, OCH(CH3)3, OC(CH3)3, OC6H6, CN, N(CH3)2, and N(CH2CH3)2.
The self-assembled olefin polymerization catalyst according to any of the preceding claims, wherein the catalyst is a homogeneous or heterogeneous catalyst.
20. The self-assembled olefin polymerization catalyst according to any of the preceding claims, further comprising a solid support. 21. The self-assembled olefin polymerization catalyst according to claim 20, wherein the solid support is an inorganic material or an organic material.
22. The self-assembled olefin polymerization catalyst according to claim 21 , wherein the solid support is an inorganic material selected from the group consisting of silica, alumina, titania, magnesium chloride, and mixtures thereof.
The self-assembled olefin polymerization catalyst according to any of the preceding claims, wherein the catalyst forms a 3 -Dimensional organo metallic framework.
The self-assembled olefin polymerization catalyst according to any of the preceding claims, wherein the catalyst forms a linear assembling structure.
25. The self-assembled olefin polymerization catalyst according to any of the preceding claims, wherein the catalyst forms a macrocyclic assembling structure containing at least two metal centres.
26. The self-assembled olefin polymerization catalyst according to any of the preceding claims further comprising at least one co-catalyst selected from the group consisting of an organometallic compound, an organo aluminum oxy-compound, and an ionizing ionic compound.
27. The self-assembled olefin polymerization catalyst according to claim 26, wherein the co-catalyst is a conventional methyl aluminoxane (MAO), a modified methyl aluminoxane (MMAO), a metal salt of (C6F5)4B" and a combination of an alkyl aluminium compound with MgCl2.
28. The self-assembled olefin polymerization catalyst according to claim 1, wherein g = h = p = q = r = t = u = v = 0, w = y = z= 1 , A = A'= B = nothing, wherein the catalyst has the formula (III)
29. The self-assembled olefin polymerization catalyst according to any one of claim 1 to 28, wherein the catalyst comprises one or more of the units
30. The self-assembled olefin polymerization catalyst according to any one of claim 1 to 29, wherein the catalyst comprises one or more of the units
31. A process for polymerization or copolymerization of an olefin or a mixture of olefins in the presence of the self-assembled olefin polymerization catalyst according to any of claims 1 to 30.
32. The process according to claim 31, wherein the process is carried out at a pressure in the range of about 0.1 MPa to about 10 MPa.
33. The process according to claim 31 or 32, wherein the process is carried out in a temperature range of about -50 °C to about 150 °C.
34. The process according to claims 31 to 33, wherein the process is carried out at a catalystxo-catalyst mole ratio of about 1 :1 to about 1 :5000.
The process according to claim 34, wherein the process is carried out at a catalyst: catalyst mole ratio of about 1 :1 to about 1 :2000.
36. The process according to claims 31 to 35, wherein the olefin is selected from the group consisting of C2-C30 a-olefins, C2-C30 functionalized alkenes, cycloalkenes, norborene and derivatives thereof, dienes, acetylenes, styrene, alkenols, alkenoic acids, and their derivatives or mixtures thereof.
37. The process according to claim 36, wherein the olefins are selected from the group consisting of ethylene, C6 alkenes, and their derivatives or mixtures thereof.
38. The process according to claim 37, wherein the olefins are ethylene and 1 -hexene, their derivatives or mixtures thereof.
39. Polyolefins obtainable according to the process of any of claims 31 to 38.
40. Polyolefins according to claim 38 having a molecular weight in the range from low molecular weight polyolefins to ultra high molecular weight polyolefins.
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JP2013501217A JP2013523911A (en) | 2010-03-25 | 2011-03-25 | Self-assembled polynuclear catalysts for olefin polymerization. |
SG2012069456A SG184150A1 (en) | 2010-03-25 | 2011-03-25 | Self-assembled multi-nuclear catalyst for olefin polymerization |
EP11759812.8A EP2550308A4 (en) | 2010-03-25 | 2011-03-25 | Self-assembled multi-nuclear catalyst for olefin polymerization |
US13/637,362 US20130137841A1 (en) | 2010-03-25 | 2011-03-25 | Self-assembled multi-nuclear catalyst for olefin polymerization |
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CN104211726A (en) * | 2014-08-11 | 2014-12-17 | 中南民族大学 | Non-metallocene tridentate binuclear titanium complex, preparation method and purpose thereof |
CN107652320A (en) * | 2017-09-30 | 2018-02-02 | 南京晓庄学院 | One kind limitation configuration bimetallic compound and preparation method and application |
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CN105218590B (en) * | 2015-10-09 | 2018-01-23 | 武汉科技大学 | Biphenyl bridging dinuclear iron complex and preparation method thereof and application method |
CN107266638B (en) * | 2016-04-07 | 2019-08-20 | 中国石油化工股份有限公司 | A kind of block copolymer and preparation method thereof |
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WO2009091334A1 (en) * | 2008-01-14 | 2009-07-23 | Agency For Science, Technology And Research | Self-assembled olefin polymerization catalyst |
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WO2004108775A1 (en) * | 2003-06-05 | 2004-12-16 | Dow Global Technologies Inc. | Activated multinuclear transition metal catalyst compositions |
US20060004155A1 (en) * | 2004-07-01 | 2006-01-05 | Daelim Industrial Co., Ltd. | Multinuclear transition metal compound and catalyst system including the same |
WO2009091334A1 (en) * | 2008-01-14 | 2009-07-23 | Agency For Science, Technology And Research | Self-assembled olefin polymerization catalyst |
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CN104211726A (en) * | 2014-08-11 | 2014-12-17 | 中南民族大学 | Non-metallocene tridentate binuclear titanium complex, preparation method and purpose thereof |
CN107652320A (en) * | 2017-09-30 | 2018-02-02 | 南京晓庄学院 | One kind limitation configuration bimetallic compound and preparation method and application |
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