US20090018293A1 - Process for the preparation of a metaloorganic compound comprising at least one imine ligand - Google Patents
Process for the preparation of a metaloorganic compound comprising at least one imine ligand Download PDFInfo
- Publication number
- US20090018293A1 US20090018293A1 US12/230,991 US23099108A US2009018293A1 US 20090018293 A1 US20090018293 A1 US 20090018293A1 US 23099108 A US23099108 A US 23099108A US 2009018293 A1 US2009018293 A1 US 2009018293A1
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- United States
- Prior art keywords
- metal
- group
- formula
- base
- radical
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
- 238000000034 method Methods 0.000 title claims abstract description 62
- 239000003446 ligand Substances 0.000 title claims abstract description 43
- 150000002466 imines Chemical class 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 150000001875 compounds Chemical class 0.000 title 1
- 150000002902 organometallic compounds Chemical class 0.000 claims abstract description 34
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 25
- 125000001424 substituent group Chemical group 0.000 claims abstract description 20
- 125000005843 halogen group Chemical group 0.000 claims abstract description 19
- 150000001336 alkenes Chemical class 0.000 claims abstract description 10
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 6
- 125000004437 phosphorous atom Chemical class 0.000 claims abstract description 6
- 229920000098 polyolefin Polymers 0.000 claims abstract description 6
- 239000002253 acid Substances 0.000 claims abstract description 5
- -1 alkoxy radical Chemical class 0.000 claims description 39
- 239000002585 base Substances 0.000 claims description 36
- 238000006243 chemical reaction Methods 0.000 claims description 13
- 150000003839 salts Chemical class 0.000 claims description 9
- 125000000041 C6-C10 aryl group Chemical group 0.000 claims description 8
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 8
- 150000002901 organomagnesium compounds Chemical class 0.000 claims description 8
- 239000011734 sodium Substances 0.000 claims description 8
- 150000007529 inorganic bases Chemical class 0.000 claims description 7
- 229910052700 potassium Inorganic materials 0.000 claims description 7
- 229910052708 sodium Inorganic materials 0.000 claims description 7
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims description 6
- MDFFNEOEWAXZRQ-UHFFFAOYSA-N aminyl Chemical compound [NH2] MDFFNEOEWAXZRQ-UHFFFAOYSA-N 0.000 claims description 6
- 229910052744 lithium Inorganic materials 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 6
- 150000002900 organolithium compounds Chemical group 0.000 claims description 6
- 229910052701 rubidium Inorganic materials 0.000 claims description 6
- 229910052783 alkali metal Inorganic materials 0.000 claims description 5
- 150000001340 alkali metals Chemical class 0.000 claims description 5
- 150000001408 amides Chemical class 0.000 claims description 5
- 229910052792 caesium Inorganic materials 0.000 claims description 5
- 125000004122 cyclic group Chemical group 0.000 claims description 5
- 229910052749 magnesium Inorganic materials 0.000 claims description 5
- 229910019142 PO4 Inorganic materials 0.000 claims description 4
- 150000004678 hydrides Chemical class 0.000 claims description 4
- 238000000746 purification Methods 0.000 claims description 4
- CSDQQAQKBAQLLE-UHFFFAOYSA-N 4-(4-chlorophenyl)-4,5,6,7-tetrahydrothieno[3,2-c]pyridine Chemical compound C1=CC(Cl)=CC=C1C1C(C=CS2)=C2CCN1 CSDQQAQKBAQLLE-UHFFFAOYSA-N 0.000 claims description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical group [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 3
- 229940010415 calcium hydride Drugs 0.000 claims description 3
- 239000010452 phosphate Substances 0.000 claims description 3
- OLRJXMHANKMLTD-UHFFFAOYSA-N silyl Chemical compound [SiH3] OLRJXMHANKMLTD-UHFFFAOYSA-N 0.000 claims description 3
- 125000004209 (C1-C8) alkyl group Chemical group 0.000 claims description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 2
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 claims description 2
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical group [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 claims description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 2
- 229910052795 boron group element Inorganic materials 0.000 claims description 2
- 229910052791 calcium Inorganic materials 0.000 claims description 2
- 150000007942 carboxylates Chemical class 0.000 claims description 2
- 229910001849 group 12 element Inorganic materials 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 2
- 239000012312 sodium hydride Substances 0.000 claims description 2
- 229910000104 sodium hydride Inorganic materials 0.000 claims description 2
- 229910021515 thallium hydroxide Inorganic materials 0.000 claims description 2
- QGYXCSSUHCHXHB-UHFFFAOYSA-M thallium(i) hydroxide Chemical compound [OH-].[Tl+] QGYXCSSUHCHXHB-UHFFFAOYSA-M 0.000 claims description 2
- 239000000010 aprotic solvent Substances 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-M phenolate Chemical compound [O-]C1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-M 0.000 claims 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical class N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 8
- 229910052799 carbon Inorganic materials 0.000 abstract description 5
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 5
- 150000001721 carbon Chemical class 0.000 abstract description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 18
- 125000006659 (C1-C20) hydrocarbyl group Chemical group 0.000 description 13
- 239000002904 solvent Substances 0.000 description 13
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 10
- 125000003454 indenyl group Chemical group C1(C=CC2=CC=CC=C12)* 0.000 description 10
- 125000004429 atom Chemical group 0.000 description 9
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 229910052736 halogen Inorganic materials 0.000 description 7
- QLNAVQRIWDRPHA-UHFFFAOYSA-N iminophosphane Chemical compound P=N QLNAVQRIWDRPHA-UHFFFAOYSA-N 0.000 description 7
- OULQIRTYSJHFKP-UHFFFAOYSA-N 4h-imidazol-5-amine Chemical compound N=C1CNC=N1 OULQIRTYSJHFKP-UHFFFAOYSA-N 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 6
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 6
- 0 [11*]P([12*])[13*] Chemical compound [11*]P([12*])[13*] 0.000 description 6
- 125000005842 heteroatom Chemical group 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 239000006227 byproduct Substances 0.000 description 5
- QOXHZZQZTIGPEV-UHFFFAOYSA-K cyclopenta-1,3-diene;titanium(4+);trichloride Chemical compound Cl[Ti+](Cl)Cl.C=1C=C[CH-]C=1 QOXHZZQZTIGPEV-UHFFFAOYSA-K 0.000 description 5
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 5
- NXPHGHWWQRMDIA-UHFFFAOYSA-M magnesium;carbanide;bromide Chemical compound [CH3-].[Mg+2].[Br-] NXPHGHWWQRMDIA-UHFFFAOYSA-M 0.000 description 5
- 150000003254 radicals Chemical class 0.000 description 5
- 238000004679 31P NMR spectroscopy Methods 0.000 description 4
- 239000007983 Tris buffer Substances 0.000 description 4
- 239000000706 filtrate Substances 0.000 description 4
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 description 4
- 150000002357 guanidines Chemical class 0.000 description 4
- 239000011777 magnesium Substances 0.000 description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 4
- 239000012041 precatalyst Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000011541 reaction mixture Substances 0.000 description 4
- 239000000725 suspension Substances 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Chemical group C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 3
- ZRALSGWEFCBTJO-UHFFFAOYSA-N Guanidine Chemical compound NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Chemical compound N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 description 3
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical group C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 description 3
- ZSWFCLXCOIISFI-UHFFFAOYSA-N endo-cyclopentadiene Chemical group C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 3
- PFRDRCIPKPEULG-UHFFFAOYSA-N imidazol-2-imine Chemical class N=C1N=CC=N1 PFRDRCIPKPEULG-UHFFFAOYSA-N 0.000 description 3
- MLAXVEHWMLUSFO-UHFFFAOYSA-N indol-2-imine Chemical class C1=CC=CC2=NC(=N)C=C21 MLAXVEHWMLUSFO-UHFFFAOYSA-N 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- IJUJQZNGLZFJGP-UHFFFAOYSA-N pyrrol-2-imine Chemical class N=C1C=CC=N1 IJUJQZNGLZFJGP-UHFFFAOYSA-N 0.000 description 3
- MVXVYAKCVDQRLW-UHFFFAOYSA-N 1h-pyrrolo[2,3-b]pyridine Chemical compound C1=CN=C2NC=CC2=C1 MVXVYAKCVDQRLW-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 description 2
- DDBXPEANNMKJMA-UHFFFAOYSA-L [Cl-].[Cl-].[Ti+3]C1C=CC=C1 Chemical compound [Cl-].[Cl-].[Ti+3]C1C=CC=C1 DDBXPEANNMKJMA-UHFFFAOYSA-L 0.000 description 2
- 239000012190 activator Substances 0.000 description 2
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 125000004104 aryloxy group Chemical group 0.000 description 2
- 150000001540 azides Chemical class 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- UORVGPXVDQYIDP-UHFFFAOYSA-N borane Chemical compound B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 150000004673 fluoride salts Chemical class 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 238000012544 monitoring process Methods 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- GKTNLYAAZKKMTQ-UHFFFAOYSA-N n-[bis(dimethylamino)phosphinimyl]-n-methylmethanamine Chemical compound CN(C)P(=N)(N(C)C)N(C)C GKTNLYAAZKKMTQ-UHFFFAOYSA-N 0.000 description 2
- 125000001979 organolithium group Chemical group 0.000 description 2
- 235000021317 phosphate Nutrition 0.000 description 2
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 150000003568 thioethers Chemical class 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- SEDZOYHHAIAQIW-UHFFFAOYSA-N trimethylsilyl azide Chemical group C[Si](C)(C)N=[N+]=[N-] SEDZOYHHAIAQIW-UHFFFAOYSA-N 0.000 description 2
- VCHPDFCGMIQJNZ-UHFFFAOYSA-N (2-methylquinolin-8-yl)phosphane Chemical compound C1=CC=C(P)C2=NC(C)=CC=C21 VCHPDFCGMIQJNZ-UHFFFAOYSA-N 0.000 description 1
- DPZNOMCNRMUKPS-UHFFFAOYSA-N 1,3-Dimethoxybenzene Chemical compound COC1=CC=CC(OC)=C1 DPZNOMCNRMUKPS-UHFFFAOYSA-N 0.000 description 1
- NPZSGBFEDXTRCH-UHFFFAOYSA-N 1,3-bis(2,6-dimethylphenyl)imidazolidin-4-imine Chemical compound CC1=CC=CC(C)=C1N1CC(=N)N(C=2C(=CC=CC=2C)C)C1 NPZSGBFEDXTRCH-UHFFFAOYSA-N 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- BAXOFTOLAUCFNW-UHFFFAOYSA-N 1H-indazole Chemical compound C1=CC=C2C=NNC2=C1 BAXOFTOLAUCFNW-UHFFFAOYSA-N 0.000 description 1
- NBYLBWHHTUWMER-UHFFFAOYSA-N 2-Methylquinolin-8-ol Chemical compound C1=CC=C(O)C2=NC(C)=CC=C21 NBYLBWHHTUWMER-UHFFFAOYSA-N 0.000 description 1
- JHIAOWGCGNMQKA-UHFFFAOYSA-N 2-methyl-8-quinolinamine Chemical compound C1=CC=C(N)C2=NC(C)=CC=C21 JHIAOWGCGNMQKA-UHFFFAOYSA-N 0.000 description 1
- 239000005725 8-Hydroxyquinoline Substances 0.000 description 1
- WREVVZMUNPAPOV-UHFFFAOYSA-N 8-aminoquinoline Chemical compound C1=CN=C2C(N)=CC=CC2=C1 WREVVZMUNPAPOV-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N CCC Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910000799 K alloy Inorganic materials 0.000 description 1
- CHJJGSNFBQVOTG-UHFFFAOYSA-N N-methyl-guanidine Natural products CNC(N)=N CHJJGSNFBQVOTG-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 229910000528 Na alloy Inorganic materials 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical class OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-L Phosphate ion(2-) Chemical compound OP([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-L 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 238000003800 Staudinger reaction Methods 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 229910010062 TiCl3 Inorganic materials 0.000 description 1
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- 235000010210 aluminium Nutrition 0.000 description 1
- XESYSKJARUWZEV-UHFFFAOYSA-M amino(tritert-butyl)phosphanium;chloride Chemical compound [Cl-].CC(C)(C)[P+](N)(C(C)(C)C)C(C)(C)C XESYSKJARUWZEV-UHFFFAOYSA-M 0.000 description 1
- 125000005228 aryl sulfonate group Chemical group 0.000 description 1
- 238000006254 arylation reaction Methods 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- AZWXAPCAJCYGIA-UHFFFAOYSA-N bis(2-methylpropyl)alumane Chemical compound CC(C)C[AlH]CC(C)C AZWXAPCAJCYGIA-UHFFFAOYSA-N 0.000 description 1
- 229910000085 borane Inorganic materials 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 238000001460 carbon-13 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 150000003983 crown ethers Chemical class 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 150000004292 cyclic ethers Chemical class 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-M dihydrogenphosphate Chemical compound OP(O)([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-M 0.000 description 1
- SIPUZPBQZHNSDW-UHFFFAOYSA-N diisobutylaluminium hydride Substances CC(C)C[Al]CC(C)C SIPUZPBQZHNSDW-UHFFFAOYSA-N 0.000 description 1
- SWSQBOPZIKWTGO-UHFFFAOYSA-N dimethylaminoamidine Natural products CN(C)C(N)=N SWSQBOPZIKWTGO-UHFFFAOYSA-N 0.000 description 1
- KZLUHGRPVSRSHI-UHFFFAOYSA-N dimethylmagnesium Chemical compound C[Mg]C KZLUHGRPVSRSHI-UHFFFAOYSA-N 0.000 description 1
- RJWLXGOSIRVRAR-UHFFFAOYSA-N dimethylresorcinol Natural products CC1=CC=C(O)C(C)=C1O RJWLXGOSIRVRAR-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- JUINSXZKUKVTMD-UHFFFAOYSA-N hydrogen azide Chemical compound N=[N+]=[N-] JUINSXZKUKVTMD-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-M hydrogensulfate Chemical compound OS([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-M 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 150000004658 ketimines Chemical class 0.000 description 1
- YNXURHRFIMQACJ-UHFFFAOYSA-N lithium;methanidylbenzene Chemical compound [Li+].[CH2-]C1=CC=CC=C1 YNXURHRFIMQACJ-UHFFFAOYSA-N 0.000 description 1
- UNIVWSDJPORCGO-UHFFFAOYSA-N magnesium;1,3,5-trimethylbenzene-6-ide Chemical compound [Mg+2].CC1=CC(C)=[C-]C(C)=C1.CC1=CC(C)=[C-]C(C)=C1 UNIVWSDJPORCGO-UHFFFAOYSA-N 0.000 description 1
- WRYKIHMRDIOPSI-UHFFFAOYSA-N magnesium;benzene Chemical compound [Mg+2].C1=CC=[C-]C=C1.C1=CC=[C-]C=C1 WRYKIHMRDIOPSI-UHFFFAOYSA-N 0.000 description 1
- KJJBSBKRXUVBMX-UHFFFAOYSA-N magnesium;butane Chemical compound [Mg+2].CCC[CH2-].CCC[CH2-] KJJBSBKRXUVBMX-UHFFFAOYSA-N 0.000 description 1
- WCFJMDWWJOCLSJ-UHFFFAOYSA-N magnesium;methanidylbenzene Chemical compound [Mg+2].[CH2-]C1=CC=CC=C1.[CH2-]C1=CC=CC=C1 WCFJMDWWJOCLSJ-UHFFFAOYSA-N 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- DVSDBMFJEQPWNO-UHFFFAOYSA-N methyllithium Chemical compound C[Li] DVSDBMFJEQPWNO-UHFFFAOYSA-N 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 150000002829 nitrogen Chemical group 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- LYGJENNIWJXYER-UHFFFAOYSA-N nitromethane Chemical compound C[N+]([O-])=O LYGJENNIWJXYER-UHFFFAOYSA-N 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- 229960003540 oxyquinoline Drugs 0.000 description 1
- NHKJPPKXDNZFBJ-UHFFFAOYSA-N phenyllithium Chemical compound [Li]C1=CC=CC=C1 NHKJPPKXDNZFBJ-UHFFFAOYSA-N 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- 238000001394 phosphorus-31 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 235000011056 potassium acetate Nutrition 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- MCJGNVYPOGVAJF-UHFFFAOYSA-N quinolin-8-ol Chemical compound C1=CN=C2C(O)=CC=CC2=C1 MCJGNVYPOGVAJF-UHFFFAOYSA-N 0.000 description 1
- SUBYKQKSRBJWLB-UHFFFAOYSA-N quinolin-8-ylphosphane Chemical compound C1=CN=C2C(P)=CC=CC2=C1 SUBYKQKSRBJWLB-UHFFFAOYSA-N 0.000 description 1
- MHTSJSRDFXZFHQ-UHFFFAOYSA-N quinoline-8-thiol Chemical compound C1=CN=C2C(S)=CC=CC2=C1 MHTSJSRDFXZFHQ-UHFFFAOYSA-N 0.000 description 1
- 150000003335 secondary amines Chemical class 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 125000005207 tetraalkylammonium group Chemical group 0.000 description 1
- 125000005497 tetraalkylphosphonium group Chemical group 0.000 description 1
- YONPGGFAJWQGJC-UHFFFAOYSA-K titanium(iii) chloride Chemical compound Cl[Ti](Cl)Cl YONPGGFAJWQGJC-UHFFFAOYSA-K 0.000 description 1
- 125000004665 trialkylsilyl group Chemical group 0.000 description 1
- 229940086542 triethylamine Drugs 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- 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
- C07F17/00—Metallocenes
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- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F19/00—Metal compounds according to more than one of main groups C07F1/00 - C07F17/00
-
- 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
-
- 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
- C07F7/28—Titanium compounds
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- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/30—Germanium compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/535—Organo-phosphoranes
- C07F9/5355—Phosphoranes containing the structure P=N-
-
- 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
- C08F210/04—Monomers containing three or four carbon atoms
- C08F210/06—Propene
-
- 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
-
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- 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
- C08F2420/00—Metallocene catalysts
- C08F2420/04—Cp or analog not bridged to a non-Cp X ancillary anionic donor
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/62—Refractory metals or compounds thereof
- C08F4/64—Titanium, zirconium, hafnium or compounds thereof
- C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
- C08F4/65908—Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with an ionising compound other than alumoxane, e.g. (C6F5)4B-X+
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/62—Refractory metals or compounds thereof
- C08F4/64—Titanium, zirconium, hafnium or compounds thereof
- C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
- C08F4/6592—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring
Definitions
- the invention relates to a process for the preparation of an metal-organic compound comprising at least one imine ligand according to formula 1.
- Metal-organic compounds thus produced are typically used as precatalyst in the production of polyolefins.
- Imine ligands for these precatalyst can be guanidine, iminoimidazoline, ketimine or phosphinimine, the manufacturing of which is described in WO 02070569, U.S. Pat. No. 6,114,481 and U.S. Pat. No. 6,063,879 respectively.
- the known production processes for phosphinimine comprising metal-organic compounds require at least two steps: (i) the synthesis of a N-trialkylsilyl substituted imine ligand, followed by (ii) contacting this ligand with an metal-organic precursor.
- azide chemistry is required in the one step process for the manufacturing of the imine ligand.
- the most frequently used azide is azidotrimethylsilane, which is highly toxic and readily hydrolysable, releasing the highly toxic and both temperature and shock sensitive hydrazoic acid. Therefore, mixtures containing (partially) hydrolysed trimethylsilylazide may explosively decompose.
- Purpose of the present invention is to provide a widely applicable method for the manufacturing of a metal-organic compound from an imine and a metal-organic precursor in one step
- Y is selected from a substituted carbon, nitrogen or phosphorous atom and R represents a proton, a protic or an aprotic substituent, and:
- M represents a group 4 or group 5 metal ion
- V represents the valency of the metal ion, being 3, 4 or 5
- L 1 , L 2 , L 3 , and L 4 represent ligands on M and may be equal or different
- a base is understood to be an inorganic or metal-organic base.
- CA 02243775 describes a similar preparation of an metal-organic compound in the presence of an inorganic base. Surprisingly it was found that this reaction could also be carried out in the presence of the cheaper inorganic base like potassium carbonate.
- Another advantage is the formation of a precipitate which can be filtered off easier than the precipitate which is formed with the organic base used in CA 02243775.
- Still another advantage is the fact that inorganic bases are environmentally friendly and allows a broader range of solvents used in the process of the invention.
- An advantage of the metal-organic base is that with this base the hydrocarbylated metal-organic compound can be prepared in a one step process.
- the metal-organic dichloride has to be hydrocarbylated in a second reaction step in case this is required for exampled to use the metal-organic compound in a polymerisation process using a boron comprising activator.
- Another advantage of the process of the invention is the use of the HA adduct of the imine, which can be prepared easier than the imine of the state of the art.
- a metal-organic compound suitable as precatalyst in olefin polymerisation, is prepared in one step.
- An additional advantage of the method of the invention is, that during the process hardly any by-products are formed, so that further purification is not necessary (or very limited with respect to state of the art processes).
- the metal-organic compound prepared by the method of the invention has a higher purity than a metal-organic compound prepared via known production processes and can be used as such in olefin polymerisation processes.
- An additional advantage of the process of the invention is that the process can be carried out at room temperature, whereas the reaction of the N-trialkylsilyl substituted imine ligand with the metal-organic reagent has to be often carried out at elevated temperatures.
- the imine derivative or its HA adduct, as represented in formula 1, is substituted by an Y- and an R group.
- the Y group consists of a substituted carbon, nitrogen or phosphorous atom. If Y represents a substituted carbon atom, the number of substituents is 2. If Y represents a substituted nitrogen atom, the number of substituents is 1 and the number of substituents is 1 or 3 if Y represents a phosphorous atom, depending on the valency of the phosphorous atom.
- Substituents on carbon, nitrogen or phosphorous may be equal or different, optionally linked with each other, optionally having heteroatoms.
- Substituents may be protic or aprotic.
- a protic substituent is defined here as a substituent, which has at least one, group 15 or group 16 atom containing at least one proton.
- protic substituents include C 1 -C 20 linear, branched or cyclic hydrocarbyl radicals, substituted with a group 15 or 16 atom bearing at least one hydrogen atom.
- Preferred protic substituents include phenolic radicals, pyrrolic radicals, indolic radicals, and imidazolic radicals.
- the substituent is called aprotic if the substituent lacks a group containing a group 15 or group 16 atom bearing a proton.
- An unsubstituted aprotic hydrocarbyl radical can be a C 1 -C 20 linear, branched or cyclic radical, a hydrogen atom, a halogen atom, a C 1-8 alkoxy radical, a C 6-10 aryl or aryloxy radical, an amido radical, or a C 1-20 hydrocarbyl radical unsubstituted or substituted by a halogen atom, a C 1-8 alkoxy radical, a C 6-10 aryl or aryloxy radical, an amido radical, a silyl radical of the formula 4, or a germanyl radical of the formula 5.
- the substituent R can be H, or being equal as these for the substituent on Y.
- imine ligands according to formula (I) thus include: guanidines, iminoimidazolines, phosphinimines, phenolimines, pyrroleimines, indoleimines and imidazoleimines.
- R may be linked with Y, thus forming a ring system, optionally comprising heteroatoms, or optionally comprising functional groups.
- ligands comprising such ring systems include: 8-hydroxyquinoline, 8-aminoquinoline, 8-phosphinoquinoline, 8-thioquinoline, 8-hydroxyquinaldine, 8-aminoquinaldine, 8-phosphinoquinaldine, 8-thioquinaldine and 7-azaindole or indazole.
- R represents a hydrogen atom and Y is selected from the group consisting of:
- each R 1j is independently selected from the group consisting of a hydrogen atom, a halogen atom, a C 1-8 alkoxy radical, a C 6-10 aryl or aryloxy radical, an amido radical, or a C 1-20 hydrocarbyl radical unsubstituted or substituted by a halogen atom, a C 1-8 alkoxy radical, a C 6-10 aryl or aryloxy radical, an amido radical, a silyl radical of the formula:
- R 2j is independently selected from the group consisting of hydrogen, a C 1-8 alkyl or alkoxy radical, C 6-10 aryl or aryloxy radicals, each substituent R 1j or R 2j may be linked with another R 1j or R 2j respectively to form a ring system, ii) a substituent according to formula 6:
- each of Sub 1 and Sub 2 is independently selected from the group consisting of hydrocarbyl radicals having from 1 to 30 carbon atoms; silyl radicals, (substituted) amido radicals and (substituted) phosphido radicals, and wherein Sub 1 and Sub 2 may be linked with each other to form a ring system.
- Sub 1 and Sub 2 are each independently selected from the group of C1-C20 hydrocarbyl radicals, or substituted amido radicals optionally linked by a bridging moiety.
- the metal-organic compound is contacted with the HA adduct of an imine ligand, with more preference a phosphinimine ligand in the presence of at least two equivalents of a base.
- a process for a less dangerous azide-free preparation of phosphinimine ligands is described in Canadian patent application CA 2,261,518.
- a trialkyl aminophosphoniumhalide (which is the HX adduct of trialkylphosphinimine) is reacted with a base to a trialkyl phosphinimide salt, where after this trialkyl phosphinimide salt is quenched with trimethyl silylchloride(TMSCl).
- the thus formed trialkyl silyl substituted phosphinimine ligand is subsequently reacted in a third step with CpTiCl 3 to the metal organic compound.
- a disadvantage of the 3 step method described in CA 2,261,518, is the use of harmful and costly reagents, such as n-butyllithium.
- Another purpose of the present invention is therefore to provide a widely applicable method for the manufacturing of a metal-organic compound from an aminophosphoniumhalide and a metal-organic reagent in one step. This aim is achieved in a process wherein an HA adduct of a phosphinimine ligand (e.g.
- aminophosphonium halide according to formula 1 is contacted with a metal-organic reagent of formula 2 in the presence of at least 2 equivalents of a base, wherein HA represents an acid, of which H represents its proton and A its conjugate base, with Y ⁇ NH being the ligand in formula 1, wherein Y is represented by formula 3.
- HA represents an acid, of which H represents its proton and A its conjugate base.
- A are halogenides, such as fluoride, chloride, bromide, or iodide, sulfate, hydrogensulfate, phosphate, hydrogenphosphate, dihydrogenphosphate, carbonate, hydrogencarbonate, aromatic or aliphatic carboxylates, cyanide, tetrafluoroborate, (substituted) tetraphenylborates, fluorinated tetraarylborates, alkyl or aryl sulfonates.
- the “number of equivalents of a base” is understood to be the amount of equivalents with respect to the number of imine ligands, or functionalities in the event that one ligand comprises more than one imine functionality.
- at least 1, respectively 2 equivalens of a base and lateron in the application “at least 3, respectively 4 equivalents of a base”, is meant that at least 1, respectively 3 equivalents of a base are required when the imine ligand as such is used, but that at least 2, respectively 4 equivalents are required, in case the HA adduct of the imine ligand is used.
- the metal-organic reagent used in the method of the invention is a reagent according to formula 2.
- L 1 to L 4 can independently be a monoanionic ligand or a group 17 halogen atom.
- Examples of monoanionic ligands are: halides like a fluoride, chloride, bromide or iodide, (un)substituted aliphatic or aromatic hydrocarbyls, like C 1 -C 20 hydrocarbyl radicals, aryloxy or alkyloxy, cyclopentadienyls, indenyls, tetrahydroindenyls, fluorenyls, tetrahydrofluorenyls, and octahydrofluorenyls, amides, phosphides, sulfides, ketimides, guanidines, iminoimidazolines, phosphinimides, substituted imines, like (hetero)aryloxyimines, pyrroleimines, indoleimines, imidazoleimines or (hetero)aryloxides.
- halides like a fluoride, chloride, bromide or iodide,
- Preferred monoanionic ligands include: fluoride, chloride, bromide, iodide, C 1 -C 20 hydrocarbyl radicals, cyclopentadienyl, C 1 -C 20 hydrocarbyl substituted cyclopentadienyls, halogen substituted C 1 -C 20 hydrocarbyl substituted cyclopentadienyls, indenyl, C 1 -C 20 hydrocarbyl substituted indenyls, halogen substituted C 1 -C 20 hydrocarbyl substituted indenyls, fluorenyls, C 1 -C 20 hydrocarbyl substituted fluorenyls, halogen substituted C 1 -C 20 hydrocarbyl substituted fluorenyls, C 1 -C 45 substituted phosphinimides, C 1 -C 20 substituted ketimides, C 1 -C 30 substituted guanidines, C 1 -C 30 iminoimidazolines.
- monoanionic ligands are selected from fluoride, chloride, bromide, iodide, cyclopentadienyl, C 1 -C 20 hydrocarbyl (optionally containing hetero- or group 17 halogen atoms), substituted cyclopentadienyls, indenyl, C 1 -C 20 hydrocarbyl substituted indenyls, and halogen substituted C 1 -C 20 hydrocarbyl substituted indenyls.
- L 1 , L 2 , L 3 , or L 4 represents a group 17 atom.
- V the valency of the metal
- one or two ligands L may represent a group 17 atom.
- Preferred group 17 atom ligands are fluoride, chloride, bromide or iodide atoms. The most preferred group 17 atom ligand is chloride.
- At least one of the ligands L is chosen from cyclopentadienyl, C 1 -C 20 hydrocarbyl (optionally containing hetero- or group 17 halogen atoms), substituted cyclopentadienyls, indenyl, C 1 -C 20 hydrocarbyl substituted indenyls, and halogen substituted C 1 -C 20 hydrocarbyl substituted indenyls.
- C 1 -C 20 hydrocarbyl (optionally containing hetero- or group 17 halogen atoms) also includes aryloxy or alkyloxy, octahydrofluorenyls, amides, phosphides, sulfides, ketimides, guanidines, iminoimidazolines, phosphinimides, substituted imines, like (hetero)aryloxyimines, pyrroleimines, indoleimines, imidazoleimines and (hetero)aryloxides.
- an imine ligand or the HA adduct thereof according to formula 1 is contacted with a metal-organic reagent of formula 2 in the presence of at least 1, respectively 2, equivalents of a base.
- a base is understood to be an inorganic base or a metal-organic base.
- An inorganic base is a metal or a metal salt capable of accepting at least one proton.
- a metal-organic base is a carbanion of an element of group 1,2, 12 or 13.
- Examples of a base include, carboxylates (for example potassium acetate), fluorides, hydroxides, cyanides, amides and carbonates of Li, Na, K, Rb, Cs, ammonium and the group 2 metals Mg, Ca, & Ba, the alkali metal (Li, Na, K, Rb, Cs) phosphates and the phosphate esters (eg. C 6 H 5 OP(O)(ONa) 2 and related aryl and alkyl compounds) and their alkoxides and phenoxides, thallium hydroxide, alkylammonium hydroxides and fluorides.
- carboxylates for example potassium acetate
- fluorides for example potassium acetate
- hydroxides for example potassium acetate
- cyanides cyanides
- amides and carbonates Li, Na, K, Rb, Cs, ammonium and the group 2 metals Mg, Ca, & Ba
- bases may be used in conjunction with a phase transfer reagent, such as for example tetraalkylammonium-, tetraalkylphosphonium salts or crown ethers.
- a phase transfer reagent such as for example tetraalkylammonium-, tetraalkylphosphonium salts or crown ethers.
- stronger bases may be applied, like carbanions such as hydrocarbanions of group 1, group 2, group 12 or group 13 elements.
- the metallic alkalimetals of group 1 may be applied as a base.
- Preferred bases include, organolithium compounds, or organomagnesium compounds, alkali metals, group 1 hydrides or group 2 hydrides
- More preferred bases are organolithium compounds, organomagnesium compound, sodium hydride or calciumhydride.
- organomagnesium compounds are: methylmagnesiumhalides, phenylmagnesiumhalides, benzylmagnesiumhalides, biphenylmagnesiumhalides, naphtylmagnesiumhalides, tolylmagnesiumhalides, xylylmagnesiumhalides, mesitylmagnesiumhalides, dimethylresorcinolmagnesiumhalides, N,N-dimethylanilinemagnesiumhalides, dimethylmagnesium, diphenylmagnesium, dibenzylmagnesium, bis(biphenyl)magnesium, dinaphtylmagnesium, ditolylmagnesium, dixylylmagnesium, dimesitylmagnesium, bis(dimethylresorcinol)magnesium, bis(N,N-dimethylaniline)magnesium.
- organolithium compounds are: methyllithium, phenyllithium, benzyllithium, biphenyllithium, naphtyllithium, dimethylresorcinollithium, N N-dimethylanilinelithium.
- the halide groups of the metal-organic compound from the process of the invention have to be alkylated or arylated in an additional reaction step. This can be done for example with an organolithium compound or an organo magnesium compound.
- an organolithium compound or an organo magnesium compound Surprisingly it has been found that such alkylated or arylated metal-organic compound can also be prepared in one step by the process of the invention by carrying out the process in the presence of at least 3, respectively 4 equivalents of an organomagnesium compound or an organolithium compound as a base.
- a metal-organic reagent comprising 3 halogen ligands reacting with 1 imine functionality only.
- metal-organic reagents with 4 or 5 halogen ligands will require at least 4 respectively 5 equivalents of a base in stead of at least 3, or 5 respectively 6 equivalents in stead of 4.
- Suitable solvents are solvents that do not react with the metal-organic reagent or the metal-organic compound formed in the process of the invention.
- suitable solvents include aromatic and aliphatic hydrocarbons, halogenated hydrocarbons, amides of the aliphatic carboxylic acids and primarily, or secondary amines, DMSO, nitromethane, acetone, acetonitrile, benzonitrile, ethers, polyethers, cyclic ethers, lower aromatic and aliphatic ethers, or esters, and mixtures thereof.
- Preferred solvents include aromatic or aliphatic hydrocarbons or mixtures thereof.
- the process of the invention can be carried out, by adding at least 1, respectively at least 2 equivalents of a base to a mixture of the imine ligand or its HA adduct and the metal-organic reagent thus forming a reaction mixture.
- the desired metal-organic compound is often formed instantaneously. Excess of a base may be applied without negative effects on the reaction product.
- a salt is formed.
- the reaction mixture as obtained by contacting an imine or its HA adduct may be used as precatalyst in a polyolefin polymerisation without an additional filtration step if the salt formed during the reaction is compatible with the polymerisation process.
- the salt can be removed by using a filtration.
- the mixture may be heated and then filtered.
- An advantage of the present invention is that the filtrate may be used as such without further purification in a following process, such as an alkylation or arylation step or the polymerisation process.
- the metal-organic compound may be isolated by distillation of the solvent, by precipitation or by crystallisation from a suitable solvent.
- the invention further relates to a process for the preparation of a polyolefin as described in claim 13 .
- Such an olefin polymerisation can be carried out in solution, slurry or in the gas phase.
- the (alkylated) metal-organic compound is formed in situ.
- in situ preparation is meant in this context, that the metal-organic compound is made and subsequently activated in or anywhere before the reactor of the polymerisation equipment by contacting an imine or its HA adduct with an metal-organic reagent in the presence of an olefin polymerisation compatible base.
- bases compatible with the olefin polymerisation process include, organomagnesium compound, organolithium reagents, organozinc reagents, organoaluminum reagents.
- More preferred bases are: organomagnesium compound, organolithium reagents, organozinc reagents, organoaluminum reagents. Most preferred bases are dibutylmagnesium, n-butyllithium, C 1 -C 20 dihydrocarbylzinc derivatives, diisobutylaluminium hydride, C 1 -C 20 trihydrocarbyl aluminiums, or aluminoxanes. In the case where aluminoxanes are applied as a base, the base can be the activator.
- R preferably represents a proton and Y is preferably selected from the group consisting of:
- Advantages of the process of the invention are: mild conditions, higher yields, higher reaction rates and smaller amounts of by-products.
- the (alkylated) metal-organic compounds as obtained by the invented process can be used without further purification in the olefin polymerisation resulting in more active catalysts.
- Tri-ethylamine was distilled from calciumhydride before use.
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- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Abstract
The invention relates to a process for the preparation of a metalorganic compound, comprising at least one imine ligand, characterized in that an imine ligand according to formula 1, or the HA adduct thereof, wherein HA represents an acid, of which H represents its proton and A its conjugate base, is contacted with a metal-organic reagent of formula 2 in the presence of at least 1, respectively 2 equivalents of an inorganic or metal-organic base, wherein Y═N—R (formula 1), Y is selected from a substituted carbon, nitrogen or phosphorous atom, R represents a proton, a protic or an aprotic substituent, and the metal organic compound is: Mv(L1)k(L2)I(L3)m(L4)nX (formula 2) wherein: M represents a group 4 or group 5 metal ion, V represents the valency of the metal ion, being 3, 4 or 5, L1, L2, L3, and L4 represent ligands on M and may be equal or different, X represents a group 17 halogen atom, and k, l, m, n=0, 1, 2, 3, 4 with k+l+m+n+1=V. The invention further relates to a process for the preparation of a polyolefin by making a metal-organic compound according to the process of the invention, wherein the base is an olefin polymerisation compatible base, which metal-organic compound is activated anywhere in, or before a polymerisation reactor.
Description
- The invention relates to a process for the preparation of an metal-organic compound comprising at least one imine ligand according to formula 1. Metal-organic compounds thus produced are typically used as precatalyst in the production of polyolefins. Imine ligands for these precatalyst can be guanidine, iminoimidazoline, ketimine or phosphinimine, the manufacturing of which is described in WO 02070569, U.S. Pat. No. 6,114,481 and U.S. Pat. No. 6,063,879 respectively.
- The known production processes for phosphinimine comprising metal-organic compounds require at least two steps: (i) the synthesis of a N-trialkylsilyl substituted imine ligand, followed by (ii) contacting this ligand with an metal-organic precursor. However, in the one step process for the manufacturing of the imine ligand, as described in Z. Naturforschung. 29b, 328 (1974) (the Staudinger reaction), azide chemistry is required. In this process, the most frequently used azide is azidotrimethylsilane, which is highly toxic and readily hydrolysable, releasing the highly toxic and both temperature and shock sensitive hydrazoic acid. Therefore, mixtures containing (partially) hydrolysed trimethylsilylazide may explosively decompose.
- A process for an azide-free preparation of imine ligands (i.e. phosphinimine) is described in Canadian patent application CA 2,261,518. However, this procedure encompasses two reaction steps starting from aminophosphoniumhalides. Another disadvantage of the method described in CA 2,261,518, is the use of harmful and costly reagents, such as n-butyllithium. Finally, in this procedure the imine ligand is substituted with trimethylsilylchloride, which is removed as such in a subsequent reaction of the imine ligand with the metal-organic precursor. Known production processes for guanidine-, ketimine- and iminoimidazoline comprising metal-organic compounds are described in WO 2070569 and U.S. Pat. No. 6,114,481.They are carried out at low temperature and require in some cases a solvent change.
- Disadvantage of the known less dangerous method is thus that at least two steps are required, when starting the process with an aminophosphoniumhalide. Purpose of the present invention is to provide a widely applicable method for the manufacturing of a metal-organic compound from an imine and a metal-organic precursor in one step
- This aim is achieved in that an imine ligand according to formula 1, or the HA adduct thereof, wherein HA represents an acid, of which H represents its proton and A its conjugate base, is contacted with a metal-organic reagent of formula 2 in the presence of at least 1, respectively 2 equivalents of base, wherein
-
Y═N—R (formula 1) - wherein Y is selected from a substituted carbon, nitrogen or phosphorous atom and R represents a proton, a protic or an aprotic substituent, and:
-
MV(L1)k(L2)l(L3)m(L4)nX (formula 2) - wherein:
M represents a group 4 or group 5 metal ion
V represents the valency of the metal ion, being 3, 4 or 5
L1, L2, L3, and L4 represent ligands on M and may be equal or different
X represents a group 17 halogen atom
k, l, m, n=0, 1, 2, 3, 4 with k+l+m+n+1=V - In this application a base is understood to be an inorganic or metal-organic base. CA 02243775 describes a similar preparation of an metal-organic compound in the presence of an inorganic base. Surprisingly it was found that this reaction could also be carried out in the presence of the cheaper inorganic base like potassium carbonate. Another advantage is the formation of a precipitate which can be filtered off easier than the precipitate which is formed with the organic base used in CA 02243775. Still another advantage is the fact that inorganic bases are environmentally friendly and allows a broader range of solvents used in the process of the invention. An advantage of the metal-organic base is that with this base the hydrocarbylated metal-organic compound can be prepared in a one step process. In the known process the metal-organic dichloride has to be hydrocarbylated in a second reaction step in case this is required for exampled to use the metal-organic compound in a polymerisation process using a boron comprising activator. Another advantage of the process of the invention is the use of the HA adduct of the imine, which can be prepared easier than the imine of the state of the art.
- With the method of the invention a metal-organic compound, suitable as precatalyst in olefin polymerisation, is prepared in one step. An additional advantage of the method of the invention is, that during the process hardly any by-products are formed, so that further purification is not necessary (or very limited with respect to state of the art processes). The metal-organic compound prepared by the method of the invention has a higher purity than a metal-organic compound prepared via known production processes and can be used as such in olefin polymerisation processes. An additional advantage of the process of the invention is that the process can be carried out at room temperature, whereas the reaction of the N-trialkylsilyl substituted imine ligand with the metal-organic reagent has to be often carried out at elevated temperatures.
- The imine derivative or its HA adduct, as represented in formula 1, is substituted by an Y- and an R group. In the method of the invention, the Y group consists of a substituted carbon, nitrogen or phosphorous atom. If Y represents a substituted carbon atom, the number of substituents is 2. If Y represents a substituted nitrogen atom, the number of substituents is 1 and the number of substituents is 1 or 3 if Y represents a phosphorous atom, depending on the valency of the phosphorous atom.
- Substituents on carbon, nitrogen or phosphorous may be equal or different, optionally linked with each other, optionally having heteroatoms. Substituents may be protic or aprotic. A protic substituent is defined here as a substituent, which has at least one, group 15 or group 16 atom containing at least one proton.
- Examples of protic substituents include C1-C20 linear, branched or cyclic hydrocarbyl radicals, substituted with a group 15 or 16 atom bearing at least one hydrogen atom. Preferred protic substituents include phenolic radicals, pyrrolic radicals, indolic radicals, and imidazolic radicals.
- The substituent is called aprotic if the substituent lacks a group containing a group 15 or group 16 atom bearing a proton. An unsubstituted aprotic hydrocarbyl radical can be a C1-C20 linear, branched or cyclic radical, a hydrogen atom, a halogen atom, a C1-8alkoxy radical, a C6-10 aryl or aryloxy radical, an amido radical, or a C1-20 hydrocarbyl radical unsubstituted or substituted by a halogen atom, a C1-8 alkoxy radical, a C6-10 aryl or aryloxy radical, an amido radical, a silyl radical of the formula 4, or a germanyl radical of the formula 5.
- The substituent R can be H, or being equal as these for the substituent on Y.
- Examples of imine ligands according to formula (I) thus include: guanidines, iminoimidazolines, phosphinimines, phenolimines, pyrroleimines, indoleimines and imidazoleimines.
- R may be linked with Y, thus forming a ring system, optionally comprising heteroatoms, or optionally comprising functional groups. Examples of ligands comprising such ring systems include: 8-hydroxyquinoline, 8-aminoquinoline, 8-phosphinoquinoline, 8-thioquinoline, 8-hydroxyquinaldine, 8-aminoquinaldine, 8-phosphinoquinaldine, 8-thioquinaldine and 7-azaindole or indazole.
- In a preferred embodiment of the method of the invention, R represents a hydrogen atom and Y is selected from the group consisting of:
- i) a phosphorus substituent according to the formula:
- wherein each R1j, with j=1-3 is independently selected from the group consisting of a hydrogen atom, a halogen atom, a C1-8 alkoxy radical, a C6-10 aryl or aryloxy radical, an amido radical, or a C1-20 hydrocarbyl radical unsubstituted or substituted by a halogen atom, a C1-8 alkoxy radical, a C6-10 aryl or aryloxy radical, an amido radical, a silyl radical of the formula:
- or a germanyl radical of the formula:
- wherein R2j, with j=1-3, is independently selected from the group consisting of hydrogen, a C1-8 alkyl or alkoxy radical, C6-10 aryl or aryloxy radicals, each substituent R1j or R2j may be linked with another R1j or R2j respectively to form a ring system,
ii) a substituent according to formula 6: - wherein each of Sub1 and Sub2 is independently selected from the group consisting of hydrocarbyl radicals having from 1 to 30 carbon atoms; silyl radicals, (substituted) amido radicals and (substituted) phosphido radicals, and wherein Sub1 and Sub2 may be linked with each other to form a ring system.
- Preferably Sub1 and Sub2 are each independently selected from the group of C1-C20 hydrocarbyl radicals, or substituted amido radicals optionally linked by a bridging moiety.
- Preferably the metal-organic compound is contacted with the HA adduct of an imine ligand, with more preference a phosphinimine ligand in the presence of at least two equivalents of a base. A process for a less dangerous azide-free preparation of phosphinimine ligands is described in Canadian patent application CA 2,261,518. In a first step a trialkyl aminophosphoniumhalide (which is the HX adduct of trialkylphosphinimine) is reacted with a base to a trialkyl phosphinimide salt, where after this trialkyl phosphinimide salt is quenched with trimethyl silylchloride(TMSCl). The thus formed trialkyl silyl substituted phosphinimine ligand is subsequently reacted in a third step with CpTiCl3 to the metal organic compound. A disadvantage of the 3 step method described in CA 2,261,518, is the use of harmful and costly reagents, such as n-butyllithium. Another purpose of the present invention is therefore to provide a widely applicable method for the manufacturing of a metal-organic compound from an aminophosphoniumhalide and a metal-organic reagent in one step. This aim is achieved in a process wherein an HA adduct of a phosphinimine ligand (e.g. aminophosphonium halide) according to formula 1 is contacted with a metal-organic reagent of formula 2 in the presence of at least 2 equivalents of a base, wherein HA represents an acid, of which H represents its proton and A its conjugate base, with Y═NH being the ligand in formula 1, wherein Y is represented by formula 3.
- In the process of the invention, HA represents an acid, of which H represents its proton and A its conjugate base. Examples of A are halogenides, such as fluoride, chloride, bromide, or iodide, sulfate, hydrogensulfate, phosphate, hydrogenphosphate, dihydrogenphosphate, carbonate, hydrogencarbonate, aromatic or aliphatic carboxylates, cyanide, tetrafluoroborate, (substituted) tetraphenylborates, fluorinated tetraarylborates, alkyl or aryl sulfonates.
- The “number of equivalents of a base” is understood to be the amount of equivalents with respect to the number of imine ligands, or functionalities in the event that one ligand comprises more than one imine functionality. With “at least 1, respectively 2 equivalens of a base”, and lateron in the application “at least 3, respectively 4 equivalents of a base”, is meant that at least 1, respectively 3 equivalents of a base are required when the imine ligand as such is used, but that at least 2, respectively 4 equivalents are required, in case the HA adduct of the imine ligand is used.
- The metal-organic reagent used in the method of the invention is a reagent according to formula 2. In this formula L1 to L4 can independently be a monoanionic ligand or a group 17 halogen atom.
- Examples of monoanionic ligands are: halides like a fluoride, chloride, bromide or iodide, (un)substituted aliphatic or aromatic hydrocarbyls, like C1-C20 hydrocarbyl radicals, aryloxy or alkyloxy, cyclopentadienyls, indenyls, tetrahydroindenyls, fluorenyls, tetrahydrofluorenyls, and octahydrofluorenyls, amides, phosphides, sulfides, ketimides, guanidines, iminoimidazolines, phosphinimides, substituted imines, like (hetero)aryloxyimines, pyrroleimines, indoleimines, imidazoleimines or (hetero)aryloxides.
- Preferred monoanionic ligands include: fluoride, chloride, bromide, iodide, C1-C20 hydrocarbyl radicals, cyclopentadienyl, C1-C20 hydrocarbyl substituted cyclopentadienyls, halogen substituted C1-C20 hydrocarbyl substituted cyclopentadienyls, indenyl, C1-C20 hydrocarbyl substituted indenyls, halogen substituted C1-C20 hydrocarbyl substituted indenyls, fluorenyls, C1-C20 hydrocarbyl substituted fluorenyls, halogen substituted C1-C20 hydrocarbyl substituted fluorenyls, C1-C45 substituted phosphinimides, C1-C20 substituted ketimides, C1-C30 substituted guanidines, C1-C30 iminoimidazolines.
- Most preferably monoanionic ligands are selected from fluoride, chloride, bromide, iodide, cyclopentadienyl, C1-C20 hydrocarbyl (optionally containing hetero- or group 17 halogen atoms), substituted cyclopentadienyls, indenyl, C1-C20 hydrocarbyl substituted indenyls, and halogen substituted C1-C20 hydrocarbyl substituted indenyls.
- Depending on the valency of the metal of the metal-organic reagent, preferably at least one L1, L2, L3, or L4 represents a group 17 atom. If the valency of the metal V=3, one or two ligands L may represent a group 17 atom. If V=4, two or three ligands L may represent a group 17 atom. If V=5, two to four ligands L may represent a group 17 atom. Preferred group 17 atom ligands are fluoride, chloride, bromide or iodide atoms. The most preferred group 17 atom ligand is chloride. In a most preferred embodiment, at least one of the ligands L is chosen from cyclopentadienyl, C1-C20 hydrocarbyl (optionally containing hetero- or group 17 halogen atoms), substituted cyclopentadienyls, indenyl, C1-C20 hydrocarbyl substituted indenyls, and halogen substituted C1-C20 hydrocarbyl substituted indenyls. C1-C20 hydrocarbyl (optionally containing hetero- or group 17 halogen atoms) also includes aryloxy or alkyloxy, octahydrofluorenyls, amides, phosphides, sulfides, ketimides, guanidines, iminoimidazolines, phosphinimides, substituted imines, like (hetero)aryloxyimines, pyrroleimines, indoleimines, imidazoleimines and (hetero)aryloxides.
- In the method of the invention an imine ligand or the HA adduct thereof according to formula 1, is contacted with a metal-organic reagent of formula 2 in the presence of at least 1, respectively 2, equivalents of a base. In this application a base is understood to be an inorganic base or a metal-organic base. An inorganic base is a metal or a metal salt capable of accepting at least one proton. A metal-organic base is a carbanion of an element of group 1,2, 12 or 13. Examples of a base include, carboxylates (for example potassium acetate), fluorides, hydroxides, cyanides, amides and carbonates of Li, Na, K, Rb, Cs, ammonium and the group 2 metals Mg, Ca, & Ba, the alkali metal (Li, Na, K, Rb, Cs) phosphates and the phosphate esters (eg. C6H5OP(O)(ONa)2 and related aryl and alkyl compounds) and their alkoxides and phenoxides, thallium hydroxide, alkylammonium hydroxides and fluorides. Some of these bases may be used in conjunction with a phase transfer reagent, such as for example tetraalkylammonium-, tetraalkylphosphonium salts or crown ethers. Also stronger bases may be applied, like carbanions such as hydrocarbanions of group 1, group 2, group 12 or group 13 elements. Also the metallic alkalimetals of group 1 may be applied as a base.
- Preferred bases include, organolithium compounds, or organomagnesium compounds, alkali metals, group 1 hydrides or group 2 hydrides
- More preferred bases are organolithium compounds, organomagnesium compound, sodium hydride or calciumhydride.
- Examples of organomagnesium compounds are: methylmagnesiumhalides, phenylmagnesiumhalides, benzylmagnesiumhalides, biphenylmagnesiumhalides, naphtylmagnesiumhalides, tolylmagnesiumhalides, xylylmagnesiumhalides, mesitylmagnesiumhalides, dimethylresorcinolmagnesiumhalides, N,N-dimethylanilinemagnesiumhalides, dimethylmagnesium, diphenylmagnesium, dibenzylmagnesium, bis(biphenyl)magnesium, dinaphtylmagnesium, ditolylmagnesium, dixylylmagnesium, dimesitylmagnesium, bis(dimethylresorcinol)magnesium, bis(N,N-dimethylaniline)magnesium.
- Examples of organolithium compounds are: methyllithium, phenyllithium, benzyllithium, biphenyllithium, naphtyllithium, dimethylresorcinollithium, N N-dimethylanilinelithium.
- In order to make a polyolefin by a borane or borate activatable metal-organic compound, the halide groups of the metal-organic compound from the process of the invention have to be alkylated or arylated in an additional reaction step. This can be done for example with an organolithium compound or an organo magnesium compound. Surprisingly it has been found that such alkylated or arylated metal-organic compound can also be prepared in one step by the process of the invention by carrying out the process in the presence of at least 3, respectively 4 equivalents of an organomagnesium compound or an organolithium compound as a base. This holds for a metal-organic reagent comprising 3 halogen ligands reacting with 1 imine functionality only. One skilled in the art will understand that metal-organic reagents with 4 or 5 halogen ligands will require at least 4 respectively 5 equivalents of a base in stead of at least 3, or 5 respectively 6 equivalents in stead of 4.
- The process of the invention is preferably carried out in a solvent. Suitable solvents are solvents that do not react with the metal-organic reagent or the metal-organic compound formed in the process of the invention. Examples of suitable solvents include aromatic and aliphatic hydrocarbons, halogenated hydrocarbons, amides of the aliphatic carboxylic acids and primarily, or secondary amines, DMSO, nitromethane, acetone, acetonitrile, benzonitrile, ethers, polyethers, cyclic ethers, lower aromatic and aliphatic ethers, or esters, and mixtures thereof. Preferred solvents include aromatic or aliphatic hydrocarbons or mixtures thereof.
- The process of the invention can be carried out, by adding at least 1, respectively at least 2 equivalents of a base to a mixture of the imine ligand or its HA adduct and the metal-organic reagent thus forming a reaction mixture. The desired metal-organic compound is often formed instantaneously. Excess of a base may be applied without negative effects on the reaction product.
- During the reaction, a salt is formed. The reaction mixture as obtained by contacting an imine or its HA adduct may be used as precatalyst in a polyolefin polymerisation without an additional filtration step if the salt formed during the reaction is compatible with the polymerisation process. If a salt free metal-organic compound is required, the salt can be removed by using a filtration. Depending on the solubility of the metal-organic compound, the mixture may be heated and then filtered. An advantage of the present invention is that the filtrate may be used as such without further purification in a following process, such as an alkylation or arylation step or the polymerisation process. If desired, the metal-organic compound may be isolated by distillation of the solvent, by precipitation or by crystallisation from a suitable solvent.
- The invention further relates to a process for the preparation of a polyolefin as described in claim 13. Such an olefin polymerisation can be carried out in solution, slurry or in the gas phase.
- In a preferred embodiment of the olefin polymerisation the (alkylated) metal-organic compound is formed in situ. By in situ preparation is meant in this context, that the metal-organic compound is made and subsequently activated in or anywhere before the reactor of the polymerisation equipment by contacting an imine or its HA adduct with an metal-organic reagent in the presence of an olefin polymerisation compatible base. Examples of bases compatible with the olefin polymerisation process include, organomagnesium compound, organolithium reagents, organozinc reagents, organoaluminum reagents. More preferred bases are: organomagnesium compound, organolithium reagents, organozinc reagents, organoaluminum reagents. Most preferred bases are dibutylmagnesium, n-butyllithium, C1-C20 dihydrocarbylzinc derivatives, diisobutylaluminium hydride, C1-C20 trihydrocarbyl aluminiums, or aluminoxanes. In the case where aluminoxanes are applied as a base, the base can be the activator.
- In the olefin polymerisation according to the invention, R preferably represents a proton and Y is preferably selected from the group consisting of:
- i) a phosphorus substituent according to formula 3 of claim 2 or:
ii) a substituent according to formula 6 of claim 2. - Advantages of the process of the invention are: mild conditions, higher yields, higher reaction rates and smaller amounts of by-products. The (alkylated) metal-organic compounds as obtained by the invented process can be used without further purification in the olefin polymerisation resulting in more active catalysts.
- The invention will be elucidated with some non-limiting examples:
- Experiments were performed under a dry and oxygen-free nitrogen atmosphere using Schlenk-line techniques. 1H-NMR, 13C-NMR-spectra and 31P-NMR-spectra were measured on a Bruker Avance 300 spectrometer. Diethyl ether and ligroin were distilled from sodium/potassium alloy; THF and toluene from potassium and sodium, respectively, all having benzophenone as indicator.
- Tri-ethylamine was distilled from calciumhydride before use.
- Other starting materials were used as obtained.
- To an orange mixture of C6F5 CpTiCl3 (1.00 g, 2.59 mmol) and t-Bu3PCINH2 (0.68 g, 2.59 mmol) in toluene (60 mL) and THF (20 mL) was added a MeMgBr solution in ether (3.0M, 4.0 mL, 12 mmol) at −20° C. The reaction mixture was stirred for 45 minutes and subsequently dried in vacuo. The residue was extracted with boiling ligroin (20 and 40 mL respectively). The solvents were removed in vacuo resulting in 1.33 g (98%) of (Cp-C6F5)Ti(NP(t-Bu)3)Me2 with no detectable amounts of by-product.
- To a suspension of 1,3-bis(2,6-dimethylphenyl)-iminoimidazoline (2.93 g, 10.0 mmol) and cyclopentadienyltitanium trichloride (2.19 g, 10.0 mmol) in toluene (100 mL) was added methylmagnesiumbromide (11 mL of a 3.0 M solution in diethyl ether, 33 mmol) at −80° C. during 10 minutes. The mixture was allowed to warm to ambient temperature to give a yellow suspension. THF (30 mL) was added, and the mixture was stirred for 15 hours. The light yellow suspension was evaporated to dryness. The residue was extracted with boiling ligroin (100 mL). The resulting suspension was filtered hot. The cake was extracted further with hot ligroin (Three times with 60 mL until the filtrate became colourless). The combined yellow filtrates were partially evaporated under reduced pressure to 50 mL. Cooling to approx. 4° C. afforded yellow crystals, which were filtered and washed with cold ligroin to give 2.05 g (47% yield) of NMR pure 1,3-bis(2,6-dimethylphenyl)-iminoimidazoline cyclopentadienyl titanium dimethyl.
- To a solution of cyclopentadienyltitanium trichloride (0.51 g, 2.3 mmol) in toluene (40 mL) was added N,N,N′,N′,N″,N″-hexamethylphosphorimidic triamide (0.41 g, 2.3 mmol). Then, dry K2CO3 (0.5 g, 3.6 mmol) was added. 31P-NMR reaction monitoring showed that the desired product was formed without any detectable amount of by-product. The reaction mixture was filtered in order to remove the salts which were subsequently extracted with an extra portion of toluene (25 mL). The combined solvents of the filtrate were removed in vacuo to give 0.79 g (yield: 94%) of a yellow crystalline product, which was characterized by 31P-NMR to be pure tris(N,N-dimethylamido)phosphoraneimido cyclopentadienyl titanium(IV) dichloride.
- To a solution of cyclopentadienyltitanium trichloride (0.51 g, 2.3 mmol) and N,N,N′,N′,N″,N″-hexamethylphosphorimidic triamide (0.44 g, 2.5 mmol) in toluene (40 mL) and THF (10 mL) was added a solution of methylmagnesium bromide in ether (2.3 mL, 3.0 M, 6.9 mmol) at room temperature. The reaction was exothermal under gas evolution and the colour changed to light yellow. 31P-NMR reaction monitoring showed that the desired product was formed without any detectable amount of by-product. The solvents were removed in vacuo and the product was extracted from the residue with n-hexane twice (50 mL each). The solvents were removed in vacuo to give 0.59 g (yield: 79%) of a yellow powder, which was characterized by 1H- and 31P-NMR to be tris(N,N-dimethylamido)phosphoraneimido cyclopentadienyl titanium(IV) dimethyl.
Claims (10)
1. A process for the preparation of a metal-organic compound, comprising contacting the HA adduct of at least one imine ligand according to formula 1, wherein HA represents an acid, of which H represents its proton and A its conjugate base, is contacted with a metal-organic reagent of formula 2 in the presence of at least 1, respectively 2 equivalents of an inorganic or metal-organic base, wherein
Y═N—R (formula 1)
Y═N—R (formula 1)
wherein Y is selected from a substituted phosphorous atom and R represents a proton, a protic or an aprotic substituent, and:
MV(L1)k(L2)l(L3)m(L4)nX (formula 2)
MV(L1)k(L2)l(L3)m(L4)nX (formula 2)
wherein:
M represents a group 4 or group 5 metal ion
V represents the valency of the metal ion, being 3, 4 or 5
L1, L2, L3, and L4 represent ligands on M and may be equal or different
X represents a group 17 halogen atom
k, l, m, n=0, 1, 2, 3, 4 with k+l+m+n+1=V
2. A process according to claim 1 wherein R represents a hydrogen atom and wherein Y is:
a phosphorus substituent defined by the formula:
wherein each R1j, with j=1-3 is independently selected from the group consisting of a hydrogen atom, a halogen atom, a C1-8 alkoxy radical, a C6-10 aryl or aryloxy radical, an amido radical, a C1-20 hydrocarbyl radical unsubstituted or substituted by a halogen atom, a C1-8 alkoxy radical, a C6-10 aryl or aryloxy radical, an amido radical, a silyl radical of the formula:
3. A process according to claim 1 , wherein the inorganic base is a carboxylate, or a fluoride, or a hydroxide, or a cyanide, or an amide, or a carbonate of Li, Na, K, Rb, Cs, or a group 2 metal salt selected from Mg, Ca, or Ba, or an alkali metal selected from Li, Na, K, Rb, or Cs of phosphate or a phosphate ester alkoxide of Li, Na, K, Rb or Cs, or phenoxide of Li, Na, K, Rb or Cs, or thallium hydroxide, or a hydrocarbanion of any of the group 1, group 2, group 12 or group 13 elements, or an alkali metal, group 1 hydride or group 2 hydride.
4. A process according to claim 3 , wherein the inorganic base is selected from sodium hydride, or calciumhydride.
5. A process according to claim 1 , wherein the metal-organic base is selected from organolithium compounds, or organomagnesium compounds.
6. A process according to claim 1 , wherein the reaction is carried out in an aprotic solvent.
7. A process according to claim 1 , wherein the process is carried out in the presence of a phase transfer reagent.
8. Process for the preparation of a polyolefin by making a metal-organic compound according to the process of claim 1 , wherein the base is an olefin polymerisation compatible base, which metal-organic compound is activated anywhere in, or before a polymerisation reactor.
9. Process according to claim 8 , wherein the metal-organic compound is formed used without purification.
10. Process according to claim 8 , wherein the metal-organic compound is formed in the polymerisation equipment.
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US10/567,098 Active 2025-07-30 US7655592B2 (en) | 2003-08-04 | 2004-08-03 | Process for the preparation of a metal-organic compound comprising at least one imine ligand |
US10/567,156 Active 2026-05-20 US7737070B2 (en) | 2003-08-04 | 2004-08-03 | Process for the preparation of a metal-organic compound comprising at least one imine ligand |
US10/566,839 Active 2025-08-07 US7674867B2 (en) | 2003-08-04 | 2004-08-03 | Process for the preparation of an metal-organic compound comprising at least one imine ligand |
US10/566,979 Expired - Lifetime US7524906B2 (en) | 2003-08-04 | 2004-08-03 | Process for the preparation of a metal-organic compound comprising at least one imine ligand |
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US (5) | US7655592B2 (en) |
EP (5) | EP1506974A1 (en) |
CN (6) | CN1863823B (en) |
AT (4) | ATE466888T1 (en) |
DE (4) | DE602004026876D1 (en) |
WO (4) | WO2005014666A1 (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US10800863B2 (en) | 2015-10-21 | 2020-10-13 | Lg Chem, Ltd. | Transition metal complexes, catalyst compositions including the same, and method for preparing polyolefins therewith |
Families Citing this family (7)
Publication number | Priority date | Publication date | Assignee | Title |
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EP1764376A1 (en) | 2005-09-16 | 2007-03-21 | DSM IP Assets B.V. | Process for the preparation of a metal-organic compound comprising a spectator ligand |
CA2820501C (en) * | 2013-06-27 | 2021-01-26 | Nova Chemicals Corporation | Synthesis of phosphinimide coordination compounds |
EP3083048B1 (en) | 2013-12-19 | 2021-04-07 | Dow Global Technologies LLC | Metal-ligand complex, olefin polymerization catalyst derived therefrom, and olefin polymerization method utilizing the catalyst |
CN105148598B (en) * | 2015-07-20 | 2017-01-11 | 中广核研究院有限公司 | Connecting module for containment recycling filter |
JP6806806B2 (en) * | 2016-07-13 | 2021-01-06 | ダウ シリコーンズ コーポレーション | Metal aprotic organosilanoxide compound |
CN107868152B (en) * | 2016-09-23 | 2020-09-15 | 中国石油化工股份有限公司 | Catalyst component for olefin polymerization, catalyst and application thereof |
CN108250341B (en) * | 2016-12-28 | 2020-12-11 | 北京引发科技有限公司 | Catalyst system containing metallocene compound and method for catalyzing olefin polymerization by using catalyst system |
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US6114481A (en) * | 1997-09-15 | 2000-09-05 | Nova Chemicals (International) S.A. | Catalyst having a ketimide ligand |
US6355744B1 (en) * | 1998-07-21 | 2002-03-12 | Nova Chemicals (International) S.A. | Cyclopentadienyl/phosphinimine catalyst with one and only one activatable ligand |
US20040010142A1 (en) * | 2000-12-21 | 2004-01-15 | Nielsen Flemming Elmelund | Novel process |
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CA243775A (en) | 1924-10-21 | N. Mcgaughey Henry | Window | |
CA2206944C (en) | 1997-05-30 | 2006-08-29 | Douglas W. Stephan | High temperature solution polymerization process |
CA2210131C (en) * | 1997-07-09 | 2005-08-02 | Douglas W. Stephan | Supported phosphinimine-cp catalysts |
CA2243775C (en) * | 1998-07-21 | 2007-06-12 | Nova Chemicals Ltd. | Phosphinimine/heteroatom catalyst component |
CA2243783C (en) * | 1998-07-21 | 2007-06-05 | Nova Chemicals Ltd. | Bis-phosphinimine catalyst |
CA2261518A1 (en) * | 1999-02-12 | 2000-08-12 | Rupert Edward Von Haken Spence | Synthetic method |
ATE277092T1 (en) * | 2001-03-05 | 2004-10-15 | Stichting Dutch Polymer Inst | CATALYST COMPONENT FOR OLEFIN POLYMERIZATION AND CATALYST SYSTEM AND POLYMERIZATION PROCESS USING SUCH A CATALYST SYSTEM |
BE1014196A3 (en) * | 2001-05-23 | 2003-06-03 | Solvay | Catalyst complex and use for the polymerization of alpha-olefins. |
-
2003
- 2003-08-04 EP EP03077434A patent/EP1506974A1/en not_active Withdrawn
-
2004
- 2004-08-03 EP EP04763875A patent/EP1654292B1/en not_active Expired - Lifetime
- 2004-08-03 CN CN2004800290140A patent/CN1863823B/en not_active Expired - Lifetime
- 2004-08-03 AT AT04763766T patent/ATE466888T1/en not_active IP Right Cessation
- 2004-08-03 US US10/567,098 patent/US7655592B2/en active Active
- 2004-08-03 EP EP04741362A patent/EP1651681B1/en not_active Expired - Lifetime
- 2004-08-03 WO PCT/EP2004/008844 patent/WO2005014666A1/en active Application Filing
- 2004-08-03 CN CNB2004800281264A patent/CN100558768C/en not_active Expired - Lifetime
- 2004-08-03 DE DE602004026876T patent/DE602004026876D1/en not_active Expired - Lifetime
- 2004-08-03 CN CNA2004800281279A patent/CN1860137A/en active Pending
- 2004-08-03 CN CNB2004800290174A patent/CN100569806C/en not_active Expired - Lifetime
- 2004-08-03 US US10/567,156 patent/US7737070B2/en active Active
- 2004-08-03 AT AT04763875T patent/ATE466035T1/en not_active IP Right Cessation
- 2004-08-03 CN CNB2004800290189A patent/CN100551936C/en not_active Expired - Lifetime
- 2004-08-03 EP EP04763766A patent/EP1651682B1/en not_active Expired - Lifetime
- 2004-08-03 DE DE602004026882T patent/DE602004026882D1/en not_active Expired - Lifetime
- 2004-08-03 WO PCT/EP2004/008714 patent/WO2005014665A1/en active Application Filing
- 2004-08-03 AT AT04741360T patent/ATE466036T1/en not_active IP Right Cessation
- 2004-08-03 WO PCT/EP2004/008711 patent/WO2005014664A1/en active Application Filing
- 2004-08-03 WO PCT/EP2004/008707 patent/WO2005014663A1/en active Application Filing
- 2004-08-03 AT AT04741362T patent/ATE466034T1/en not_active IP Right Cessation
- 2004-08-03 CN CNB2004800290333A patent/CN100569807C/en not_active Expired - Lifetime
- 2004-08-03 DE DE602004026880T patent/DE602004026880D1/en not_active Expired - Lifetime
- 2004-08-03 US US10/566,839 patent/US7674867B2/en active Active
- 2004-08-03 EP EP04741360A patent/EP1656395B1/en not_active Expired - Lifetime
- 2004-08-03 DE DE602004027051T patent/DE602004027051D1/en not_active Expired - Lifetime
- 2004-08-03 US US10/566,979 patent/US7524906B2/en not_active Expired - Lifetime
-
2008
- 2008-09-09 US US12/230,991 patent/US20090018293A1/en not_active Abandoned
Patent Citations (3)
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US6114481A (en) * | 1997-09-15 | 2000-09-05 | Nova Chemicals (International) S.A. | Catalyst having a ketimide ligand |
US6355744B1 (en) * | 1998-07-21 | 2002-03-12 | Nova Chemicals (International) S.A. | Cyclopentadienyl/phosphinimine catalyst with one and only one activatable ligand |
US20040010142A1 (en) * | 2000-12-21 | 2004-01-15 | Nielsen Flemming Elmelund | Novel process |
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US10800863B2 (en) | 2015-10-21 | 2020-10-13 | Lg Chem, Ltd. | Transition metal complexes, catalyst compositions including the same, and method for preparing polyolefins therewith |
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