CN1182749A - 烯烃聚合 - Google Patents
烯烃聚合 Download PDFInfo
- Publication number
- CN1182749A CN1182749A CN97114690A CN97114690A CN1182749A CN 1182749 A CN1182749 A CN 1182749A CN 97114690 A CN97114690 A CN 97114690A CN 97114690 A CN97114690 A CN 97114690A CN 1182749 A CN1182749 A CN 1182749A
- Authority
- CN
- China
- Prior art keywords
- metallocene
- methods according
- methods
- promotor
- zirconium
- 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.)
- Granted
Links
- 230000000379 polymerizing effect Effects 0.000 title 1
- 239000003054 catalyst Substances 0.000 claims abstract description 34
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 30
- 150000001336 alkenes Chemical class 0.000 claims abstract description 15
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 11
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 42
- 229910052726 zirconium Inorganic materials 0.000 claims description 40
- 238000000034 method Methods 0.000 claims description 29
- -1 polypropylene Polymers 0.000 claims description 23
- 125000003963 dichloro group Chemical group Cl* 0.000 claims description 17
- 125000000217 alkyl group Chemical group 0.000 claims description 9
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 6
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical group C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 claims description 6
- 125000003118 aryl group Chemical group 0.000 claims description 5
- 239000002245 particle Substances 0.000 claims description 5
- 229920000642 polymer Polymers 0.000 claims description 5
- 230000008569 process Effects 0.000 claims description 5
- 239000004743 Polypropylene Substances 0.000 claims description 3
- 229920001155 polypropylene Polymers 0.000 claims description 3
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 2
- 150000004678 hydrides Chemical group 0.000 claims description 2
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 claims 2
- 229920005629 polypropylene homopolymer Polymers 0.000 claims 1
- 239000007787 solid Substances 0.000 description 23
- 239000000463 material Substances 0.000 description 14
- 239000000126 substance Substances 0.000 description 14
- 238000002360 preparation method Methods 0.000 description 12
- 239000002002 slurry Substances 0.000 description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 10
- 239000000203 mixture Substances 0.000 description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 239000007788 liquid Substances 0.000 description 9
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 8
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 8
- 229930195733 hydrocarbon Natural products 0.000 description 8
- 150000002430 hydrocarbons Chemical class 0.000 description 8
- 239000000178 monomer Substances 0.000 description 8
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 8
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 8
- 229960001866 silicon dioxide Drugs 0.000 description 8
- 239000004215 Carbon black (E152) Substances 0.000 description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 7
- 150000001875 compounds Chemical class 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
- 239000007789 gas Substances 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- 239000000741 silica gel Substances 0.000 description 6
- 229910002027 silica gel Inorganic materials 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 5
- 229910052782 aluminium Inorganic materials 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- 125000004799 bromophenyl group Chemical group 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 4
- 230000018044 dehydration Effects 0.000 description 4
- 238000006297 dehydration reaction Methods 0.000 description 4
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 4
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 4
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 3
- 239000004411 aluminium Substances 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 150000001721 carbon Chemical group 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 229910052809 inorganic oxide Inorganic materials 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 description 3
- KVNYFPKFSJIPBJ-UHFFFAOYSA-N 1,2-diethylbenzene Chemical compound CCC1=CC=CC=C1CC KVNYFPKFSJIPBJ-UHFFFAOYSA-N 0.000 description 2
- ZGEGCLOFRBLKSE-UHFFFAOYSA-N 1-Heptene Chemical compound CCCCCC=C ZGEGCLOFRBLKSE-UHFFFAOYSA-N 0.000 description 2
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-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
- 238000005698 Diels-Alder reaction Methods 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- 125000005234 alkyl aluminium group Chemical group 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000001273 butane Substances 0.000 description 2
- 239000003085 diluting agent Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 125000000219 ethylidene group Chemical group [H]C(=[*])C([H])([H])[H] 0.000 description 2
- 229910052735 hafnium Inorganic materials 0.000 description 2
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000002638 heterogeneous catalyst Substances 0.000 description 2
- 229920001519 homopolymer Polymers 0.000 description 2
- 239000012442 inert solvent Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- QWTDNUCVQCZILF-UHFFFAOYSA-N isopentane Chemical compound CCC(C)C QWTDNUCVQCZILF-UHFFFAOYSA-N 0.000 description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 2
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 2
- BKIMMITUMNQMOS-UHFFFAOYSA-N nonane Chemical compound CCCCCCCCC BKIMMITUMNQMOS-UHFFFAOYSA-N 0.000 description 2
- 125000002524 organometallic group Chemical group 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001294 propane Substances 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 239000011343 solid material Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 239000004711 α-olefin Substances 0.000 description 2
- BLRCZVHYYYNUIK-UHFFFAOYSA-N 2-(4-methoxyphenyl)-2,3,3a,4-tetrahydro-1h-indene Chemical compound C1=CC(OC)=CC=C1C1CC2=CC=CCC2C1 BLRCZVHYYYNUIK-UHFFFAOYSA-N 0.000 description 1
- MFYIWAGCRUQSLR-UHFFFAOYSA-N 2-(4-methylphenyl)-2,3,3a,4-tetrahydro-1H-indene Chemical compound C1=CC(C)=CC=C1C1CC2=CC=CCC2C1 MFYIWAGCRUQSLR-UHFFFAOYSA-N 0.000 description 1
- JNLPACMRMNKADW-UHFFFAOYSA-N 2-phenyl-2,3,3a,4-tetrahydro-1h-indene Chemical compound C1C2=CC=CCC2CC1C1=CC=CC=C1 JNLPACMRMNKADW-UHFFFAOYSA-N 0.000 description 1
- OWWRMMIWAOBBFK-UHFFFAOYSA-N 3,4-dimethylhex-1-ene Chemical compound CCC(C)C(C)C=C OWWRMMIWAOBBFK-UHFFFAOYSA-N 0.000 description 1
- YHQXBTXEYZIYOV-UHFFFAOYSA-N 3-methylbut-1-ene Chemical compound CC(C)C=C YHQXBTXEYZIYOV-UHFFFAOYSA-N 0.000 description 1
- UFERIGCCDYCZLN-UHFFFAOYSA-N 3a,4,7,7a-tetrahydro-1h-indene Chemical compound C1C=CCC2CC=CC21 UFERIGCCDYCZLN-UHFFFAOYSA-N 0.000 description 1
- FMIDFXCVRGPJHZ-UHFFFAOYSA-N 4,4-diethylhex-1-ene Chemical compound CCC(CC)(CC)CC=C FMIDFXCVRGPJHZ-UHFFFAOYSA-N 0.000 description 1
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- ZADPBFCGQRWHPN-UHFFFAOYSA-N boronic acid Chemical compound OBO ZADPBFCGQRWHPN-UHFFFAOYSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- OZWCXTBBBIAOAT-UHFFFAOYSA-N chloromethane silane Chemical compound [SiH4].ClC OZWCXTBBBIAOAT-UHFFFAOYSA-N 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 238000010908 decantation Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- HJXBDPDUCXORKZ-UHFFFAOYSA-N diethylalumane Chemical compound CC[AlH]CC HJXBDPDUCXORKZ-UHFFFAOYSA-N 0.000 description 1
- CQYBWJYIKCZXCN-UHFFFAOYSA-N diethylaluminum Chemical compound CC[Al]CC CQYBWJYIKCZXCN-UHFFFAOYSA-N 0.000 description 1
- 238000005906 dihydroxylation reaction Methods 0.000 description 1
- AFABGHUZZDYHJO-UHFFFAOYSA-N dimethyl butane Natural products CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 235000003642 hunger Nutrition 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000012535 impurity Substances 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
- 229910003480 inorganic solid Inorganic materials 0.000 description 1
- 239000002198 insoluble material Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 229920001580 isotactic polymer Polymers 0.000 description 1
- 238000005304 joining Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 238000013507 mapping Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- 229910052987 metal hydride Inorganic materials 0.000 description 1
- 150000004681 metal hydrides Chemical class 0.000 description 1
- 239000012968 metallocene catalyst Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- 125000000538 pentafluorophenyl group Chemical group FC1=C(F)C(F)=C(*)C(F)=C1F 0.000 description 1
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 1
- 125000004817 pentamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical group CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- NTTOTNSKUYCDAV-UHFFFAOYSA-N potassium hydride Chemical compound [KH] NTTOTNSKUYCDAV-UHFFFAOYSA-N 0.000 description 1
- 229910000105 potassium hydride Inorganic materials 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 230000011218 segmentation Effects 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 230000037351 starvation Effects 0.000 description 1
- 230000000707 stereoselective effect Effects 0.000 description 1
- 229920001576 syndiotactic polymer Polymers 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 235000012222 talc Nutrition 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 description 1
- OLFPYUPGPBITMH-UHFFFAOYSA-N tritylium Chemical compound C1=CC=CC=C1[C+](C=1C=CC=CC=1)C1=CC=CC=C1 OLFPYUPGPBITMH-UHFFFAOYSA-N 0.000 description 1
- 238000007738 vacuum evaporation Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000004876 x-ray fluorescence Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- 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
- C08F4/65922—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 containing at least two cyclopentadienyl rings, fused or not
- C08F4/65925—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 containing at least two cyclopentadienyl rings, fused or not two cyclopentadienyl rings being mutually non-bridged
-
- 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
- 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
- C08F4/65912—Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with an organoaluminium compound
-
- 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
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Abstract
含有一种非桥连二(2－芳基四氢茚基)茂金属和一种助催化剂的催化剂体系,以及在烯烃—尤其是具有3或更多个碳原子的烯烃—的聚合中的应用。
Description
本发明涉及使用茂金属的烯烃聚合。在特别优选的实施方案中，本发明涉及具有至少3个碳原子的烯烃的聚合。
已知具有3个或更多碳原子的烯烃能被聚合成有多种类型立体有规微观结构的聚合物。间同立构聚合物一般被认为是具有立体化学结构的，其中单体单元有不对称碳原子的对映构型，在主聚合物链上互相交替规则地结合。全同立构聚合物一般被描述为具有长的有相同叔碳原子相对构型的单体单元的序列。在无规立构聚合物中，立构中心无规则地定位。具有高度全同立构或间同立构性质的聚合物一般是结晶固体，并且不溶于二甲苯。无规聚合物一般溶于二甲苯，并且是胶或液体。
为了特定的应用，希望在聚合物中有高度的全同立构结构。已发现茂金属的一些很特定的类型具有全同立构立体选择性。例子包括外消旋亚乙基桥连的二(茚基)和外消旋亚乙基桥连的四氢茚基二氯合锆。但这些桥连的外消旋茂金属异构体必须从外消旋和内消旋异构体的混合物中离析以制备全同立构立体选择性的催化剂材料。这种分离困难并且昂贵。
据本发明人发现只有一种非桥连的茂金属已被报道能生产高度全同立构微观结构。这种茂金属是在美国专利5304523中公开的二(1-甲基芴基)二氯合锆。
本发明的一个目的是提供一种聚合烯烃的新方法。本发明的特别优选的目的是提供一种通过使用比桥连的茂金属更易制备的一种非桥连茂金属从有至少3个碳原子的烯烃制备高度全同立构微观结构的聚合物的方法。另一个目的是提供一种茂金属无需分离外消旋和内消旋异构体而具有立体选择性。
考察下面的描述将清楚本发明的其它观点、目的和优点。
根据本发明，提供了一种用于聚合具有至少3个碳原子的烯烃的方法，包括将所述烯烃与茂金属和适合的助催化剂接触，其中茂金属是IVB族金属的二(2-芳基-4，5，6，7-四氢茚基)非桥连茂金属，其中，芳基是未取代的或被烃基或烃氧基取代的。
本发明中使用的二(2-芳基四氢茚基)茂金属包括用下式表示的那些，其中每个R是具有1-20个碳原子的烃基和烃氧基，y是0-3的整数；Me是一种IVB族金属。每个Q是氢化物、卤化物或诸如芳基的烃基，或直链、支链或环烷基。金属Me优选为锆和铪。
这些化合物的一些例子包括二(2-苯基四氢茚基)二氯合锆；二(2-对甲氧基苯基四氢茚基)二氯合锆；二(2-对甲基苯基四氢茚基)二氯合锆；二(2-对甲氧基苯基四氢茚基)二甲基锆；二(2-(对甲基苯基)四氢茚基)二甲基锆；二(2-(邻甲氧基苯基)二氯合锆；二(2-(间甲氧基苯基)二氯合锆；二(2-(邻，对-二甲氧基苯基)二氯合锆及类似物。制备这类一些茂金属的技术在文献“有机金属化学杂志”J.Orgomet.Chem，465，175-179(1994)中公开。
上述茂金属的类型适用于从烯烃——包括乙烯——制备聚合物，特别适用于用具有3或更多碳原子的烯烃制备有全同立构微观结构的分子。具有3或更多碳原子的烯烃的例子包括丙烯、1-丁烯、1-戊烯、3-甲基-1-丁烯、1-己烯、4-甲基-1-戊烯、3-乙基-1-丁烯、1-庚烯、1-辛烯、1-癸烯、4，4-二甲基-1-戊烯、4，4-二乙基-1-己烯、3，4-二甲基-1-己烯和类似物。在本发明的范围中包括在均聚物的制备中使用该催化剂体系。在本发明的范围中还包括在两种或多种该α-烯烃的混合物的聚合中使用该催化剂体系。在本发明的范围中进一步包括在一种或多种α-烯烃的与乙烯联合聚合中使用该催化剂体系。一般如果乙烯的用量使生成的聚合物含少于80％wt的乙烯，所得的聚合物与其说是热塑性的，倒不如更通常地称之为是热弹性的。典型的例子是具有至少20％wt掺入的丙烯单体的乙烯-丙烯共聚物。
通过使用适合的助催化剂可活化二(2-芳基四氢茚基)茂金属以制备适用于烯烃单体聚合的催化剂体系。预期茂金属可用以往适用于活化其它类似茂金属的任何一般的技术活化，包括使用稳定的非配位抗衡离子，诸如在美国专利5155080中公开的，即三苯基碳鎓四(五氟苯基)硼酸盐(boronate)。该聚合可在均相体系中进行，其中催化剂和助催化剂均可溶；但是，在本发明的范围中还包括在淤浆或气相条件进行聚合。可使用有载体形式的催化剂和/或助催化剂。一般优选载体是在使用的聚合介质中不溶的物质。
一般的助催化剂的例子一般包括任何那些以往与含过渡金属的烯烃聚合催化剂一起使用的有机金属助催化剂。一些典型的例子包括元素周期表的IA、IIA和IIB族金属的有机金属化合物。这些化合物的例子包括有机金属卤化物、有机金属氢化物和金属氢化物。一些特别优选的离子包括三乙基铝、三异丁基铝、二乙基铝氯化物、二乙基铝氢化物以及类似物。
通常最优选的助催化剂是铝氧烷(aluminoxane)。这类化合物包括那些有所列通式的重复单元的化合物，其中R是通常有1-5个碳原子的烷基。这些铝氧烷有时也指聚(烃基铝氧化物)，在本领域中已知，通常由有机烃基铝化合物与水反应来制备。这种制备技术在美国专利3242099和4808561中公开，这些公开作为参考在此引用。通常优选的助催化剂是从三甲基铝或三乙基铝制备的。该铝氧烷经常分别指聚(甲基铝氧化物)或聚(乙基铝氧化物)。铝氧烷与三烷基铝——诸如在美国专利4794096中公开的，其公开作为参考在此引用——联合使用也在本发明范围内。
如上所述的催化剂可通过将茂金属——按照说明，优选茂锆(zirconocene)——与铝氧烷混合制成催化剂体系。可通过将必要的茂金属和铝氧烷在适合的稀释剂中有或没有单体存在下混合制备成无载体的催化剂。使用无载体的催化剂的聚合可用溶液或淤浆聚合过程进行。用将必要的茂金属和/或铝氧烷成分吸附在诸如硅胶、氧化铝或其它适合的有机或无机载体材料上的方法也可把催化剂体系制成多相催化剂并使用。
用于制备多相催化剂的载体材料可以是细的聚烯烃粉末或细分的无机固体多孔载体，诸如滑石、二氧化硅、氧化铝、二氧化硅-氧化铝或其混合物。可以单独使用或与二氧化硅或二氧化硅-氧化铝联合使用的其它无机氧化物是氧化镁、氧化钛、氧化锆和类似物，如本领域已知的，无机氧化物应被脱水以除去水分。如果希望，在无机固体多孔载体表面的残留表面羟基可用加热或用与脱水剂——诸如烷基锂、氯甲硅烷、烷基铝——或优选与铝氧烷反应的方法除去。优选的催化剂载体是脱水的用铝氧烷处理的无机氧化物，优选使用甲基铝氧烷处理的。适合的载体是脱水的又用甲基铝氧烷处理的硅胶。
通常烃可溶性的茂金属和铝氧烷用沉淀在载体材料——诸如用甲基铝氧烷处理的脱水硅胶——上的方法可制成多相载体催化剂。适合的硅胶颗粒直径在1-600微米，优选10-100微米；表面积为50-1000m2/g，优选100-500m2/g；孔隙体积为0.5-3.5cm3/g。硅胶可在100-1000℃、优选300-800℃加热处理1-100小时，优选3-24小时，以确保它以脱水形式使用。
通过接触茂金属和铝氧烷助催化剂得到的催化剂体系可在将这些成分引入反应器之前形成，或用另一种方法，在反应器里形成。在使用茂锆并且活性体系在反应器中形成的情况下，在反应器中Al对Zr的摩尔比需在10-5000、优选20-4000、最优选20-1000范围内。在活性体系在反应器外形成的情况下，Al对Zr优选的比例在1-200、希望在20-200范围。在该情况下，在反应器中可使用附加的铝氧烷助催化剂，这样Al对Zr的总比在10-5000、优选20-4000、最优选20-1000范围内。同样，在该情况下，少量的其它烷基铝化合物诸如三乙基铝或三异丁基铝可以与附加的铝氧烷一起或代替附加的铝氧烷加入到反应器中，用来清除任何杂质或带来其它好处。在所有上述情况中，催化剂或助催化剂可在反应器中与已存在于适合载体上的一种成分接触。
如前所述，所述情况的茂锆是优选的茂金属。因此催化剂的进一步讨论可明确参考茂锆，不过应明白，相似的条件和过程也适用于茂钛和茂铪。
在用于制备载体催化剂体系的一个优选的技术中，脱水的硅胶与铝氧烷接触，接着与茂锆接触。但是，如果需要，茂锆可在载体材料与铝氧烷接触之前加入到脱羟基化的载体材料中。根据本发明优选的实施方案，溶于适合的惰性烃溶剂中的铝氧烷被加到干的或在相同或其它适合的烃液体中浆化的载体材料中，然后茂锆被加到淤浆中，优选在真空中干燥载体并在轻质烃中再浆化后加入。在该实施方案中，基于催化剂总重量，茂锆加入到淤浆中的量足以提供约0.02-5.0％wt的锆金属。基于催化剂总重量，更优选加入的茂锆的量提供约0.10-1.0％wt的锆金属。
如上所述，载体材料的处理在惰性溶剂中进行。相同或不同的惰性溶剂也用于溶解茂锆和铝氧烷。优选的溶剂包括各种在处理温度和压力下是液态的烃，并且各种成分都可溶于其中。有用的溶剂的具体例子包括烷烃，诸如丙烷、丁烷、戊烷、异戊烷、己烷、庚烷、辛烷、壬烷；环烷烃，诸如环戊烷和环己烷；芳烃，诸如苯、甲苯、二甲苯、乙基苯和二乙基苯。应使用足够的溶剂以在反应期间从催化剂成分转移适当的热并提供良好的混合。
在制备催化剂体系期间采用的温度可大范围变动诸如例如0-100℃。高些或低些的温度也可采用。但是，铝氧烷与载体材料之间的反应很快，希望铝氧烷与载体材料接触约半小时至18小时或更多。优选反应在25-100℃保持约1小时。
不论什么时候，各个成分和再生的催化剂成分必须隔绝氧气和水分。因此，反应在无氧气和水分的气氛中进行，催化剂在无氧气和水分的气氛中再生。因此反应优选在惰性干气体诸如例如氮气的存在下进行。再生的固体催化剂保存在惰性气体气氛中。
当茂锆和铝氧烷在载体上的沉淀完成时，优选用少量单体——例如乙烯——处理固体材料以在固体催化剂材料上形成一些聚合物使催化剂重量基于催化剂和载体材料的总重量提高至少50％，希望约100-500％。后来的这种处理称为催化剂的预聚。然后固体材料——本身或预聚后的——可用任何已知技术回收。例如固体催化剂材料可由过滤、真空蒸发、倾析法从液体中回收。固体然后在纯的干氮气气流中或在真空中干燥。
固体催化剂材料的预聚有助于得到在淤浆聚合期间制备的明确限定的颗粒形式的EPC弹性体。预聚的催化剂可用烃漂洗以得到好的规则的颗粒形式。预聚也大大减少了对铝氧烷的需要。例如当铝氧烷加到反应器的液相中时，约1000∶1的Al∶Zr的比或对于铝氧烷∶茂锆更大的比对高活性是必须的，但当铝氧烷混合到预聚的催化剂中时，小于约100∶1的比是足够的。对于预聚的催化剂，铝对锆的比一般应在从约1∶1到500∶1、优选从约20∶1到100∶1的范围，仍能得到高活性。
最优选载体催化剂按下列方法制备：1)将溶于适合溶剂——例如甲苯——的铝氧烷加到载体中形成淤浆；2)在60-80℃搅拌淤浆30-60分钟；3)在真空除去溶剂并充分加热以制备干燥粉末；4)加入轻质烃——例如戊烷——以浆化粉末；5)加入茂锆在戊烷或最少量甲苯中的溶液，并在20-60℃搅拌15-60分钟；6)在戊烷淤浆中预聚乙烯或其它烯烃，然后收集、漂洗及干燥催化剂。为获得最好的颗粒形式，优选除在预聚的催化剂上的铝氧烷不再向反应器中加入铝氧烷。烷基铝，诸如三乙基铝或三异丁基铝也可在催化剂体系中使用。
催化剂体系的多相形式特别适用于淤浆聚合过程。根据本发明优选的方法，可使用液态α-烯烃单体作为聚合稀释剂。作为实际的限制，淤浆聚合在聚合物产物大体不溶于其中的液体稀释剂中进行。优选用于淤浆聚合的稀释剂是一种或多种少于5个碳原子的烃。如果希望，饱和的烃，诸如乙烷、丙烷或丁烷可全部或部分地用作稀释剂。同样，α-烯烃单体或不同的α-烯烃单体的混合物可以全部或部分地用作稀释剂。最优选的稀释剂包括大部分将被聚合的α-烯烃单体。
对本发明及其目的和优点的进一步理解将由下列实施例说明。
实施例1
二(2-苯基四氢茚基)二氯合锆
在0℃和氩气气氛下向在装有侧臂的Schlenk仪器中20ml的2-苯基四氢茚的乙醚溶液中缓缓加入1.13ml2.62M正丁基锂的庚烷溶液，得到白色悬浮液，使其在室温保温2小时。然后经侧臂加入固体四氯化锆，将反应混合物在室温搅拌24小时。泵干所得黄色悬浊液至干燥，用苯滴定，母液在真空中浓缩以提供一种黄色固体，鉴定为二(2-苯基四氢茚基)二氯合锆。
实施例2
二(2-(对甲氧基苯基)四氢茚基)三氯合锆
将1.3mmol的2-(对甲氧基苯基)四氢茚结合制备一种溶液。其与1.46mmol正丁基锂在庚烷溶液中如实施例1那样反应。然后经侧臂加入0.6mmol四氯化锆，将反应混合物在室温搅拌24小时。粗产物通过用己烷研制，在氩气气氛中过滤，并在真空中除去溶剂而纯化。得到533mg黄色固体，鉴定为二(2-(对甲氧基苯基)四氢茚基)二氯合锆。
实施例3
二(2-(对甲基苯基)四氢茚基)二氯合锆
在这种情况，使用实施例1的过程，但需使用0.476mmol的2-(对甲基苯基)四氢茚、0.52mmol丁基锂、0.242mmol四氯化锆和4ml乙醚。固体鉴定为二(2-对甲基苯基)四氢茚基二氯合锆。
实施例4
二(2-(对溴苯基)四氢茚基)二氯合锆
使用实施例1的过程，但在这种情况，使用0.677mmol氢化钾代替正丁基锂，并且起始材料是在8ml乙醚中的0.615mmol2-(对溴苯基)四氢茚。过程使用0.31mmol四氯化锆。所得产物被纯化，鉴定为二(2-(对溴苯基)四氢茚基)二氯合锆。
实施例5
控制聚合反应以评估在丙烯的聚合中各种茂金属的作用。
在手套箱里在氩气气氛中，将固体茂金属置于Diels Alder管中，然后封闭，制备催化剂体系。然后在室温用注射器将7.5ml 10％wt的甲基铝氧烷的甲苯溶液加入到管里。然后将管起涡流直至固体溶解。
聚合在装有机械搅拌器和自动控温装置的4升不锈钢高压釜反应器里进行。用注射器将催化剂体系从Diels Alder管中抽出，经一个小口注入洁净吹洗的反应器中，与丙烯气体逆流。然后封闭反应器并在室温充入全部的2/3的液体丙烯。在一些操作中还加入氢气。然后混合物的温度通过使用蒸气加热的间接热传导升至希望的水平。反应器温度随后保持在这个水平2小时，此后将液体丙烯排到火炬结束聚合反应。排气进行几秒钟。然后打开反应器，移出聚合物。在真空炉内干燥聚合物1小时，随后称重。催化剂的生产效率用由X-射线荧光确定的在聚合物中的锆的水平来测定。分子量由胶体渗透色谱分析确定。
一系列的试验包括一系列的聚合，各自使用由8mg二(2-(对甲氧基苯基)四氢茚基二氯合锆制备的催化剂体系。在表1中总结了这些试验的结果。
表1
| 试验号 | ℃ | g/g催化剂 | Mw(×103) | Mw/Mn | [M]％ | [mm]％ |
| 1 | 40 | 229 | 277 | 6.0 | 90.7 | 86.2 |
| 2 | 50 | 433 | 262 | 5.6 | 90.2 | 85.4 |
| 3 | 60 | 2350 | 131 | 5.2 | 86.8 | 80.7 |
| 4 | 70 | 1125 | 120 | 5.7 | 85.7 | 79.0 |
| 5* | 60 | 5720 | 11 | 3.1 | 74.2 | 62.8 |
| *使用氢气 | ||||||
表1的结果证明，茂金属二(2-(对甲氧基苯基)四氢茚基二氯合锆能制备具有相对高含量的全同立构微观结构的聚丙烯均聚物。它表明全同立构微观结构含量与温度成反比关系。试验3和5的对照表明氢气降低聚合物的分子量并减少全同立构微观结构的生成。没有氢气参与的试验制备的聚合物具有的分子量分布比一般只从单点茂金属催化剂预期的分布要宽。聚合物的熔点在152.5-157℃范围，熔化热在51.2-70.5J/g范围。
类似的一系列试验进行时使用由3mg茂金属二(2-(对溴苯基)四氢茚基二氯合锆制备的催化剂体系。不加氢气进行5个反应，温度以10℃为间隔从30℃到变化到70℃。当催化剂体系表现出更有活性时，所有那些反应的产物是低分子量的粘稠的油。分子量分布小于2，重均分子量在8700-37000范围内，分子量较高的产物在较低的反应温度生成。
Claims (20)
1一种用于烯烃聚合的方法，包括将所述烯烃与催化剂体系接触，该催化剂体系通过结合一种助催化剂和一种选自IVB族金属的二(2-芳基四氢茚基)茂金属的茂金属制备，其中芳基可以是未取代的或被选自由烃基或烃氧基组成的组的取代基取代。
2根据权利要求1的方法，其中所述的茂金属选自下式表示的那些
其中每个R是具有1-20个碳原子的烃基和烃氧基，y是0-3的整数；Me是一种IVB族金属；每个Q是氢化物、卤化物或诸如芳基的烃基，或有1-12个碳原子的直链的、支链的烷基或环烷基。
3根据权利要求2的方法，其中所述的助催化剂是烷基铝氧烷，至少一种被聚合的烯烃是有至少3个碳原子的烯烃。
4根据权利要求3的方法，其中聚合在颗粒形式的条件下进行，这样最终聚合物产物不溶于聚合介质。
5根据权利要求4的方法，其中聚合丙烯。
6根据权利要求5的方法，其中Me是锆。
7根据权利要求6的方法，其中所述的助催化剂是甲基铝氧烷。
8根据权利要求7的方法，其中所述的茂金属是二(2-(对甲氧基苯基)四氢茚基)二氯合锆。
9根据权利要求8的方法，其中均聚丙烯。
10根据权利要求4的方法，其中所述的茂金属是二(2-(对甲氧基苯基)四氢茚基)二氯合锆。
11根据权利要求3的方法，其中所述的茂金属是二(2-(对甲氧基苯基)四氢茚基)二氯合锆。
12根据权利要求11的方法，其中聚合丙烯。
13根据权利要求12的方法，其中所述的助催化剂包括甲基铝氧烷。
14根据权利要求13的方法，其中聚合在40-70℃的温度范围进行。
15根据权利要求14的方法，进行来制备具有[mm]至少为约62.8％的丙烯均聚物，[mm]用C13NMR测定。
16根据权利要求14的方法，进行来制备具有[mm]至少为约79％的丙烯均聚物，[mm]用C13NMR测定。
17一种催化剂体系，通过结合一种选自IVB族金属的二(2-芳基四氢茚基)茂金属的茂金属制备，其中芳基可以是未取代的或被选自由烃基或烃氧基组成的组的取代基取代。
18根据权利要求17的催化剂体系，其中所述的助催化剂是烷基铝氧烷。
19根据权利要求18的催化剂体系，其中所述的茂金属是二(2-(对甲氧基苯基)四氢茚基)二氯合锆。
20根据权利要求19的催化剂体系，其中所述的助催化剂是甲基铝氧烷。
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| US682223 | 1996-07-17 | ||
| US08/682,223 US5705579A (en) | 1996-07-17 | 1996-07-17 | Olefin polymerization |
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| TW505664B (en) | 2002-10-11 |
| CA2210730C (en) | 2001-09-11 |
| NO311525B1 (no) | 2001-12-03 |
| DK0819705T3 (da) | 1999-12-20 |
| RU2193042C2 (ru) | 2002-11-20 |
| KR980008316A (ko) | 1998-04-30 |
| ZA976084B (en) | 1998-02-02 |
| CA2210730A1 (en) | 1998-01-17 |
| EP0819705A1 (en) | 1998-01-21 |
| JPH1067815A (ja) | 1998-03-10 |
| US5705579A (en) | 1998-01-06 |
| DE69700490D1 (de) | 1999-10-14 |
| ID19682A (id) | 1998-07-30 |
| BR9704007A (pt) | 1998-09-01 |
| ES2135966T3 (es) | 1999-11-01 |
| NO973314D0 (no) | 1997-07-17 |
| ATE184291T1 (de) | 1999-09-15 |
| HU9701223D0 (en) | 1997-08-28 |
| MX9705210A (es) | 1998-04-30 |
| HUP9701223A3 (en) | 2001-04-28 |
| EP0819705B1 (en) | 1999-09-08 |
| GR3032033T3 (en) | 2000-03-31 |
| NO973314L (no) | 1998-01-19 |
| AU2850397A (en) | 1998-01-29 |
| AU694073B2 (en) | 1998-07-09 |
| MY132781A (en) | 2007-10-31 |
| DE69700490T2 (de) | 2000-01-05 |
| AR007910A1 (es) | 1999-11-24 |
| HUP9701223A2 (hu) | 1999-06-28 |
| CN1113070C (zh) | 2003-07-02 |
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