CA2181268A1 - Synthesis of cyclopentadienyl metal coordination complexes from metal hydrocarbyloxides - Google Patents
Synthesis of cyclopentadienyl metal coordination complexes from metal hydrocarbyloxidesInfo
- Publication number
- CA2181268A1 CA2181268A1 CA002181268A CA2181268A CA2181268A1 CA 2181268 A1 CA2181268 A1 CA 2181268A1 CA 002181268 A CA002181268 A CA 002181268A CA 2181268 A CA2181268 A CA 2181268A CA 2181268 A1 CA2181268 A1 CA 2181268A1
- Authority
- CA
- Canada
- Prior art keywords
- group
- metal
- formula
- process according
- optionally
- 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
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 110
- 239000002184 metal Substances 0.000 title claims abstract description 110
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 title claims abstract description 32
- ZSWFCLXCOIISFI-UHFFFAOYSA-N endo-cyclopentadiene Natural products C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 title abstract description 13
- 230000015572 biosynthetic process Effects 0.000 title description 7
- 238000003786 synthesis reaction Methods 0.000 title description 4
- -1 salt compound Chemical class 0.000 claims abstract description 53
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 33
- 239000003085 diluting agent Substances 0.000 claims abstract description 25
- 230000026030 halogenation Effects 0.000 claims abstract description 20
- 238000005658 halogenation reaction Methods 0.000 claims abstract description 20
- 238000004519 manufacturing process Methods 0.000 claims abstract description 16
- 150000002736 metal compounds Chemical class 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims description 59
- 150000004696 coordination complex Chemical class 0.000 claims description 39
- 125000001424 substituent group Chemical group 0.000 claims description 38
- 125000001183 hydrocarbyl group Chemical group 0.000 claims description 36
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 35
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 32
- 125000005843 halogen group Chemical group 0.000 claims description 30
- 239000000203 mixture Chemical group 0.000 claims description 28
- 125000000217 alkyl group Chemical group 0.000 claims description 27
- 125000004432 carbon atom Chemical group C* 0.000 claims description 27
- 125000001181 organosilyl group Chemical group [SiH3]* 0.000 claims description 26
- 239000002904 solvent Substances 0.000 claims description 25
- 125000003800 germyl group Chemical group [H][Ge]([H])([H])[*] 0.000 claims description 21
- 125000003118 aryl group Chemical group 0.000 claims description 20
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 20
- 239000001301 oxygen Substances 0.000 claims description 20
- 229910052760 oxygen Inorganic materials 0.000 claims description 20
- 125000004429 atom Chemical group 0.000 claims description 19
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 18
- 239000003446 ligand Substances 0.000 claims description 18
- 239000011593 sulfur Substances 0.000 claims description 18
- 229910052717 sulfur Inorganic materials 0.000 claims description 18
- 239000010936 titanium Substances 0.000 claims description 18
- 229910052757 nitrogen Inorganic materials 0.000 claims description 16
- 229930195733 hydrocarbon Natural products 0.000 claims description 15
- 239000001257 hydrogen Substances 0.000 claims description 15
- 229910052739 hydrogen Inorganic materials 0.000 claims description 15
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 14
- 229910052799 carbon Chemical group 0.000 claims description 14
- 150000002430 hydrocarbons Chemical class 0.000 claims description 14
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 13
- 125000004122 cyclic group Chemical group 0.000 claims description 13
- 229910052698 phosphorus Inorganic materials 0.000 claims description 13
- 239000011574 phosphorus Substances 0.000 claims description 13
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical group [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 11
- 230000000737 periodic effect Effects 0.000 claims description 11
- 229910052710 silicon Inorganic materials 0.000 claims description 11
- 239000010703 silicon Substances 0.000 claims description 11
- 229910052719 titanium Inorganic materials 0.000 claims description 11
- 239000004215 Carbon black (E152) Substances 0.000 claims description 10
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical group [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 10
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 10
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 10
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 10
- 229910052735 hafnium Chemical group 0.000 claims description 10
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical group [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 claims description 10
- 229910052726 zirconium Inorganic materials 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 9
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 8
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 8
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 7
- 125000000129 anionic group Chemical group 0.000 claims description 7
- 229910052796 boron Inorganic materials 0.000 claims description 7
- 125000001246 bromo group Chemical group Br* 0.000 claims description 7
- 125000002346 iodo group Chemical group I* 0.000 claims description 7
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims description 6
- 125000001931 aliphatic group Chemical group 0.000 claims description 5
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 5
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical group C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 claims description 5
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 3
- FAQYAMRNWDIXMY-UHFFFAOYSA-N trichloroborane Chemical class ClB(Cl)Cl FAQYAMRNWDIXMY-UHFFFAOYSA-N 0.000 claims description 3
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 150000002367 halogens Chemical class 0.000 claims description 2
- FDNAPBUWERUEDA-UHFFFAOYSA-N silicon tetrachloride Chemical class Cl[Si](Cl)(Cl)Cl FDNAPBUWERUEDA-UHFFFAOYSA-N 0.000 claims description 2
- 125000005234 alkyl aluminium group Chemical group 0.000 claims 1
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims 1
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 claims 1
- JMXKSZRRTHPKDL-UHFFFAOYSA-N titanium ethoxide Chemical compound [Ti+4].CC[O-].CC[O-].CC[O-].CC[O-] JMXKSZRRTHPKDL-UHFFFAOYSA-N 0.000 claims 1
- 235000013350 formula milk Nutrition 0.000 description 84
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 48
- 150000001875 compounds Chemical class 0.000 description 27
- 239000007787 solid Substances 0.000 description 21
- 239000000047 product Substances 0.000 description 19
- YSRFHVJGXPIDGR-UHFFFAOYSA-N dimethylsilane titanium Chemical compound [Ti].C[SiH2]C YSRFHVJGXPIDGR-UHFFFAOYSA-N 0.000 description 18
- 239000000463 material Substances 0.000 description 18
- 239000003054 catalyst Substances 0.000 description 16
- 239000000243 solution Substances 0.000 description 15
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 13
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 12
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- 239000006227 byproduct Substances 0.000 description 11
- 238000002360 preparation method Methods 0.000 description 11
- 125000003710 aryl alkyl group Chemical group 0.000 description 10
- 239000000178 monomer Substances 0.000 description 9
- 125000002877 alkyl aryl group Chemical group 0.000 description 8
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- 229940099990 ogen Drugs 0.000 description 7
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 7
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 6
- UHOVQNZJYSORNB-MZWXYZOWSA-N benzene-d6 Chemical compound [2H]C1=C([2H])C([2H])=C([2H])C([2H])=C1[2H] UHOVQNZJYSORNB-MZWXYZOWSA-N 0.000 description 6
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 6
- 239000000376 reactant Substances 0.000 description 6
- QWUWMCYKGHVNAV-UHFFFAOYSA-N 1,2-dihydrostilbene Chemical group C=1C=CC=CC=1CCC1=CC=CC=C1 QWUWMCYKGHVNAV-UHFFFAOYSA-N 0.000 description 5
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 5
- 238000001914 filtration Methods 0.000 description 5
- 238000001228 spectrum Methods 0.000 description 5
- VXEGSRKPIUDPQT-UHFFFAOYSA-N 4-[4-(4-methoxyphenyl)piperazin-1-yl]aniline Chemical compound C1=CC(OC)=CC=C1N1CCN(C=2C=CC(N)=CC=2)CC1 VXEGSRKPIUDPQT-UHFFFAOYSA-N 0.000 description 4
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 150000002170 ethers Chemical class 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- 239000005049 silicon tetrachloride Substances 0.000 description 4
- 229910052723 transition metal Inorganic materials 0.000 description 4
- 238000005160 1H NMR spectroscopy Methods 0.000 description 3
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- NHTMVDHEPJAVLT-UHFFFAOYSA-N Isooctane Chemical compound CC(C)CC(C)(C)C NHTMVDHEPJAVLT-UHFFFAOYSA-N 0.000 description 3
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 3
- 230000003213 activating effect Effects 0.000 description 3
- 238000013019 agitation Methods 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- JVSWJIKNEAIKJW-UHFFFAOYSA-N dimethyl-hexane Natural products CCCCCC(C)C JVSWJIKNEAIKJW-UHFFFAOYSA-N 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 3
- ZWYDDDAMNQQZHD-UHFFFAOYSA-L titanium(ii) chloride Chemical class [Cl-].[Cl-].[Ti+2] ZWYDDDAMNQQZHD-UHFFFAOYSA-L 0.000 description 3
- 150000003624 transition metals Chemical class 0.000 description 3
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 2
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 2
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 2
- OCKGFTQIICXDQW-ZEQRLZLVSA-N 5-[(1r)-1-hydroxy-2-[4-[(2r)-2-hydroxy-2-(4-methyl-1-oxo-3h-2-benzofuran-5-yl)ethyl]piperazin-1-yl]ethyl]-4-methyl-3h-2-benzofuran-1-one Chemical compound C1=C2C(=O)OCC2=C(C)C([C@@H](O)CN2CCN(CC2)C[C@H](O)C2=CC=C3C(=O)OCC3=C2C)=C1 OCKGFTQIICXDQW-ZEQRLZLVSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- YFONKFDEZLYQDH-OPQQBVKSSA-N N-[(1R,2S)-2,6-dimethyindan-1-yl]-6-[(1R)-1-fluoroethyl]-1,3,5-triazine-2,4-diamine Chemical compound C[C@@H](F)C1=NC(N)=NC(N[C@H]2C3=CC(C)=CC=C3C[C@@H]2C)=N1 YFONKFDEZLYQDH-OPQQBVKSSA-N 0.000 description 2
- 241000282320 Panthera leo Species 0.000 description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000012644 addition polymerization Methods 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 125000003368 amide group Chemical group 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 150000001805 chlorine compounds Chemical class 0.000 description 2
- LPIQUOYDBNQMRZ-UHFFFAOYSA-N cyclopentene Chemical compound C1CC=CC1 LPIQUOYDBNQMRZ-UHFFFAOYSA-N 0.000 description 2
- SMBQBQBNOXIFSF-UHFFFAOYSA-N dilithium Chemical class [Li][Li] SMBQBQBNOXIFSF-UHFFFAOYSA-N 0.000 description 2
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 150000004820 halides Chemical class 0.000 description 2
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000003454 indenyl group Chemical group C1(C=CC2=CC=CC=C12)* 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- 125000002868 norbornyl group Chemical group C12(CCC(CC1)C2)* 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 229910000077 silane Inorganic materials 0.000 description 2
- ZCBSOTLLNBJIEK-UHFFFAOYSA-N silane titanium Chemical compound [SiH4].[Ti] ZCBSOTLLNBJIEK-UHFFFAOYSA-N 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000005292 vacuum distillation Methods 0.000 description 2
- GHPYJLCQYMAXGG-WCCKRBBISA-N (2R)-2-amino-3-(2-boronoethylsulfanyl)propanoic acid hydrochloride Chemical compound Cl.N[C@@H](CSCCB(O)O)C(O)=O GHPYJLCQYMAXGG-WCCKRBBISA-N 0.000 description 1
- OJOWICOBYCXEKR-KRXBUXKQSA-N (5e)-5-ethylidenebicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(=C/C)/CC1C=C2 OJOWICOBYCXEKR-KRXBUXKQSA-N 0.000 description 1
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Natural products C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 description 1
- PWYJJQYPSILKKB-UHFFFAOYSA-N 2-(diethylamino)ethyl 2-(1-hydroxycyclopentyl)-2-phenylacetate;hydrochloride Chemical compound Cl.C1CCCC1(O)C(C(=O)OCCN(CC)CC)C1=CC=CC=C1 PWYJJQYPSILKKB-UHFFFAOYSA-N 0.000 description 1
- AQZWEFBJYQSQEH-UHFFFAOYSA-N 2-methyloxaluminane Chemical compound C[Al]1CCCCO1 AQZWEFBJYQSQEH-UHFFFAOYSA-N 0.000 description 1
- OOVQLEHBRDIXDZ-UHFFFAOYSA-N 7-ethenylbicyclo[4.2.0]octa-1,3,5-triene Chemical class C1=CC=C2C(C=C)CC2=C1 OOVQLEHBRDIXDZ-UHFFFAOYSA-N 0.000 description 1
- 239000004604 Blowing Agent Substances 0.000 description 1
- FOSCDBCOYQJHPN-UHFFFAOYSA-M Cl[Mg] Chemical compound Cl[Mg] FOSCDBCOYQJHPN-UHFFFAOYSA-M 0.000 description 1
- HPYIUKIBUJFXII-UHFFFAOYSA-N Cyclopentadienyl radical Chemical class [CH]1C=CC=C1 HPYIUKIBUJFXII-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 101150083807 HSD17B10 gene Proteins 0.000 description 1
- 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 1
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 1
- 239000002879 Lewis base Substances 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 229910003676 SiBr4 Inorganic materials 0.000 description 1
- FXXACINHVKSMDR-UHFFFAOYSA-N acetyl bromide Chemical compound CC(Br)=O FXXACINHVKSMDR-UHFFFAOYSA-N 0.000 description 1
- WETWJCDKMRHUPV-UHFFFAOYSA-N acetyl chloride Chemical compound CC(Cl)=O WETWJCDKMRHUPV-UHFFFAOYSA-N 0.000 description 1
- 239000012346 acetyl chloride Substances 0.000 description 1
- 239000002671 adjuvant Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 150000001642 boronic acid derivatives Chemical class 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 239000013256 coordination polymer Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- SINKOGOPEQSHQD-UHFFFAOYSA-N cyclopentadienide Chemical compound C=1C=C[CH-]C=1 SINKOGOPEQSHQD-UHFFFAOYSA-N 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- YNLAOSYQHBDIKW-UHFFFAOYSA-M diethylaluminium chloride Chemical compound CC[Al](Cl)CC YNLAOSYQHBDIKW-UHFFFAOYSA-M 0.000 description 1
- ORVACBDINATSAR-UHFFFAOYSA-N dimethylaluminum Chemical compound C[Al]C ORVACBDINATSAR-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- CHDFNIZLAAFFPX-UHFFFAOYSA-N ethoxyethane;oxolane Chemical compound CCOCC.C1CCOC1 CHDFNIZLAAFFPX-UHFFFAOYSA-N 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- AHAREKHAZNPPMI-UHFFFAOYSA-N hexadiene group Chemical group C=CC=CCC AHAREKHAZNPPMI-UHFFFAOYSA-N 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 125000003253 isopropoxy group Chemical group [H]C([H])([H])C([H])(O*)C([H])([H])[H] 0.000 description 1
- 150000007527 lewis bases Chemical class 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical compound C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 description 1
- DVSDBMFJEQPWNO-UHFFFAOYSA-N methyllithium Chemical compound C[Li] DVSDBMFJEQPWNO-UHFFFAOYSA-N 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 230000007935 neutral effect Effects 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
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 1
- 125000005062 perfluorophenyl group Chemical group FC1=C(C(=C(C(=C1F)F)F)F)* 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 239000003504 photosensitizing agent Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 150000004291 polyenes Chemical class 0.000 description 1
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- TURAMGVWNUTQKH-UHFFFAOYSA-N propa-1,2-dien-1-one Chemical compound C=C=C=O TURAMGVWNUTQKH-UHFFFAOYSA-N 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- AIFMYMZGQVTROK-UHFFFAOYSA-N silicon tetrabromide Chemical compound Br[Si](Br)(Br)Br AIFMYMZGQVTROK-UHFFFAOYSA-N 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 150000003440 styrenes Chemical class 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 125000006318 tert-butyl amino group Chemical group [H]N(*)C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- AUZMWGNTACEWDV-UHFFFAOYSA-L titanium(2+);dibromide Chemical compound Br[Ti]Br AUZMWGNTACEWDV-UHFFFAOYSA-L 0.000 description 1
- YONPGGFAJWQGJC-UHFFFAOYSA-K titanium(iii) chloride Chemical compound Cl[Ti](Cl)Cl YONPGGFAJWQGJC-UHFFFAOYSA-K 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 230000007704 transition Effects 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
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000003039 volatile agent Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F17/00—Metallocenes
-
- C—CHEMISTRY; METALLURGY
- 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
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S526/00—Synthetic resins or natural rubbers -- part of the class 520 series
- Y10S526/943—Polymerization with metallocene catalysts
Abstract
A process for preparing bridged mono- and bis(cyclopendadienyl) metal dihydrocarbyloxy coordination complexes (I) by contacting in the presence of an aprotic organic diluent a metal compound of the formula M(OR)4 with a dianionic salt compound. A process for preparing bridged mono- and bis(cyclopentadienyl)dihydrocarbyl metal coordination complexes (II) by contacting a complex (I) with a hydrocarbylation agent. A process for preparing bridged mono- and bis(cyclopentadienyl) metal dihalide coordination complexes (III) by contacting a complex (I) with a halogenation agent.
Description
SYNTHESIS OF CYCLOPENTADIENYL METAL COORDINATION COMPLEXES FROM METAL
HYDROCARBYLOXIDES
The present invention relates to a process for preparing certain bridged mono-5 and bis-cyclopentadienyl metal dihyJ, O~dl t~yloxy coordination complexes starting from metal hydrocarbyloxide compounds. The present invention also relates to a process for preparing bridged mono- and bis-cy.lopentadienyl l ~"~J, ocdrL,yl metal coordination complexes and to a process for preparing bridged mono- and bis-cy.lopehladienyl metal dihalide coordination cc.~ lexes both starting from the corresponding bridged mono- or bis-cyclopentadienyl metal 10 dihydrocarbyloxy coordination complexes.
Bridged mono- and bis-cyclopentadienyl metal dihalide coordination complexes and bridged mono- and bis-cyclopentadienyl dihydrocarbyl metal coordination complexes are known and usef ul as addition poly".e. i~ation catalysts or as components or precursors thereof.
In N Metallkomplexe mit verbrueckten permethylierten 15 Cy~lopenlddienylliganden" of P. Jutzi and R. Dickbreder, Chem. Ber.119,1750-1754(1986) the synthesis is described of dimethylsilanediyl-bridged bis(permethylated cy~lopenladienyl) titanium dichlorides from the lel- dhyd- c furan (THF) adducts of titanium tetrachloride and the dimethylsilanediyl-bridged bis(permethylated cyclopentadienyl) dianion derivatives.
In ansa-Metallocene derivatives: XVII. Racemic and meso diastereoisomers of 20 group IV metallocene derivatives with symmetrically substituted, dimethylsilanediyl-bridged ligand t-a,.,~wc)rks. Crystal structure of R,S-Me2Si(3-t-Bu-MeC5H2)2ZrCI2N of H. Wiesenfeldt et al., Journal of Orqanometallic Chemistrv,369 (1989) 359-370 the synthesis is described of dimethylsilanediyl-bridged bis(substituted cyclopenldJienyl) titanium dichloride complexes from the THF-adducts of titanium trichloride and the dimethylsilanediyl-bridged 25 bis(suhstituted cy.lopenladienyl) dianion derivatives.
In nSynthesis and Complexation of Linked Cyclopentadienyl-Amido Ligands of J.
Okuda, Chem. Ber. 123 (1990) 1649-1651 the preparation isdes~,ibed of a bridged mono(substituted cy.lopenladienyl) titanium dichloride complex from the THF-adduct of titanium tetrachloride and the dilithium salt of [(tert-butylamino)dimethylsilyl](tert-30 butyl)cyclopentadienide.
Bridged mono-cyclopentadienyl metal dihalide coordination complexes are also prepared in USP 5,026,798 from titanium tetrachloride compounds or ether adducts thereof and the dilithium salts of bridged mono-cyclopentadienyl ligand compounds.
Further, EP-A-0,416,815 teaches a process to prepare bridged mono-35 cy~lopenladienyl metal dihalide coordination complexes starting from the transition metaltetrahalide and a Group 1 or 6rignard derivative of the bridged mono-q,clopenlddienyl ligand compounds.
WO 95/1998~ 2 l 8 l 2 6 8 PCT/US95/00882 The above-mentioned synthesis methods to prepare the bridged mono- and bis-cyclopentadienyl metal dihalide coordination complexes use metal tetrahalide compounds as starting materials, which are corrosive, toxic, and air and moisture sensitive. In order to facilitate handling thereof, prior to the reaction step the transition metal tetrahalide 5 compound is typically converted to its ether-adduct in a separate step with for example THF or diethyl ether. This adduct formation step in itself proceeds with difficulty, requiring low to very iow temperatures, and an inert atmosphere. The adduct is usually recovered before it is reacted with the dianionic derivative of the ligand compound. The yield of the adduct formation step or steps is less than quantitative. Furthermore, the reaction mixture of the 10 Lransi Lion metal tetrahalide compound and the dianionic derivative of the bridged cyclopentadienyl ligand compound requires a multi-step, laborious recovery and purification procedure. Typically, after the reaction step, the solvent is removed, the product redissolved by adding dichloromethane or toluene or a mixture thereof, the metal halide byproduct, typically lithium chloride, removed by filtration of the mixture, the solvent removed at least partially, followed by redissolving the solid product and crystallizing the product, optionally followed by one or more further recrystallization procedures.
Further, it is known to from EP-A-0,416,815 and EP-A-0,514,828 to prepare bridged mono-cyclopentadienyl metal dihalide coordination complexes, by reacting the THF-adduct of a L,a, silion metal trihalide compound, especially TiCI3, with the dianionic derivative 20 Of the cyclopentadienyl ligand. The resulting complex is conla~Led with a non-i,-te. reri..g oxidizing agent, such as for example AgCI (EP-A-0,416,815), or with an organic halide to raise the oxidation state of the metal to form the desired dihalide complex. Apart from requiring an extra reaction step, that is the oxidation step, this process also starts from the transition metal trihalide or an ether-adduct thereof which has the disadvantages listed above, and requires 25 long reaction times to be prepared. Furthermore, the complex resulting from the reaction between the ether adduct of the transition metal trihalide compound with the dianionic derivative of the cyclopentadienyl ligand, i.e. the cyclopentadienyl metal(lll) monohalide coordination complex, is thermally unstable.
The bridged mono-cyclopentadienyl dihydrocarbyl metal coordination complexes 30 can be prepared by hydrocarbylating the corresponding bridged mono-cyclopentadienyl metal dihalide coordination complexes with a Grignard, lithium, sodium or potassium salt of the hydrocarbyl ligand. This is described, for example, in EP-A-0,418,044, example 3 and WO
92/00333. These preparation processes inherently have the disadvantages associated with the preparations of the bridged mono-cyclopentadienyl metal dihalide coordination complexes.
In one aspect, the present invention relates to a process f or preparing a metaldihydrocarbyloxy coordination complex cc r,esponding to the formula:
WO 95/19984 2 1 8 1 2 6 8 PCTtUS95tOn882 ~Z Y
Cp* M (I ) (0R)2 wherein:
M is titanium, zirconium, or hafnium;
Cp* is a cyclopentadienyl group bound in an rl5 bonding mode to M or such a cyclopentadienyl group substituted with from one to four substituents selected from the group consisting of hydrocarbyl, silyl, germyl, halo, hydrocarbyloxy, cyano, amino, and mixtures thereof, said substituent having up to 20 nonhydrogen atoms, or optionally, two substituents together cause Cp* to have a fused ring structure;
Z is a divalent moiety comprising boron, or a member of Group 14 of the PeriodicTable of the Elements, and optionally sulfur or oxygen, said moiety having up to 50 non-htd~ ogen atoms, and optionally Cp* and Z together form a fused ring system;
Y is a) a divalent anionic ligand group comprising nitrogen, phosphorus, oxygen or sulfur and having up to 20 non-hydrogen atoms, said Y being bonded to Z and M through said nitrogen, phosphorus, oxygen or sulfur, and optionally Y and Z together form a fused ring system, or b) a cyclopentadienyl group bound in a sigma bonding mode to Z and in an rl5 bonding mode to M or such a cycloper,lddienyl group substituted with from one to four substituents selected from the group con,i~li"g of hydrocarbyl, silyl, germyl, halo, hyJlOcarLyloxy, cyano, amino, and mixtures thereof, said substituent having up to 20 nonhydrogen atoms, or optionally, two substituents logelller cause Y to have a fused ring 25 structure; and R il ldependenlly each occurrence is a hydrocarbyl group having from 1 to 20 carbon atoms; the steps of the process comprising:
contacting in the presence of an aprotic organic diluent a metal compound of theformula: M(OR)4 wherein M and R are as previously defined with a dianionic salt compound cor,esponding to the formula:
(L+X) (cp* z y)-2 or ((LX)+X) (cp* z y)-2 wherein:
L is a metal of Group 1 or 2 of the Periodic Table of the Elements, X independently is chloro, bromo, or iodo, x and y are either 1 or 2 and the product of x and y equals 2, and Cp*, Z, and Y are as previously defined;
to form the complex of formula (l) 2l8l268 WO 9S/1998~ PCT/US95/(~_32 In another aspect, the present invention relates to a process for preparing a metal dihydrocarbyl coordination complex corresponding to the formula:
/Z y Cp* M (I I ) (R"')2 wherein:
M is titanium, zirconium, or hafnium;
Cp* is a cyclopentadienyl group bound in an rl5 bonding mode to M or such a cy.loper lddienyl group substituted with from one to four substituents selected from the group consisting of hydrocarbyl, silyl, germyl, halo, hydrocarbyloxy, cyano, amino, and mixtures thereof, said substituent having up to 20 nonhydrogen atoms, or optionally, two substituents together cause Cp* to have a fused ring structure;
Z is a divalent moiety comprising boron, or a member of 6roup 14 of the PeriodicTable of the Elements, and optionally sulfur or oxygen, said moiety having up to 50 non-hydrogen atoms, and optionally Cp* and Z together form a fused ring system;
Y is a) a divalent anionic ligand group comprising nitrogen, phosphorus, oxygen or sulfur and having up to 20 non-hydrogen atoms, said Y being bonded to Z and M through said nitrogen, phosphorus, oxygen or sulfur, and optionally Y and Z together form a fused ring system, or b) a cyclopentadienyl group bound in a sigma bonding mode to Z and in an rl5 bonding mode to M or such a cyclopenlddirnyl group substituted with from one to four substituents selected from the group consi~li,.g of hydrocarbyl, silyl, germyl, halo, hydrocarbyloxy, cyano, amino, and mixtures thereof, said substituent having up to 20 nonhyd~ ogen atoms, or optionally, two substituents lugelher cause Y to have a fused ring structure; and Rn' independenlly each occurrence is a hydrocarbyl group containing from 1 to 20carbon atoms;
the process comprising contacting in the presence of an aprotic organic diluent a metal coordination complex of formula:
/Z --Y
Cp* M (I ) (OR)2 2181268 ` `
WO 95/19984 PCT/US~SI'G~)882 wherein R independently each occurrence is a hydrocarbyl group having from 1 to 20 carbon atoms and Cp*, Z, Y, M, are as previously defined;
with a hydrocarbylation agent comprising a group 1, 2, 12 or 13 metal or metal derivative and at least one hydrocarbyl group R ', to form the metal dihydrocarbyl 5 coordination complex of formula (Il).
In yet another aspect the present invention relates to a process for preparing ametal dihalide coordination complex corresponding to the formula:
/Z Y
CP* M (III ) (X ~ ) 2 wherein:
M is titanium, zirconium, or hafnium;
Cp* is a cyclopentadienyl group bound in an tl5 bonding mode to M or such a cy~lopenladienyl group substituted with from one to four substituents selected from the group consisting of hydrocarbyl, silyl, germyl, halo, hydrocarbyloxy, cyano, amino, and mixtures thereof, said substituent having up to 20 nonhyd~ ogen atoms, or optionally, two substituents together cause Cp* to have a fused ring structure;
Z is a divalent moiety comprising boron, or a member of Group 14 of the PeriodicTable of the Elements, and optionally sulfur or oxygen, said moiety having up to 50 non-hydrogen atoms, and optionally Cp* and Z together form a fused ring system;
Y is a) a divalent anionic ligand group comprising nitrogen, phosphorus, oxygen or sulfur and having up to 20 non-l-"d~ ogen atoms, said Y being bonded to Z and M through said nitrogen, phosphorus, oxygen or sulfur, and optionally Y and Z together form a fused ring system, or b) a cyclopenLad:enyl group bound in a sigma bonding mode to Z and in an rl5 bonding mode to M or such a cyclopent~ l ~nyl group substituted with from one to four substituents selected from the group consisting of hydrocarbyl, silyl, germyl, halo, hyd~ OCal LYIOAY, amino, and mixtures thereof, said substituent having up to 20 nonhydrogen atoms, or optionally, two substituents together cause Y to have a fused ring structure; and X' i..dependently each occurrence is a halo group;
the process comprising contacting in the presence of an aprotic organic diluent a metal coordination complex of formula W O 95/19984 ~ PCTAUS95/00882 ~Z --Y
Cp* M (I ) (0R)2 wherein R independently each occurrence is a hydrocarbyl group having from 1 to 20 carbon atoms and Cp*, Z, Y, M, are as previously defined;
with a halogenation agent comprising at least a member of Group 13 or 14 of the Periodic Table of the Elements and at least one halo group X', to form the metal dihalide coordination complex of formula (Ill).
All reference to the Periodic Table of the Elements herein shall refer to the Periodic Table of the Elements, published and copyrighted by CRC Press, Inc., 1989. Also, any reference to a Group or Groups shall be to the Group or Groups as reflected in this Periodic Table of the Elements using the IUPAC system for numbering Groups.
Surprisingly, it has been found that two hydrocarbyloxy groups on the titanium, zirconium, or hafnium (hereinafter referred to as Group 4 metal) center can be removed readily by contacting the compound M(OR)4 where M and R are as previously defined with the dianionic salt compound to give the complexes of formulas (I), (la), or (Ib) in high yield and high purity. This discovery was indeed surprising as hydrocarbyloxy-transition metal bonds are considered to be stronger bondsthan halogen-l.ah,ilion metal bonds and lt.erefo,e the hydrocdrLyloxy groups are considered less suitable leaving groups than halogen groups. The starting Group 4 metal hydrocarbyloxy compounds, typically the titanium tetraisopropoxide, tetra-n-butoxide and tetra-t-butoxide, are non-viscous liquids, only mildly air-sensitive, co."".er, ially available, and readily soluble in hyJ, ucarLons, as compared to the corrosive, air-sensitive and difficult to handle Group 4 metal tetrachlorides. This new process typically provides the complexes of formulas (I), (la), and (Ib) in yields of 9û percent and higher. The product complexes can be readily isolated in high purity by filtration.
In the present process bridged mono- or bis(cyclopenladienyl) metal dihydrocarbyloxy coordination complexes of formulas (I), (la), or (Ib) are prepared by contacting a Group 4 metal tetr,ahydrocarbyloxy compound of the formula: M(OR)4, wherein M and R are as previously defined, with a dianionic salt compound. The dianionic salt is preferably a double Group 1 metal derivative or double Grignard (Group 2 metal monohalide) derivative of the -Cp*-Z-Y- moiety, the anionic charges formally residing on the Cp* and Y groups. In the relevant part of the formula for the dianionic salt compound the double Group 1 metal WO 95/1998~ PCTIUS95/00882 ._ derivative corresponds to (L+x)y wherein x is 1 and y is 2, and the double 6rignard derivative corresponds to ((LX)+x)y wherein x is 1 and y is 2.
In the metal dihydrocarbyloxy coordination complexes of formula (I), M is titanium, zirconium, or hafnium and R independently each occurrence is a hydrocarbyl group 5 having from 1 to 20 carbon atoms, more preferably R each occurrence is independently selected from the group consisting of alkyl, aryl, alkaryl, and aralkyl groups, even more preferably from alkyl groups having from 1 to 6 carbon atoms, and aryl, aralkyl and alkaryl groups having from 6-10 carbon atoms, and most preferably R each occurrence is independently selected from the group consi,ling of ethyl, isopropyl, n-butyl, and t-butyl.
A neutral Lewis base, such as an ether or amine compound, may also be associated with the complex, if desired, however, such is generally not preferred.
The term substituted cyclopentadienylN includes, but is not limited to, indenyl,tetrahydroindenyl, fluorenyl, tetrahydrofluorenyl, and octahydrofluorenyl groups.
6eneric formula (I) embraces bridged monocyclopen~adienyl metal dihydrocarbyloxy coordination complexes and bridged bis(cyclopentddienyl) metal dihydrocdrL.yloxy coordination complexes.
Pl er~r.ed bridged monocyclopentadienyl metal dihydrocarbyloxy coordination complexes of formula (I) prepared in the present process include those having constrained geometry.
By the term " constrained geometryn as used herein is meant that the metal atom in the metal coordination complex and also in the catalyst resulting therefrom is forced to greater exposure of the active catalyst site because of a specific ring structure of a ligand group including the metal atom, wherein the metal is both bonded to an adjacent covalent moiety and held in association with the delocalized n-bonded cyclopentadienyl group through an rl5 25 or other n-bonding interaction. It is understood that each respective bond belween the metal atom and the constituent atoms of the n-bonded moiety need not be equivalent. That is, the metal may be symmetrically or unsy.. el. i dlly n-bound thereto.
The concept of constrained geometry and specific con,L. ain inducing ligand groups are described in more detail in U.S. Patent Application Serial Number 545,403, filed July 30 3, 1990 (cor.es~.onding to EP-A-0,416,815) which is incorporated herein by reference.
Suitable examples of moiety Z in formula (I) include SiR 2, CR 2, SiR 2SiR 2, CR~2CR~2, CR*=CR*, CR~2SiRt2, GeR~2, or BR~ wherein R* each occurrence is i.,dependenlly selected from the group consisting of hydrogen, alkyl, aryl, silyl, halogenated alkyl, halogenated aryl groups having up to 20 non-hydrogen atoms, and mixtures thereof, or two or 35 more R* groups from Z, or an R* group from Z together with Y form a fused ring system.
Further more preferably, Y in formula (I) is -O-, -S-, -NR~-, -PR~-. Highly prererably Y is a nitrogen or phosphorus containing group Wo 95/1998~ 2 18 12 6 PCT/US9~/00882 cor,espond.ng to the formula -N(R')- or -P(R')-, i.e. an amido or phosphido group, wherein R' is as defined hereinafter.
More preferably, in the present process is prepared a metal coordination dihydrocarbyloxy complex of formula (I) corresponding to the formula:
~(ER 2)m~N R~
R~ M (Ia) R~ R (OR)2 wherein R' each occurrence is independently selected from the group consisting of hydrogen, silyl, alkyl, aryl, germyl, cyano, halo and combinations thereof having up to 20 non-hydrogen atoms, or two R' groups together form a divalent derivative thereof;
E is silicon or carbon;
m is 1 or 2; and M and R are as previously defined; and ~ ,vherei, . the metal compound of the formula: M(OR)4 is contacted with a dianionic salt compound cc " e" onding to the formula:
(L )y(C5R 4-(ER 2)m-NR )-2 or ((LX)+X)y(C5R~4~(ER~2)m~NR~)~2 20 v~/hel ein L, R', E, X, x, y, and m are as previously defined. It is remarked that when a substituent, such as R', on a cy~lopenlddienyl group is hydrogen, halo or cyano, two of such substituents can not together form a divalent derivative thereof or cause the groups to have a fused ring structure.
In the complexes of formula (la), M is prererably titanium, and prererably R
25 i.,dependehlly each occurrence is alkyl, aryl, aralkyl, and alkaryl groups, more p,e~e,dbly scle~led from an alkyl group having from 1 to 6 carbon atoms, and aryl, aralkyl and alkaryl groups having from 6-10 carbon atoms, even more preferably R is a C1 4-alkyl, and especially ethyl, isopropyl, n-butyl, or t-butyl.
Examples of the above most highly preferred metal dihydrocarbyloxy 30 coordination compounds include compoundsw"erei.) the R' on the amido group is methyl, ethyl, propyl, butyl, pentyl, hexyl, and isomers of these alkyl radicals, norbornyl, benzyl, phenyl, etc.; the cyclopenlddienyl group is cyclopentadienyl, indenyl, telldhyJ, oindenyl, fluorenyl, tetrahydrofluorenyl, octahydrofluorenyl, etc.; R' on the foregoing cyclopentadienyl groups each occurrence is hydrogen, methyl, ethyl, propyl, butyl, pentyl, hexyl, and isomers of these 35 alkyl radicals, norbornyl, benzyl, phenyl, etc.; and R is ethyl, isopropyl, n-butyl or t-butyl.
Specific highly prefer,ed compounds include: (tert-butylamido)(tetramethyl-rl5-cyclopentadienyl)-1,2-ethanediyltitanium di-ethoxide, (tert-butylamido)(tetramethyl-rl5-cyclopentadienyl)-1,2-ethanediyltitanium di-isopropoxide, (tert-butylamido)(tetramethyl-rl5-cyclopentadienyl)-1,2-ethanediyltitanium di-n-butoxide, (tert-butylamido)(tetramethyl-r~5-cyclopentadienyl)dimethylsilanetitanium di-ethoxide, (tert-butylamido)(tetramethyl-rl5-cyclopentadienyl)dimethylsilanetitanium di-isopropoxide, (tert-butylamido)(tetramethyl-rl5-5 cyclopentadienyl)dimethylsilanetitanium di-n-butoxide, (methylamido)(tetramethyl-rl5-cyclopentadienyl)dimethylsilar,eLiLanium di-ethoxide, (methylamido)(tetramethyl-rl5-cy.loper,tadienyl)dimethylsilanetitanium di-isopropoxide, (methylamido)(tetramethyl-rl5-cyclopentadienyl)dimethylsilanetitanium di-n-butoxide, (phenylamido)(tetramethyl-rl5-cyclopentadienyl)dimethylsilanetitanium di-ethoxide, (phenylamido)(tetramethyl-r~5-10 cyclopentadienyl)dimethylsilanetitanium di-isopropoxide, (phenylamido)(l~l.dmethyl-rl5-cyclopentadienyl)dimethylsilanetitanium di-n-butoxide, (benzylamido)(tetramethyl-rl5-cyclopentadienyl)dimethylsilanetitanium di-ethoxide, (benzylamido)(tetramethyl-rl5-cy~lope"ladienyl)dimethylsilanetitanium di-isopropoxide, (benzylamido)(tetramethyl-rl5-cyclopentadienyl)dimethylsilanelil~,nium di-n-butoxide, (tert-butylamido)(rl5-cyclopentadienyl)-1 ,2-ethanediyltitanium di-ethoxide, (tert-butylamido)(rl5-cy~lopenLddienyl)-1,2-ethanediyltitanium di-isopropoxide, (tert-butylamido)(rl5-cyclopentadienyl)-1,2-ethanediyltitanium di-n-butoxide, (tert-butylamido)(rl5-cyclopenladienyl)-dimethylsilanetitanium di-ethoxide, (tert-butylamido)(rl5-cyclopentadienyl)-dimethylsilanetitanium di-isopropoxide, (tert-butylamido)(rl5-20 cyclopentadienyl)dimethylsilanetitanium di-n-butoxide, (methylamido)(rl5-cy~lopentadienyl)dimethylsilanetitanium di-ethoxide, (methylamido)(rl5-cyclopentadienyl)dimethylsilanetitanium di-isopropoxide, (t-butylamido)(rl5-cyclopenta-dienyl)dimethylsilan~:Lildnium di-n-butoxide, (t-butylamido)indenyldi,.,elt.ylsilanetitanium di-ethoxide, (t-butylamido)indenyldimethylsilanetitanium di-isopropoxide, (t-25 butylamido)indenyldimethylsilanetitanium di-n-butoxide, (benzylamido)i..denyld;"~_lt"~l,ilaoelil..nium di-ethoxide, and (benzylamido)indenyldimethylsilanetitanium di-isopropoxide.
According to another prefer.~d er..bod,...ent of the present process, there is prepared a metal coordination complex of formula (I) corresponding to the formula:
-2~ 6~
R~ R' ( Rn2E~ R I
M- ( oR ) 2 Rl R' R' wherein:
R' each occurrence is independently selected from the group consisting of hydrogen, silyl, alkyl, aryl, germyl, cyano, halo and combinations thereof having up to 20 non-hydrogen atoms, or two R' groups together form a divalent derivative thereof;
E is silicon or carbon;
R" independently each occurrence is hydrogen or a group selected from silyl, hydrocarbyl and combinations thereof, said Ru having up to 30 carbon or silicon atoms;
m is 1 to 8; and M and R are as previously defined; and wherein the metal compound of the formula: M(OR)4 is contacted with a dianionic salt compound corresponding to the formula:
(L+X)y(c5R~4-(ERn2)m-c5R~4) 2 or ((Lx)+~)"(csR~4-(ER 2)m-csR 4) 2 wherein L, R', E, R, X, m, x and y are as previously defined.
Exemplary metal complexes of bridged bis-cy.loper,~adienyl metal dihydrocarbyloxy coordination complexes include those complexes of formula (Ib) wherein E is silicon or carbon, R" independently each occurrence is hydrogen or a group selected from silyl, hydrocarbyl and combinations thereof, said R" having up to 30 carbon or silicon atoms, and m is 1 to 8. Preferably R independently each occurrence is methyl, benzyl, tert-butyl, or phenyl.
Such bridged bis(cy.lopentadienyl) structures are especially suited for use as catalysts, or precursors thereof, for the preparation of polymers having stereoregular molecular structure. In such capacity it is preferred that the complex be nonsymmetrical or possess a chiral, stereorigid structure. Examples of the first type are compounds possessing dif~erenL delocalized n-bonded systems, such as one cyclopenta-dienyl group and one indenyl group. Examples of chiral structures include bis-indenyl complexes.
2l8l26~
.~, Exemplary bridged bis(cy-lopenladienyl) metal dihydrocarbyloxy complexes of formula (Ib) are those wherein the bridged ligand group is: dimethylsilyl-bis-cyclopentadienyl, dimethylsilyl-bis-tetramethylcyclopentadienyl, dimethylsilyl-bis-indenyl, isopropylidene-cyclopentadienyl-fluorenyl, 2,2'-biphenyldiylbis(3,4-dimethyl-1-cyclopentadienyl), and - 5 6,6-dimethyl-2,2'-biphenylbis(3,4-dimethyl-1-cyclopentadienyl).
In a prerer,ed embodiment, the moiety ((LX)+x)y in the dianionic salt compound - corresponds to ((MgCI)+)2. In another p~efer~ed embodiment, the moiety (L+x)z in the dianionic salt corresponds to (Li+)2. Use of the former dianionic salt compound in the present process gives as a byproduct MgCl(OR) which can be easily separated from the desired product.
The molar ratio of the dianionic salt compound to the metal dihy:l. Ocarl"~loxy compound M(OR)4 can vary between wide limits. Although an improved process can be obtained with dianionic salt compound to metal compound molar ratios of 0.5:1 and higher, for example, up to 10:1, or preferably up to 5:1, the yield of the process and the purity of the desired products are high at ratios of 1:1 and slightly higher, for example, up to 1.5:1, 15 pref~rably up to 1.2:1.
In the present process an aprotic organic diluent is used. Suitable examples of such diluents are ethers and hydrocarbons. Preferably the hydrocarbon solvent is an aliphatic or cycloaliphatic I ryJ~ O~arL,on solvent having from 5 to 10 carbon atoms. Suitable solvents are pentane, hexane, heptane, Isopar E (a mixture of isoparaffinic hydrocarbons available from 20 Exxon Chemical Inc.), isooctane, cyclohexane, and methylcyclohexane.
Carrying out the reaction in a hydrocarbon solvent has the advantage that the product dihydrocarbyloxy complexes of formulas (I), (la), and (Ib) are soluble, whereas the byproduct L-OR or LX-OR generally is not. The desired products thus can be easily recovered, if desired, by filtration or other liquid-solid separation methods. By subjecting the liquid thus 25 obtained to a stripping step tQ strip off the volatile solvent a highly pure product is obtained.
The temperature at which the process is conducted is not critical, but is p,eferably below the boiling point of the diluent. Preferred temperatures range from 0C to 1 00C, more preferably from 1 0C to 80C, and most preferably from 20 to 60C.
Generally the reactants are contacted under an inert atmosphere for a time from 30 several minutes to several days. The presence of oxygen and moisture are preferably avoided.
The reactants can be added in any order. Agitation may be employed if desired.
According to a f urther aspect the present invention pl olides a process for preparing bridged mono- or biscy~lopenladienyl dihyJ~ocarbyl metal coordination complexes of formulas (Il), (lla), and (llb) by contacting a corresponding metal dihydrocarbyloxy 35 coordination complex of formula (I), (la), or (Ib) obtainable as described hereinbefore with a hydrocarbylation agent comprising a 6roup 1, 2, 12 or 13 metal or metal derivative and at least one hydrocarbyl group Rn', to form the dihydrocarbyl metal coordination complex of formula (Il), (lla) or (llb).
w o 95/19984 2 18 12 6 8 PCT~US95/00882 Surprisingly, it has been found that the dihydrocarbyloxy complexes of formulas (1), (la), and (Ib) are stable compounds which can readily be converted to the corresponding dihydrocarbyl compounds of formulas (Il), (lla), or (llb) in high yields and purity. The present hydrocarbylation process, especially in combination with the process for preparing the metal 5 dihydrocarbyloxy coordination complexes of formulas (1), (la), or (Ib) as described herein before, enables the valuable complexes of formulas (Il), (lla), or (llb) to be prepared in high overall yields compared to a process starting from metal tetrahalide compounds.
In a pre~er,ed embodiment, a metal dihydrocarbyl coordination complex ~or,e,pon~i ~9 to the formula:
R' (ER 2)~
R ~ M (IIa) R' (R ' )2 wl ,e~ ei., R' each occurrence is independently selected from the group consisting of I "/J~ ogen, silyl, alkyl, aryl, germyl, cyano, halo and combinations thereof having up to 20 non-hydrogen atoms, or two R' groups to9elher form a divalent derivative thereof;
E is silicon or carbon;
m is 1 or 2; and M and RN' are as previously defined;
is prepared by contacting a metal dihydrocarbyloxy coordination cc""plex corresponding to the formula:
~ (ER 2)~
[ ~ (Ia) R (OR)2 R
wherein: M, R', E, R, and m are as previously defined;
with the hydrocarbylation agent.
In another preferred embodiment, a metal dihydrocarbyl coordination complex corresponding to the formula:
R~ R~
;
( Rll2E~ R I
R~M- ( R ~ I ) 2 R 1~ R ' (IIb) R' wherein:
R' each occurrence is independer,lly selected from the group .onsi,ling of hydrogen, silyl, alkyl, aryl, germyl, cyano, halo and combinations thereof having up to 20 non-hydrogen atoms, or two R' groups together form a divalent derivative thereof;
E is silicon or carbon;
R" i-,depender,lly each occurrence is l,yd~ogen or a group selected from silyl, hydrocarbyl and combinations thereof, said R" having up to 30 carbon or silicon atoms;
m i5 1 to 8; and M and Rn' are as previously defined;
is prepared by cor,la.li--g a metal dihydrocarbyloxy coordination complex corresponding to the formula:
(Rn2E~ R~
\ ~,, M-(OR)2 1~
R~ \/ R' (Ib) R' wherein R', E, R", M, R, and m are as previously defined;
W O 95/19984 2 ¦ 8 ¦ ~ 6 8 PCTAUS95/00882 with the hydrocarbylation agent.
In a further preferred embodiment, the metal dihydrocarbyloxy coordination complex of formula (I), (la), or (Ib), used as starting compound in the preparation of complexes of formulas (Il), (lla) or (llb), is prepared by contacting in the presence of an aprotic organic 5 diluent a metal compound of the formula: M(OR)4 wherein M and R are as previously defined with a dianionic salt compound cor,esponding to the formula:
(L+X)y(Cp* Z y) 2 or ((LX)+X) (Cp* Z Y) 2 wherein:
Li5 a metal of Group 1 or 2 of the Periodic Table of the Elements, X independently is chloro, bromo, or iodo, x and y are either 1 or 2 and the product of x and y equals 2, and Cp*, Z, and Y are as previously defined;optionally followed by recovering the complex corresponding to formula (I).
In the complexes of formulas (I), (la), and (Ib), M is titanium, zirconium, or hafnium and R independently each occurrence is a hydrocarbyl group having from 1 to 20 carbon atoms, preferably R each occurrence is independently selected from the group consisting of alkyl, aryl, aralkyl, and alkaryl groups, more prefe~dbly alkyl groups having from 2 to 6 carbon atoms and aryl, aralkyl, and alkaryl groups having from 6-10 carbon atoms, and most prere, ~.bly R each occurrence is independen~ly selected from the group consi~li"g of 20 ethyl, isopropyl, n-butyl, and t-butyl.
P~ere,-edembodimentsofthepresentprocesstopreparethecomplexesof formulas (I), (la), and (Ib) are illustrated he,einbefore and hereby incorporated by reference.
The complexes of formulas (I), (la), and (Ib) as obtained can be recovered or purified, if desired, prior to proceeding with the hydrocarbylation step.
The hydrocarbyl group R"' in formulas (Il), (lla), and (llb) and present in the h"J. ~cal Lylation agent generally has from 1 to 20 carbon atoms and can be an aliphatic, cycloaliphatic, or aromatic hydrocarbon or a mixture thereof. P~ eferably, Rn' is selected from the group consi,~ing of alkyl, aryl and aralkyl groups, more preferablyfrom alkyl groups having from 1 to 6 carbon atoms, or aralkyl groups having from 7 to 10 carbon atoms. Most prererdbly 30 RN' is methyl, neopen~yl, or benzyl.
The hydrocarbylation agent comprises a Group 1,2,12 or 13 metal or metal derivative and at least one hydrocarbyl group RN'. Suitable examples of the hydrocarbylation agent include LiRN', MgRN'2, MgRN'XN (wherein Xn is halogen, preferably chloro), AlRn'3, and Rn'-substituted aluminoxane. Suitable RN'-substituted aluminoxanes p-ererably include C1-6-35 alkylaluminoxanes, especially methylaluminoxane. Alkylaluminoxanes are well known in theart and methods for their preparation are illustrated by U.S. Patent Nos. 4,592,199; 4,544,762;
5,015,749 and 5,041,585. P~ ~re-dbly, the hydrocarbylation agent comprises LiRN' or AlRn'3.
WO 95/19984 21 81 ~ 6 8 PCT/US9~/00882 More preferably the hydrocarbylation agent is trialkyl aluminum, most prefel ably trimethyl aluminum.
Specific highly prefer.ed complexes of formula (lla) include: (tert-butylamido)(tetramethyl-rl5-cy-lopenlddienyl)-1,2-ethanediyltitanium dimethyl, (tert-5 butylamido)(tetramethyl-rl5-cy~lopenlddienyl)-1,2-ethanediyltitanium dibenzyl, (tert-butylamido)(tetramethyl-rl5-cyclopentadienyl)dimethylsilaneLildnium dimethyl, (tert-butylamido)(tetramethyl-rl5-cy~lopenlddienyl)dimethylsilanetitanium dibenzyl, (methylamido)(tetramethyl-rl5-cyclopenladienyl)dimethylsilanetitanium dimethyl, (methylamido)(tetramethyl-rl5-cyclopenladienyl)d;.,-elhylsilanetitanium dibenzyl, 10 (phenylamido)(tetramethyl-rl5-cyclopentadienyl)dimethylsilanetitanium dimethyl, (phenylamido)(tetramethyl-ll5-cyclopentadienyl)dimethylsilanetitanium dibenzyl, (benzylamido)(tetramethyl-rl5-cyclopentadienyl)dimethylsilanetitanium dimethyl, (benzylamido)(tetramethyl-rl5-cyclopentadienyl)dimethylsilanetitanium dibenzyl, (tert-butylamido)(rl5-cyclopentadienyl)-1,2-ethanediyltitanium dimethyl, (tert-butylamido)(rl5-cy~lopenlddienyl)-1,2-ethanediyltitanium dibenzyl, (tert-butylamido)(rl5-cy~lG,uel.ladienyl)-di...elhylsilanetitanium dimethyl, (tert-butylamido)(rl5-cy~lopenlddienyl)dimethylsilanetitanium dibenzyl, (methylamido)(rl5-cyclopentadienyl)dimethylsilanetitanium dimethyl, (t-butylamido)(rl5-cyclopenta-dienyl)dimethylsilanetitanium dibenzyl, (t-butylamido)indenyldimethylsilanelilanium 20 dimethyl, (t-butylamido)indenyldimethylsilanetitanium dibenzyl, and (benzylamido)indenyldimethylsilanelilanium dibenzyl.
The molar ratio of the hyd~ ocdrL.jlation agent to the complex of formulas (I), (la), and (Ib) can vary between wide limits, but is preferably between 0.1:1 and 20:1, more p,eferdblybetween0.5:1to10:1. Advantageously,anequivalentamountoraslightexcessof25 RN'-groups in the I "~drocdrL"Ilation agent is used with respect to the metal hydlOl.dl Lyloxy compound of formulas (i), (la), or (Ib), i.e., a ratio of from 2.0:1 to 4.0:1, more p. erl:r~bly of from 2.1:1 to3:1.
The temperature at which the hydrocarbylation step is conducted is not critical,but is preferably below the boiling point of the aprotic organic diluent F~ efe. red temperatures 30 rangefrom 0Cto 100C, morepreferablyfrom 10~Cto80C.
Generally the reactants are contacted under an inert atmosphere for a time from several minutes to several days. The reactants can be added in any order. Agitation may be employed if desired.
In the present hydrocarbylation step an aprotic organic diluent is used.
35 Preferably, diluents are used in which the complexes of formulas (I), (la), and (Ib) are readily soluble, optionally upon heating. Suitable examples of such solvents are ethers and hydrocarbons. Preferably the solvent is a hydrocarbon, advantageously an aliphatic or 6~
WO 95/19984 . PCT/US95100882 cycloaliphatic hydrocarbon solvent having from 5 to 10 carbon atoms. Suitable solvents are pentane, hexane, heptane, Isopar E, isooctane, cyclohexane, and methylcyclohexane.
Carrying out the reaction in a hydrocarbon solvent has the advantage that the product hydrocarbyl complexes of formulas (Il), (lla), and (llb) are soluble and non-volatile, 5 while the byproduct Group 1, 2, 12 or 13 metal or metal derivative hyd.ocdrL.yloxides are often either insoluble or volatil, especially when R is a lower alkyl, such as a C1 4 alkyl. Thus, the byproducts LiOR and Mg(OR)R ' generally are not soluble in hydrocarbons when R is a lower alkyl, and may be easily removed from the desired hydrocarbyl product by fillrdtion, decdntalion, or other liquid-solid separation method. By subjecting the liquid thus obtained to 10 a stripping step to remove the volatile solvent a highly pure product may be obtained.
However, the byproduct formed when using the highly prefer,ed trimethylaluminum as the hydrocarbylation agent cc" "p- ises a dimethylaluminum hydrocarbyloxide which is volatile.
This byproduct can be removed from the desired product by applying a vacuum so as to remove both the byproduct and the solvent/diluent in one step.
According to another aspect the present invention provides a process for preparing bridged mono- or bis(cy.lopenlddienyl) metal dihalide coordination complexes of formulas (Ill), (Illa) or (Illb) by conlacli"g a co,~".onding metal dihycl, ocd,L~rloxy coordination complex of formula (I), (la), or (Ib) obtainable as described her~i. ,berore, with a halogenation agent comprising a Group 13 or 14 element or derivative thereof and at least one halo group 20 X', to form the metal dihalide coordination complex of formulas (Ill), (Illa) or (Illb).
Surprisingly, it has been found that the dihydrocarbyloxy complexes of formulas (1), (la) or (b) are stable compounds which can easily be con~r~. led to the corresponding dihalide compounds of formulas (Ill), (Illa) or (Illb) in high yields and purity. The present halogenation process, especially in combination with the process for preparing the metal dihydrocarbyloxy 25 coordination complexes of form ulas (I), (la) or (Ib) as described herein before, enables the culllrlFxes of formulas (Ill), (Illa) or ~IIIb) to be prepared in high yields compared to a process starting from metal tetrahalide compounds.
In a preferred embodiment, a metal dihalide coordination complex corresponding to the formula (Illa):
R ( ER 2 )m~ N R ~
R~ M (IIIa) R' (X' )2 WO95/19984 21 81 2 ~8 PCT/US95/00882 wherein R' each occurrence is independently selected from the group consisting of hydrogen, silyl, alkyl, aryl, germyl, cyano, halo and combinations thereof having up to 20 non-hydrogen atoms, or two R' groups together form a divalent derivative thereof;
E is silicon or carbon;
- 5 m is 1 or 2; and M and X' are as previously defined;
is prepared by cGnla~ lg a metal dihydrocarbyloxy coordination co",Flex cc."esponding to the formula:
~ ~ (ER ' 2)m~
R~ M ( Ia) R ' (OR)2 wherein: M, R', E, R, and m are as previously defined;
with the halogenation agent.
In another p,~rerled embodiment, a metal dihalide coordination complex cor~esponding to formula (Illb) R' R' (R"2E)m R' \~ M- ( X ' ) 2 1(~' R' \/ R' ( IIIb) R' WO 95/19984 ~ ,6~ PCT/US95/00882 wherein:
R' each occurrence is independently selected from the group consisting of hydrogen, silyl, alkyl, aryl, germyl, cyano, halo and combinations thereof having up to 20 non-hydrogen atoms, or two R' groups together form a divalent derivative thereof;
E is silicon or carbon;
R" independently each occurrence is hydrogen or a group selected from silyl, hydrocarbyl and combinations thereof, said R" having up to 30 carbon or silicon atoms;
m is 1 to 8; and M and X' are as previously defined;
is prepared by contacting a metal dihydrocarbyloxy coordination complex cur.esponding to the formula:
R~ R~
(R~l2E)m R' R' M-(OR)2 R' \/ R' (Ib) R~
wherein R', E, R, M, R, and m are as previously defined;
with the halogenation agent.
Inafurtherp~efe,-edembodiment,themetaldihyd~oc~.Lyloxycoordination complex of formulas (I), (la) or (Ib), used as starting compound in the preparation of complexes of formulas (Ill), (Illa) or (Illb), is prepared by contacting in the presence of an aprotic organic 30 diluent a metal compound of the formula: M(OR)4 wherein M and R are as previously defined with a dianionic salt compound corresponding to the formula:
(E+x)y(Cp*-z-y)-z or ((LX)+X) (Cp* Z y)-2 wl ,erein:
L is a metal of Group 1 or 2 of the Periodic Table of the Elements, X independently is chloro, bromo, or iodo, x and y are either 1 or 2 and the product of x and y equals 2, and Cp*, Z, and Y are as previously defined;
optionally followed by recoveri.)g the complex WO 95/19984 1 81~ ~ 8 PCT/US9~i/00882 corresponding to formula (I).
In the complexes of formulas (I), (la), and (Ib), M is titanium, zirconium or hafnium and R independently each occurrence is a hydrocarbyl group having from 1 to 20 carbon atoms, preferdbly R each occurrence is independently selected from the group consisting of alkyl, aryl, 5 aralkyl, and alkaryl groups, more preferdbly alkyl groups having from 2 to 6 carbon atoms and aryl, aralkyl, and alkaryl groups having from 6-10 carbon atoms, and most preferably R each occurrence is i"dependenlly selected from a C1 4-alkyl, especially from the group consi~li"g of ethyl, isopropyl, n-butyl, and t-butyl.
~l efer, ed embodiments of the present process to prepare the complexes of 10 formulas (I), (la), and (Ib) are illustrated hereinbefore and hereby incorporated by reference.
The complexes of formulas (I), (la), and (Ib) as obtained can be recovered or purified, if desired, before proceedi,)g with the halogenation process.
The halo group X' in formulas (Ill), (Illa), and (Illb) and in the halogenation agent can be chloro, bromo, or iodo, but is prefe, ably chloro.
The halogenation agent comprises a 6roup 13 or 14 element or derivative thereof and at least one halo group X. Suitable examples of the halogenation agent include the halides, p,er~,ably chlorides, of boron, aluminum and silicon and acetyl halides such as acetyl bromide and acetyl chloride. ~ efe. ably, the halogenation agent is selected from the group con,i~ling of silicon tetrachloride, boron trichloride, and alkylaluminum chlorides, more 20 preferdbly dialkylaluminum chlorides such as diethylaluminum chloride. Most preferred halogenation agents are silicon tetrachloride and boron trichloride.
Specific highly prefe, lèd complexes of formula Illb include: (tert-butylamido)(tetramethyl-rl5-cyclopentadienyl)-1,2-ethanediyltitanium dichloride, (tert-butylamido)(tetramethyl-rl5-cy~lopenl~,dienyl)dimethylsilanetitanium dichloride,25 (methylamido)(lel..-."ethyl-rl5-cycloper,lddienyl)dimethylsilanetitanium dichloride, (phenylamido)(tel,~h,etl,yl-rl5-cyclopentadienyl)dimetl"~li;lanetitanium dichloride, (benzylamido)(lèl,a..,ethyl-rl5-cyclopenladienyl)dimethylsilanetitanium dichloride, (tert-butylamido)(rl5-cyJopenl.Adicnyl)-1,2-ethan~cliyllil.Anium di.l.loride, (tert-butylamido)(ll5-cyclopentadienyl)dimethylsilanetitanium dichloride, (methylamido)(rl5-30 cyclopentadienyl)dimethylsilanetitanium dichloride, and (t-butylamido)indenyldimethylsilane-titanium dichloride.
The molar ratio of the halogenation agent to the complex of formulas (I), (la), and (Ib) can vary belwe~n wide limits, but is preferdbly between 0.1:1 and 20:1, more pre~e, ably between 0.5:1 to 10:1. Advanlageously, an equivalent amount or slight stoichiometric excess 35 of halogenation agent is used with respect to the metal dihydrocarbyloxy compound of formula (I), (la) or (Ib), i.e. a ratio of 2.0:1 to 4.0:1, more pre~erdbly of from 2.1:1 to 3:1.
_19_ WO 95119984 2 18 1~ 6 g PCT/US9~100882 The temperature at which the halogenation step is conducted is not critical, but is p,eferably below the boiling point of the diluent. Preferred temperatures range trom 0C to 100C, more pref erab Iy from 10C to 80C.
Generally the reactants are contacted under an inert atmosphere for a time from 5 several minutes to several days. The reactants can be added in any order. Agitation may be employed if desired.
In the present halogenation step an aprotic organic diluent is used. Preferably,diluents are used in which the cc.,.,~lcxes of formulas (I), (la), and (Ib) are readily soluble, optionally upon heating. Suitable exd",ples of such solvents are ethers and hydrocarbons.
10 P~ererablythesolventisailycllo~alLon~advantageouslyanaliphaticorcycloaliphatic hydrocarbon solvent having from 5 to 10 carbon atoms. Suitable solvents are pentane, hexane, heptane, Isopar E, isooctane, cyclohexane, and methylcyclohexane.
In general, isolation of the desired complexes can take place as required by thebyproducts. Removal of volatiles, such as the solvent, is prertrdbly carried out by vacuum distillation at elevated ter"perdlures. When silicon tetrachloride is used as halogenation agent the byproduct formed cc.",pri~es a hydrocarbyloxy silicon chloride. Byproducts containing lower alkyls in the hydrocarbyloxy portion, especially C1 4 alkyls, may be volatile. These volatile byproducts can be easily removed from the desired product by using vacuum distillation.
Highly pure products are generally obtained, as coi"pared to the prior art methods which 20 require extensive filtration and recrystallization steps.
The compounds prepared with the processes according to the present invention, that is the complexes of formulas (I), (la), (Ib), (Il), (lla), (llb), (Ill), (Illa) and (Illb) can be used as components of catalyst systems, or precursors ll,erefor, useful in addition polymerization processes.
In a process for preparing a polymer of one or more addition polymerizable monomers, a catalyst comprising a metal coordination complex of any of the above-mentioned formulas and an activating cocatalyst are contacted with one or more addition polymerizable monomers under addition polymerization conditions. Suitable activating cocatalysts are, for example, described in U.S. Patent Application Nos. 545,403, filed July 3,1990 (cc,r, e",onding to EP-A-0,416,815) and 817,202, filed January 6,1992 (correspond;ng to WO-A-92/10360), which are incorporated herein by reference. P~ efer,~d examples of activating cocatalysts include alumoxanes, advdhldgeously methylalumoxane, tris(perfluorophenyl) borane, and tetra(perfluorophenyl) borates.
Addition polymerizable monomers" include for example ethylenically 35 unsaturated monomers, conjugated or nonconj ugated dienes, polyenes, etc. P~ erer,ed monomers include the C2-10 a-olefins especially ethylene, propylene, isobutylene,1-butene,1 -hexene, 4-methyl-1-pentene, and 1-octene. Other preferred monomers include styrene, halo--or alkyl substituted styrene, vinylbenzocyclobutane, 1 ,~hexadiene, ethylidenenorbornene, cyclopentene, and norbornene.
Suitable catalysts for use according to the present invention are prepared by combining the metal coordination complex of formulas (I), (Il), or (Ill) and a.li~dling cocatalyst 5 compound in any order and in any suitable manner. ~ eferably the ratio of the coordination complex and cocatalyst on a molar basis is from about 1:0.1 to about 1:10,000. It will, of course, be appreciated that the catalyst system may also be formed in situ if the components thereof are added directly to the polymeri~dlion process and a suitable solvent or diluent, including .undensed ",ono",er, is used in said poly",e, iCd lion process. Suitable solvents 10 include toluene, ethylbenzene, alkanes and mixtures thereof. In certain cases the catalysts may be isolated from solution and retained under inert atmosphere prior to use. The catalysts' ccn"ponenl~ are sensitive to both moisture and oxygen and should be handled and lrd"~t~r~ ed in an inert dl",o~,here such as nitrogen, argon or helium or under vacuum.
The poly",eri~dlion is conducted according to known techniques for Ziegler-15 Natta or Kaminsky-Sinn type polymerizations. That is, the monomer(s) and catalyst are contacted at a te",perdt.lre from -30C to 250C, at reduced, elevated or atmospheric pressures.
The poly",eri~alion is conducted under an inert atmosphere which may be a blanketing gas such as nitrogen, argon, hydrogen, ethylene, etc. or under vacuum. I Iy.J~ ogen may additionally be utilized in the control of molecular weight through chain termination as is previously 20 known in the art. The catalyst may be used as is or SUIJpGl led on a suitable support such as alumina, MgCI2 or silica to provide a heterogeneous suppo, led catalyst. A solvent may be e" ,~ I Dyed if desired. Suitable solvents incl ude toluene, ethyll,enzene, alkanes and excess vinyl aromatic or olefin monomer. The reaction may also be conducted under solution or slurry conditions, in a suspension utilizing a perfluorinated hydrocarbon or similar liquid, in the gas 25 phase, i.e. utilizing a fluidized bed reactor, or in a solid phase powder poly",eri~alion. A
catalytically effective amount of the present catalyst and cocatalyst is any amount that successfully results in formation of polymer. Such amounts may be readily determined by the routine experimentation by the skilled artisan. P~ erer, ed amounts of catalyst and cocatalyst are sufficient to provide an equivalent ratio of addition poly",eri~dble monomer:catalyst of 30 from 1 x 1 olo: 1 to 100:1, preferably from 1 x 1 Os 1 to 500:1, most prete, ably 1 x 1 o6 1 to 1000:1.
The cocatalyst is generally utilized in an amount to provide an eq uivalent ratio of cocatalyst:catalystfrom 10,000:1 toO.1:1,preferablyfrom 1,000:1 to 1:1.
It is to be understood that the metal complex may undergo various l,dn,tur,,,ations or form inter",ediate species prior to and during the course of a 35 polymerization.
The resulting polymeric product is recovered by filtering or other suitable technique. Additives and adjuvants may be incorporated in the polymers of the present invention in order to provide desirable characteristics. Suitable additives include pigments, UV
-6Q~
WO 95/19984 PCT/US9~/00882 stabilizers, antioxidants, blowing agents, lubricants, plasticizers, photosensitizers, and mixtures thereof.
Having described the invention, the following examples are provided to further illustrate the same and are not to be construed as limiting.
5 Example 1: Preparation of (tert-butvlamido)dimethyl(tetramethvl-ns-cvclopentadienyl)silane titanium diisopropoxide In a drybox, 24.95 9 of titaniumtetraisopropoxide (Ti(OiPr)4) (Aldrich Chemical Company) (88 mmol) was dissolved in about 200 ml of hexane. 58 9 of solid di(chloromagnesium) (tert-butylamido)-dimethyl(tel~a~eLhylcy~loper~ladienyl)silane 10 complexed with dimethoxyethane, lMe4CsSiMe2NtBul[MgCII2(DME)n (effective molecular weight by titration: about 629 g/mole; 92 mmol)(prepared accor ';ng to the following procedure: In an apparatus consi,li,-g of a 3 I round bottom flask which was equipped with a stirrer, a condenser, and a nitrogen inlet was loaded 500 ml of toluene, followed by 106 9 of Me4C5HSiMe2NHtBu, and then 380 ml of 2.2 M iPrMgCI in EtzO. The mixture was then heated, 15 and the ether removed by distillation and trapped in a condenser cooled to -78C. After five hours of heating, the heater was turned off, and 450 ml of dimethoxyethane (DME) was slowly added to the hot, stirred solution, resulting in the precipitation of a white solid. The solution was allowed to cool to room temperature, the solid was allowed to settle, and the supernatant was cle.dnted from the solid. The solid was resuspended in Isopar E and filtered. 210 9 (79 20 percent yield) lMe4cssiMe2NtBul[Mgcl]2(DME)n was obtained as off-white solid.) was added to the flask, using about 50 ml of additional hexane. The mixture was stirred overnight at room temperature,thenfilteredthroughamediumporosityfrittedglassfilter(10-15l1mporosity).
The solids remaining on the frit were washed with additional hexane until the washings are colorless. A yellow/orange solution was obtained, and the volatile materials were removed 25 from this solution under reduced pressure to leave (Me4CsSiMe2N'Bu)Ti(OiPr)2 as a yellow crystalline solid in essentially quantitative yield. 1H NMR (C6D6): 4.57 ppm (septet, 2H),2.16 ppm (s, 6H),1.91 ppm (s,6H),1.37 ppm (s, 9H),1.15 ppm (d,12H), and 0.65 ppm (6H).
Example 2: Preparation of (tert-butvlamidoh'iul~ l(tetramethvl-ns-cv~lopenladienvl)silane titanium dichloride 3o A. In a drybox, 5.0 9 of (Me4CsSiMe2NtBu)Ti(OiPr)2 (12.0 mmol) was dissolved in about 50 ml of hexane. Silicon tetrachloride (Aldrich,99.999%,2.9 ml,25.3 mMol) was added by syringe. The color immediately darkened and a precipitate began to form. The reaction mixture was stirred overnight (about 18 hours). At the end of this time, the volatile materials were removed under reduced pressure to leave (Me4CsSiMeNtBu)TiCI2 as a yellow solid (4.35 9, 35 98% yield). The material was identified by comparison of its 1H NMR spectrum with spectra of the complex made by other routes. 1H NMR (4D6): 2.00 ppm (s, 6H),1.99 ppm (s, 6H),1.42 ppm (s,9H), 0.42 ppm (s, 6H).
-B. In a drybox,1.01 g of IMe4C5SiMe2N'Bu]Ti(OiPr)2 (2.43 mmol) was dissolved in 25 ml of hexane in a Schlenck tube. BCI3 (5.5 ml of a 1.0M solution in hexane) was added by syringe; the color became orange and the mixture turned cloudy. The mixture was stirred for three hours, then the volatile materials were removed under reduced pressure. The Schlenk - 5 tube was sealed and removed from the drybox to a Schlenk line, where it was heated to 70C
overnight under dynamic vacuum to remove the remaining volatile components. The next day, - the Schlenk tube was returned to the drybox, where 0.74 9 of orange/yellow powder was obtained (83%). The 1H NMR spectrum of this material indicated it to be l(Me4Cs)SiMe2NtBulTiCI2 by comparison with the spectrum described in Example 2A.10 C. In a drybox, 0.25 9 of l(Me4C5)SiMe2NtBulTi(OiPr)2 (0.60 mmol) was d;,solved in 20 ml of pentane. Et2AlCI (1.2 ml of a 1.0 M solution in hexane) was added by syringe, and the color darkened immediately. The mixture was stirred for one hour, then the volatile materials were removed under reduced pressure to leave an oily yellow solid. The material was slurried in 3 ml of pentane and filtered to leave a bright yellow solid on the filter; this solid was washed 15 with 2 ml of additional penldne and dried under vacuum. The 1H NMR spectrum of this material indicated it to be e~ e"~ely pure l(Me4c5)siMe2NtBulTicl2 by comparison with the spectrum described in Example 2A.
Example 3: Preparation of (tert-butylamido)dimethyl(tetramethyl-nS-cyclopentad ~nyl)silane titanium dimethyl 20 A. In a drybox, 0.26 9 of (Me4CsSiMe2NtBu)Ti(OiPr)2 (0.63 mMol) was dissolved in about 15 ml of hexane. Trimethylaluminum (Aldrich, 2M in hexane, O.g5 ml,1.9 mmol) was added by syringe. The sol ution was heated to gentle ref lux. After ove. n. ~' . t (about 18 hours) reflux, the solution turned brown. The volatile materials were then removed under reduced pressure to leave (Me4CsSiMe2NtBu)TiMe2 as a pale brown solid. The material was identified by 25 comparison of its 1 H NMR spectrum with spectra of the cor"plex made by other routes. 1 H NM R
(C6D6): 1.96 ppm (s, 6H),1.85 ppm (s,6H),1.56 ppm (s,9H), 0.51 ppm (s, 6H), 0.43 ppm (s,6H).
B. In a drybox, 0.255 9 of l(Me4C5)SiMe2NtBu]Ti(OiPr)2 (0.614 mmol) was dissolved in 20 ml of ether. Methyl lithium (1.75 ml of a 1.4M solution in ether) was added by syringe. The mixture was stirred overnight. At the end of this time, the solution was pale brown with a 30 lightly colored precipitate. The volatile materials were removed under reduced pressure to leave a pale solid. The residue was extracted with pentane (20 ml), filtered, and dried under vacuum to leave an off-white crystalline solid. The 1H NMR spectrum of this material indicated it to be primarily [(Me4C5)SiMe2NtBulTiMe2; small peaks from [(Me4C5)SiMe2NtBul(Me)OiPr and LiOiPr were also observed.
35 C. In a drybox,1.00 9 of [(Me4C5)SiMe2NtBu]Ti(OiPr)2 (2.41 mmol) was dissolved in 20 ml of hexane. Trimethyl aluminum (3.0 ml of a 2.0 M solution in hexane) was added by syringe;
the solution color darkened slightly. The mixture was heated to a gentle reflux with stirring overnight. At the end of this time, the solution was pale brown. The volatile materials were W O 95/19984 2 i ~ ~ 2 PCTAUS95/00882 removed under reduced pressure to leave an off-white crystalline solid (0.79 9,100%). The 1 H
NMR spectrum of this material indicated it to be extremely pure l(Me4C5)SiMe2NtB u1TiMe2 by comparison with the spectrum in described Example 3A.
Example 4: Preparation of (tert-butylamido)dimethyl(tetramethyle-r~5-cyclopen Lad;enyl) silane 5 titanium dibromide In a drybox, 4.75 9 of SiBr4 (13.7 mmol; Aldrich) was weighed into a 100 ml flask and dissolved in 25 ml of hexane. I(Me4Cs)SiMe2NtBu]Ti(OiPr)2 (2.25 9, 6.0 mmol) was added, using 10 ml of hexane to wash the material into the flask. The mixture was heated to reflux with stirring for four hours; the color changed to bright orange and the mixture became 10 cloudy. At the end of this time, the volatile materials were re,..ov~d under reduced pressure to leave a sticky orange solid. The material was slurried in a small volume of penLdne and filtered to leave a bright orange solid on the filter; this solid was dried under vacuum to give 1.2 9 of product (44% ). The 1 H NMR spectrum of this material indicated it to be (Me4C5)SiMe2NtBulTiBr2bycomparisonwithpreviousspectra. 1H NMR(C6D6,~): 2.10(2H),15 1.96 (2H),1.50 (3H), 0.40 (2H).
HYDROCARBYLOXIDES
The present invention relates to a process for preparing certain bridged mono-5 and bis-cyclopentadienyl metal dihyJ, O~dl t~yloxy coordination complexes starting from metal hydrocarbyloxide compounds. The present invention also relates to a process for preparing bridged mono- and bis-cy.lopentadienyl l ~"~J, ocdrL,yl metal coordination complexes and to a process for preparing bridged mono- and bis-cy.lopehladienyl metal dihalide coordination cc.~ lexes both starting from the corresponding bridged mono- or bis-cyclopentadienyl metal 10 dihydrocarbyloxy coordination complexes.
Bridged mono- and bis-cyclopentadienyl metal dihalide coordination complexes and bridged mono- and bis-cyclopentadienyl dihydrocarbyl metal coordination complexes are known and usef ul as addition poly".e. i~ation catalysts or as components or precursors thereof.
In N Metallkomplexe mit verbrueckten permethylierten 15 Cy~lopenlddienylliganden" of P. Jutzi and R. Dickbreder, Chem. Ber.119,1750-1754(1986) the synthesis is described of dimethylsilanediyl-bridged bis(permethylated cy~lopenladienyl) titanium dichlorides from the lel- dhyd- c furan (THF) adducts of titanium tetrachloride and the dimethylsilanediyl-bridged bis(permethylated cyclopentadienyl) dianion derivatives.
In ansa-Metallocene derivatives: XVII. Racemic and meso diastereoisomers of 20 group IV metallocene derivatives with symmetrically substituted, dimethylsilanediyl-bridged ligand t-a,.,~wc)rks. Crystal structure of R,S-Me2Si(3-t-Bu-MeC5H2)2ZrCI2N of H. Wiesenfeldt et al., Journal of Orqanometallic Chemistrv,369 (1989) 359-370 the synthesis is described of dimethylsilanediyl-bridged bis(substituted cyclopenldJienyl) titanium dichloride complexes from the THF-adducts of titanium trichloride and the dimethylsilanediyl-bridged 25 bis(suhstituted cy.lopenladienyl) dianion derivatives.
In nSynthesis and Complexation of Linked Cyclopentadienyl-Amido Ligands of J.
Okuda, Chem. Ber. 123 (1990) 1649-1651 the preparation isdes~,ibed of a bridged mono(substituted cy.lopenladienyl) titanium dichloride complex from the THF-adduct of titanium tetrachloride and the dilithium salt of [(tert-butylamino)dimethylsilyl](tert-30 butyl)cyclopentadienide.
Bridged mono-cyclopentadienyl metal dihalide coordination complexes are also prepared in USP 5,026,798 from titanium tetrachloride compounds or ether adducts thereof and the dilithium salts of bridged mono-cyclopentadienyl ligand compounds.
Further, EP-A-0,416,815 teaches a process to prepare bridged mono-35 cy~lopenladienyl metal dihalide coordination complexes starting from the transition metaltetrahalide and a Group 1 or 6rignard derivative of the bridged mono-q,clopenlddienyl ligand compounds.
WO 95/1998~ 2 l 8 l 2 6 8 PCT/US95/00882 The above-mentioned synthesis methods to prepare the bridged mono- and bis-cyclopentadienyl metal dihalide coordination complexes use metal tetrahalide compounds as starting materials, which are corrosive, toxic, and air and moisture sensitive. In order to facilitate handling thereof, prior to the reaction step the transition metal tetrahalide 5 compound is typically converted to its ether-adduct in a separate step with for example THF or diethyl ether. This adduct formation step in itself proceeds with difficulty, requiring low to very iow temperatures, and an inert atmosphere. The adduct is usually recovered before it is reacted with the dianionic derivative of the ligand compound. The yield of the adduct formation step or steps is less than quantitative. Furthermore, the reaction mixture of the 10 Lransi Lion metal tetrahalide compound and the dianionic derivative of the bridged cyclopentadienyl ligand compound requires a multi-step, laborious recovery and purification procedure. Typically, after the reaction step, the solvent is removed, the product redissolved by adding dichloromethane or toluene or a mixture thereof, the metal halide byproduct, typically lithium chloride, removed by filtration of the mixture, the solvent removed at least partially, followed by redissolving the solid product and crystallizing the product, optionally followed by one or more further recrystallization procedures.
Further, it is known to from EP-A-0,416,815 and EP-A-0,514,828 to prepare bridged mono-cyclopentadienyl metal dihalide coordination complexes, by reacting the THF-adduct of a L,a, silion metal trihalide compound, especially TiCI3, with the dianionic derivative 20 Of the cyclopentadienyl ligand. The resulting complex is conla~Led with a non-i,-te. reri..g oxidizing agent, such as for example AgCI (EP-A-0,416,815), or with an organic halide to raise the oxidation state of the metal to form the desired dihalide complex. Apart from requiring an extra reaction step, that is the oxidation step, this process also starts from the transition metal trihalide or an ether-adduct thereof which has the disadvantages listed above, and requires 25 long reaction times to be prepared. Furthermore, the complex resulting from the reaction between the ether adduct of the transition metal trihalide compound with the dianionic derivative of the cyclopentadienyl ligand, i.e. the cyclopentadienyl metal(lll) monohalide coordination complex, is thermally unstable.
The bridged mono-cyclopentadienyl dihydrocarbyl metal coordination complexes 30 can be prepared by hydrocarbylating the corresponding bridged mono-cyclopentadienyl metal dihalide coordination complexes with a Grignard, lithium, sodium or potassium salt of the hydrocarbyl ligand. This is described, for example, in EP-A-0,418,044, example 3 and WO
92/00333. These preparation processes inherently have the disadvantages associated with the preparations of the bridged mono-cyclopentadienyl metal dihalide coordination complexes.
In one aspect, the present invention relates to a process f or preparing a metaldihydrocarbyloxy coordination complex cc r,esponding to the formula:
WO 95/19984 2 1 8 1 2 6 8 PCTtUS95tOn882 ~Z Y
Cp* M (I ) (0R)2 wherein:
M is titanium, zirconium, or hafnium;
Cp* is a cyclopentadienyl group bound in an rl5 bonding mode to M or such a cyclopentadienyl group substituted with from one to four substituents selected from the group consisting of hydrocarbyl, silyl, germyl, halo, hydrocarbyloxy, cyano, amino, and mixtures thereof, said substituent having up to 20 nonhydrogen atoms, or optionally, two substituents together cause Cp* to have a fused ring structure;
Z is a divalent moiety comprising boron, or a member of Group 14 of the PeriodicTable of the Elements, and optionally sulfur or oxygen, said moiety having up to 50 non-htd~ ogen atoms, and optionally Cp* and Z together form a fused ring system;
Y is a) a divalent anionic ligand group comprising nitrogen, phosphorus, oxygen or sulfur and having up to 20 non-hydrogen atoms, said Y being bonded to Z and M through said nitrogen, phosphorus, oxygen or sulfur, and optionally Y and Z together form a fused ring system, or b) a cyclopentadienyl group bound in a sigma bonding mode to Z and in an rl5 bonding mode to M or such a cycloper,lddienyl group substituted with from one to four substituents selected from the group con,i~li"g of hydrocarbyl, silyl, germyl, halo, hyJlOcarLyloxy, cyano, amino, and mixtures thereof, said substituent having up to 20 nonhydrogen atoms, or optionally, two substituents logelller cause Y to have a fused ring 25 structure; and R il ldependenlly each occurrence is a hydrocarbyl group having from 1 to 20 carbon atoms; the steps of the process comprising:
contacting in the presence of an aprotic organic diluent a metal compound of theformula: M(OR)4 wherein M and R are as previously defined with a dianionic salt compound cor,esponding to the formula:
(L+X) (cp* z y)-2 or ((LX)+X) (cp* z y)-2 wherein:
L is a metal of Group 1 or 2 of the Periodic Table of the Elements, X independently is chloro, bromo, or iodo, x and y are either 1 or 2 and the product of x and y equals 2, and Cp*, Z, and Y are as previously defined;
to form the complex of formula (l) 2l8l268 WO 9S/1998~ PCT/US95/(~_32 In another aspect, the present invention relates to a process for preparing a metal dihydrocarbyl coordination complex corresponding to the formula:
/Z y Cp* M (I I ) (R"')2 wherein:
M is titanium, zirconium, or hafnium;
Cp* is a cyclopentadienyl group bound in an rl5 bonding mode to M or such a cy.loper lddienyl group substituted with from one to four substituents selected from the group consisting of hydrocarbyl, silyl, germyl, halo, hydrocarbyloxy, cyano, amino, and mixtures thereof, said substituent having up to 20 nonhydrogen atoms, or optionally, two substituents together cause Cp* to have a fused ring structure;
Z is a divalent moiety comprising boron, or a member of 6roup 14 of the PeriodicTable of the Elements, and optionally sulfur or oxygen, said moiety having up to 50 non-hydrogen atoms, and optionally Cp* and Z together form a fused ring system;
Y is a) a divalent anionic ligand group comprising nitrogen, phosphorus, oxygen or sulfur and having up to 20 non-hydrogen atoms, said Y being bonded to Z and M through said nitrogen, phosphorus, oxygen or sulfur, and optionally Y and Z together form a fused ring system, or b) a cyclopentadienyl group bound in a sigma bonding mode to Z and in an rl5 bonding mode to M or such a cyclopenlddirnyl group substituted with from one to four substituents selected from the group consi~li,.g of hydrocarbyl, silyl, germyl, halo, hydrocarbyloxy, cyano, amino, and mixtures thereof, said substituent having up to 20 nonhyd~ ogen atoms, or optionally, two substituents lugelher cause Y to have a fused ring structure; and Rn' independenlly each occurrence is a hydrocarbyl group containing from 1 to 20carbon atoms;
the process comprising contacting in the presence of an aprotic organic diluent a metal coordination complex of formula:
/Z --Y
Cp* M (I ) (OR)2 2181268 ` `
WO 95/19984 PCT/US~SI'G~)882 wherein R independently each occurrence is a hydrocarbyl group having from 1 to 20 carbon atoms and Cp*, Z, Y, M, are as previously defined;
with a hydrocarbylation agent comprising a group 1, 2, 12 or 13 metal or metal derivative and at least one hydrocarbyl group R ', to form the metal dihydrocarbyl 5 coordination complex of formula (Il).
In yet another aspect the present invention relates to a process for preparing ametal dihalide coordination complex corresponding to the formula:
/Z Y
CP* M (III ) (X ~ ) 2 wherein:
M is titanium, zirconium, or hafnium;
Cp* is a cyclopentadienyl group bound in an tl5 bonding mode to M or such a cy~lopenladienyl group substituted with from one to four substituents selected from the group consisting of hydrocarbyl, silyl, germyl, halo, hydrocarbyloxy, cyano, amino, and mixtures thereof, said substituent having up to 20 nonhyd~ ogen atoms, or optionally, two substituents together cause Cp* to have a fused ring structure;
Z is a divalent moiety comprising boron, or a member of Group 14 of the PeriodicTable of the Elements, and optionally sulfur or oxygen, said moiety having up to 50 non-hydrogen atoms, and optionally Cp* and Z together form a fused ring system;
Y is a) a divalent anionic ligand group comprising nitrogen, phosphorus, oxygen or sulfur and having up to 20 non-l-"d~ ogen atoms, said Y being bonded to Z and M through said nitrogen, phosphorus, oxygen or sulfur, and optionally Y and Z together form a fused ring system, or b) a cyclopenLad:enyl group bound in a sigma bonding mode to Z and in an rl5 bonding mode to M or such a cyclopent~ l ~nyl group substituted with from one to four substituents selected from the group consisting of hydrocarbyl, silyl, germyl, halo, hyd~ OCal LYIOAY, amino, and mixtures thereof, said substituent having up to 20 nonhydrogen atoms, or optionally, two substituents together cause Y to have a fused ring structure; and X' i..dependently each occurrence is a halo group;
the process comprising contacting in the presence of an aprotic organic diluent a metal coordination complex of formula W O 95/19984 ~ PCTAUS95/00882 ~Z --Y
Cp* M (I ) (0R)2 wherein R independently each occurrence is a hydrocarbyl group having from 1 to 20 carbon atoms and Cp*, Z, Y, M, are as previously defined;
with a halogenation agent comprising at least a member of Group 13 or 14 of the Periodic Table of the Elements and at least one halo group X', to form the metal dihalide coordination complex of formula (Ill).
All reference to the Periodic Table of the Elements herein shall refer to the Periodic Table of the Elements, published and copyrighted by CRC Press, Inc., 1989. Also, any reference to a Group or Groups shall be to the Group or Groups as reflected in this Periodic Table of the Elements using the IUPAC system for numbering Groups.
Surprisingly, it has been found that two hydrocarbyloxy groups on the titanium, zirconium, or hafnium (hereinafter referred to as Group 4 metal) center can be removed readily by contacting the compound M(OR)4 where M and R are as previously defined with the dianionic salt compound to give the complexes of formulas (I), (la), or (Ib) in high yield and high purity. This discovery was indeed surprising as hydrocarbyloxy-transition metal bonds are considered to be stronger bondsthan halogen-l.ah,ilion metal bonds and lt.erefo,e the hydrocdrLyloxy groups are considered less suitable leaving groups than halogen groups. The starting Group 4 metal hydrocarbyloxy compounds, typically the titanium tetraisopropoxide, tetra-n-butoxide and tetra-t-butoxide, are non-viscous liquids, only mildly air-sensitive, co."".er, ially available, and readily soluble in hyJ, ucarLons, as compared to the corrosive, air-sensitive and difficult to handle Group 4 metal tetrachlorides. This new process typically provides the complexes of formulas (I), (la), and (Ib) in yields of 9û percent and higher. The product complexes can be readily isolated in high purity by filtration.
In the present process bridged mono- or bis(cyclopenladienyl) metal dihydrocarbyloxy coordination complexes of formulas (I), (la), or (Ib) are prepared by contacting a Group 4 metal tetr,ahydrocarbyloxy compound of the formula: M(OR)4, wherein M and R are as previously defined, with a dianionic salt compound. The dianionic salt is preferably a double Group 1 metal derivative or double Grignard (Group 2 metal monohalide) derivative of the -Cp*-Z-Y- moiety, the anionic charges formally residing on the Cp* and Y groups. In the relevant part of the formula for the dianionic salt compound the double Group 1 metal WO 95/1998~ PCTIUS95/00882 ._ derivative corresponds to (L+x)y wherein x is 1 and y is 2, and the double 6rignard derivative corresponds to ((LX)+x)y wherein x is 1 and y is 2.
In the metal dihydrocarbyloxy coordination complexes of formula (I), M is titanium, zirconium, or hafnium and R independently each occurrence is a hydrocarbyl group 5 having from 1 to 20 carbon atoms, more preferably R each occurrence is independently selected from the group consisting of alkyl, aryl, alkaryl, and aralkyl groups, even more preferably from alkyl groups having from 1 to 6 carbon atoms, and aryl, aralkyl and alkaryl groups having from 6-10 carbon atoms, and most preferably R each occurrence is independently selected from the group consi,ling of ethyl, isopropyl, n-butyl, and t-butyl.
A neutral Lewis base, such as an ether or amine compound, may also be associated with the complex, if desired, however, such is generally not preferred.
The term substituted cyclopentadienylN includes, but is not limited to, indenyl,tetrahydroindenyl, fluorenyl, tetrahydrofluorenyl, and octahydrofluorenyl groups.
6eneric formula (I) embraces bridged monocyclopen~adienyl metal dihydrocarbyloxy coordination complexes and bridged bis(cyclopentddienyl) metal dihydrocdrL.yloxy coordination complexes.
Pl er~r.ed bridged monocyclopentadienyl metal dihydrocarbyloxy coordination complexes of formula (I) prepared in the present process include those having constrained geometry.
By the term " constrained geometryn as used herein is meant that the metal atom in the metal coordination complex and also in the catalyst resulting therefrom is forced to greater exposure of the active catalyst site because of a specific ring structure of a ligand group including the metal atom, wherein the metal is both bonded to an adjacent covalent moiety and held in association with the delocalized n-bonded cyclopentadienyl group through an rl5 25 or other n-bonding interaction. It is understood that each respective bond belween the metal atom and the constituent atoms of the n-bonded moiety need not be equivalent. That is, the metal may be symmetrically or unsy.. el. i dlly n-bound thereto.
The concept of constrained geometry and specific con,L. ain inducing ligand groups are described in more detail in U.S. Patent Application Serial Number 545,403, filed July 30 3, 1990 (cor.es~.onding to EP-A-0,416,815) which is incorporated herein by reference.
Suitable examples of moiety Z in formula (I) include SiR 2, CR 2, SiR 2SiR 2, CR~2CR~2, CR*=CR*, CR~2SiRt2, GeR~2, or BR~ wherein R* each occurrence is i.,dependenlly selected from the group consisting of hydrogen, alkyl, aryl, silyl, halogenated alkyl, halogenated aryl groups having up to 20 non-hydrogen atoms, and mixtures thereof, or two or 35 more R* groups from Z, or an R* group from Z together with Y form a fused ring system.
Further more preferably, Y in formula (I) is -O-, -S-, -NR~-, -PR~-. Highly prererably Y is a nitrogen or phosphorus containing group Wo 95/1998~ 2 18 12 6 PCT/US9~/00882 cor,espond.ng to the formula -N(R')- or -P(R')-, i.e. an amido or phosphido group, wherein R' is as defined hereinafter.
More preferably, in the present process is prepared a metal coordination dihydrocarbyloxy complex of formula (I) corresponding to the formula:
~(ER 2)m~N R~
R~ M (Ia) R~ R (OR)2 wherein R' each occurrence is independently selected from the group consisting of hydrogen, silyl, alkyl, aryl, germyl, cyano, halo and combinations thereof having up to 20 non-hydrogen atoms, or two R' groups together form a divalent derivative thereof;
E is silicon or carbon;
m is 1 or 2; and M and R are as previously defined; and ~ ,vherei, . the metal compound of the formula: M(OR)4 is contacted with a dianionic salt compound cc " e" onding to the formula:
(L )y(C5R 4-(ER 2)m-NR )-2 or ((LX)+X)y(C5R~4~(ER~2)m~NR~)~2 20 v~/hel ein L, R', E, X, x, y, and m are as previously defined. It is remarked that when a substituent, such as R', on a cy~lopenlddienyl group is hydrogen, halo or cyano, two of such substituents can not together form a divalent derivative thereof or cause the groups to have a fused ring structure.
In the complexes of formula (la), M is prererably titanium, and prererably R
25 i.,dependehlly each occurrence is alkyl, aryl, aralkyl, and alkaryl groups, more p,e~e,dbly scle~led from an alkyl group having from 1 to 6 carbon atoms, and aryl, aralkyl and alkaryl groups having from 6-10 carbon atoms, even more preferably R is a C1 4-alkyl, and especially ethyl, isopropyl, n-butyl, or t-butyl.
Examples of the above most highly preferred metal dihydrocarbyloxy 30 coordination compounds include compoundsw"erei.) the R' on the amido group is methyl, ethyl, propyl, butyl, pentyl, hexyl, and isomers of these alkyl radicals, norbornyl, benzyl, phenyl, etc.; the cyclopenlddienyl group is cyclopentadienyl, indenyl, telldhyJ, oindenyl, fluorenyl, tetrahydrofluorenyl, octahydrofluorenyl, etc.; R' on the foregoing cyclopentadienyl groups each occurrence is hydrogen, methyl, ethyl, propyl, butyl, pentyl, hexyl, and isomers of these 35 alkyl radicals, norbornyl, benzyl, phenyl, etc.; and R is ethyl, isopropyl, n-butyl or t-butyl.
Specific highly prefer,ed compounds include: (tert-butylamido)(tetramethyl-rl5-cyclopentadienyl)-1,2-ethanediyltitanium di-ethoxide, (tert-butylamido)(tetramethyl-rl5-cyclopentadienyl)-1,2-ethanediyltitanium di-isopropoxide, (tert-butylamido)(tetramethyl-rl5-cyclopentadienyl)-1,2-ethanediyltitanium di-n-butoxide, (tert-butylamido)(tetramethyl-r~5-cyclopentadienyl)dimethylsilanetitanium di-ethoxide, (tert-butylamido)(tetramethyl-rl5-cyclopentadienyl)dimethylsilanetitanium di-isopropoxide, (tert-butylamido)(tetramethyl-rl5-5 cyclopentadienyl)dimethylsilanetitanium di-n-butoxide, (methylamido)(tetramethyl-rl5-cyclopentadienyl)dimethylsilar,eLiLanium di-ethoxide, (methylamido)(tetramethyl-rl5-cy.loper,tadienyl)dimethylsilanetitanium di-isopropoxide, (methylamido)(tetramethyl-rl5-cyclopentadienyl)dimethylsilanetitanium di-n-butoxide, (phenylamido)(tetramethyl-rl5-cyclopentadienyl)dimethylsilanetitanium di-ethoxide, (phenylamido)(tetramethyl-r~5-10 cyclopentadienyl)dimethylsilanetitanium di-isopropoxide, (phenylamido)(l~l.dmethyl-rl5-cyclopentadienyl)dimethylsilanetitanium di-n-butoxide, (benzylamido)(tetramethyl-rl5-cyclopentadienyl)dimethylsilanetitanium di-ethoxide, (benzylamido)(tetramethyl-rl5-cy~lope"ladienyl)dimethylsilanetitanium di-isopropoxide, (benzylamido)(tetramethyl-rl5-cyclopentadienyl)dimethylsilanelil~,nium di-n-butoxide, (tert-butylamido)(rl5-cyclopentadienyl)-1 ,2-ethanediyltitanium di-ethoxide, (tert-butylamido)(rl5-cy~lopenLddienyl)-1,2-ethanediyltitanium di-isopropoxide, (tert-butylamido)(rl5-cyclopentadienyl)-1,2-ethanediyltitanium di-n-butoxide, (tert-butylamido)(rl5-cyclopenladienyl)-dimethylsilanetitanium di-ethoxide, (tert-butylamido)(rl5-cyclopentadienyl)-dimethylsilanetitanium di-isopropoxide, (tert-butylamido)(rl5-20 cyclopentadienyl)dimethylsilanetitanium di-n-butoxide, (methylamido)(rl5-cy~lopentadienyl)dimethylsilanetitanium di-ethoxide, (methylamido)(rl5-cyclopentadienyl)dimethylsilanetitanium di-isopropoxide, (t-butylamido)(rl5-cyclopenta-dienyl)dimethylsilan~:Lildnium di-n-butoxide, (t-butylamido)indenyldi,.,elt.ylsilanetitanium di-ethoxide, (t-butylamido)indenyldimethylsilanetitanium di-isopropoxide, (t-25 butylamido)indenyldimethylsilanetitanium di-n-butoxide, (benzylamido)i..denyld;"~_lt"~l,ilaoelil..nium di-ethoxide, and (benzylamido)indenyldimethylsilanetitanium di-isopropoxide.
According to another prefer.~d er..bod,...ent of the present process, there is prepared a metal coordination complex of formula (I) corresponding to the formula:
-2~ 6~
R~ R' ( Rn2E~ R I
M- ( oR ) 2 Rl R' R' wherein:
R' each occurrence is independently selected from the group consisting of hydrogen, silyl, alkyl, aryl, germyl, cyano, halo and combinations thereof having up to 20 non-hydrogen atoms, or two R' groups together form a divalent derivative thereof;
E is silicon or carbon;
R" independently each occurrence is hydrogen or a group selected from silyl, hydrocarbyl and combinations thereof, said Ru having up to 30 carbon or silicon atoms;
m is 1 to 8; and M and R are as previously defined; and wherein the metal compound of the formula: M(OR)4 is contacted with a dianionic salt compound corresponding to the formula:
(L+X)y(c5R~4-(ERn2)m-c5R~4) 2 or ((Lx)+~)"(csR~4-(ER 2)m-csR 4) 2 wherein L, R', E, R, X, m, x and y are as previously defined.
Exemplary metal complexes of bridged bis-cy.loper,~adienyl metal dihydrocarbyloxy coordination complexes include those complexes of formula (Ib) wherein E is silicon or carbon, R" independently each occurrence is hydrogen or a group selected from silyl, hydrocarbyl and combinations thereof, said R" having up to 30 carbon or silicon atoms, and m is 1 to 8. Preferably R independently each occurrence is methyl, benzyl, tert-butyl, or phenyl.
Such bridged bis(cy.lopentadienyl) structures are especially suited for use as catalysts, or precursors thereof, for the preparation of polymers having stereoregular molecular structure. In such capacity it is preferred that the complex be nonsymmetrical or possess a chiral, stereorigid structure. Examples of the first type are compounds possessing dif~erenL delocalized n-bonded systems, such as one cyclopenta-dienyl group and one indenyl group. Examples of chiral structures include bis-indenyl complexes.
2l8l26~
.~, Exemplary bridged bis(cy-lopenladienyl) metal dihydrocarbyloxy complexes of formula (Ib) are those wherein the bridged ligand group is: dimethylsilyl-bis-cyclopentadienyl, dimethylsilyl-bis-tetramethylcyclopentadienyl, dimethylsilyl-bis-indenyl, isopropylidene-cyclopentadienyl-fluorenyl, 2,2'-biphenyldiylbis(3,4-dimethyl-1-cyclopentadienyl), and - 5 6,6-dimethyl-2,2'-biphenylbis(3,4-dimethyl-1-cyclopentadienyl).
In a prerer,ed embodiment, the moiety ((LX)+x)y in the dianionic salt compound - corresponds to ((MgCI)+)2. In another p~efer~ed embodiment, the moiety (L+x)z in the dianionic salt corresponds to (Li+)2. Use of the former dianionic salt compound in the present process gives as a byproduct MgCl(OR) which can be easily separated from the desired product.
The molar ratio of the dianionic salt compound to the metal dihy:l. Ocarl"~loxy compound M(OR)4 can vary between wide limits. Although an improved process can be obtained with dianionic salt compound to metal compound molar ratios of 0.5:1 and higher, for example, up to 10:1, or preferably up to 5:1, the yield of the process and the purity of the desired products are high at ratios of 1:1 and slightly higher, for example, up to 1.5:1, 15 pref~rably up to 1.2:1.
In the present process an aprotic organic diluent is used. Suitable examples of such diluents are ethers and hydrocarbons. Preferably the hydrocarbon solvent is an aliphatic or cycloaliphatic I ryJ~ O~arL,on solvent having from 5 to 10 carbon atoms. Suitable solvents are pentane, hexane, heptane, Isopar E (a mixture of isoparaffinic hydrocarbons available from 20 Exxon Chemical Inc.), isooctane, cyclohexane, and methylcyclohexane.
Carrying out the reaction in a hydrocarbon solvent has the advantage that the product dihydrocarbyloxy complexes of formulas (I), (la), and (Ib) are soluble, whereas the byproduct L-OR or LX-OR generally is not. The desired products thus can be easily recovered, if desired, by filtration or other liquid-solid separation methods. By subjecting the liquid thus 25 obtained to a stripping step tQ strip off the volatile solvent a highly pure product is obtained.
The temperature at which the process is conducted is not critical, but is p,eferably below the boiling point of the diluent. Preferred temperatures range from 0C to 1 00C, more preferably from 1 0C to 80C, and most preferably from 20 to 60C.
Generally the reactants are contacted under an inert atmosphere for a time from 30 several minutes to several days. The presence of oxygen and moisture are preferably avoided.
The reactants can be added in any order. Agitation may be employed if desired.
According to a f urther aspect the present invention pl olides a process for preparing bridged mono- or biscy~lopenladienyl dihyJ~ocarbyl metal coordination complexes of formulas (Il), (lla), and (llb) by contacting a corresponding metal dihydrocarbyloxy 35 coordination complex of formula (I), (la), or (Ib) obtainable as described hereinbefore with a hydrocarbylation agent comprising a 6roup 1, 2, 12 or 13 metal or metal derivative and at least one hydrocarbyl group Rn', to form the dihydrocarbyl metal coordination complex of formula (Il), (lla) or (llb).
w o 95/19984 2 18 12 6 8 PCT~US95/00882 Surprisingly, it has been found that the dihydrocarbyloxy complexes of formulas (1), (la), and (Ib) are stable compounds which can readily be converted to the corresponding dihydrocarbyl compounds of formulas (Il), (lla), or (llb) in high yields and purity. The present hydrocarbylation process, especially in combination with the process for preparing the metal 5 dihydrocarbyloxy coordination complexes of formulas (1), (la), or (Ib) as described herein before, enables the valuable complexes of formulas (Il), (lla), or (llb) to be prepared in high overall yields compared to a process starting from metal tetrahalide compounds.
In a pre~er,ed embodiment, a metal dihydrocarbyl coordination complex ~or,e,pon~i ~9 to the formula:
R' (ER 2)~
R ~ M (IIa) R' (R ' )2 wl ,e~ ei., R' each occurrence is independently selected from the group consisting of I "/J~ ogen, silyl, alkyl, aryl, germyl, cyano, halo and combinations thereof having up to 20 non-hydrogen atoms, or two R' groups to9elher form a divalent derivative thereof;
E is silicon or carbon;
m is 1 or 2; and M and RN' are as previously defined;
is prepared by contacting a metal dihydrocarbyloxy coordination cc""plex corresponding to the formula:
~ (ER 2)~
[ ~ (Ia) R (OR)2 R
wherein: M, R', E, R, and m are as previously defined;
with the hydrocarbylation agent.
In another preferred embodiment, a metal dihydrocarbyl coordination complex corresponding to the formula:
R~ R~
;
( Rll2E~ R I
R~M- ( R ~ I ) 2 R 1~ R ' (IIb) R' wherein:
R' each occurrence is independer,lly selected from the group .onsi,ling of hydrogen, silyl, alkyl, aryl, germyl, cyano, halo and combinations thereof having up to 20 non-hydrogen atoms, or two R' groups together form a divalent derivative thereof;
E is silicon or carbon;
R" i-,depender,lly each occurrence is l,yd~ogen or a group selected from silyl, hydrocarbyl and combinations thereof, said R" having up to 30 carbon or silicon atoms;
m i5 1 to 8; and M and Rn' are as previously defined;
is prepared by cor,la.li--g a metal dihydrocarbyloxy coordination complex corresponding to the formula:
(Rn2E~ R~
\ ~,, M-(OR)2 1~
R~ \/ R' (Ib) R' wherein R', E, R", M, R, and m are as previously defined;
W O 95/19984 2 ¦ 8 ¦ ~ 6 8 PCTAUS95/00882 with the hydrocarbylation agent.
In a further preferred embodiment, the metal dihydrocarbyloxy coordination complex of formula (I), (la), or (Ib), used as starting compound in the preparation of complexes of formulas (Il), (lla) or (llb), is prepared by contacting in the presence of an aprotic organic 5 diluent a metal compound of the formula: M(OR)4 wherein M and R are as previously defined with a dianionic salt compound cor,esponding to the formula:
(L+X)y(Cp* Z y) 2 or ((LX)+X) (Cp* Z Y) 2 wherein:
Li5 a metal of Group 1 or 2 of the Periodic Table of the Elements, X independently is chloro, bromo, or iodo, x and y are either 1 or 2 and the product of x and y equals 2, and Cp*, Z, and Y are as previously defined;optionally followed by recovering the complex corresponding to formula (I).
In the complexes of formulas (I), (la), and (Ib), M is titanium, zirconium, or hafnium and R independently each occurrence is a hydrocarbyl group having from 1 to 20 carbon atoms, preferably R each occurrence is independently selected from the group consisting of alkyl, aryl, aralkyl, and alkaryl groups, more prefe~dbly alkyl groups having from 2 to 6 carbon atoms and aryl, aralkyl, and alkaryl groups having from 6-10 carbon atoms, and most prere, ~.bly R each occurrence is independen~ly selected from the group consi~li"g of 20 ethyl, isopropyl, n-butyl, and t-butyl.
P~ere,-edembodimentsofthepresentprocesstopreparethecomplexesof formulas (I), (la), and (Ib) are illustrated he,einbefore and hereby incorporated by reference.
The complexes of formulas (I), (la), and (Ib) as obtained can be recovered or purified, if desired, prior to proceeding with the hydrocarbylation step.
The hydrocarbyl group R"' in formulas (Il), (lla), and (llb) and present in the h"J. ~cal Lylation agent generally has from 1 to 20 carbon atoms and can be an aliphatic, cycloaliphatic, or aromatic hydrocarbon or a mixture thereof. P~ eferably, Rn' is selected from the group consi,~ing of alkyl, aryl and aralkyl groups, more preferablyfrom alkyl groups having from 1 to 6 carbon atoms, or aralkyl groups having from 7 to 10 carbon atoms. Most prererdbly 30 RN' is methyl, neopen~yl, or benzyl.
The hydrocarbylation agent comprises a Group 1,2,12 or 13 metal or metal derivative and at least one hydrocarbyl group RN'. Suitable examples of the hydrocarbylation agent include LiRN', MgRN'2, MgRN'XN (wherein Xn is halogen, preferably chloro), AlRn'3, and Rn'-substituted aluminoxane. Suitable RN'-substituted aluminoxanes p-ererably include C1-6-35 alkylaluminoxanes, especially methylaluminoxane. Alkylaluminoxanes are well known in theart and methods for their preparation are illustrated by U.S. Patent Nos. 4,592,199; 4,544,762;
5,015,749 and 5,041,585. P~ ~re-dbly, the hydrocarbylation agent comprises LiRN' or AlRn'3.
WO 95/19984 21 81 ~ 6 8 PCT/US9~/00882 More preferably the hydrocarbylation agent is trialkyl aluminum, most prefel ably trimethyl aluminum.
Specific highly prefer.ed complexes of formula (lla) include: (tert-butylamido)(tetramethyl-rl5-cy-lopenlddienyl)-1,2-ethanediyltitanium dimethyl, (tert-5 butylamido)(tetramethyl-rl5-cy~lopenlddienyl)-1,2-ethanediyltitanium dibenzyl, (tert-butylamido)(tetramethyl-rl5-cyclopentadienyl)dimethylsilaneLildnium dimethyl, (tert-butylamido)(tetramethyl-rl5-cy~lopenlddienyl)dimethylsilanetitanium dibenzyl, (methylamido)(tetramethyl-rl5-cyclopenladienyl)dimethylsilanetitanium dimethyl, (methylamido)(tetramethyl-rl5-cyclopenladienyl)d;.,-elhylsilanetitanium dibenzyl, 10 (phenylamido)(tetramethyl-rl5-cyclopentadienyl)dimethylsilanetitanium dimethyl, (phenylamido)(tetramethyl-ll5-cyclopentadienyl)dimethylsilanetitanium dibenzyl, (benzylamido)(tetramethyl-rl5-cyclopentadienyl)dimethylsilanetitanium dimethyl, (benzylamido)(tetramethyl-rl5-cyclopentadienyl)dimethylsilanetitanium dibenzyl, (tert-butylamido)(rl5-cyclopentadienyl)-1,2-ethanediyltitanium dimethyl, (tert-butylamido)(rl5-cy~lopenlddienyl)-1,2-ethanediyltitanium dibenzyl, (tert-butylamido)(rl5-cy~lG,uel.ladienyl)-di...elhylsilanetitanium dimethyl, (tert-butylamido)(rl5-cy~lopenlddienyl)dimethylsilanetitanium dibenzyl, (methylamido)(rl5-cyclopentadienyl)dimethylsilanetitanium dimethyl, (t-butylamido)(rl5-cyclopenta-dienyl)dimethylsilanetitanium dibenzyl, (t-butylamido)indenyldimethylsilanelilanium 20 dimethyl, (t-butylamido)indenyldimethylsilanetitanium dibenzyl, and (benzylamido)indenyldimethylsilanelilanium dibenzyl.
The molar ratio of the hyd~ ocdrL.jlation agent to the complex of formulas (I), (la), and (Ib) can vary between wide limits, but is preferably between 0.1:1 and 20:1, more p,eferdblybetween0.5:1to10:1. Advantageously,anequivalentamountoraslightexcessof25 RN'-groups in the I "~drocdrL"Ilation agent is used with respect to the metal hydlOl.dl Lyloxy compound of formulas (i), (la), or (Ib), i.e., a ratio of from 2.0:1 to 4.0:1, more p. erl:r~bly of from 2.1:1 to3:1.
The temperature at which the hydrocarbylation step is conducted is not critical,but is preferably below the boiling point of the aprotic organic diluent F~ efe. red temperatures 30 rangefrom 0Cto 100C, morepreferablyfrom 10~Cto80C.
Generally the reactants are contacted under an inert atmosphere for a time from several minutes to several days. The reactants can be added in any order. Agitation may be employed if desired.
In the present hydrocarbylation step an aprotic organic diluent is used.
35 Preferably, diluents are used in which the complexes of formulas (I), (la), and (Ib) are readily soluble, optionally upon heating. Suitable examples of such solvents are ethers and hydrocarbons. Preferably the solvent is a hydrocarbon, advantageously an aliphatic or 6~
WO 95/19984 . PCT/US95100882 cycloaliphatic hydrocarbon solvent having from 5 to 10 carbon atoms. Suitable solvents are pentane, hexane, heptane, Isopar E, isooctane, cyclohexane, and methylcyclohexane.
Carrying out the reaction in a hydrocarbon solvent has the advantage that the product hydrocarbyl complexes of formulas (Il), (lla), and (llb) are soluble and non-volatile, 5 while the byproduct Group 1, 2, 12 or 13 metal or metal derivative hyd.ocdrL.yloxides are often either insoluble or volatil, especially when R is a lower alkyl, such as a C1 4 alkyl. Thus, the byproducts LiOR and Mg(OR)R ' generally are not soluble in hydrocarbons when R is a lower alkyl, and may be easily removed from the desired hydrocarbyl product by fillrdtion, decdntalion, or other liquid-solid separation method. By subjecting the liquid thus obtained to 10 a stripping step to remove the volatile solvent a highly pure product may be obtained.
However, the byproduct formed when using the highly prefer,ed trimethylaluminum as the hydrocarbylation agent cc" "p- ises a dimethylaluminum hydrocarbyloxide which is volatile.
This byproduct can be removed from the desired product by applying a vacuum so as to remove both the byproduct and the solvent/diluent in one step.
According to another aspect the present invention provides a process for preparing bridged mono- or bis(cy.lopenlddienyl) metal dihalide coordination complexes of formulas (Ill), (Illa) or (Illb) by conlacli"g a co,~".onding metal dihycl, ocd,L~rloxy coordination complex of formula (I), (la), or (Ib) obtainable as described her~i. ,berore, with a halogenation agent comprising a Group 13 or 14 element or derivative thereof and at least one halo group 20 X', to form the metal dihalide coordination complex of formulas (Ill), (Illa) or (Illb).
Surprisingly, it has been found that the dihydrocarbyloxy complexes of formulas (1), (la) or (b) are stable compounds which can easily be con~r~. led to the corresponding dihalide compounds of formulas (Ill), (Illa) or (Illb) in high yields and purity. The present halogenation process, especially in combination with the process for preparing the metal dihydrocarbyloxy 25 coordination complexes of form ulas (I), (la) or (Ib) as described herein before, enables the culllrlFxes of formulas (Ill), (Illa) or ~IIIb) to be prepared in high yields compared to a process starting from metal tetrahalide compounds.
In a preferred embodiment, a metal dihalide coordination complex corresponding to the formula (Illa):
R ( ER 2 )m~ N R ~
R~ M (IIIa) R' (X' )2 WO95/19984 21 81 2 ~8 PCT/US95/00882 wherein R' each occurrence is independently selected from the group consisting of hydrogen, silyl, alkyl, aryl, germyl, cyano, halo and combinations thereof having up to 20 non-hydrogen atoms, or two R' groups together form a divalent derivative thereof;
E is silicon or carbon;
- 5 m is 1 or 2; and M and X' are as previously defined;
is prepared by cGnla~ lg a metal dihydrocarbyloxy coordination co",Flex cc."esponding to the formula:
~ ~ (ER ' 2)m~
R~ M ( Ia) R ' (OR)2 wherein: M, R', E, R, and m are as previously defined;
with the halogenation agent.
In another p,~rerled embodiment, a metal dihalide coordination complex cor~esponding to formula (Illb) R' R' (R"2E)m R' \~ M- ( X ' ) 2 1(~' R' \/ R' ( IIIb) R' WO 95/19984 ~ ,6~ PCT/US95/00882 wherein:
R' each occurrence is independently selected from the group consisting of hydrogen, silyl, alkyl, aryl, germyl, cyano, halo and combinations thereof having up to 20 non-hydrogen atoms, or two R' groups together form a divalent derivative thereof;
E is silicon or carbon;
R" independently each occurrence is hydrogen or a group selected from silyl, hydrocarbyl and combinations thereof, said R" having up to 30 carbon or silicon atoms;
m is 1 to 8; and M and X' are as previously defined;
is prepared by contacting a metal dihydrocarbyloxy coordination complex cur.esponding to the formula:
R~ R~
(R~l2E)m R' R' M-(OR)2 R' \/ R' (Ib) R~
wherein R', E, R, M, R, and m are as previously defined;
with the halogenation agent.
Inafurtherp~efe,-edembodiment,themetaldihyd~oc~.Lyloxycoordination complex of formulas (I), (la) or (Ib), used as starting compound in the preparation of complexes of formulas (Ill), (Illa) or (Illb), is prepared by contacting in the presence of an aprotic organic 30 diluent a metal compound of the formula: M(OR)4 wherein M and R are as previously defined with a dianionic salt compound corresponding to the formula:
(E+x)y(Cp*-z-y)-z or ((LX)+X) (Cp* Z y)-2 wl ,erein:
L is a metal of Group 1 or 2 of the Periodic Table of the Elements, X independently is chloro, bromo, or iodo, x and y are either 1 or 2 and the product of x and y equals 2, and Cp*, Z, and Y are as previously defined;
optionally followed by recoveri.)g the complex WO 95/19984 1 81~ ~ 8 PCT/US9~i/00882 corresponding to formula (I).
In the complexes of formulas (I), (la), and (Ib), M is titanium, zirconium or hafnium and R independently each occurrence is a hydrocarbyl group having from 1 to 20 carbon atoms, preferdbly R each occurrence is independently selected from the group consisting of alkyl, aryl, 5 aralkyl, and alkaryl groups, more preferdbly alkyl groups having from 2 to 6 carbon atoms and aryl, aralkyl, and alkaryl groups having from 6-10 carbon atoms, and most preferably R each occurrence is i"dependenlly selected from a C1 4-alkyl, especially from the group consi~li"g of ethyl, isopropyl, n-butyl, and t-butyl.
~l efer, ed embodiments of the present process to prepare the complexes of 10 formulas (I), (la), and (Ib) are illustrated hereinbefore and hereby incorporated by reference.
The complexes of formulas (I), (la), and (Ib) as obtained can be recovered or purified, if desired, before proceedi,)g with the halogenation process.
The halo group X' in formulas (Ill), (Illa), and (Illb) and in the halogenation agent can be chloro, bromo, or iodo, but is prefe, ably chloro.
The halogenation agent comprises a 6roup 13 or 14 element or derivative thereof and at least one halo group X. Suitable examples of the halogenation agent include the halides, p,er~,ably chlorides, of boron, aluminum and silicon and acetyl halides such as acetyl bromide and acetyl chloride. ~ efe. ably, the halogenation agent is selected from the group con,i~ling of silicon tetrachloride, boron trichloride, and alkylaluminum chlorides, more 20 preferdbly dialkylaluminum chlorides such as diethylaluminum chloride. Most preferred halogenation agents are silicon tetrachloride and boron trichloride.
Specific highly prefe, lèd complexes of formula Illb include: (tert-butylamido)(tetramethyl-rl5-cyclopentadienyl)-1,2-ethanediyltitanium dichloride, (tert-butylamido)(tetramethyl-rl5-cy~lopenl~,dienyl)dimethylsilanetitanium dichloride,25 (methylamido)(lel..-."ethyl-rl5-cycloper,lddienyl)dimethylsilanetitanium dichloride, (phenylamido)(tel,~h,etl,yl-rl5-cyclopentadienyl)dimetl"~li;lanetitanium dichloride, (benzylamido)(lèl,a..,ethyl-rl5-cyclopenladienyl)dimethylsilanetitanium dichloride, (tert-butylamido)(rl5-cyJopenl.Adicnyl)-1,2-ethan~cliyllil.Anium di.l.loride, (tert-butylamido)(ll5-cyclopentadienyl)dimethylsilanetitanium dichloride, (methylamido)(rl5-30 cyclopentadienyl)dimethylsilanetitanium dichloride, and (t-butylamido)indenyldimethylsilane-titanium dichloride.
The molar ratio of the halogenation agent to the complex of formulas (I), (la), and (Ib) can vary belwe~n wide limits, but is preferdbly between 0.1:1 and 20:1, more pre~e, ably between 0.5:1 to 10:1. Advanlageously, an equivalent amount or slight stoichiometric excess 35 of halogenation agent is used with respect to the metal dihydrocarbyloxy compound of formula (I), (la) or (Ib), i.e. a ratio of 2.0:1 to 4.0:1, more pre~erdbly of from 2.1:1 to 3:1.
_19_ WO 95119984 2 18 1~ 6 g PCT/US9~100882 The temperature at which the halogenation step is conducted is not critical, but is p,eferably below the boiling point of the diluent. Preferred temperatures range trom 0C to 100C, more pref erab Iy from 10C to 80C.
Generally the reactants are contacted under an inert atmosphere for a time from 5 several minutes to several days. The reactants can be added in any order. Agitation may be employed if desired.
In the present halogenation step an aprotic organic diluent is used. Preferably,diluents are used in which the cc.,.,~lcxes of formulas (I), (la), and (Ib) are readily soluble, optionally upon heating. Suitable exd",ples of such solvents are ethers and hydrocarbons.
10 P~ererablythesolventisailycllo~alLon~advantageouslyanaliphaticorcycloaliphatic hydrocarbon solvent having from 5 to 10 carbon atoms. Suitable solvents are pentane, hexane, heptane, Isopar E, isooctane, cyclohexane, and methylcyclohexane.
In general, isolation of the desired complexes can take place as required by thebyproducts. Removal of volatiles, such as the solvent, is prertrdbly carried out by vacuum distillation at elevated ter"perdlures. When silicon tetrachloride is used as halogenation agent the byproduct formed cc.",pri~es a hydrocarbyloxy silicon chloride. Byproducts containing lower alkyls in the hydrocarbyloxy portion, especially C1 4 alkyls, may be volatile. These volatile byproducts can be easily removed from the desired product by using vacuum distillation.
Highly pure products are generally obtained, as coi"pared to the prior art methods which 20 require extensive filtration and recrystallization steps.
The compounds prepared with the processes according to the present invention, that is the complexes of formulas (I), (la), (Ib), (Il), (lla), (llb), (Ill), (Illa) and (Illb) can be used as components of catalyst systems, or precursors ll,erefor, useful in addition polymerization processes.
In a process for preparing a polymer of one or more addition polymerizable monomers, a catalyst comprising a metal coordination complex of any of the above-mentioned formulas and an activating cocatalyst are contacted with one or more addition polymerizable monomers under addition polymerization conditions. Suitable activating cocatalysts are, for example, described in U.S. Patent Application Nos. 545,403, filed July 3,1990 (cc,r, e",onding to EP-A-0,416,815) and 817,202, filed January 6,1992 (correspond;ng to WO-A-92/10360), which are incorporated herein by reference. P~ efer,~d examples of activating cocatalysts include alumoxanes, advdhldgeously methylalumoxane, tris(perfluorophenyl) borane, and tetra(perfluorophenyl) borates.
Addition polymerizable monomers" include for example ethylenically 35 unsaturated monomers, conjugated or nonconj ugated dienes, polyenes, etc. P~ erer,ed monomers include the C2-10 a-olefins especially ethylene, propylene, isobutylene,1-butene,1 -hexene, 4-methyl-1-pentene, and 1-octene. Other preferred monomers include styrene, halo--or alkyl substituted styrene, vinylbenzocyclobutane, 1 ,~hexadiene, ethylidenenorbornene, cyclopentene, and norbornene.
Suitable catalysts for use according to the present invention are prepared by combining the metal coordination complex of formulas (I), (Il), or (Ill) and a.li~dling cocatalyst 5 compound in any order and in any suitable manner. ~ eferably the ratio of the coordination complex and cocatalyst on a molar basis is from about 1:0.1 to about 1:10,000. It will, of course, be appreciated that the catalyst system may also be formed in situ if the components thereof are added directly to the polymeri~dlion process and a suitable solvent or diluent, including .undensed ",ono",er, is used in said poly",e, iCd lion process. Suitable solvents 10 include toluene, ethylbenzene, alkanes and mixtures thereof. In certain cases the catalysts may be isolated from solution and retained under inert atmosphere prior to use. The catalysts' ccn"ponenl~ are sensitive to both moisture and oxygen and should be handled and lrd"~t~r~ ed in an inert dl",o~,here such as nitrogen, argon or helium or under vacuum.
The poly",eri~dlion is conducted according to known techniques for Ziegler-15 Natta or Kaminsky-Sinn type polymerizations. That is, the monomer(s) and catalyst are contacted at a te",perdt.lre from -30C to 250C, at reduced, elevated or atmospheric pressures.
The poly",eri~alion is conducted under an inert atmosphere which may be a blanketing gas such as nitrogen, argon, hydrogen, ethylene, etc. or under vacuum. I Iy.J~ ogen may additionally be utilized in the control of molecular weight through chain termination as is previously 20 known in the art. The catalyst may be used as is or SUIJpGl led on a suitable support such as alumina, MgCI2 or silica to provide a heterogeneous suppo, led catalyst. A solvent may be e" ,~ I Dyed if desired. Suitable solvents incl ude toluene, ethyll,enzene, alkanes and excess vinyl aromatic or olefin monomer. The reaction may also be conducted under solution or slurry conditions, in a suspension utilizing a perfluorinated hydrocarbon or similar liquid, in the gas 25 phase, i.e. utilizing a fluidized bed reactor, or in a solid phase powder poly",eri~alion. A
catalytically effective amount of the present catalyst and cocatalyst is any amount that successfully results in formation of polymer. Such amounts may be readily determined by the routine experimentation by the skilled artisan. P~ erer, ed amounts of catalyst and cocatalyst are sufficient to provide an equivalent ratio of addition poly",eri~dble monomer:catalyst of 30 from 1 x 1 olo: 1 to 100:1, preferably from 1 x 1 Os 1 to 500:1, most prete, ably 1 x 1 o6 1 to 1000:1.
The cocatalyst is generally utilized in an amount to provide an eq uivalent ratio of cocatalyst:catalystfrom 10,000:1 toO.1:1,preferablyfrom 1,000:1 to 1:1.
It is to be understood that the metal complex may undergo various l,dn,tur,,,ations or form inter",ediate species prior to and during the course of a 35 polymerization.
The resulting polymeric product is recovered by filtering or other suitable technique. Additives and adjuvants may be incorporated in the polymers of the present invention in order to provide desirable characteristics. Suitable additives include pigments, UV
-6Q~
WO 95/19984 PCT/US9~/00882 stabilizers, antioxidants, blowing agents, lubricants, plasticizers, photosensitizers, and mixtures thereof.
Having described the invention, the following examples are provided to further illustrate the same and are not to be construed as limiting.
5 Example 1: Preparation of (tert-butvlamido)dimethyl(tetramethvl-ns-cvclopentadienyl)silane titanium diisopropoxide In a drybox, 24.95 9 of titaniumtetraisopropoxide (Ti(OiPr)4) (Aldrich Chemical Company) (88 mmol) was dissolved in about 200 ml of hexane. 58 9 of solid di(chloromagnesium) (tert-butylamido)-dimethyl(tel~a~eLhylcy~loper~ladienyl)silane 10 complexed with dimethoxyethane, lMe4CsSiMe2NtBul[MgCII2(DME)n (effective molecular weight by titration: about 629 g/mole; 92 mmol)(prepared accor ';ng to the following procedure: In an apparatus consi,li,-g of a 3 I round bottom flask which was equipped with a stirrer, a condenser, and a nitrogen inlet was loaded 500 ml of toluene, followed by 106 9 of Me4C5HSiMe2NHtBu, and then 380 ml of 2.2 M iPrMgCI in EtzO. The mixture was then heated, 15 and the ether removed by distillation and trapped in a condenser cooled to -78C. After five hours of heating, the heater was turned off, and 450 ml of dimethoxyethane (DME) was slowly added to the hot, stirred solution, resulting in the precipitation of a white solid. The solution was allowed to cool to room temperature, the solid was allowed to settle, and the supernatant was cle.dnted from the solid. The solid was resuspended in Isopar E and filtered. 210 9 (79 20 percent yield) lMe4cssiMe2NtBul[Mgcl]2(DME)n was obtained as off-white solid.) was added to the flask, using about 50 ml of additional hexane. The mixture was stirred overnight at room temperature,thenfilteredthroughamediumporosityfrittedglassfilter(10-15l1mporosity).
The solids remaining on the frit were washed with additional hexane until the washings are colorless. A yellow/orange solution was obtained, and the volatile materials were removed 25 from this solution under reduced pressure to leave (Me4CsSiMe2N'Bu)Ti(OiPr)2 as a yellow crystalline solid in essentially quantitative yield. 1H NMR (C6D6): 4.57 ppm (septet, 2H),2.16 ppm (s, 6H),1.91 ppm (s,6H),1.37 ppm (s, 9H),1.15 ppm (d,12H), and 0.65 ppm (6H).
Example 2: Preparation of (tert-butvlamidoh'iul~ l(tetramethvl-ns-cv~lopenladienvl)silane titanium dichloride 3o A. In a drybox, 5.0 9 of (Me4CsSiMe2NtBu)Ti(OiPr)2 (12.0 mmol) was dissolved in about 50 ml of hexane. Silicon tetrachloride (Aldrich,99.999%,2.9 ml,25.3 mMol) was added by syringe. The color immediately darkened and a precipitate began to form. The reaction mixture was stirred overnight (about 18 hours). At the end of this time, the volatile materials were removed under reduced pressure to leave (Me4CsSiMeNtBu)TiCI2 as a yellow solid (4.35 9, 35 98% yield). The material was identified by comparison of its 1H NMR spectrum with spectra of the complex made by other routes. 1H NMR (4D6): 2.00 ppm (s, 6H),1.99 ppm (s, 6H),1.42 ppm (s,9H), 0.42 ppm (s, 6H).
-B. In a drybox,1.01 g of IMe4C5SiMe2N'Bu]Ti(OiPr)2 (2.43 mmol) was dissolved in 25 ml of hexane in a Schlenck tube. BCI3 (5.5 ml of a 1.0M solution in hexane) was added by syringe; the color became orange and the mixture turned cloudy. The mixture was stirred for three hours, then the volatile materials were removed under reduced pressure. The Schlenk - 5 tube was sealed and removed from the drybox to a Schlenk line, where it was heated to 70C
overnight under dynamic vacuum to remove the remaining volatile components. The next day, - the Schlenk tube was returned to the drybox, where 0.74 9 of orange/yellow powder was obtained (83%). The 1H NMR spectrum of this material indicated it to be l(Me4Cs)SiMe2NtBulTiCI2 by comparison with the spectrum described in Example 2A.10 C. In a drybox, 0.25 9 of l(Me4C5)SiMe2NtBulTi(OiPr)2 (0.60 mmol) was d;,solved in 20 ml of pentane. Et2AlCI (1.2 ml of a 1.0 M solution in hexane) was added by syringe, and the color darkened immediately. The mixture was stirred for one hour, then the volatile materials were removed under reduced pressure to leave an oily yellow solid. The material was slurried in 3 ml of pentane and filtered to leave a bright yellow solid on the filter; this solid was washed 15 with 2 ml of additional penldne and dried under vacuum. The 1H NMR spectrum of this material indicated it to be e~ e"~ely pure l(Me4c5)siMe2NtBulTicl2 by comparison with the spectrum described in Example 2A.
Example 3: Preparation of (tert-butylamido)dimethyl(tetramethyl-nS-cyclopentad ~nyl)silane titanium dimethyl 20 A. In a drybox, 0.26 9 of (Me4CsSiMe2NtBu)Ti(OiPr)2 (0.63 mMol) was dissolved in about 15 ml of hexane. Trimethylaluminum (Aldrich, 2M in hexane, O.g5 ml,1.9 mmol) was added by syringe. The sol ution was heated to gentle ref lux. After ove. n. ~' . t (about 18 hours) reflux, the solution turned brown. The volatile materials were then removed under reduced pressure to leave (Me4CsSiMe2NtBu)TiMe2 as a pale brown solid. The material was identified by 25 comparison of its 1 H NMR spectrum with spectra of the cor"plex made by other routes. 1 H NM R
(C6D6): 1.96 ppm (s, 6H),1.85 ppm (s,6H),1.56 ppm (s,9H), 0.51 ppm (s, 6H), 0.43 ppm (s,6H).
B. In a drybox, 0.255 9 of l(Me4C5)SiMe2NtBu]Ti(OiPr)2 (0.614 mmol) was dissolved in 20 ml of ether. Methyl lithium (1.75 ml of a 1.4M solution in ether) was added by syringe. The mixture was stirred overnight. At the end of this time, the solution was pale brown with a 30 lightly colored precipitate. The volatile materials were removed under reduced pressure to leave a pale solid. The residue was extracted with pentane (20 ml), filtered, and dried under vacuum to leave an off-white crystalline solid. The 1H NMR spectrum of this material indicated it to be primarily [(Me4C5)SiMe2NtBulTiMe2; small peaks from [(Me4C5)SiMe2NtBul(Me)OiPr and LiOiPr were also observed.
35 C. In a drybox,1.00 9 of [(Me4C5)SiMe2NtBu]Ti(OiPr)2 (2.41 mmol) was dissolved in 20 ml of hexane. Trimethyl aluminum (3.0 ml of a 2.0 M solution in hexane) was added by syringe;
the solution color darkened slightly. The mixture was heated to a gentle reflux with stirring overnight. At the end of this time, the solution was pale brown. The volatile materials were W O 95/19984 2 i ~ ~ 2 PCTAUS95/00882 removed under reduced pressure to leave an off-white crystalline solid (0.79 9,100%). The 1 H
NMR spectrum of this material indicated it to be extremely pure l(Me4C5)SiMe2NtB u1TiMe2 by comparison with the spectrum in described Example 3A.
Example 4: Preparation of (tert-butylamido)dimethyl(tetramethyle-r~5-cyclopen Lad;enyl) silane 5 titanium dibromide In a drybox, 4.75 9 of SiBr4 (13.7 mmol; Aldrich) was weighed into a 100 ml flask and dissolved in 25 ml of hexane. I(Me4Cs)SiMe2NtBu]Ti(OiPr)2 (2.25 9, 6.0 mmol) was added, using 10 ml of hexane to wash the material into the flask. The mixture was heated to reflux with stirring for four hours; the color changed to bright orange and the mixture became 10 cloudy. At the end of this time, the volatile materials were re,..ov~d under reduced pressure to leave a sticky orange solid. The material was slurried in a small volume of penLdne and filtered to leave a bright orange solid on the filter; this solid was dried under vacuum to give 1.2 9 of product (44% ). The 1 H NMR spectrum of this material indicated it to be (Me4C5)SiMe2NtBulTiBr2bycomparisonwithpreviousspectra. 1H NMR(C6D6,~): 2.10(2H),15 1.96 (2H),1.50 (3H), 0.40 (2H).
Claims (24)
1. A process for preparing a metal dihydrocarbyloxy coordination complex corresponding to the formula:
(I) wherein:
M is titanium,zirconium, or hafnium;
Cp* is a cyclopentadienyl group bound in an n5 bonding mode to M or such a cyclopentadienyl group substituted with from one to four substituents selected from the group consisting of hydrocarbyl, silyl, germyl, halo, hydroxycarbyloxy, cyano, amino, and mixtures thereof, said substituent having up to 20 nonhydrogen atoms, or optionally, two substituents together cause Cp* to have a fused ring structure;
Z is a divalent moiety comprising boron, or a member of Group 14 of the PeriodicTable of the Elements, and optionally sulfur or oxygen, said moiety having up to 50 non-hydrogen atoms, and optionally Cp* and Z together form a fused ring system;
Y is a) a divalent anionic ligand group comprising nitrogen, phosphorus, oxygen or sulfur and having up to 20 non-hydrogen atoms, said Y being bonded to Z and M through said nitrogen, phosphorus, oxygen or sulfur, and optionally Y and Z together form a fused ring system, or b) a cyclopentadienyl group bound in a sigma bonding mode to Z and in an n5 bonding mode to M or such a cyclopentadienyl group substituted with from one to four substituents selected from the group consisting of hydrocarbyl, silyl, germyl, halo, hydrocarbyloxy, cyano, amino, and mixtures thereof, said substituent having up to 20 nonhydrogen atoms, or optionally, two substituents together cause Y to have a fused ring structure; and R independently each occurrence is a hydrocarbyl group having from 1 to 20 carbon atoms; the steps of the process comprising:
contacting in the presence of an aprotic organic diluent a metal compound of theformula: M(OR)4 wherein M and R are as previously defined with a dianionic salt compound corresponding to the formula:
(L+x)y(Cp*-Z-Y)- or ((LX)+X)y(Cp*-Z-Y)-wherein:
L is a metal of Group 1 or 2 of the Periodic Table of the Elements, X independently is chloro, bromo, or iodo, x and y are either 1 or 2 and the product of x and y equals 2, and Cp*, Z, and Y are as previously defined;
to form the complex of formula (I).
(I) wherein:
M is titanium,zirconium, or hafnium;
Cp* is a cyclopentadienyl group bound in an n5 bonding mode to M or such a cyclopentadienyl group substituted with from one to four substituents selected from the group consisting of hydrocarbyl, silyl, germyl, halo, hydroxycarbyloxy, cyano, amino, and mixtures thereof, said substituent having up to 20 nonhydrogen atoms, or optionally, two substituents together cause Cp* to have a fused ring structure;
Z is a divalent moiety comprising boron, or a member of Group 14 of the PeriodicTable of the Elements, and optionally sulfur or oxygen, said moiety having up to 50 non-hydrogen atoms, and optionally Cp* and Z together form a fused ring system;
Y is a) a divalent anionic ligand group comprising nitrogen, phosphorus, oxygen or sulfur and having up to 20 non-hydrogen atoms, said Y being bonded to Z and M through said nitrogen, phosphorus, oxygen or sulfur, and optionally Y and Z together form a fused ring system, or b) a cyclopentadienyl group bound in a sigma bonding mode to Z and in an n5 bonding mode to M or such a cyclopentadienyl group substituted with from one to four substituents selected from the group consisting of hydrocarbyl, silyl, germyl, halo, hydrocarbyloxy, cyano, amino, and mixtures thereof, said substituent having up to 20 nonhydrogen atoms, or optionally, two substituents together cause Y to have a fused ring structure; and R independently each occurrence is a hydrocarbyl group having from 1 to 20 carbon atoms; the steps of the process comprising:
contacting in the presence of an aprotic organic diluent a metal compound of theformula: M(OR)4 wherein M and R are as previously defined with a dianionic salt compound corresponding to the formula:
(L+x)y(Cp*-Z-Y)- or ((LX)+X)y(Cp*-Z-Y)-wherein:
L is a metal of Group 1 or 2 of the Periodic Table of the Elements, X independently is chloro, bromo, or iodo, x and y are either 1 or 2 and the product of x and y equals 2, and Cp*, Z, and Y are as previously defined;
to form the complex of formula (I).
2. A process according to Claim 1 wherein the metal dihydrocarbyloxy coordination complex of formula (I) corresponds to the formula:
(Ia) wherein R' each occurrence is independently selected from the group consisting of hydrogen, silyl, alkyl, aryl, germyl, cyano, halo and combinations thereof having up to 20 non-hydrogen atoms, or two R' groups together form a divalent derivative thereof;
E is silicon or carbon;
m is 1 or 2; and M and R are as previously defined; and wherein the metal compound of the formula: M(OR)4 is contacted with a dianionic salt compound corresponding to the formula:
(L+x)y(C5R'4-(ER'2)m-NR')- or ((LX)+x)y(C5R'4-(ER'2)m-NR')-wherein L, R', E, X, x, y, and m are as previously defined.
(Ia) wherein R' each occurrence is independently selected from the group consisting of hydrogen, silyl, alkyl, aryl, germyl, cyano, halo and combinations thereof having up to 20 non-hydrogen atoms, or two R' groups together form a divalent derivative thereof;
E is silicon or carbon;
m is 1 or 2; and M and R are as previously defined; and wherein the metal compound of the formula: M(OR)4 is contacted with a dianionic salt compound corresponding to the formula:
(L+x)y(C5R'4-(ER'2)m-NR')- or ((LX)+x)y(C5R'4-(ER'2)m-NR')-wherein L, R', E, X, x, y, and m are as previously defined.
3. A process according to Claim 1 wherein R each occurrence is independently selected from the group consisting of ethyl, isopropyl, n-butyl, and t-butyl.
4. A process according to Claim 1 wherein the metal compound of the formula: M(OR)4 is selected from the group consisting of tetra(ethoxy)titanium, tetra(isopropoxy) titanium, tetra(n-butoxy) titanium.
5. A process according to Claim 1 wherein the dianionic salt compound corresponds to the formula: ((MgCl)+)2(Cp*-Z-Y)-, or (Li+)2(Cp*-Z-Y)-, wherein Cp*,Z, and Y
are as previously defined.
are as previously defined.
6. A process according to Claim 1 wherein the aprotic organic diluent is analiphatic or cycloaliphatic hydrocarbon solvent having from 5 to 10 carbon atoms.
7. A process according to Claim 1 wherein the process is conducted at a temperature between 0°C and 100°C.
8. A process for preparing a metal dihydrocarbyl coordination complex corresponding to the formula:
(II) wherein:
M is titanium, zirconium, or hafnium;
Cp* is a cyclopentadienyl group bound in an n5 bonding mode to M or such a cyclopentadienyl group substituted with from one to four substituents selected from the group consisting of hydrocarbyl, silyl, germyl, halo, hydrocarbyloxy, cyano, amino, and mixtures thereof, said substituent having up to 20 nonhydrogen atoms, or optionally, two substituents together cause Cp* to have a fused ring structure;
Z is a divalent moiety comprising boron, or a member of Group 14 of the PeriodicTable of the Elements, and optionally sulfur or oxygen, said moiety having up to 50 non-hydrogen atoms, and optionally Cp* and Z together form a fused ring system;
Y is a) a divalent anionic ligand group comprising nitrogen, phosphorus, oxygen or sulfur and having up to 20 non-hydrogen atoms, said Y being bonded to Z and M through said nitrogen, phosphorus, oxygen or sulfur, and optionally Y and Z together form a fused ring system, or b) a cyclopentadienyl group bound in a sigma bonding mode to Z and in an n5 bonding mode to M or such a cyclopentadienyl group substituted with from one to four substituents selected from the group consisting of hydrocarbyl, silyl, germyl, halo, hydrocarbyloxy, amino, and mixtures thereof, said substituent having up to 20 nonhydrogen atoms, or optionally, two substituents together cause Y to have a fused ring structure; and R"' independenlly each occurrence is a hydrocarbyl group, containing from 1 to 20 carbon atoms;
the process comprising contacting in the presence of an aprotic organic diluent a metal coordination complex of formula:
(I) wherein R independently each occurrence is a hydrocarbyl group having from 1 to 20 carbon atoms and Cp*, Z, Y, M, are as previously defined;
with a hydrocarbylation agent comprising a group 1, 2, 12 or 13 metal or metal derivative and at least one hydrocarbyl group R"', to form the metal dihydrocarbyl coordination complex of formula (II).
(II) wherein:
M is titanium, zirconium, or hafnium;
Cp* is a cyclopentadienyl group bound in an n5 bonding mode to M or such a cyclopentadienyl group substituted with from one to four substituents selected from the group consisting of hydrocarbyl, silyl, germyl, halo, hydrocarbyloxy, cyano, amino, and mixtures thereof, said substituent having up to 20 nonhydrogen atoms, or optionally, two substituents together cause Cp* to have a fused ring structure;
Z is a divalent moiety comprising boron, or a member of Group 14 of the PeriodicTable of the Elements, and optionally sulfur or oxygen, said moiety having up to 50 non-hydrogen atoms, and optionally Cp* and Z together form a fused ring system;
Y is a) a divalent anionic ligand group comprising nitrogen, phosphorus, oxygen or sulfur and having up to 20 non-hydrogen atoms, said Y being bonded to Z and M through said nitrogen, phosphorus, oxygen or sulfur, and optionally Y and Z together form a fused ring system, or b) a cyclopentadienyl group bound in a sigma bonding mode to Z and in an n5 bonding mode to M or such a cyclopentadienyl group substituted with from one to four substituents selected from the group consisting of hydrocarbyl, silyl, germyl, halo, hydrocarbyloxy, amino, and mixtures thereof, said substituent having up to 20 nonhydrogen atoms, or optionally, two substituents together cause Y to have a fused ring structure; and R"' independenlly each occurrence is a hydrocarbyl group, containing from 1 to 20 carbon atoms;
the process comprising contacting in the presence of an aprotic organic diluent a metal coordination complex of formula:
(I) wherein R independently each occurrence is a hydrocarbyl group having from 1 to 20 carbon atoms and Cp*, Z, Y, M, are as previously defined;
with a hydrocarbylation agent comprising a group 1, 2, 12 or 13 metal or metal derivative and at least one hydrocarbyl group R"', to form the metal dihydrocarbyl coordination complex of formula (II).
9. A process according to Claim 8 wherein a metal dihydrocarbyl coordination complex corresponding to the formula:
(IIa) wherein R' each occurrence is independently selected from the group consisting of hydrogen, silyl, alkyl, aryl, germyl, cyano, halo and combinations thereof having up to 20 non-hydrogen atoms, or two R' groups together form a divalent derivative thereof;
E is silicon or carbon;
m is 1 or 2; and M and R"' are as previously defined;
is prepared by contacting a metal dihydrocarbyloxy coordination complex corresponding to the formula:
(Ia) wherein: M, R', E, R, and m are as previously defined;
with the hydrocarbylation agent.
(IIa) wherein R' each occurrence is independently selected from the group consisting of hydrogen, silyl, alkyl, aryl, germyl, cyano, halo and combinations thereof having up to 20 non-hydrogen atoms, or two R' groups together form a divalent derivative thereof;
E is silicon or carbon;
m is 1 or 2; and M and R"' are as previously defined;
is prepared by contacting a metal dihydrocarbyloxy coordination complex corresponding to the formula:
(Ia) wherein: M, R', E, R, and m are as previously defined;
with the hydrocarbylation agent.
10. A process according to Claim 8 wherein the metal coordination complex corresponding to formula (I) is prepared by contacting in the presence of an aprotic organic diluent a metal compound of the formula: M(OR)4 wherein M and R are as previously defined with a dianionic salt compound corresponding to the formula:
(L+x)y(Cp*-Z-Y)-2 or ((LX)+x)y(Cp*-Z-Y)-2 wherein:
L is a metal of Group 1 or 2 of the Periodic Table of the Elements, X independently is chloro, bromo, or iodo, x and y are either 1 or 2 and the product of x and y equals 2, and Cp*, Z, and Y are as previously defined;
optionally followed by recovering the complex corresponding to formula (I).
(L+x)y(Cp*-Z-Y)-2 or ((LX)+x)y(Cp*-Z-Y)-2 wherein:
L is a metal of Group 1 or 2 of the Periodic Table of the Elements, X independently is chloro, bromo, or iodo, x and y are either 1 or 2 and the product of x and y equals 2, and Cp*, Z, and Y are as previously defined;
optionally followed by recovering the complex corresponding to formula (I).
11. A process according to Claim 8 wherein R each occurrence is independently selected from the group consisting of ethyl, isopropyl, n-butyl, and t-butyl.
12. A process according to Claim 8 wherein R"' is a methyl, benzyl, or neopentyl group.
13. A process according to Claim 8 wherein the hydrocarbylation agent is selected from the group consisting of R"'Li,R"'2Mg, R"'MgX", R"'3AI, and R"'-substituted aluminoxanes, wherein X" is halogen.
14. A process according to Claim 13 wherein the hydrocarbylation agent is trimethylaluminum.
15. A process according to Claim 8 wherein the aprotic organic diluent comprises an aliphatic or cycloaliphatic hydrocarbon solvent having from 5 to 10 carbon atoms.
16. A process according to Claim 8 wherein the process is conducted at a temperature between 0 and 100°C.
17. A process for preparing a metal dihalide coordination complex corresponding to the formula:
(III) wherein:
M is titanium, zirconium, or hafnium;
Cp* is a cyclopentadienyl group bound in an n5 bonding mode to M or such a cyclopehtadienyl group substituted with from one to four substituents selected from the group consisting of hydrocarbyl, silyl, germyl, halo, hydrocarbyloxy, cyano, amino, and mixtures thereof, said substituent having up to 20 nonhydrogen atoms, or optionally, two substituents together cause Cp* to have a fused ring structure;
Z is a divalent moiety comprising boron, or a member of Group 14 of the PeriodicTable of the Elements, and optionally sulfur or oxygen, said moiety having up to 50 non-hydrogen atoms, and optionally Cp* and Z together form a fused ring system;
Y is a) a divalent anionic ligand group comprising nitrogen, phosphorus, oxygen or sulfur and having up to 20 non-hydrogen atoms, said Y being bonded to Z and M through said nitrogen, phosphorus, oxygen or sulfur, and optionally Y and Z together form a fused ring system, or b) a cyclopentadienyl group bound in a sigma bonding mode to Z and in an n5 bonding mode to M or such a cyclopentadienyl group substituted with from one to four substituents selected from the group consisting of hydrocarbyl, silyl, germyl, halo, hydrocarbyloxy, amino, and mixtures thereof, said substituent having up to 20 nonhydrogen atoms, or optionally, two substituents together cause Y to have a fused ring structure; and X' independently each occurrence is a halo group;
the process comprising contacting in the presence of an aprotic organic diluent a metal coordination complex of formula:
(I) wherein R independently each occurrence is a hydrocarbyl group having from 1 to 20 carbon atoms and Cp*, Z, Y, M, are as previously defined;
with a halogenation agent comprising at least a member of Group 13 or 14 of the Periodic Table of the Elements and at least one halo group X', to form the metal dihalide coordination complex of formula (III).
(III) wherein:
M is titanium, zirconium, or hafnium;
Cp* is a cyclopentadienyl group bound in an n5 bonding mode to M or such a cyclopehtadienyl group substituted with from one to four substituents selected from the group consisting of hydrocarbyl, silyl, germyl, halo, hydrocarbyloxy, cyano, amino, and mixtures thereof, said substituent having up to 20 nonhydrogen atoms, or optionally, two substituents together cause Cp* to have a fused ring structure;
Z is a divalent moiety comprising boron, or a member of Group 14 of the PeriodicTable of the Elements, and optionally sulfur or oxygen, said moiety having up to 50 non-hydrogen atoms, and optionally Cp* and Z together form a fused ring system;
Y is a) a divalent anionic ligand group comprising nitrogen, phosphorus, oxygen or sulfur and having up to 20 non-hydrogen atoms, said Y being bonded to Z and M through said nitrogen, phosphorus, oxygen or sulfur, and optionally Y and Z together form a fused ring system, or b) a cyclopentadienyl group bound in a sigma bonding mode to Z and in an n5 bonding mode to M or such a cyclopentadienyl group substituted with from one to four substituents selected from the group consisting of hydrocarbyl, silyl, germyl, halo, hydrocarbyloxy, amino, and mixtures thereof, said substituent having up to 20 nonhydrogen atoms, or optionally, two substituents together cause Y to have a fused ring structure; and X' independently each occurrence is a halo group;
the process comprising contacting in the presence of an aprotic organic diluent a metal coordination complex of formula:
(I) wherein R independently each occurrence is a hydrocarbyl group having from 1 to 20 carbon atoms and Cp*, Z, Y, M, are as previously defined;
with a halogenation agent comprising at least a member of Group 13 or 14 of the Periodic Table of the Elements and at least one halo group X', to form the metal dihalide coordination complex of formula (III).
18. A process according to Claim 17 wherein a metal dihalide coordination complex corresponding to the formula:
(IIIa) wherein R' each occurrence is independently selected from the group consisting of hydrogen, silyl, alkyl, aryl, germyl, cyano, halo and combinations thereof having up to 20 non-hydrogen atoms, or two R' groups together form a divalent derivative thereof;
E is silicon or carbon;
m is 1 or 2; and M and X' are as previously defined;
is prepared by contacting a metal dihydrocarbyloxy coordination complex corresponding to the formula:
(Ia) wherein: M, R', E, R, and m are as previously defined;
with the halogenation agent.
(IIIa) wherein R' each occurrence is independently selected from the group consisting of hydrogen, silyl, alkyl, aryl, germyl, cyano, halo and combinations thereof having up to 20 non-hydrogen atoms, or two R' groups together form a divalent derivative thereof;
E is silicon or carbon;
m is 1 or 2; and M and X' are as previously defined;
is prepared by contacting a metal dihydrocarbyloxy coordination complex corresponding to the formula:
(Ia) wherein: M, R', E, R, and m are as previously defined;
with the halogenation agent.
19. A process according to Claim 17 wherein the metal coordination complex corresponding to formula (I) is prepared by contacting in the presence of an aprotic organic diluent a metal compound of the formula: M(OR)4 wherein M and R are as previously defined with a dianionic salt compound corresponding to the formula:
(L+x)y(Cp* Z-Y)- or ((LX)+X)y(Cp*-Z-Y)-wherein:
L is a metal of Group 1 or 2 of the Periodic Table of the Elements, X independently is chloro, bromo, or iodo, x and y are either 1 or 2 and the product of x and y equals 2, and Cp*, Z, and Y are as previously defined;
optionally followed by recovering the complex corresponding to formula (I).
(L+x)y(Cp* Z-Y)- or ((LX)+X)y(Cp*-Z-Y)-wherein:
L is a metal of Group 1 or 2 of the Periodic Table of the Elements, X independently is chloro, bromo, or iodo, x and y are either 1 or 2 and the product of x and y equals 2, and Cp*, Z, and Y are as previously defined;
optionally followed by recovering the complex corresponding to formula (I).
20. A process according to Claim 17 wherein R each occurrence is independently selected from the group consisting of ethyl, isopropyl, n-butyl, and t-butyl.
21. A process according to Claim 17 wherein X' is chloro.
22. A process according to Claim 17 wherein the halogenation agent is selectedfrom the group consisting of silicon chlorides, boron chlorides and alkyl aluminum chlorides.
23. A process according to Claim 17 wherein the aprotic organic diluent comprises an aliphatic or cycloaliphatic hydrocarbon solvent having from 5 to 10 carbon atoms.
24. A process according to Claim 17 wherein the process is conducted at a temperature of between 0°C and 100°C.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US08/186,402 | 1994-01-25 | ||
| US08/186,402 US5504223A (en) | 1994-01-25 | 1994-01-25 | Synthesis of cyclopentadienyl metal coordination complexes from metal hydrocarbyloxides |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2181268A1 true CA2181268A1 (en) | 1995-07-27 |
Family
ID=22684809
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002181268A Abandoned CA2181268A1 (en) | 1994-01-25 | 1995-01-23 | Synthesis of cyclopentadienyl metal coordination complexes from metal hydrocarbyloxides |
Country Status (8)
| Country | Link |
|---|---|
| US (2) | US5504223A (en) |
| EP (1) | EP0741739B1 (en) |
| JP (1) | JPH09509149A (en) |
| CA (1) | CA2181268A1 (en) |
| DE (1) | DE69505642T2 (en) |
| ES (1) | ES2122563T3 (en) |
| FI (1) | FI962959A0 (en) |
| WO (1) | WO1995019984A2 (en) |
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| IT1272923B (en) * | 1995-01-23 | 1997-07-01 | Spherilene Srl | METALLOCENIC COMPOUNDS, PROCEDURE FOR THEIR PREPARATION, AND THEIR USE IN CATALYSTS FOR THE POLYMERIZATION OF OLEFINS |
| IT1275856B1 (en) * | 1995-03-03 | 1997-10-24 | Spherilene Srl | BIS-FLUORENYL METALLOCENE COMPOUNDS, PROCEDURE FOR THEIR PREPARATION AND THEIR USE IN CATALYSTS FOR POLYMERIZATION |
| JPH1112289A (en) * | 1997-06-19 | 1999-01-19 | Sumitomo Chem Co Ltd | Production of crosslinking-type transition metal complex |
| DE69935815T2 (en) | 1998-07-01 | 2007-12-27 | Exxonmobil Chemical Patents Inc., Baytown | Elastic mixture with crystal polymers and crystallizable polymers of propene |
| US6090961A (en) * | 1998-07-09 | 2000-07-18 | Sumitomo Chemical Company, Limited | Method for producing titanium complex |
| US6087290A (en) * | 1999-01-19 | 2000-07-11 | Hughes Electronics Corporation | Si-N-Si-bridged metallocenes, their production and use |
| WO2000075151A1 (en) * | 1999-06-04 | 2000-12-14 | Basell Technology Company B.V. | Process for the preparation of titanium complexes |
| US6239062B1 (en) | 1999-09-02 | 2001-05-29 | Equistar Chemicals, L.P. | Olefin polymerization catalysts containing indolyl-amido ligands |
| BR0111317A (en) * | 2000-05-31 | 2003-06-10 | Basell Polyolefine Gmbh | Process for preparing compounds, compost, catalyst system, and uses of a compound and catalyst system |
| EP1390417B1 (en) | 2001-04-12 | 2010-10-20 | ExxonMobil Chemical Patents Inc. | Process for polymerizing propylene and ethylene in solution |
| US6960635B2 (en) * | 2001-11-06 | 2005-11-01 | Dow Global Technologies Inc. | Isotactic propylene copolymers, their preparation and use |
| US6943215B2 (en) | 2001-11-06 | 2005-09-13 | Dow Global Technologies Inc. | Impact resistant polymer blends of crystalline polypropylene and partially crystalline, low molecular weight impact modifiers |
| SG147306A1 (en) * | 2001-11-06 | 2008-11-28 | Dow Global Technologies Inc | Isotactic propylene copolymers, their preparation and use |
| US6906160B2 (en) * | 2001-11-06 | 2005-06-14 | Dow Global Technologies Inc. | Isotactic propylene copolymer fibers, their preparation and use |
| US6927256B2 (en) | 2001-11-06 | 2005-08-09 | Dow Global Technologies Inc. | Crystallization of polypropylene using a semi-crystalline, branched or coupled nucleating agent |
| US6590114B2 (en) * | 2001-11-09 | 2003-07-08 | Boulder Scientific Company | Conversion of cyclopentadienyl silyl amines to organometallic complexes comprising titanium bisalkoxy moiety or titanium dichloride moiety |
| US6452031B1 (en) * | 2001-11-21 | 2002-09-17 | Boulder Scientific Company | Preparation of titanium organometallic complexes comprising a titanium bisalkoxide or dihalide moiety |
| US7169489B2 (en) * | 2002-03-15 | 2007-01-30 | Fuelsell Technologies, Inc. | Hydrogen storage, distribution, and recovery system |
| AU2003299143A1 (en) * | 2002-10-02 | 2004-04-23 | Dow Global Technologies Inc. | Liquid and gel-like low molecular weight ethylene polymers |
| US20040065171A1 (en) * | 2002-10-02 | 2004-04-08 | Hearley Andrew K. | Soild-state hydrogen storage systems |
| BR0314562B1 (en) * | 2002-10-17 | 2013-11-19 | Polymeric composition. | |
| US7579407B2 (en) | 2002-11-05 | 2009-08-25 | Dow Global Technologies Inc. | Thermoplastic elastomer compositions |
| US7459500B2 (en) | 2002-11-05 | 2008-12-02 | Dow Global Technologies Inc. | Thermoplastic elastomer compositions |
| RU2335504C2 (en) | 2003-05-08 | 2008-10-10 | Базелль Полиолефине Гмбх | Method of obtaining metallocene halogenide compounds |
| JP5237553B2 (en) | 2003-08-19 | 2013-07-17 | ダウ グローバル テクノロジーズ エルエルシー | Interpolymers suitable for use in hot melt adhesives and methods for their production |
| EP1805229A1 (en) | 2004-10-28 | 2007-07-11 | Dow Gloval Technologies Inc. | Method of controlling a polymerization reactor |
Family Cites Families (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5158920A (en) * | 1988-07-15 | 1992-10-27 | Fina Technology, Inc. | Process for producing stereospecific polymers |
| NZ235032A (en) * | 1989-08-31 | 1993-04-28 | Dow Chemical Co | Constrained geometry complexes of titanium, zirconium or hafnium comprising a substituted cyclopentadiene ligand; use as olefin polymerisation catalyst component |
| US5026798A (en) * | 1989-09-13 | 1991-06-25 | Exxon Chemical Patents Inc. | Process for producing crystalline poly-α-olefins with a monocyclopentadienyl transition metal catalyst system |
| US5064802A (en) * | 1989-09-14 | 1991-11-12 | The Dow Chemical Company | Metal complex compounds |
| ES2079330T5 (en) * | 1990-06-22 | 2005-10-01 | Exxonmobil Chemical Patents Inc. | METALOCENE CATALYZERS OF ALUMINUM-FREE MONOCICLOPENTADIENYL FOR THE POLYMERIZATION OF OLEFINS. |
| JP2545006B2 (en) * | 1990-07-03 | 1996-10-16 | ザ ダウ ケミカル カンパニー | Addition polymerization catalyst |
| JP2931642B2 (en) * | 1990-07-12 | 1999-08-09 | 出光興産株式会社 | Method for producing styrenic polymer and its catalyst |
| SE9004006L (en) * | 1990-12-14 | 1992-01-20 | Volvo Ab | DEVICE FOR TRANSFER OF THE WORK PIECE FROM A MACHINE TO ANOTHER, PRIOR TO PRESSURE |
| JP3275211B2 (en) * | 1991-05-20 | 2002-04-15 | ザ ダウ ケミカル カンパニー | Method for producing addition polymerization catalyst |
| NL9101502A (en) * | 1991-09-06 | 1993-04-01 | Dsm Nv | A METHOD FOR PREPARING A BRIDGED METALLOCENE COMPOUND, A CATALYST COMPONENT AND A METHOD FOR THE POLYMERIZATION OF OLEFINS. |
-
1994
- 1994-01-25 US US08/186,402 patent/US5504223A/en not_active Expired - Fee Related
-
1995
- 1995-01-23 CA CA002181268A patent/CA2181268A1/en not_active Abandoned
- 1995-01-23 WO PCT/US1995/000882 patent/WO1995019984A2/en active IP Right Grant
- 1995-01-23 EP EP95910875A patent/EP0741739B1/en not_active Expired - Lifetime
- 1995-01-23 DE DE69505642T patent/DE69505642T2/en not_active Expired - Fee Related
- 1995-01-23 ES ES95910875T patent/ES2122563T3/en not_active Expired - Lifetime
- 1995-01-23 JP JP7519710A patent/JPH09509149A/en not_active Ceased
- 1995-06-06 US US08/469,185 patent/US5703257A/en not_active Expired - Fee Related
-
1996
- 1996-07-24 FI FI962959A patent/FI962959A0/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| US5504223A (en) | 1996-04-02 |
| EP0741739B1 (en) | 1998-10-28 |
| DE69505642D1 (en) | 1998-12-03 |
| JPH09509149A (en) | 1997-09-16 |
| WO1995019984A2 (en) | 1995-07-27 |
| FI962959A (en) | 1996-07-24 |
| ES2122563T3 (en) | 1998-12-16 |
| MX9602890A (en) | 1997-12-31 |
| WO1995019984A3 (en) | 1995-12-28 |
| US5703257A (en) | 1997-12-30 |
| EP0741739A1 (en) | 1996-11-13 |
| DE69505642T2 (en) | 1999-06-17 |
| FI962959A0 (en) | 1996-07-24 |
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