CN1278265A - 制备富烯金属配合物的方法 - Google Patents
制备富烯金属配合物的方法 Download PDFInfo
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- CN1278265A CN1278265A CN98810873.9A CN98810873A CN1278265A CN 1278265 A CN1278265 A CN 1278265A CN 98810873 A CN98810873 A CN 98810873A CN 1278265 A CN1278265 A CN 1278265A
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- formula
- fulvene
- metal
- alkyl
- fluvene
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- 229910052751 metal Inorganic materials 0.000 title claims abstract description 37
- 239000002184 metal Substances 0.000 title claims abstract description 37
- 238000000034 method Methods 0.000 title claims description 21
- 239000003054 catalyst Substances 0.000 claims abstract description 16
- 150000001875 compounds Chemical class 0.000 claims abstract description 15
- 150000001993 dienes Chemical class 0.000 claims abstract description 7
- 150000001336 alkenes Chemical class 0.000 claims abstract description 6
- -1 Silyl Chemical group 0.000 claims description 55
- 238000006243 chemical reaction Methods 0.000 claims description 27
- 238000006116 polymerization reaction Methods 0.000 claims description 23
- 229910052739 hydrogen Inorganic materials 0.000 claims description 22
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical group [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 15
- 239000010936 titanium Substances 0.000 claims description 15
- 229910052719 titanium Inorganic materials 0.000 claims description 15
- 125000000217 alkyl group Chemical group 0.000 claims description 12
- 238000002360 preparation method Methods 0.000 claims description 11
- 239000003795 chemical substances by application Substances 0.000 claims description 10
- 230000002829 reductive effect Effects 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 9
- 239000001257 hydrogen Substances 0.000 claims description 8
- 150000002736 metal compounds Chemical class 0.000 claims description 8
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 7
- 239000003426 co-catalyst Substances 0.000 claims description 7
- 229910052735 hafnium Inorganic materials 0.000 claims description 7
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 claims description 7
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 7
- 229910052726 zirconium Inorganic materials 0.000 claims description 7
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 6
- 229910052804 chromium Inorganic materials 0.000 claims description 6
- 239000011651 chromium Substances 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 125000002097 pentamethylcyclopentadienyl group Chemical group 0.000 claims description 6
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 5
- 239000003446 ligand Substances 0.000 claims description 5
- 229910052758 niobium Inorganic materials 0.000 claims description 5
- 239000010955 niobium Substances 0.000 claims description 5
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 5
- 229910052715 tantalum Inorganic materials 0.000 claims description 5
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims description 5
- 229910052720 vanadium Inorganic materials 0.000 claims description 5
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 claims description 5
- 125000006374 C2-C10 alkenyl group Chemical group 0.000 claims description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 4
- 125000004429 atom Chemical group 0.000 claims description 4
- 229910052744 lithium Inorganic materials 0.000 claims description 4
- 125000001181 organosilyl group Chemical group [SiH3]* 0.000 claims description 4
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 4
- 239000012429 reaction media Substances 0.000 claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- 125000001931 aliphatic group Chemical group 0.000 claims description 3
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 3
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 3
- 150000001450 anions Chemical class 0.000 claims description 3
- 229910052728 basic metal Inorganic materials 0.000 claims description 3
- 150000003818 basic metals Chemical class 0.000 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- 230000003647 oxidation Effects 0.000 claims description 3
- 238000007254 oxidation reaction Methods 0.000 claims description 3
- 125000005865 C2-C10alkynyl group Chemical group 0.000 claims description 2
- 150000001257 actinium Chemical class 0.000 claims description 2
- 125000003118 aryl group Chemical group 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 2
- 125000004122 cyclic group Chemical group 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 125000005843 halogen group Chemical group 0.000 claims description 2
- 150000002367 halogens Chemical class 0.000 claims description 2
- 125000005842 heteroatom Chemical group 0.000 claims description 2
- 229910052747 lanthanoid Inorganic materials 0.000 claims description 2
- 150000002602 lanthanoids Chemical class 0.000 claims description 2
- 230000007935 neutral effect Effects 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 230000000737 periodic effect Effects 0.000 claims description 2
- 229910052717 sulfur Inorganic materials 0.000 claims description 2
- 125000000101 thioether group Chemical group 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims 1
- PGTKVMVZBBZCKQ-UHFFFAOYSA-N Fulvene Chemical compound C=C1C=CC=C1 PGTKVMVZBBZCKQ-UHFFFAOYSA-N 0.000 abstract description 35
- 238000004519 manufacturing process Methods 0.000 abstract 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 51
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 40
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 37
- 239000011777 magnesium Substances 0.000 description 37
- 229910052749 magnesium Inorganic materials 0.000 description 36
- 239000000203 mixture Substances 0.000 description 24
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 18
- 239000007787 solid Substances 0.000 description 18
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 16
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 14
- 238000001914 filtration Methods 0.000 description 13
- 125000000538 pentafluorophenyl group Chemical group FC1=C(F)C(F)=C(*)C(F)=C1F 0.000 description 13
- 238000013329 compounding Methods 0.000 description 12
- 239000004615 ingredient Substances 0.000 description 12
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 11
- 238000005160 1H NMR spectroscopy Methods 0.000 description 11
- 229910007926 ZrCl Inorganic materials 0.000 description 9
- WXACXMWYHXOSIX-UHFFFAOYSA-N 5-propan-2-ylidenecyclopenta-1,3-diene Chemical compound CC(C)=C1C=CC=C1 WXACXMWYHXOSIX-UHFFFAOYSA-N 0.000 description 8
- 239000007789 gas Substances 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 8
- 238000002425 crystallisation Methods 0.000 description 7
- 230000008025 crystallization Effects 0.000 description 7
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical group C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 6
- RYLMKTLFCIGRQD-UHFFFAOYSA-N 2,3,4,5-tetramethylfulvene Chemical compound CC1=C(C)C(=C)C(C)=C1C RYLMKTLFCIGRQD-UHFFFAOYSA-N 0.000 description 5
- 229910052782 aluminium Inorganic materials 0.000 description 5
- 239000002585 base Substances 0.000 description 5
- 239000012141 concentrate Substances 0.000 description 5
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 5
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 5
- 238000001149 thermolysis Methods 0.000 description 5
- IPRROFRGPQGDOX-UHFFFAOYSA-K 1,2,3,4,5-pentamethylcyclopenta-1,3-diene;trichlorotitanium Chemical group Cl[Ti](Cl)Cl.CC=1C(C)=C(C)[C-](C)C=1C IPRROFRGPQGDOX-UHFFFAOYSA-K 0.000 description 4
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 4
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 4
- 150000004645 aluminates Chemical class 0.000 description 4
- 239000004411 aluminium Substances 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000007334 copolymerization reaction Methods 0.000 description 4
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 description 4
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 4
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 150000001399 aluminium compounds Chemical class 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 3
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 3
- 239000004327 boric acid Substances 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- AFABGHUZZDYHJO-UHFFFAOYSA-N dimethyl butane Natural products CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 3
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 238000003672 processing method Methods 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- 229910052723 transition metal Inorganic materials 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
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Natural products C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- 239000007818 Grignard reagent Substances 0.000 description 2
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
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- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 2
- 229910052796 boron Inorganic materials 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 description 2
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- LPIQUOYDBNQMRZ-UHFFFAOYSA-N cyclopentene Chemical compound C1CC=CC1 LPIQUOYDBNQMRZ-UHFFFAOYSA-N 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 125000003250 fulvenyl group Chemical group C1(=CC=CC1=C)* 0.000 description 2
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- QWTDNUCVQCZILF-UHFFFAOYSA-N isopentane Chemical compound CCC(C)C QWTDNUCVQCZILF-UHFFFAOYSA-N 0.000 description 2
- 238000001819 mass spectrum Methods 0.000 description 2
- 229910052987 metal hydride Inorganic materials 0.000 description 2
- 150000004681 metal hydrides Chemical class 0.000 description 2
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 2
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- 125000002221 trityl group Chemical group [H]C1=C([H])C([H])=C([H])C([H])=C1C([*])(C1=C(C(=C(C(=C1[H])[H])[H])[H])[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 2
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- 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
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- NSIKFNOYIGGILA-UHFFFAOYSA-N [Na].[Na].[K] Chemical compound [Na].[Na].[K] NSIKFNOYIGGILA-UHFFFAOYSA-N 0.000 description 1
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- RUMPJKFMCQWQCW-UHFFFAOYSA-N [Zr].C1(=CC=CC=C1)C1=CC=CC=C1 Chemical compound [Zr].C1(=CC=CC=C1)C1=CC=CC=C1 RUMPJKFMCQWQCW-UHFFFAOYSA-N 0.000 description 1
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- 230000029936 alkylation Effects 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical compound [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910000085 borane Inorganic materials 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 238000001460 carbon-13 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 239000012876 carrier material Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 150000004292 cyclic ethers Chemical class 0.000 description 1
- 150000001925 cycloalkenes Chemical class 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- URYYVOIYTNXXBN-UPHRSURJSA-N cyclooctene Chemical compound C1CCC\C=C/CC1 URYYVOIYTNXXBN-UPHRSURJSA-N 0.000 description 1
- 239000004913 cyclooctene Substances 0.000 description 1
- MIODROMBEUMZIF-UHFFFAOYSA-N cyclopenta-2,4-dien-1-ylidenecyclohexane Chemical compound C1CCCCC1=C1C=CC=C1 MIODROMBEUMZIF-UHFFFAOYSA-N 0.000 description 1
- IGSGWPUSCLPKER-UHFFFAOYSA-N cyclopenta-2,4-dien-1-ylidenemethylbenzene Chemical group C=1C=CC=CC=1C=C1C=CC=C1 IGSGWPUSCLPKER-UHFFFAOYSA-N 0.000 description 1
- JZLAYHCMSHSZKE-UHFFFAOYSA-N cyclopenta-2,4-dien-1-ylidenemethylcyclohexane Chemical compound C1CCCCC1C=C1C=CC=C1 JZLAYHCMSHSZKE-UHFFFAOYSA-N 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- PBGGNZZGJIKBMJ-UHFFFAOYSA-N di(propan-2-yl)azanide Chemical compound CC(C)[N-]C(C)C PBGGNZZGJIKBMJ-UHFFFAOYSA-N 0.000 description 1
- 150000001983 dialkylethers Chemical class 0.000 description 1
- 229910000071 diazene Inorganic materials 0.000 description 1
- YNLAOSYQHBDIKW-UHFFFAOYSA-M diethylaluminium chloride Chemical compound CC[Al](Cl)CC YNLAOSYQHBDIKW-UHFFFAOYSA-M 0.000 description 1
- UZBQIPPOMKBLAS-UHFFFAOYSA-N diethylazanide Chemical compound CC[N-]CC UZBQIPPOMKBLAS-UHFFFAOYSA-N 0.000 description 1
- SIPUZPBQZHNSDW-UHFFFAOYSA-N diisobutylaluminium hydride Substances CC(C)C[Al]CC(C)C SIPUZPBQZHNSDW-UHFFFAOYSA-N 0.000 description 1
- 125000002147 dimethylamino group Chemical group [H]C([H])([H])N(*)C([H])([H])[H] 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical compound [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 description 1
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 1
- 125000003454 indenyl group Chemical group C1(C=CC2=CC=CC=C12)* 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 229920000592 inorganic polymer Polymers 0.000 description 1
- 150000008040 ionic compounds Chemical class 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000001282 iso-butane Substances 0.000 description 1
- 235000013847 iso-butane Nutrition 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000012280 lithium aluminium hydride Substances 0.000 description 1
- 229910000103 lithium hydride Inorganic materials 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- 229910012375 magnesium hydride Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- MJGFBOZCAJSGQW-UHFFFAOYSA-N mercury sodium Chemical compound [Na].[Hg] MJGFBOZCAJSGQW-UHFFFAOYSA-N 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 239000012968 metallocene catalyst Substances 0.000 description 1
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical group C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 description 1
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
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- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- URXNVXOMQQCBHS-UHFFFAOYSA-N naphthalene;sodium Chemical compound [Na].C1=CC=CC2=CC=CC=C21 URXNVXOMQQCBHS-UHFFFAOYSA-N 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-M phenolate Chemical compound [O-]C1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-M 0.000 description 1
- 229940031826 phenolate Drugs 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- PMJHHCWVYXUKFD-UHFFFAOYSA-N piperylene Natural products CC=CC=C PMJHHCWVYXUKFD-UHFFFAOYSA-N 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000011403 purification operation Methods 0.000 description 1
- ASRAWSBMDXVNLX-UHFFFAOYSA-N pyrazolynate Chemical compound C=1C=C(Cl)C=C(Cl)C=1C(=O)C=1C(C)=NN(C)C=1OS(=O)(=O)C1=CC=C(C)C=C1 ASRAWSBMDXVNLX-UHFFFAOYSA-N 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910001023 sodium amalgam Inorganic materials 0.000 description 1
- 239000012279 sodium borohydride Substances 0.000 description 1
- 229910000033 sodium borohydride Inorganic materials 0.000 description 1
- 229910000104 sodium hydride Inorganic materials 0.000 description 1
- 239000012312 sodium hydride Substances 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- UORVGPXVDQYIDP-UHFFFAOYSA-N trihydridoboron Substances B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 description 1
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Images
Classifications
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- 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
- C08F10/02—Ethene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F110/02—Ethene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F110/04—Monomers containing three or four carbon atoms
- C08F110/06—Propene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/62—Refractory metals or compounds thereof
- C08F4/64—Titanium, zirconium, hafnium or compounds thereof
- C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
- C08F4/65908—Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with an ionising compound other than alumoxane, e.g. (C6F5)4B-X+
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/62—Refractory metals or compounds thereof
- C08F4/64—Titanium, zirconium, hafnium or compounds thereof
- C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
- C08F4/65912—Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with an organoaluminium compound
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- 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
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- 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
- Y10S526/941—Synthetic resins or natural rubbers -- part of the class 520 series having the transition metal bonded directly to carbon
Abstract
本发明涉及一种制备富烯金属配合物的方法、新的富烯金属配合物和它们用作催化剂用于不饱和化合物的聚合,特别是用于烯烃和/或二烯烃的聚合和共聚。
Description
本发明涉及一种制备富烯金属配合物的方法、新的富烯金属配合物和它们用作催化剂用于不饱和化合物的聚合,特别是用于烯烃和/或二烯烃的聚合和共聚。
自从发现二茂铁以来,有环戊二烯配体的金属配合物就成为非常热门的研究课题。很久以前就已经知道了将环戊二烯基金属配合物,尤其是将金属茂作为与活性共催化剂、优选alumoxanes的混合物用于烯烃和二烯烃的聚合(例如EP-A-69 951,129 368,351 392,485821,485 823)。已经证实,在烯烃聚合中,金属茂是高活性特效催化剂。因此在近几年已经开发了大量新的用于烯烃化合物聚合的金属茂催化剂和金属茂催化剂体系,以提高活性、选择性、对微观结构、分子量和分子量分布的控制。
对有富烯配体的金属配合物相对所知甚少。
J.Am.Chem.Soc.1997,119,5132描述了两性离子烯烃聚合催化剂,其在特定的(η6-2,3,4,5-四甲基环戊二烯基-1-亚甲基)(η5-五甲基环戊二烯基)锆化合物与三(五氟苯基)硼或二(五氟苯基)硼烷的反应中生成。(η6-2,3,4,5-四甲基环戊二烯基-1-亚甲基)(η5-五甲基环戊二烯基)锆化合物的合成非常昂贵,其首先需要制备有五甲基环戊二烯基配体的金属茂,在最后的合成步骤将其通过热分解反应分解。在该文献中描述了这类热分解反应。
根据Bercaw等人的JACS(1972),94,1219,通过热分解双(η5-五甲基环戊二烯基)二甲基钛生成(η6-2,3,4,5-四甲基环戊二烯基-1-亚甲基)(η5-五甲基环戊二烯基)甲基钛。T.J.Marks等人的JACS(1988),110,7701描述了锆和铪的五甲基环戊二烯基配合物的热分解。通过热分解双(η5-五甲基环戊二烯基)二苯基锆生成(η5-2,3,4,5-四甲基环戊二烯基-1-亚甲基)(η5-五甲基环戊二烯基)苯基锆。
通过热分解方法制备富烯配合物局限于几种结构变体。热分解方法并不能总生成均一产物。
G.Wilkinson等人在J.Chem.Soc.1960,1321-1324中描述了6,6-二烷基富烯与六羰基合铬或六羰基合钼的反应。但是,得到环戊二烯基合金属配合物,而不是富烯合金属配合物。
在J.Chem.Soc.Dalton Trans.(1985),2037,M.L.H.Green等人报道了通过双(甲苯)合钛与6,6-二苯基富烯的反应合成双(η6-6,6-二苯基富烯)钛。但是,双(甲苯)合钛必须通过复杂和昂贵的金属原子汽化技术制备。为此,将金属钛汽化并在一种基质中与气态甲苯缩合。二(甲苯)合钛的产率非常低。因此二(甲苯)合钛的使用仅仅是有限程度的。
因此,本发明的目的是发现一种改进的制备富烯金属配合物的方法,其避免了上述的缺陷。
现已令人惊奇地发现,通过富烯化合物与适合的过渡金属配合物在还原剂存在下反应可制备富烯金属配合物。
其中
M是根据IUPAC元素周期表的IIIb族、IVb族、Vb族或VIb族或镧系或锕系的金属,20 A表示任选有一个或多个桥的阴离子配体,
X表示氢原子、C1-C10烷基、C1-C10烷氧基、C6-C10芳基、C6-C10芳氧基、C2-C10链烯基、C7-C40芳烷基、C7-C40烷芳基、C8-C40芳链烯基、被C1-C10烃基取代的甲硅烷基、卤原子或式NR7 2的酰胺基,
L表示中性配体,
R1、R2、R3、R4、R5、R6彼此相同或不同,表示氢、卤素、氰基、C1-C20烷基、C1-C10氟代烷基、C6-C10氟代芳基、C1-C10烷氧基,C6-C20芳基,C6-C10芳氧基、C2-C10链烯基、C7-C40芳烷基、C7-C40烷芳基、C8-C40芳链烯基、C2-C10链炔基、被C1-C10烃基取代的甲硅烷基、被C1-C10烃基取代的硫化物基团或任选地被C1-C20烃基取代的氨基,
或
R1、R2、R3、R4、R5、R6在每种情况下同与其相连的原子形成一个或多个脂族或芳族环系,其可含有一个或多个杂原子(O、N、S)和5-10个碳原子,
R7表示氢、C1-C20烷基、C6-C20芳基、C7-C40芳烷基、C7-C40烷芳基、被C1-C10烃基取代的甲硅烷基或任选地被C1-C20烃基取代的氨基,
m、p表示0、1、2、3或4,其取决于M的价态和结合状态,和
k表示1、2或3,并且k+m+p的总和是1-5,其取决于M的氧化水平,和
n是0-10的数,
该方法通过式(IIa)或(IIb)的过渡金属化合物
AmXsM (IIa) 或 AmXsLnM (IIb)
其中A、X、L、M、m、s和n具有上述定义,和
s是2、3、4、5或6且s>p,
其中
R1、R2、R3、R4、R5和R6具有上述定义,
在还原剂存在下反应。
本发明可以单一的反应步骤进行,即,一釜反应,加入各个反应成分的顺序不固定。反应还可以以分开的反应步骤进行。例如,可首先将式(IIa)或(IIb)的过渡金属化合物与还原剂接触,在另一个反应步骤中与式(III)的富烯化合物反应。还优选首先将式(IIa)或(IIb)的过渡金属化合物加入富烯化合物(III),然后加入还原剂。
适合的还原剂的例子是碱金属、碱土金属、铝、锌、碱金属的合金,诸如例如钠-钾合金或钠汞齐,碱土金属合金,和金属氢化物。金属氢化物的例子是氢化锂、氢化钠、氢化镁、氢化铝、氢化铝锂和硼氢化钠。还原剂特别的例子是萘基钠、钾石墨、烷基化锂、丁二烯合镁、蒽合镁、三烷基铝化合物和格氏试剂。优选的还原剂是碱金属或碱土金属、C1-C6烷基锂、三C1-C6烷基铝化合物和格氏试剂。优选的还原剂是锂、镁、正丁基锂和三乙基铝和三异丁基铝。还可以用电化学还原代替上述还原试剂。
制备式(I)富烯金属配合物的方法在适合的反应介质中在-100~+250℃、优选-78~+130℃、特别是-10~+120℃的温度进行。
可能适合的反应介质的例子是脂族或芳族烃类、卤代烃类、醚或环醚。这些例子是非支化的脂族烃类,诸如丁烷、戊烷、己烷、庚烷和辛烷,支化的脂族烃类,诸如异丁烷、异戊烷和异己烷,环脂族烃类,诸如环己烷和甲基环己烷,芳烃类,诸如苯、甲苯和二甲苯,以及醚类,诸如二烷基醚,二甲氧基乙烷和四氢呋喃。各种溶剂的混合物也是合适的。
在惰性气体条件下排除空气和水制备和处理式(I)的富烯金属配合物(惰性气体工艺方法)。惰性气体的例子是氮气或氩气。作为惰性气体工艺方法,例如一般常用于有机金属物质的Schlenk工艺方法是适用的。
式(I)的富烯金属配合物可进行分离,或直接用于进一步的反应。如果需要分离,可通过常规的提纯方法分离生成的副产物,例如通过过滤。或者,也可以用溶剂萃取需要的产物。如果需要,可进行提纯操作,例如重结晶。
可能的式(IIa)或(IIb)的过渡金属配合物特别是下列那些,其中
M是选自钛、锆、铪、钒、铌、钽和铬的金属,
A是式N2C3R8 3的吡唑化物(pyrazolate),其中R8表示氢或C1-C10烷基或C6-C10芳基,
式R7B(N2C3R8 3)3的吡唑硼酸酯,
式OR7的醇化物或酚化物,
式OSiR7 3的硅氧烷,
式SR7的硫醇盐,
式(R7CO)2CR7的乙酰基丙酮化物,
式(R7N=CR7)2的二亚胺,
式R7C(NR7 2)2的脒化物,
式C8HqR7 8-q的环辛四烯基,其中q是0、1、2、3、4、5、6或7,
式C5HqR7 5-q的环戊二烯基,其中其中q是0、1、2、3、4或5,
式C9H7-rR7 r的茚基,其中其中r是0、1、2、3、4、5、6或7,
式C13H9-sR7 s的芴基,其中s是0、1、2、3、4、5、6、7、8或9,或
C1-C30烷基、C6-C10芳基或C7-C40烷芳基,和
L、X、R7、m、s和n具有上述定义。
特别优选的式(IIa)或(IIb)的过渡金属配合物特别是这样一些,其中
M表示钛、锆或铪,
A表示二(三甲基甲硅烷基)酰胺、二甲基酰胺、二乙基酰胺、二异丙基酰胺、2,6-二叔丁基-4-甲基苯酚盐,环辛四烯基、环戊二烯基、甲基环戊二烯基、苄基环戊二烯基、正丙基环戊二烯基、正丁基环戊二烯基、异丁基环戊二烯基、叔丁基环戊二烯基、环戊基环戊二烯基、十八烷基环戊二烯基、1,2-二甲基环戊二烯基、1,3-二甲基环戊二烯基、1,3-二异丙基环戊二烯基、1,3-二叔丁基环戊二烯基、1-乙基-2-甲基环戊二烯基、1-异丙基-3-甲基环戊二烯基、1-(正丁基)-3-甲基环戊二烯基、1-(叔丁基)-3-甲基环戊二烯基、五甲基环戊二烯基、1,2,3,4-四甲基环戊二烯基、1,2,4-三甲基环戊二烯基、1,2,4-三异丙基环戊二烯基、1,2,4-三-(叔丁基)-环戊二烯基、茚基、四氢茚基、2-甲基茚基、4,7-二甲基茚基、2-甲基-4,5-苯并茚基、2-甲基-4-苯基茚基、芴基或9-甲基芴基,
X表示氟或氯,和
L、m、s和n具有上述定义。
可能的富烯化合物特别是那些式(III)化合物,其中
R1-6表示c1-c30烷基、C6-C10芳基或C7-C40烷芳基、特别是氢、甲基、三氟甲基、乙基、正丙基、异丙基、正丁基、异丁基、叔丁基、苯基、五氟苯基、甲基苯基、环己基或苄基。
或式(V)的富烯化合物其中
R1、R2、R3和R4具有上述定义。
特别优选的式(III)化合物是6-环己基富烯、6-异丙基富烯、6-叔丁基富烯、6-苯基富烯、6-(二甲基氨基)富烯、6,6-双(二甲基氨基)富烯、6,6-二甲基富烯、6,6-双(三氟甲基)富烯、6,6-二苯基富烯、6,6-双(五氟苯基)富烯,6,6-五亚甲基富烯、6,6-四亚甲基富烯、6,6-三亚甲基富烯、2-(2,4-环戊二烯-1-亚基)-1,3-二硫戊环、5-苯亚甲基-1,2,3-三苯基-1,3-环戊二烯、1,2,3,4-四甲基富烯、1,2,3,4-四苯基富烯、2,3-二甲基富烯,2,3-二异丙基富烯、2,3-二苯基富烯、1,4-二甲基-2,3-二苯基富烯和1,4-二乙基-2,3-二苯基富烯。
式(III)、(IV)和(V)的富烯化合物的合成可例如根据J.Org.Chem.Vol.49,No.11(1984),1849的方法进行。
式(I)给出的富烯金属配合物被认为是结合状态的正式描述。在金属配合物中的结合状态尤其取决于中心原子、氧化水平和富烯配体的取代基。
图1表示可根据本发明制备的富烯金属配合物的透视结构,通过诸如X-射线结构分析获得,以(6-叔丁基富烯基)五甲基环戊二烯基氯化钛为例。
根据本发明的方法开拓了新的例如不能通过热分解制备的式(I)的富烯金属配合物。
本发明因此还提供式(I)的富烯金属配合物,其中
M是选自钛、锆、铪、钒、铌、钽和铬的金属,
k是1,和
A、X、m、p、R1、R2、R3、R4、R5和R6具有上述定义,
除了其中R1和R2表示氢并同时R3、R4、R5和R6表示甲基、同时A表示五甲基环戊二烯基或式C2B9H11的碳硼烷二基的式(I)化合物。
本发明还提供了一种催化体系,包括
a)根据本发明方法制备的富烯金属配合物,其中
M是选自钛、锆、铪、钒、铌、钽和铬的金属,
k是1,和
A、X、m、p、R1、R2、R3、R4、R5和R6具有上述定义,
和
b)适合活化金属配合物a)的共催化剂,组分a)对组分b)的摩尔比在1∶0.1-1∶10000范围内,优选1∶1-1∶1000范围内。
可能的共催化剂是金属茂催化剂领域已知的共催化剂,诸如聚合或低聚aluminoxane、路易斯酸和铝酸盐和硼酸盐。在此特别参考Macromol.Symp.Vol.97,July 1995,p.1-246(对于alumoxane)和EP 277 003、EP 277 004和Organometallics 1997,16,842-857(对于硼酸盐)和EP 573 403(对于铝酸盐)。
特别适合的共催化剂是甲基aluminoxane、被三异丁基铝改性的甲基alumoxane以及二叔丁基alumoxane、三烷基铝化合物,诸如三甲基铝、三乙基铝、三异丁基铝和三异辛基铝,还有二烷基铝化合物,诸如二异丁基氢化铝、二异丁基氟化铝和二乙基氯化铝,取代的三芳基铝化合物,诸如三(五氟苯基)铝,和含有四(五氟苯基)铝酸根作为阴离子的离子化合物,诸如三苯基甲基四(五氟苯基)铝酸盐,以及四(五氟苯基)铝酸N,N-二甲基苯铵,取代的三芳基硼化合物,诸如三(五氟苯基)硼,以及含有四(五氟苯基)硼酸根作为阴离子的离子化合物,诸如三苯基甲基四(五氟苯基)硼酸盐和四(五氟苯基)硼酸N,N-二甲基苯铵。各种共催化剂的混合物也适用于活化式(I)的富烯金属配合物。
本发明还提供新的催化剂体系用于不饱和化合物聚合的应用,特别是用于烯烃和二烯烃聚合。在此,所述不饱和化合物的均聚和共聚均认为是聚合。聚合中使用的化合物特别是C2-C10烯烃,诸如乙烯、丙烯、丁-1-烯、戊-1-烯和己-1-烯、辛-1-烯以及异丁烯,还有芳基烯烃,诸如苯乙烯。使用的二烯烃特别是共轭二烯烃,诸如1,3-丁二烯、异戊二烯和1,3-戊二烯,非共轭二烯烃,诸如1,4-己二烯、1,5-庚二烯、5,7-二甲基-1,6-辛二烯、4-乙烯基-1-环己烯、5-亚乙基-2-降冰片烯、5-乙烯基-2-降冰片烯和二环戊二烯。
本发明的催化剂适用于基于乙烯与一种或多种所述的α-烯烃和所述的二烯烃的共聚物的橡胶的制备。本发明的催化剂体系还适用于环烯烃聚合,诸如降冰片烯、环戊烯、环己烯和环辛烯,以及环烯烃与乙烯或α-烯烃的共聚。
聚合可在液相进行,存在或不存在惰性溶剂,或在气相进行。适合的溶剂是芳烃,诸如苯和/或甲苯,或脂族烃,诸如丙烷、己烷、庚烷、辛烷、异丁烷或环己烷,或各种烃的混合物。
可将本发明的催化剂体系施加到载体上。在此可述及的适合的载体材料是例如:无机或有机聚合物载体,诸如硅胶、沸石、碳黑、活性炭、氧化铝、聚苯乙烯和聚丙烯。
本发明的催化剂体系在此可以常规的方法施加到载体材料上。在例如US 4 808 561、4 912 075、5 008 228和4 914 253中描述了承载催化剂体系的方法。
聚合一般在1-1000巴、优选1-100巴的压力和-100~+250℃、优选0~+150℃的温度进行。聚合可连续或非连续地在常用反应器中进行。
借助下述实施例更详细地说明本发明。
一般信息:在氩气保护下排除空气和水分进行有机金属化合物的制备和处理(Schlenk工艺技术)。所有需要的溶剂在使用前确保与适合的干燥剂沸腾数小时并随后在氩气下蒸馏以使之干燥。用1H-MNR、13C-NMR和质谱对化合物特征化。
缩写:
Cp :环戊二烯基
Cp* :五甲基环戊二烯基
HV :高真空
RT :室温
THF :四氢呋喃
MS :质谱
EA :元素分析
Tg :玻璃化温度(DSC测定)
de :非对映体过量
合成式(I)化合物
实施例1
通过6,6-二甲基富烯与Cp*TiCl3在镁[(C5(CH3)5)(C5H4)C(CH3)2TiCl]存在下反应合成富烯配合物
Cp*TiCl3(0.610g,2.11mmol)和1.05当量镁(0.054g,2.21mmol)在开始加入到25ml THF中。将1.05当量的6,6-二甲基富烯(0.227g,2.14mmol)在室温滴加到该混合物中。随后将混合物在室温搅拌过夜,从而所有的Mg都被消耗。在HV下将溶剂除去,绿色的残余物用己烷溶解。滤除固体,溶液浓缩到一半,沉淀出绿色有光泽的小片。为了重结晶,将混合物冷却到-20℃。分离橄榄绿色晶体,在HV下干燥。得到0.429g(59%)[(C5(CH3)5)(C5H4)C(CH3)2TiCl]。1H-NMR:(C6D6,300MHz):δ=1,16(s,3H,C(CH3)2),1,70(s,15H,C5(CH3)5),1,75(s,3H,C(CH3)2),3,43,4,65,6,03,6,70(m,1H,C5H4)ppm.13C-NMR:(C6D6,75MHz):δ=12,82(C5(CH3)5),22,76,24,50(C(CH3)2),108,10(C(CH3)2)117,23,117,46,120,04,124,09(C4H4),122,55(C5(CH3)5),132,16(ipso-C5H4)ppm.MS(70eV)m/e(%):324(40)[M+],288(40)[M+-HCl],135(5)[Cp*],106(100)[二甲基富烯]。
实施例2
通过6,6-二甲基富烯与Cp*TiCl3在丁基锂[(Cp*)(C5H4=C(CH3)2)TiCl]存在下反应合成富烯配合物
400mg(1.38mmol)Cp*TiCl3、154mg(1.45mmol)6,6-二甲基富烯和1.11ml(2.76mmol)正丁基锂在Schlenk容器中在-78℃合并在25mlTHF中。使混合物缓慢温热至0℃,在该温度再搅拌2小时,使反应完全。然后在HV下除去溶剂,用正己烷溶解绿色的残余物。滤除固体,溶液浓缩到一半,沉淀出绿色晶体。得到290mg(65%)[(C5(CH3)5)(C5H4)C(CH3)2TiCl]。1H-NMR:(C6D6,300MHz)δ=1,16(s,3H,C(CH3)2),1,70(s,15H,C5(CH3)5),1,75(s,3H,C(CH3)2),3,43/4,65/6,03/6,70(s,1H,C5H4).13C-NMR:(C6D6,75MHz)δ=12,82(C5(CH3)5),22,76/24,50(C(CH3)2),108,10(C(CH3)2)117,23/117,46/120,04/124,09(C4H4),122,55(C5(CH3)5),132,16(ipso-C).
实施例3
通过6,6-二甲基富烯与Cp*ZrCl3在镁[(C5(CH3)5(C5H4)C(CH3)2ZrCl]存在下反应合成富烯配合物
Cp*ZrCl3(0.380g,1.14mmol)和1.1当量镁(0.031g,1.26mmol)在开始加入到10mlTHF中。将1.1当量6,6-二甲基富烯(0.134g,1.26mmol)滴加到该溶液中。5分钟后,反应溶液发生浑浊。将混合物搅拌过夜,从而镁完全溶解。在HV下浓缩至干,残余物用10ml己烷溶解,滤除生成的沉淀。从滤液分离到197mg(47%)[(C5(CH3)5)(C5H4)C(CH3)2ZrCl]棕红色的固体。1H-NMR:(C6D6,300MHz):δ=1,77(s,15H,C5(CH3)5),1,98,1,99(s,3H,C(CH3)2),5,40(dd,1H,3J(H,H)=2,69,3,02Hz,C5H4),5,58(dd,1H,3J(H,H)=2,69,2,68Hz,C5H4),5,85(dd,1H,3J(H,H)=2,68,3,02Hz,C5H4),5,92(dd,1H,3J=2,69,2,68Hz,C5H4)ppm.13C-NMR:(C6D6,75MHz):δ=10,98(C5(CH3)5),21,35,21,90(C(CH3)3),109,78(C(CH3)2),107,75,110,68,113,88,118,11(C5H4),115,69(ipso-C5H4),122,35(C5(CH3)5)ppmMS(70eV)m/e(%):366(10)[M+],330(5)[M+-HCl],259(2),135(5)[Cp*],106(100)[二甲基富烯]。
实施例4
通过6,6-二苯基富烯与四氯化钛在镁存在下反应合成双(η6-6,6-二苯基富烯)钛
610mg(1.83mmol)TiCl4(THF)2、89mg(3.65mmol)镁屑和841mg(3.65mmol)6,6-二苯基富烯在Schlenk容器中在作为反应介质的30mlTHF中合并。混合物搅拌12小时,直到镁屑完全消耗,以使反应完全。通过将反应溶液浓缩至干,得到绿色固体,通过用正己烷溶解并过滤将其与生成的氯化镁分离。分步浓缩并冷却滤液,得到640mg(70%)双(η6-6,6-二苯基富烯)钛。
实施例5
通过6,6-二甲基富烯与CpTiCl3在镁[(C5H5)(C5H4)C(CH3)2TiCl]存在下反应合成富烯配合物
CpTiCl3(0.410g,1.87mmol)和1.05当量镁(0.048g,1.96mmol)在开始加入到20mlTHF中。将1.03当量6,6-二甲基富烯(0.204g,1.92mmol)在RT滴加到该黄色溶液中,搅拌混合物直到所用的镁被消耗完。在HV下浓缩,绿色的残余物用20ml己烷溶解。滤除固体后,深绿色的溶液在HV下浓缩至一半。在-20℃结晶,得到0.2g(42%)[(C5H5)(C5H4)C(CH3)2TiCl]深绿色固体。1H-NMR:(C6D6,300MHz):δ=0,94,1,64(s,3H,C(CH3)2),3,66(m,1H,C5H4),4,76(m,1H,C5H4),5,80s,5H,C5H5),6,23(m,1H,C5H4),6,66(m,1H,C5H4)ppm13C-NMR:(C6D6,75MHz):δ=10,98(C5(CH3)5),21,35,21,90(C(CH3)2),109,78(C(CH3)2),107,75,110,68,113,88,118,11(C5H4),115,69(ipso-C5H4),122,35(C5(CH3)5)ppm.
实施例6
通过6,6-二苯基富烯与Cp*TiCl3在镁[(C5(CH3)5)(C5H4)C(C6H5)2TiCl]存在下反应合成富烯配合物
Cp*TiCl3(0.690g,2.38mmol)和1.1当量镁(0.064g,2.62mmol)在开始加入到20mlTHF中。1.1当量的6,6-二苯基富烯(0.604g,2.62mmol)在RT滴加到该溶液中。将混合物在RT搅拌过夜,从而所有的镁被消耗。在HV下将溶剂除去,绿色的残余物用己烷溶解。滤除沉淀,将溶液浓缩到一半。将混合物冷却到-20℃结晶,得到0.29g(27%)[(C5(CH3)5)(C5H4)C(C6H5)2TiCl]绿色固体。1H-NMR:(C6D6,300MHz):δ=1,55(s,15H,C5(CH3)5),4,20,4,55,5,89,6,37(m,1H,C5H4),6,89-7,41(m,10H,C6H5)ppm.13C-NMR:(C6D6,75MHz):δ=12,38(C5(CH3)5),116,29,117,24,118,22,121,82(C4H4),124,04(C5(CH3)5),125,61(ipso-C5H4),126,50,126,84,127,26,128,07,128,83,129,81(C6H5),130,72(-C(C6H5)),141,93,144,23(ipso-C6H5)ppm.MS(70eV)m/e(%):448(5)[M+],413(2)[M+-HCl],230(100)[6,6-二苯基富烯],135(15)[Cp*],78(12)[Ph].
实施例7
通过6,6-二苯基富烯与Cp*ZrCl3在镁[(C5(CH3)5)(C5H4)C(C6H5)2ZrCl]存在下反应合成富烯配合物
Cp*ZrCl3(0.310g,0.93mmol)和1.05当量镁(0.024g,0.98mmol)在开始加入到10mlTHF中。1.05当量的6,6-二苯基富烯(0.225g,0.98mmol)滴加到该溶液中。将混合物搅拌过夜,从而镁完全反应。在HV下浓缩至干,残余物用20ml甲苯溶解,滤除不溶解的沉淀。用一层己烷在-20℃覆盖后,得到178mg(39%)[(C5(CH3)5)(C5H4)C(C6H5)2ZrCl]红色固体。1H-NMR:(C6D6,300MHz):δ=1,63(s,15H,C5(CH3)5),4,65,5,20,5,22,6,06(m,1H,C5H4),6,98-7,16(m,8H,C6H5),7,26-7,49(m,2H,C6H5)ppm.13C-NMR:(C6D6,75MHz):δ=11,66(C5(CH3)5),104,67,111,14,113,62,117,52(C4H4),120,82(C5(CH3)5),125,61(ipso-C5H4),126,50,126,84,127,26,128,07,128,83,129,81(C6H5),130,72(-C(C6H5)),141,93,144,23(ipso-C6H5)ppm.MS(70eV)m/e(%):448(5)[M+],413(2)[M+-HCl],230(100)[6,6-二苯基富烯],135(15)[Cp*],78(12)[Ph].
实施例8
通过2,3,4,5-四甲基富烯与Cp*TiCl3在镁[(C5(CH3)5)(C5(CH3)4)CH2TiCl]存在下反应合成富烯配合物
Cp*TiCl3(0.370g,1.28mmol)和1.05当量镁(0.033g,1.35mmol)在开始加入到25mlTHF中。1.05当量的2,3,4,5-四甲基富烯(0.185g,1.35mmol)在室温滴加到该红色溶液中。将混合物在RT搅拌过夜,从而所有的镁都被消耗。在HV下将溶剂除去,绿色的残余物用己烷溶解。滤除固体,将溶液浓缩至一半。将混合物冷却到-20℃结晶,得到0.23g(52%)[(C5(CH3)5)(C5(CH3)4)CH2TiCl]绿色固体。1H-NMR:(C6D6,300MHz):δ=1,21,1,47,1,70(s,3H,C5(CH3)4=CH2),1,79(s,3H,C5(CH3)5),2,07(s,3H,C5(CH3)4=CH2),1,43(d,1H,3J(H,H)=3,66Hz,C5(CH3)4=CHH),2,54(d,1H,2J(H,H)=3,66Hz,C5(CH3)4=CHH)ppm.13C-NMR:(C6D6,75MHz):δ=9,82,10,22(C5(CH3)4=CH2),11,13(C5(CH3)5),11,85,14,00(C5(CH3)4=CH2),77,65(C5(CH3)4=CH2),120,08(C5(CH3)5),120,32,124,43,124,73,128,61,135,17(C5(CH3)4=CH2)ppm.
实施例9
通过2,3,4,5-四甲基富烯与CpTiCl3在镁[(C5H5)(C5(CH3)4)CH2TiCl]存在下反应合成富烯配合物
CpTiCl3(0.350g,1.60mmol)和1.05当量镁(0.041g,1.67mmol)在开始加入到20mlTHF中。1.1当量的2,3,4,5-四甲基富烯(0.260g,1.67mmol)在室温滴加到该溶液中。将混合物搅拌直到所用的镁被消耗。在HV下浓缩,绿色的残余物用20ml己烷溶解。滤除固体后,在HV将深绿色溶液浓缩至一半。通过冷却到-20℃结晶,得到0.3g(67%)[(C5H5)(C5(CH3)4)CH2TiCl]深绿色固体。1H-NMR:(C6D6,300MHz):δ=0,82,1,27,1,74(s,3H,C5(CH5)4=CH2),1,99(d,1H,2J(H,H)=3,7Hz,C5(CH3)4=CHH),2,05(s,3H,C5(CH3)4=CH2),2,56(d,1H,2J(H,H)=3,7Hz,C5(CH3)4=CHH),5,77(s,5H,C5H5)ppm.13C-NMR:(C6D6,75MHz):δ=9,47,10,35,12,01,12,95(C5(CH3)4=CH2),74,47(C5(CH3)4=CH2),110,80(C5H5),119,92,124,60,127,82,129,43,134,80(C5(CH3)4=CH2)ppm.MS(70eV)m/e(%):283(10)[M+],247(15)[M+-HCl],134(50)[2,3,4,5-四甲基富烯],119(100)[2,3,4,5-四甲基富烯]-CH4],65(30)[Cp].
实施例10
通过1,2,3,4,6-五甲基富烯与CpTiCl3在镁[(C5H5)(C5(CH3)4)C(H)(CH3)TiCl]存在下反应合成富烯配合物
CpTiCl3(0.450g,2.05mmol)和1.05当量镁(0.054g,2.15mmol)在开始加入到20mlTHF中。1.03当量的1,2,3,4,6-五甲基富烯(0.320g,2.15mmol)在RT滴加到该溶液中,将混合物搅拌直到所用的镁被消耗。在HV下浓缩,生成的绿色固体用20ml己烷溶解。滤除固体后,在HV将深绿色溶液浓缩至一半。通过冷却到-20℃结晶,得到0.17g(28%)[(C5H5)(C5(CH3)4)C(H)(CH3)TiCl]深绿色固体。de:25%1H-NMR:(C6D6,300MHz):δ=0,73,1,12(s,3H,C5(CH3)4=C(CH3)(H)),1,64(d,3H,3J(H,H)=7,25Hz,C5(CH3)4=C(CH3)(H)),1,71(s,3H,C5(CH3)4=C(CH3)(H)),2,29(q,1H,3J(H,H)=7,25Hz,C5(CH3)4=C(CH3)(H)),2,55(s,3H,C5(CH3)4=C(CH3)(H)),5,79(s,5H,C5H5)ppm.13C-NMR:(C6D6,75MHz):δ=10,87,13,35,16,19,16,97(C5(CH3)4=C(CH3)(H)),37,62(C5(CH3)4=C(CH3)(H)),94,39(C5(CH3)4=C(CH3)(H)),112,02(C5H5),121,46,125,56,130,91,131,46,136,90(C5(CH3)4=C(CH3)(H))ppm.
实施例11
通过6-叔丁基富烯与Cp*TiCl3在镁[(C5(CH3)5)(C5H4)C(H)(C(CH3)3)TiCl]存在下反应合成富烯配合物
Cp*TiCl3(0.450g,1.55mmol)和1.05当量镁(0.039g,1.63mmol)在开始加入到15mlTHF中。1.05当量叔丁基富烯(0.249g,1.63mmol)在RT滴加到该溶液中。将混合物在RT搅拌过夜,从而所有的镁被消耗。在HV下将溶剂除去,绿色的残余物用己烷溶解。滤除固体,溶液浓缩到一半。将混合物冷却到-20℃结晶,得到0.35g(64%)[(C5(CH3)5)(C5H4)C(H)(C(CH3)3)TiCl]。
进行X-射线结构分析(图1)。de:≥98%1H-NMR:(C6D6,300MHz):δ=1,16(s,9H,C5H4=C(H)(C(CH3)3)),1,68(s,1H,C5H4=C(H)(C(CH3)3)),1,70(s,15H,C5(CH3)5),3,15,4,74,5,97,6,63(m,1H,C5H4=C(H)(C(CH3)3)),)ppm.13C-NMR:(C6D6,75MHz):δ=11,69(C5(CH3)5),32,20(C5H4=C(H)(C(CH3)3)),34,28)C5H4=C(H)(C(CH3)3)),114,31(C5H4=C(H)(C(CH3)3)),117,83,118,31,118,77(C5H4=C(H)(C(CH3)3)),120,46(C5(CH3)5),124,72,128,23(C5H4=C(H)(C(CH3)3))ppm.MS(70eV)m/e(%):353(12)[M+],316(5)[M+-HCl],270(18),235(8),135(100)[Cp*],119(35),80(85),57(90)[C(CH3)3].
实施例12
通过6-叔丁基富烯与CpTiCl3在镁[(C5H5)(C5H4)C(H)(C(CH3)3)TiCl]存在下反应合成富烯配合物
CpTiCl3(0.420g,1.91mmol)和1.05当量镁(0.048g,2.01mmol)在开始加入到10mlTHF中。1.03当量叔丁基富烯(0.295g,1.91mmol)在RT滴加到该溶液中,将混合物搅拌,所有的镁被消耗。然后在HV下浓缩,生成的绿色固体用20ml己烷溶解。滤除固体后,在HV下将深绿色溶液浓缩到一半。在-20℃结晶,得到0.23g(44%)[(C5H5)(C5H4)C(H)(C(CH3)3)TiCl]深绿色晶体。de:≥98%1H-NMR:(C6D6,300MHz):δ=1,05(s,9H,C5H4=C(H)(C(CH3)3)),2,05(s,1H,C5H4=C(H)(C(CH3)3)),3,28,4,83(m,1H,C5H4=C(H)(C(CH3)3)),)5,85(s,5H,C5H5),6,17,6,59(m,1H,C5H4=C(H)(C(CH3)3)),)ppm.13C-NMR:(C6D6,75MHz):δ=32,84(C5H4=C(H)(C(CH3)3)),35,76(C5H4=C(H)(C(CH3)3)),111,23(C5H5),111,63(C5H4=C(H)(C(CH3)3)),116,62,117,41,121,63,127,65,127,50(C5H4=C(H)(C(CH3)3)),ppm.MS(70eV)m/e(%):282(5)[M+],246(45)[M+-HCl],228(15),135(10)[Cp*],119(35).
聚合实施例
实施例13
制备催化剂溶液
8.3mg(22.6μmol)实施例3的[(Cp*)(C5H4=C(CH3)2)ZrCl]溶于11.3ml甲苯。
乙烯的聚合
在开始将100ml甲苯加入到250ml玻璃反应器中,加入1ml 0.1摩尔的三异丁基铝在甲苯中的溶液和0.5ml催化剂溶液。然后用气体输入管连续将乙烯在1.1巴压力通入到溶液中。通过加入1ml四(五氟苯基)硼酸N,N-二甲基苯铵在甲苯中0.001摩尔的溶液引发聚合。在40℃和1.1巴的乙烯压力下聚合5分钟后,通过加入10ml甲醇停止反应,滤出形成的聚合物,用丙酮洗涤,在真空干燥室中干燥。得到1.16g聚乙烯。
实施例14
乙烯和丙烯的共聚
在开始将500ml甲苯和5ml 10%的MAO在甲苯中的溶液加入到1.4L装有机械搅拌器、压力计、温度探头、温度控制元件、催化剂闸门和用于乙烯和丙烯的单体计量元件的钢高压釜中,搅拌10分钟。然后量入52g丙烯。用恒温器将内部温度调节到40℃。然后量入乙烯,直到反应器内的内部压力上升到6巴。通过加入5ml实施例5的催化剂溶液引发聚合,连续量入乙烯,从而使在40℃时的内部压力恒定在6巴。聚合1小时后,用HCl在甲醇中的1%的溶液终止聚合,搅拌混合物10分钟,然后聚合物在甲醇中沉淀。这样得到的聚合物用甲醇洗涤,分离,在60℃真空下干燥20小时,得到48g共聚物。用IR光谱确定的共聚物的组成表明结合了82.9%乙烯和17.1%丙烯。用DSC法确定Tg为-24℃。
实施例15
制备催化剂
73.9mg(0.221mmol)TiCl4(THF)2溶于3mlTHF中。然后加入5.4mg(0.22mmol)镁和51mg(0.221mmol)6,6-二苯基富烯。在20℃搅拌20小时后,得到深绿色溶液。浓缩溶液至干,生成的残余物在HV下干燥2小时,然后加入22ml甲苯,生成深绿色悬浮液。1ml催化剂悬浮液含有0.01mmol钛。
乙烯的聚合
在开始将90ml甲苯和5ml MAO的溶液(10%,在甲苯中)加入到250ml玻璃反应器中搅拌5分钟。然后加入5ml催化剂悬浮液,混合物在40℃搅拌10分钟。然后用气体输入管连续将乙烯通入到溶液中。在40℃和1.1巴的乙烯压力下聚合10分钟后,通过加入10ml HCl在甲醇中的1%的溶液终止反应,滤出形成的聚合物,用甲醇洗涤,在真空干燥室中干燥。得到8.9g聚乙烯。
Claims (8)
M是根据IUPAC元素周期表的IIIb族、IVb族、Vb族或VIb族或镧系或锕系的金属,
A表示任选地有一个或多个桥的阴离子配体,
X表示氢原子、C1-C10烷基、C1-C10烷氧基、C6-C10芳基、C6-C10烷氧基、C2-C10链烯基、C7-C40芳烷基、C7-C40烷芳基、C8-C40芳链烯基、被C1-C10烃基取代的甲硅烷基、卤原子或式NR7 2的酰胺基,
L表示中性配体,
R1、R2、R3、R4、R5、R6彼此相同或不同,表示氢、卤素、氰基、C1-C20烷基、C1-C10氟代烷基、C6-C10氟代芳基、C1-C10烷氧基,C6-C20芳基,C6-C10芳氧基、C2-C10链烯基、C7-C40芳烷基、C7-C40烷芳基、C8-C40芳链烯基、C2-C10链炔基、被C1-C10烃基取代的甲硅烷基、被C1-C10烃基取代的硫化物基团或任选地被C1-C20烃基取代的氨基,
或
R1、R2、R3、R4、R5、R6各同与其相连的原子形成一个或多个脂族或芳族环系,其可含有一个或多个杂原子(O、N、S)和5-10个碳原子,
R7表示氢、C1-C20烷基、C6-C20芳基、C7-C40芳烷基、C7-C40烷芳基、被C1-C10烃基取代的甲硅烷基或任选地被C1-C20烃基取代的氨基,
m、p表示0、1、2、3或4,其取决于M的价态和结合状态,和
k表示1、2或3,并且k+m+p的总和是1-5,其取决于M的氧化水平,和
n是0-10的数,
该方法通过式(IIa)或(IIb)的过渡金属化合物
AmXsM (IIa) 或 AmXsLnM (IIb)
其中A、X、L、M、m、s和n具有上述定义,和
s是2、3、4、5或6且s>p,
与式(III)富烯化合物其中
R1、R2、R3、R4、R5和R6具有上述定义,
在还原剂存在下反应。
2.根据权利要求1的方法,其特征在于,反应在适合的反应介质中在-100~+250℃的温度进行。
3.根据权利要求1的方法,其特征在于,使用碱金属、碱土金属或烷基锂作为还原剂。
4.根据权利要求1的方法,其特征在于,反应在溶剂中进行。
5.根据权利要求4的方法,其特征在于,反应在醚中进行。
6.式(Ia)或(Ib)的富烯金属配合物,其中
M是选自钛、锆、铪、钒、铌、钽和铬的金属,
k是1,和
A、x、L、m、n、p、R1、R2、R3、R4、R5和R6具有上述定义,
除了其中R1和R2表示氢并同时R3、R4、R5和R6表示甲基、同时A表示五甲基环戊二烯基或式C2B9H11的碳硼烷二基的式(Ia)或(Ib)化合物。
7.一种催化剂体系,包括
a)根据本发明方法制备的式(Ia)或(Ib)富烯金属配合物,其中
M是选自钛、锆、铪、钒、铌、钽和铬的金属,
k是1,和
A、X、L、m、n、p、R1、R2、R3、R4、R5和R6具有上述定义,
和
b)适合活化金属配合物a)的共催化剂,组分a)对组分b)的摩尔比在1∶0.1-1∶10000范围内。
8.权利要求7的催化剂体系在烯烃和/或二烯烃聚合中的应用。
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DE19850898A1 (de) * | 1998-11-05 | 2000-05-11 | Bayer Ag | Verfahren zur Herstellung von EP(D)M |
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AU2003261617A1 (en) * | 2002-08-29 | 2004-03-19 | Lg Chem, Ltd. | Fulvene, metallocene catalysts and preparation method thereof, and preparation of polyolefines copolymer using the same |
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US10273315B2 (en) | 2012-06-20 | 2019-04-30 | Chevron Phillips Chemical Company Lp | Methods for terminating olefin polymerizations |
KR102251989B1 (ko) | 2014-03-10 | 2021-05-14 | 삼성전자주식회사 | 유기 금속 전구체 및 이를 이용한 박막 형성 방법 |
US9377533B2 (en) * | 2014-08-11 | 2016-06-28 | Gerard Dirk Smits | Three-dimensional triangulation and time-of-flight based tracking systems and methods |
EP3256518B1 (en) * | 2015-02-10 | 2021-05-05 | Milliken & Company | Thermoplastic polymer compositions |
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DE3127133A1 (de) | 1981-07-09 | 1983-01-27 | Hoechst Ag, 6000 Frankfurt | Verfahren zur herstellung von polyolefinen und deren copolymerisaten |
US5324800A (en) | 1983-06-06 | 1994-06-28 | Exxon Chemical Patents Inc. | Process and catalyst for polyolefin density and molecular weight control |
US5580939A (en) | 1983-06-06 | 1996-12-03 | Exxon Chemical Patents Inc. | Process and catalyst for polyolefin density and molecular weight control |
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PL276385A1 (en) | 1987-01-30 | 1989-07-24 | Exxon Chemical Patents Inc | Method for polymerization of olefines,diolefins and acetylene unsaturated compounds |
IL85097A (en) | 1987-01-30 | 1992-02-16 | Exxon Chemical Patents Inc | Catalysts based on derivatives of a bis(cyclopentadienyl)group ivb metal compound,their preparation and their use in polymerization processes |
US4912075A (en) | 1987-12-17 | 1990-03-27 | Exxon Chemical Patents Inc. | Method for preparing a supported metallocene-alumoxane catalyst for gas phase polymerization |
US5008228A (en) | 1988-03-29 | 1991-04-16 | Exxon Chemical Patents Inc. | Method for preparing a silica gel supported metallocene-alumoxane catalyst |
US4892851A (en) | 1988-07-15 | 1990-01-09 | Fina Technology, Inc. | Process and catalyst for producing syndiotactic polyolefins |
US4914253A (en) | 1988-11-04 | 1990-04-03 | Exxon Chemical Patents Inc. | Method for preparing polyethylene wax by gas phase polymerization |
ES2071888T3 (es) | 1990-11-12 | 1995-07-01 | Hoechst Ag | Bisindenilmetalocenos sustituidos en posicion 2, procedimiento para su preparacion y su utilizacion como catalizadores en la polimerizacion de olefinas. |
EP0485821B1 (de) | 1990-11-12 | 1996-06-12 | Hoechst Aktiengesellschaft | Metallocene mit Liganden aus 2-substituierten Indenylderivaten, Verfahren zu ihrer Herstellung und ihre Verwendung als Katalysatoren |
US6054405A (en) * | 1997-12-29 | 2000-04-25 | Union Carbide Chemicals & Plastics Technology Corporation | Catalyst composition for the polymerization of olefins |
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1998
- 1998-10-28 CA CA002309174A patent/CA2309174A1/en not_active Abandoned
- 1998-10-28 AU AU20479/99A patent/AU2047999A/en not_active Abandoned
- 1998-10-28 CN CN98810873.9A patent/CN1278265A/zh active Pending
- 1998-10-28 BR BR9813196-6A patent/BR9813196A/pt not_active IP Right Cessation
- 1998-10-28 JP JP2000520454A patent/JP2001522856A/ja active Pending
- 1998-10-28 US US09/530,812 patent/US6403735B1/en not_active Expired - Fee Related
- 1998-10-28 EP EP98965145A patent/EP1028968A1/de not_active Withdrawn
- 1998-10-28 WO PCT/EP1998/006821 patent/WO1999024445A1/de not_active Application Discontinuation
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2000
- 2000-05-02 NO NO20002319A patent/NO20002319L/no not_active Application Discontinuation
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2001
- 2001-08-03 US US09/922,365 patent/US20020010084A1/en not_active Abandoned
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101765604B (zh) * | 2007-07-24 | 2013-06-05 | 道达尔石油化学产品研究弗吕公司 | 基于富烯络合物的催化剂组分 |
Also Published As
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BR9813196A (pt) | 2000-08-29 |
NO20002319L (no) | 2000-06-29 |
NO20002319D0 (no) | 2000-05-02 |
US20020010084A1 (en) | 2002-01-24 |
AU2047999A (en) | 1999-05-31 |
JP2001522856A (ja) | 2001-11-20 |
EP1028968A1 (de) | 2000-08-23 |
US6403735B1 (en) | 2002-06-11 |
WO1999024445A1 (de) | 1999-05-20 |
CA2309174A1 (en) | 1999-05-20 |
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