CN1259964A - Process for polymerization olefins in gas phase - Google Patents
Process for polymerization olefins in gas phase Download PDFInfo
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- CN1259964A CN1259964A CN 97182266 CN97182266A CN1259964A CN 1259964 A CN1259964 A CN 1259964A CN 97182266 CN97182266 CN 97182266 CN 97182266 A CN97182266 A CN 97182266A CN 1259964 A CN1259964 A CN 1259964A
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- cyclopentadienyl
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- 238000000034 method Methods 0.000 title claims abstract description 56
- 230000008569 process Effects 0.000 title claims abstract description 9
- 238000006116 polymerization reaction Methods 0.000 title claims description 34
- 150000001336 alkenes Chemical class 0.000 title abstract description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 74
- 239000003054 catalyst Substances 0.000 claims abstract description 65
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 36
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 25
- 150000003624 transition metals Chemical class 0.000 claims abstract description 24
- 239000012190 activator Substances 0.000 claims abstract description 14
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 claims description 46
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 33
- -1 5-cyclopentadienyl Chemical group 0.000 claims description 25
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 claims description 25
- 125000000217 alkyl group Chemical group 0.000 claims description 20
- 238000003756 stirring Methods 0.000 claims description 20
- 239000007789 gas Substances 0.000 claims description 19
- 239000004711 α-olefin Substances 0.000 claims description 19
- 239000005977 Ethylene Substances 0.000 claims description 17
- 229910052751 metal Inorganic materials 0.000 claims description 17
- 239000002184 metal Substances 0.000 claims description 16
- ZSWFCLXCOIISFI-UHFFFAOYSA-N endo-cyclopentadiene Natural products C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 claims description 15
- 229910052739 hydrogen Inorganic materials 0.000 claims description 14
- 239000001257 hydrogen Substances 0.000 claims description 14
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 14
- 125000000538 pentafluorophenyl group Chemical group FC1=C(F)C(F)=C(*)C(F)=C1F 0.000 claims description 14
- 239000002002 slurry Substances 0.000 claims description 14
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 13
- 229910052796 boron Inorganic materials 0.000 claims description 13
- 229910052757 nitrogen Inorganic materials 0.000 claims description 12
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical class [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 11
- 125000001181 organosilyl group Chemical group [SiH3]* 0.000 claims description 11
- 229910052719 titanium Inorganic materials 0.000 claims description 11
- 239000010936 titanium Substances 0.000 claims description 11
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 10
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 9
- 125000003118 aryl group Chemical group 0.000 claims description 9
- 229910052726 zirconium Inorganic materials 0.000 claims description 9
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 6
- 125000001188 haloalkyl group Chemical group 0.000 claims description 6
- 230000003647 oxidation Effects 0.000 claims description 6
- 238000007254 oxidation reaction Methods 0.000 claims description 6
- 238000007334 copolymerization reaction Methods 0.000 claims description 5
- 125000003800 germyl group Chemical group [H][Ge]([H])([H])[*] 0.000 claims description 5
- 125000005843 halogen group Chemical group 0.000 claims description 5
- 239000003446 ligand Substances 0.000 claims description 5
- 230000007935 neutral effect Effects 0.000 claims description 5
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 claims description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 4
- 125000003545 alkoxy group Chemical group 0.000 claims description 4
- 125000004104 aryloxy group Chemical group 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- 125000004122 cyclic group Chemical group 0.000 claims description 4
- 229910052735 hafnium Inorganic materials 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- 229910052698 phosphorus Inorganic materials 0.000 claims description 4
- 239000011574 phosphorus Substances 0.000 claims description 4
- NHYFQMARGINDIH-UHFFFAOYSA-N C[Ti]C.C[SiH2]C Chemical compound C[Ti]C.C[SiH2]C NHYFQMARGINDIH-UHFFFAOYSA-N 0.000 claims description 3
- 239000002879 Lewis base Substances 0.000 claims description 3
- 150000001399 aluminium compounds Chemical class 0.000 claims description 3
- 125000002897 diene group Chemical group 0.000 claims description 3
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 claims description 3
- 125000001475 halogen functional group Chemical group 0.000 claims description 3
- 150000002431 hydrogen Chemical class 0.000 claims description 3
- 150000007527 lewis bases Chemical class 0.000 claims description 3
- 125000005353 silylalkyl group Chemical group 0.000 claims description 3
- GMSBPKZRTZHCPB-UHFFFAOYSA-N C=CC=CC.[Ti+2].C[SiH2]C Chemical compound C=CC=CC.[Ti+2].C[SiH2]C GMSBPKZRTZHCPB-UHFFFAOYSA-N 0.000 claims description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 2
- 239000005864 Sulphur Substances 0.000 claims description 2
- 125000004183 alkoxy alkyl group Chemical group 0.000 claims description 2
- 125000002877 alkyl aryl group Chemical group 0.000 claims description 2
- 150000001408 amides Chemical class 0.000 claims description 2
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 2
- 125000005325 aryloxy aryl group Chemical group 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 150000002367 halogens Chemical class 0.000 claims description 2
- 150000004678 hydrides Chemical class 0.000 claims description 2
- 125000005647 linker group Chemical group 0.000 claims description 2
- 230000000737 periodic effect Effects 0.000 claims description 2
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims 2
- 230000000694 effects Effects 0.000 abstract description 8
- 238000011065 in-situ storage Methods 0.000 abstract 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Natural products CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 47
- 239000000203 mixture Substances 0.000 description 22
- 239000000126 substance Substances 0.000 description 22
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 20
- 229910052799 carbon Inorganic materials 0.000 description 17
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 description 17
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 16
- 150000002500 ions Chemical class 0.000 description 13
- 230000003197 catalytic effect Effects 0.000 description 12
- 238000001816 cooling Methods 0.000 description 10
- 238000002360 preparation method Methods 0.000 description 10
- 238000010926 purge Methods 0.000 description 10
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 10
- 239000011780 sodium chloride Substances 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 7
- 239000000843 powder Substances 0.000 description 7
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical group [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 230000004913 activation Effects 0.000 description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical compound C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 description 5
- 150000001639 boron compounds Chemical class 0.000 description 4
- YSRFHVJGXPIDGR-UHFFFAOYSA-N dimethylsilane titanium Chemical compound [Ti].C[SiH2]C YSRFHVJGXPIDGR-UHFFFAOYSA-N 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical group C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 229910052809 inorganic oxide Inorganic materials 0.000 description 3
- 229910052752 metalloid Inorganic materials 0.000 description 3
- 150000002738 metalloids Chemical group 0.000 description 3
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 229920000098 polyolefin Polymers 0.000 description 3
- 239000011435 rock Substances 0.000 description 3
- 229910000077 silane Inorganic materials 0.000 description 3
- UWNADWZGEHDQAB-UHFFFAOYSA-N 2,5-dimethylhexane Chemical group CC(C)CCC(C)C UWNADWZGEHDQAB-UHFFFAOYSA-N 0.000 description 2
- RQDMEYLMEMRZME-UHFFFAOYSA-N C=1C=CC=CC=1C[Zr]CC1=CC=CC=C1 Chemical compound C=1C=CC=CC=1C[Zr]CC1=CC=CC=C1 RQDMEYLMEMRZME-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 239000002841 Lewis acid Substances 0.000 description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 239000011954 Ziegler–Natta catalyst Substances 0.000 description 2
- 230000003213 activating effect Effects 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 229910000085 borane Inorganic materials 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 150000001993 dienes Chemical class 0.000 description 2
- GGSUCNLOZRCGPQ-UHFFFAOYSA-N diethylaniline Chemical compound CCN(CC)C1=CC=CC=C1 GGSUCNLOZRCGPQ-UHFFFAOYSA-N 0.000 description 2
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 150000004820 halides Chemical class 0.000 description 2
- 150000007517 lewis acids Chemical class 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- UORVGPXVDQYIDP-UHFFFAOYSA-N trihydridoboron Substances B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- RSSDWSPWORHGIE-UHFFFAOYSA-N $l^{1}-phosphanylbenzene Chemical compound [P]C1=CC=CC=C1 RSSDWSPWORHGIE-UHFFFAOYSA-N 0.000 description 1
- PMJHHCWVYXUKFD-SNAWJCMRSA-N (E)-1,3-pentadiene Chemical compound C\C=C\C=C PMJHHCWVYXUKFD-SNAWJCMRSA-N 0.000 description 1
- QWUWMCYKGHVNAV-UHFFFAOYSA-N 1,2-dihydrostilbene Chemical group C=1C=CC=CC=1CCC1=CC=CC=C1 QWUWMCYKGHVNAV-UHFFFAOYSA-N 0.000 description 1
- QLKINISCYVCLTE-UHFFFAOYSA-N 6-phenylhexa-2,4-dienylbenzene Chemical compound C=1C=CC=CC=1CC=CC=CCC1=CC=CC=C1 QLKINISCYVCLTE-UHFFFAOYSA-N 0.000 description 1
- 239000007848 Bronsted acid Substances 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- XJONFIGVOQMBIP-UHFFFAOYSA-L Cl[Zr](Cl)C1C=CC=C1 Chemical class Cl[Zr](Cl)C1C=CC=C1 XJONFIGVOQMBIP-UHFFFAOYSA-L 0.000 description 1
- 240000004859 Gamochaeta purpurea Species 0.000 description 1
- CMEWLCATCRTSGF-UHFFFAOYSA-N N,N-dimethyl-4-nitrosoaniline Chemical compound CN(C)C1=CC=C(N=O)C=C1 CMEWLCATCRTSGF-UHFFFAOYSA-N 0.000 description 1
- AYDQIZKZTQHYIY-UHFFFAOYSA-N OC(=O)C1(C)CC(C(O)=O)=CC=C1 Chemical compound OC(=O)C1(C)CC(C(O)=O)=CC=C1 AYDQIZKZTQHYIY-UHFFFAOYSA-N 0.000 description 1
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 1
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 1
- UCIKZESDXASJNG-UHFFFAOYSA-L [Cl-].[Cl-].C1=CC=C2C([Zr+2])C=CC2=C1 Chemical class [Cl-].[Cl-].C1=CC=C2C([Zr+2])C=CC2=C1 UCIKZESDXASJNG-UHFFFAOYSA-L 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 125000005103 alkyl silyl group Chemical group 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 150000001449 anionic compounds Chemical class 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 229910052728 basic metal Inorganic materials 0.000 description 1
- 238000006758 bulk electrolysis reaction Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000021615 conjugation Effects 0.000 description 1
- KKNWHLHBSVUXKT-UHFFFAOYSA-N dimethyl-(2-methyl-1H-inden-1-yl)silane titanium(2+) Chemical compound [Ti+2].CC=1C(C2=CC=CC=C2C1)[SiH](C)C KKNWHLHBSVUXKT-UHFFFAOYSA-N 0.000 description 1
- WODAGJKOTBCQIL-UHFFFAOYSA-N dimethylsilane titanium(2+) Chemical compound [Ti+2].C[SiH2]C WODAGJKOTBCQIL-UHFFFAOYSA-N 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 238000012685 gas phase polymerization Methods 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical group [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 230000026030 halogenation Effects 0.000 description 1
- 238000005658 halogenation reaction Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 239000002955 immunomodulating agent Substances 0.000 description 1
- 229940121354 immunomodulator Drugs 0.000 description 1
- 230000002584 immunomodulator Effects 0.000 description 1
- 238000005304 joining Methods 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
- 239000000155 melt Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 150000001457 metallic cations Chemical class 0.000 description 1
- 239000012968 metallocene catalyst Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 238000006384 oligomerization reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- PMJHHCWVYXUKFD-UHFFFAOYSA-N piperylene Natural products CC=CC=C PMJHHCWVYXUKFD-UHFFFAOYSA-N 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- ZCBSOTLLNBJIEK-UHFFFAOYSA-N silane titanium Chemical compound [SiH4].[Ti] ZCBSOTLLNBJIEK-UHFFFAOYSA-N 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 235000012222 talc Nutrition 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- MJOXZELXZLIYPI-UHFFFAOYSA-N titanium(2+) Chemical compound [Ti+2] MJOXZELXZLIYPI-UHFFFAOYSA-N 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 150000003623 transition metal compounds Chemical class 0.000 description 1
- ZMANZCXQSJIPKH-UHFFFAOYSA-O triethylammonium ion Chemical compound CC[NH+](CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-O 0.000 description 1
- HWVLYABDVUZMFQ-UHFFFAOYSA-N zirconium(2+) Chemical compound [Zr+2] HWVLYABDVUZMFQ-UHFFFAOYSA-N 0.000 description 1
- VPGLGRNSAYHXPY-UHFFFAOYSA-L zirconium(2+);dichloride Chemical compound Cl[Zr]Cl VPGLGRNSAYHXPY-UHFFFAOYSA-L 0.000 description 1
Landscapes
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Abstract
A process for the polymerisation of olefins in the gas phase is carried out in the presence of a supported transition metal catalyst. The process involves a prepolymerisation step which may be performed in-situ and in particular the prepolymer may be prepared in the dry phase. The catalyst may for example comprise a constrained geometry transition metal complex supported on silica and used in the pressure of an activator. The prepolymerisation step unables the activity of the catalyst to be improved.
Description
The present invention relates to a kind of olefine polymerizing process, specifically, the present invention relates to the prepolymerized transition metal compound catalizer of a kind of use, the method for equal polymerization ethene or copolymerization of ethylene and alpha-olefin in gas phase.
Traditional olefin polymerization catalysis is normally based on the transition metal salt of the basic metal alkyls of IV-VIII family metal and I-III family metal.This catalyzer is known as Ziegler-Natta catalyst, in the solution of being everlasting, slurry and gas phase process, and olefin polymerization.Another is used for the catalyst system of olefinic polymerization based on chromic oxide, and is commonly called Philips-type catalyst system.
Known after this catalyst system uses in gas phase and a problem of meeting is the control of prepared polymer morphology.The polymer morphology for preparing in gas phase is by using prepolymerization method to improve.Generally, in the fs of this method, one or more alkene contact with Ziegler-Natta catalyst, have formed solids form prepolymer.In subordinate phase, described prepolymer contacts under polymerizing condition with in the gas phase with one or more alkene, directly obtains the polymkeric substance of powder form.Make in this way, can improve the form of final polymkeric substance.Described wherein a kind of typical prepolymerization method has been described among the EP 99774.
Be widely used in the polymerization of alkene based on the catalyzer of cyclopentadienyl-containing metal complexes.These title complexs use in the catalyst system that comprises a kind of two (cyclopentadienyl) transition metal complexes and a kind of promotor.This two (cyclopentadienyl) transition metal complex is called as metallocenes and is base with titanium or zirconium metal generally, uses aluminum compound such as aikyiaiurnirsoxan beta as promotor during use.When using in gas phase process, this two (cyclopentadienyl) metallocenes systems can be stated from the silica.
Recently, an other class transition metal complex has been used to prepare olefin polymer.This title complex has the heteroatoms of a single cyclopentadienyl rings ligand and a bond atom and also can be used in combination with aikyiaiurnirsoxan beta.These ' the restriction geometrical shape ' catalyzer have been described among EP 420436 and the EP 416815.
Instructed similar catalyst system among EP 418044 and the WO 92/00333.In these systems, catalyzer is that the product as a kind of list (cyclopentadienyl) heteroatoms metal complexes and a kind of ion-activated immunomodulator compounds prepares, and this system has been called as ion list (cyclopentadienyl) catalyzer.Typical ion-activated dose of this system of being used for that can exemplify is borate.
Title complex described above can be randomly by prepolymerization.For example, WO 93/23439 has described with two (cyclopentadienyl) metallocene catalyst systems on the aikyiaiurnirsoxan beta activatory carrier, described catalyst system can be randomly by prepolymerization so that the catalyst particle intensity of improvement to be provided.In this documents, described prepolymerization is at-15 ℃ to 30 ℃, is lower than preferably that 25 ℃ of slurry under the temperature carry out in mutually.
In addition, use the prepolymerized example of this two (cyclopentadienyl) metallocene complexes in EP 452920, EP 516458, EP 582480 and EP 605952, to find.
WO 94/03506 has described based on the ionic catalyst on the carrier of list (cyclopentadienyl) title complex and ion-activated dose, this catalyzer also can be randomly by prepolymerization with catalyst particle intensity and size that reaches improvement and the fouling that between polymerization period, has reduced reactor.
WO 94/28034 described two (cyclopentadienyl) metalloscene catalysts of the bridging on the carrier, prepolymerization wherein reduced catalyzer be subjected to reactor scaling fouling trend and strengthened the control of particle shape of the polymkeric substance of final formation.
It is luxuriant that WO 96/00243 has described the chiral metal that is used to prepare high isotactic polyprophlene multipolymer, found that prepolymerization wherein can improve particle shape.
In these all systems, the valency of the transition metal in the described metallocenes is+3 or most is+4 highest oxidation state.
WO 95/00526 has described titanium or reduced the fouling of reactor between polymerization period.
WO 94/28034 has described two (cyclopentadienyl) metalloscene catalysts of the bridging on the carrier, and prepolymerization has wherein reduced the trend of hydrogen-catalyst reactor fouling and strengthened the control of particle shape of the polymkeric substance of final formation.
It is luxuriant that WO 96/00243 has described the chiral metal that is used to prepare high isotactic polyprophlene multipolymer, found that prepolymerization wherein can improve particle shape.
In these all systems, the valence state of the transition metal of title complex is+3 or most is+4 highest oxidation state in the described metallocenes.
WO 95/00526 has described titanium or zirconium complex, and wherein said transition metal is+2 form oxidation state.Described title complex comprises that also one forms neutrality, conjugation or the non-conjugated diene ligand of a π-title complex with described metal.This title complex is by for example aikyiaiurnirsoxan beta, borine or borate combine and formed catalyzer with a kind of active cocatalyst.When using in gas phase polymerization process, this catalyzer also is suitable for being stated from the silica.Yet record is not when using this catalyst system in gas phase, and prepolymerization is as the description of one of them selection.
Therefore, in above-mentioned title complex, when hint had prepolymerization, purpose was in order to reduce reactor fouling or to improve the form of final polymkeric substance, these two kinds of advantages in early days the ziegler-natta catalyzed system or the chromium system in be protected.
Now, the inventor has had been found that and can use the incompatible improvement reactivity of pre-polymerization in the presence of transition metal complex, especially improves the reactivity when carrying out in gas phase, for example in a kind of dry phase reactor of stirring.
Specifically, the inventor had been found that now, can be in the stage of separating before the final polymerization stage or the initial prepolymerization step that carries out of in-field use a kind of at low temperatures (with respect to final polymerization temperature) improve the catalytic activity of some transition metal complex in gas phase.
Therefore according to the present invention, provide a kind of method that is used at gas phase polymerising ethylene or copolymerization of ethylene and one or more alpha-olefins, this method comprises:
(1) in the fs, comprise on (a) a kind of carrier transition metal complex and (b) a kind of activator catalyst system in the presence of, pre-polymerization of ethylene or ethene and one or more alpha-olefins in the gas phase under 20-70 ℃ temperature,
(2) randomly, reclaim pre-polymerized catalyst and
(3) in subordinate phase, in the presence of described pre-polymerized catalyst, polymerising ethylene or ethene and one or more alpha-olefins in the gas phase under 65-100 ℃ temperature.
The present invention especially is fit to use with ' title complex of restriction geometrical shape '.
Term ' title complex of restriction geometrical shape ' can be interpreted as easily by those skilled in the art: representative is because delocalized pi-bond is partly gone up one or more substituent existence, and atoms metal is compelled to expose the title complex at more reactive metal center.The detailed content of this title complex has been described in EP 416815, and incorporates the application into as a reference.
Method of the present invention can be carried out in one Gas-phase reactor, and described two stages all carry out therein, after perhaps described pre-polymerized catalyst can being reclaimed from the fs, is used for final polymerization.
Described pre-polymerized catalyst can reclaim by ordinary method.
Described prepolymerisation stage is most preferably carried out under 25-40 ℃ temperature preferably at 20-65 ℃, and described final polymerization stage most preferably carries out under 70-85 ℃ temperature preferably at 65-100 ℃.
During the prepolymerisation stage, pressure is generally 0.1-10bar.In final polymerization stage, the pressure increase also is generally 5-20bar.
Titanium (II) or zirconium (II) title complex are particularly suitable for as the title complex that is used for the restriction geometrical shape of the inventive method.This title complex is disclosed among the above-mentioned WO95/00526 incorporated herein by reference.Described title complex has following general formula:
Wherein:
R ' always is independently selected from hydrogen, alkyl, silyl, germyl, halo, cyano group and its combination, described R ' has 20 non-hydrogen atoms at the most and optional two R ' groups (wherein R ' is not hydrogen, halo or cyano group) form a kind of its divalent derivative together, and it links to each other with the consecutive position of cyclopentadienyl rings and forms a condensed ring structure;
X is one and has the neutral η of 30 non-hydrogen atoms at the most
4The diene group of-bonding, it and M form a kind of π-title complex;
Y is-O-,-S-,-NR
*-,-PR
*-;
M is+titanium or the zirconium of 2 form oxidation state;
Z
*Be SiR
2, CR
* 2, SiR
* 2SiR
* 2, CR
* 2CR
* 2, CR
*=CR
*, CR
2SiR
* 2Or GeR
* 2Wherein
R
*Always independently for hydrogen or for being selected from a member of alkyl, silyl, haloalkyl, halogenated aryl and its combination, described R
*Have 10 non-hydrogen atoms at the most, and choose two wantonly from Z
*(work as R
*When being not hydrogen) R
*Group or one are from Z
*R
*Group and a R from Y
*Group forms a loop systems.
Most preferred title complex is amido silane or amido alkane 2 basis title complex, and wherein said metal is a titanium.
Highly preferred diene group is 1,4-phenylbenzene-1,3-butadiene, 1,3-pentadiene, 1,4-dibenzyl-1,3-butadiene, 3-methyl isophthalic acid, 3-pentadiene.
The illustrative of preferred title complex but not determinate example has (tertiary butyl amido) (tetramethyl--η
5-cyclopentadienyl) dimethylsilane titanium (II) 1,4-phenylbenzene-1,3-butadiene,
(tertiary butyl amido) (tetramethyl--η
5-cyclopentadienyl) dimethylsilane titanium (II) 1,3-pentadiene,
(tertiary butyl amido) (2-methyl indenyl) dimethylsilane titanium (II) 1,4-phenylbenzene-1,3-butadiene.
These title complexs are by combining with active cocatalyst or being endowed catalytic activity by activating technology.The active cocatalyst that is used for the application that is fit to comprises the aikyiaiurnirsoxan beta, particularly methylaluminoxane of polymeric or oligomerization, the methylaluminoxane of triisobutyl aluminium modification, or diisobutyl alumina alkane; Strong lewis acid such as C
1-3013 compounds of group that alkyl replaces, particularly three (alkyl) aluminium or three (alkyl) boron compound and halide derivatives thereof, each alkyl or halogenation alkyl have 1-10 carbon, more especially fluoridized three (aryl) boron compounds and the most particularly three (pentafluorophenyl group) borine; Non-polymeric, inertia, compatible, non-coordinate (noncoordinating), ion form compound (being included in this compound of use oxidizing condition under); The combination of whole electrolysis (bulk electrolysis) and aforementioned active cocatalyst and technology.Aforesaid active cocatalyst has been disclosed among the above-mentioned WO 95/00526 of relevant this metal complexes with activating technology.
A kind of especially preferred activator is three (pentafluorophenyl group) boron.
The ion that can be used as promotor that is fit to forms compound and comprises a kind of positively charged ion, and this positively charged ion is to provide the Bronsted acid of proton and a kind of inertia, compatible, non-coordinate negatively charged ion, A-.Preferred anionic surfactants is those negatively charged ion that contain the single coordinate complex that comprises carrying electric charge (charge-bearing) metal or metalloid core (metalloid core), negatively charged ion wherein can equilibrium activity catalyzer class (metallic cation) electric charge, this catalyzer two kinds of compositions in conjunction with the time generate.In addition, described negatively charged ion should have abundant unstable to be enough to be substituted by alkene, diolefine and acetylene unsaturated compound or other neutral Lewis base such as ether or nitrile.The metal that is fit to includes, but not limited to aluminium, gold and platinum.The metalloid that is fit to includes, but not limited to boron, phosphorus and silicon.Contain anionic compound (wherein negatively charged ion comprises the coordinate complex that contains single metal or metalloid atom), especially this compound that contains single boron atom at anionicsite has commercially available.
Preferred boron compound is for example following salt:
Four (pentafluorophenyl group) borate,
Triethyl ammonium four (pentafluorophenyl group) borate,
N, accelerine four (pentafluorophenyl group) borate,
N, N-Diethyl Aniline four (pentafluorophenyl group) borate.
Other is applicable to that the title complex of the restriction geometrical shape in the inventive method is the title complex that those wherein contained metals are higher valence state.This title complex is disclosed among EP 416815 and the WO91/04257, and both all incorporate the application as a reference into.Described title complex has following general formula:
Wherein:
Cp
*Be a single η
5-cyclopentadienyl or η
5-the cyclopentadienyl group that replaces optionally is covalently bound to M by-Z-Y-and goes up and accord with following formula:
Wherein R is always hydrogen or for being selected from halogen, alkyl, aryl, haloalkyl, alkoxyl group, aryloxy, silyl and its part of the combination of 20 non-hydrogen atoms at the most, perhaps two or more R groups form a condensed ring system together;
M is with η
5Bonding scheme be attached to zirconium, titanium or the hafnium on cyclopentadienyl or the substituted cyclopentadienyl group and be in+3 or+4 valence state;
X be always hydride or for be selected from halo, alkyl, aryl, silyl, germyl, aryloxy, alkoxyl group, acid amides, siloxy-and have at the most 20 non-hydrogen atoms its combination (for example haloalkyl, halogenated aryl, halo silyl, alkaryl, aralkyl, silyl alkyl, aryloxy aryl and alkoxyalkyl, amidoalkyl, amido aryl) part and have the neutral Lewis base ligand of 20 non-hydrogen atoms at the most;
N is 1 or 2 according to the valence state of M;
Z is a divalent moiety, comprises a member of oxygen, boron or the periodic table of elements 14 families;
Y is a linking group that is covalently bound on the described metal, comprises nitrogen, phosphorus, oxygen or sulphur, or optional Z and Y form a condensed ring system together.
Most preferred title complex is that wherein Y is corresponding to formula (NR
1) or (PR
1) the title complex of nitrogenous or phosphorus-containing groups, R wherein
1Be C
1-C
10Alkyl or C
6-C
10Aryl and wherein Z be SiR "
2, CR "
2, SiR "
2SiR "
2, CR "=CR " or GeR "
2, R wherein " and be hydrogen or alkyl.
Most preferred title complex is that those M are the title complex of titanium or zirconium.
The illustrative of the title complex that is fit to but not determinate example has (tertiary butyl amido) (tetramethyl--η
5-cyclopentadienyl) dimethylsilane dimethyl titanium, (tertiary butyl amido) dibenzyl (tetramethyl--η
5-cyclopentadienyl) silane dibenzyl zirconium, (benzyl amido) dimethyl (tetramethyl--η
5-cyclopentadienyl) silane titanium dichloride, (phenyl phosphorus base (phosphido)) dimethyl (tetramethyl--η
5-cyclopentadienyl) silane dibenzyl zirconium etc.
These title complexs be similar to above-mentioned active cocatalyst and combine and be endowed catalytic activity.The promotor that is suitable for comprises aikyiaiurnirsoxan beta, and particularly methylaluminoxane (MAO) or strong lewis acid are as three (alkyl) boron compound or halide derivatives.
What be particularly suitable as activator is three (pentafluorophenyl group) boron.
These title complexs also can combine with above-mentioned ion formation compound and be endowed activity.
The transition metal complex that is applicable to method of the present invention also can be traditional two (cyclopentadienyl) transition metal complexes among a kind of EP129368 of being disclosed in or the EP 206794.These title complexs can be used formula Cp
2MX
2Representative, wherein M is Zr, Ti or Hf and X represent anion ligand.This title complex can preferably comprise by the cyclopentadienyl rings of alkyl such as alkyl replacement.The example of these title complexs is two (cyclopentadienyl) zirconium dichlorides or two (tetramethyl-ring pentadienyl) zirconium dichloride.
The title complex that is fit to also can be the transition metal complex that wherein forms a bridge between the replacement on the cyclopentadienyl rings is based on two rings, for example EP 659773 disclosed title complexs.Especially the title complex of Shi Heing is two (indenyl) zirconium dichlorides of ethene.
Above-mentioned two (cyclopentadienyl) transition metal complex is suitable for by aikyiaiurnirsoxan beta most, especially methylaluminoxane activation.
An other class is that the transition metal complex that is used for the inventive method is WO 96/04920 disclosed two (cyclopentadienyl) diene complexes, and incorporates the application as a reference into.
This title complex can be represented with following formula:
Wherein:
M is+2 or+titanium, zirconium or the hafnium of 4 form oxidation state;
R ' and R " always be independently selected from hydrogen, alkyl, silyl, germyl, cyano group, halo and its combination; described R ' and R " have 20 non-hydrogen atoms at the most, perhaps adjacent R ' group and/or R " group (work as R ' and R " be not hydrogen, halo or cyano group) form a kind of its divalent derivative together, form a condensed ring system thus;
E is silicon, germanium or carbon;
X is the integer of 1-8;
R " ' always be hydrogen or be selected from silyl, alkyl,-oxyl and its combination independently, or two R " ' group forms a loop systems, described R together " ' have at the most 30 carbon atoms or Siliciumatom and
D is a stable conjugated diolefine, and optional by one or more alkyl, silyl, alkyl silyl, silyl alkyl or its combination replacement, described D has 4-40 non-hydrogen atom.
Especially the title complex of Shi Heing is that wherein M is that zirconium and E are the title complexs of carbon.
Above-mentioned title complex can be suitable for by above-mentioned promotor activation.A kind of especially preferred promotor is three (pentafluorophenyl group) boron.
The molar ratio range of title complex of Shi Yonging and activator is 1: 10000 to 100: 1 in the method for the invention.Preferred range is 1: 5000 to 10: 1, and most preferred scope is 1: 10 to 1: 1.
The title complex according to the inventive method that uses in gas phase is stated from the carrier.
Generally, described carrier can be any organic or inorganic inert solid thing.Particularly porous support such as talcum, inorganic oxide and resinous support material such as polyolefine.Operable suitable inorganic oxide material comprises metal oxide such as silica, alumina, silica-alumina and its mixture of 2,13,14 or 15 families.Other inorganic oxide that can use separately or be used in combination with silica, alumina or silica-alumina is magnesium oxide, titanium dioxide or zirconium white.Also can use other solid support material that is suitable for such as polyolefine such as polyethylene in small, broken bits.
According to the inventive method, the most preferably solid support material that is used for supported catalyst is a silica.The silica that is fit to comprises Crossfield ES70 and Davidson 948 silicas.
Preferred described silica is dry before use, and this is generally by carrying out in the temperature that raises such as 200-850 ℃ of following heating.
In a preferred scheme, supported catalyst can prepare by joining the transition metal complex solution that also then is added in the same solvent in the slurry of the activation silica of handling with trialkyl aluminium compound at the activator soln in the solvent that is fit to.Perhaps described title complex also can join in the silica of trialkylaluminium processing before adding activator.
A kind of solvent that is suitable for preparing supported catalyst is a toluene.
The trialkyl aluminium compound that is suitable for is trimethyl aluminium (TMA), triethyl aluminum (TEA) or triisobutyl aluminium (TIBAL).
Fs and subordinate phase can be carried out in a kind of dry phase reactor of stirring or in a kind of fluidized-bed reactor.
Perhaps can in subordinate phase, in a kind of different Gas-phase reactor, use the pre-polymerized catalyst that reclaims from the fs.
The most preferred Gas-phase reactor that is used for the fs of the present invention is a kind of dry phase reactor, especially a kind of dry phase reactor (ADPR) of stirring.
A kind of most preferred method when using fluidized-bed reactor has been described in WO 94/28032.Other bed process also is disclosed in EP 89691, WO 94/25495 and WO94/25497.
The present invention also provides a kind of method for preparing pre-polymerized catalyst.
Therefore, the another one scheme according to the present invention, a kind of method for preparing pre-polymerized catalyst is provided, this method is included in the transition metal complex that comprises on (a) a kind of carrier and (b) under a kind of existence of catalyst system of activator, pre-polymerization of ethylene or ethene and one or more alpha-olefins are to form pre-polymerized catalyst and to reclaim this pre-polymerized catalyst subsequently.
The present invention also goes for carrying out prepolymerized method at slurry in mutually.
Therefore, the another one scheme according to the present invention provides the method for a kind of polymerising ethylene or ethene and one or more alpha-olefins, and this method comprises:
(1) in the fs, comprise on (a) a kind of carrier transition metal complex and (b) a kind of activator catalyst system in the presence of, under-20 to+60 ℃ temperature, pre-polymerization of ethylene or ethene and one or more alpha-olefins are to form pre-polymerized catalyst;
(2) randomly, reclaim described pre-polymerized catalyst and
(3) in subordinate phase, in the presence of described pre-polymerized catalyst, in the gas phase under 65-100 ℃ temperature, polymerising ethylene or ethene and one or more alpha-olefins.
Fs can be in a kind of slurry-phase reactor, in a kind of dry phase reactor of stirring or in a kind of fluidized-bed reactor, carry out.
Described pre-polymerized catalyst can be recovered before subordinate phase or in-field use.
Method of the present invention is applicable to that the homopolymerization of the polymerization of alkene, particularly ethene or ethene and other alpha-olefin particularly have the copolymerization of the alpha-olefin of 3 to 10 carbon atoms.Most preferred alpha-olefin is 1-butylene, 1-hexene and 4-methyl-1-pentene.
Use method of the present invention, can prepare the polymkeric substance of the melt index [according to ASTM D 1238 condition E (2.16kg is at 190 ℃)] of density with 0.905-0.960 g/cc and 0.1-20.
The present invention will further be illustrated with following embodiment.These embodiment clearly illustrate by using separately or prepolymerisation stage on the spot, have improved the activity of catalyst system.The preparation of EXAMPLE Example 1 catalyst A
10g Crosfield ES 70 silicas (500 ℃ of activation) are made slurry in the dry hexane of 50ml.The hexane solution (1.5mmol Al/g silica) that adds 30ml 0.5M TMA, and with slurry stirring 2 hours.The silica of handling filtered and with 20ml hexane wash three times, then with silica vacuum-drying to one fine powder.
ES 70 silicas that the described TMA of 2g handles are made slurry in the 10ml dry toluene.Add the toluene solution of 1.95ml 7.85 weight % three (pentafluorophenyl group) boron and mixture is acutely rocked.Add 0.62ml 12.25 weight % (tertiary butyl amido) (tetramethyl--η then
5-cyclopentadienyl) toluene solution of dimethylsilane dimethyl titanium.Mixture is rocked even back obtain a kind of yellow powder 20 ℃ of solvent removed in vacuo.The preparation of embodiment 2 catalyst B
7.0kg Crosfield ES 70 silicas (500 ℃ of activation) are made slurry in 100 liters of hexanes.The hexane solution (1.3mmol Al/g silica) that adds 9.32 liters of 0.976M TEA, and slurry stirred 2 hours at 30 ℃.Allow the silica sedimentation, and remove the hexane supernatant liquor.Further silica is reached up to the concentration of Al in elutant＜1mmol Al/ liter with hexane wash.Then with silica 40 ℃ of vacuum-dryings.
ES 70 silicas that the described TEA of 3g handles are made slurry in the 15ml dry toluene.Add the toluene solution of 1.8ml 7.85 weight % three (pentafluorophenyl group) boron and mixture is acutely rocked.Add 0.62ml 10.7 weight % (tertiary butyl amido) (tetramethyl--η then
5-cyclopentadienyl) the dimethylsilane titanium penta-1, the toluene solution of 3-diene.Mixture is rocked even back obtain a kind of olive-green powder 20 ℃ of solvent removed in vacuo.The preparation of embodiment 3 catalyzer C
ES 70 silicas that the described TEA of the preparation of 50g catalyst B handles are made slurry in the 150ml dry toluene.Add 10.4ml 10.7 weight % (tertiary butyl amido) (tetramethyl--η
5-cyclopentadienyl) the dimethylsilane titanium penta-1, and the toluene solution of 3-diene also acutely rocks mixture.The toluene solution that adds 29.4ml 7.85 weight % three (pentafluorophenyl group) boron then.Mixture is rocked even back obtain a kind of olive-green powder 40 ℃ of solvent removed in vacuo.The preparation of embodiment 4 catalyzer D
ES 70 silicas that the described TEA of the preparation of 10g catalyst B handles are made slurry in the 50ml dry toluene.Add 2.1ml 10.7 weight % (tertiary butyl amido) (tetramethyl--η
5-cyclopentadienyl) the dimethylsilane titanium penta-1, and the toluene solution of 3-diene also acutely rocks mixture.The toluene solution that adds 5.9ml 7.85 weight % three (pentafluorophenyl group) boron then.Mixture is rocked even back obtain a kind of olive-green powder 20 ℃ of solvent removed in vacuo.The preparation of embodiment 5 catalyzer E
ES 70 silicas that the described TEA of the preparation of 45.76g catalyst B handles are made slurry in the 225ml dry toluene.Add 9.51ml 10.7 weight % (tertiary butyl amido) (tetramethyl--η
5-cyclopentadienyl) the dimethylsilane titanium penta-1, and the toluene solution of 3-diene also rocks mixture evenly.The toluene solution that adds 26.9ml 7.85 weight % three (pentafluorophenyl group) boron then.Mixture is rocked even back obtain a kind of olive-green powder 20 ℃ of solvent removed in vacuo.The preparation of the prepolymer of embodiment 6 catalyzer C
At 85 ℃, N
2Purge flow is the dry phase reactor of stirring of 2.5 liters of volumes of oven dry down.Add reactor with reactor cooling to 25 ℃ and with 44.41g catalyzer C.Use N
2Reactor is pressurized to 0.47 crust.Under 300rpm, stir described catalyzer.Add 0.30 crust C
2H
4, keep the temperature of reactor to be lower than 40 ℃ but this pressure is reduced to 0.08 Palestine and Israel soon.Continued 126 minutes like this.At N
2Down from reactor, reclaimed the catalyzer that 34.0g is wrapping polymkeric substance (polymer-coated).The yield of polymkeric substance is a 0.5g PE/g catalyzer.The preparation of the prepolymer of embodiment 7 catalyzer E
At 85 ℃, N
2Purge flow is the dry phase reactor of stirring of 2.5 liters of volumes of oven dry down.Add reactor with reactor cooling to 25 ℃ and with 46.3g catalyzer E.Use N
2Reactor is pressurized to 1.05 crust.Under 325rpm, stir described catalyzer.Add C
2H
4, to provide the total pressure of 1.25 crust.Kept under these conditions 3.75 hours.Then with reactor N
2Clean, at 1 crust N
2Lower seal and keeping spent the night in 16 hours.
Once more with C
2H
4Add reactor, provide the total pressure of 1.25 crust.Begin after 50 minutes, pressure is increased to 1.30 crust, and after beginning 5 hours, further increase to 1.42 crust.After the polymerization 6 hours, use N
2Cleaning reaction device and at N
2Reclaimed the catalyzer that 68.1g is wrapping polymkeric substance down.The yield of polymkeric substance is a 2.0g PE/g catalyzer.The prepolymerization on the spot of embodiment 8 catalyst A
285g NaCl is joined in advance at 85 ℃, N
2In the dry phase reactor of the stirring of 2.5 liters of volumes that purge flow is dried down.The silica that 1.67g TEA is handled adds reactor and stirred 15 minutes.Reduce the temperature to 30 ℃ 2 and cling to C 7
2H
4Import reactor.The mixture high pressure N of the silica that 0.22g catalyst A and 1.04g TEA are handled then
2Injecting reactor.With C
2H
4Pressure remain on 7 crust and simultaneously temperature increased apace to 80 ℃, and in all the other times of described test, keep this temperature.The total polymerization time is 120 minutes.With reactor emptying and cooling, and reclaimed the 127g polymkeric substance, catalytic activity is 41g/g. hour. crust.The comparative example 1
Except being omitted in 30 minutes that begin under 30 ℃, carry out according to the scheme of embodiment 8.The mixture of the silica of under 70 ℃ temperature 0.243g catalyst A and 0.935g TEA being handled injects, and then temperature is increased to 80 ℃ at once.Operating time is 100 minutes.Reclaimed the polymkeric substance of 64g, catalytic activity is 20.5g/g. hour. crust.
Comparison sheet between embodiment 8 and the comparative example 1 is illustrated in the prepolymerization on the spot of stirring in the dry phase reactor and has obtained higher homopolymerization catalytic activity.The prepolymerization on the spot of embodiment 9 catalyst B
320g NaCl is joined in advance at 85 ℃, N
2In the dry phase reactor of the stirring of 2.5 liters of volumes that purge flow is dried down.The silica that 1.25g TIBAL is handled adds reactor and stirred 15 minutes.Reduce the temperature to 30 ℃ and with 1 the crust C
2H
4Import reactor.The mixture high pressure N of the silica that 0.308g catalyst B and 0.825g TIBAL are handled then
2Injecting reactor.With C
2H
4Pressure remain on following 5 minutes of the pressure of 1 crust, then pressure is increased to fast 6.5 crust and temperature is increased to 70 ℃ fast.Then with H
2Import reactor with the 1-hexene.In all the other times of described test, temperature, C
2H
4Pressure and H
2And 1-hexene level all keeps constant.The total polymerization time is 191 minutes.At duration of test, average H
2/ C
2H
4Than being 0.0046, average 1-hexene/C
2H
4Ratio is 0.0052.With reactor emptying and cooling, reclaimed the 278g polymkeric substance, catalytic activity is 43.6g/g. hour. crust.Polymkeric substance M1
216Be 7.41 and density be 0.926g/ml.The prepolymerization on the spot of embodiment 10 catalyst B
288g NaCl is joined in advance at 85 ℃, N
2In the dry phase reactor of the stirring of 2.5 liters of volumes that purge flow is dried down.The silica that 1.30g TIBAL is handled adds reactor and stirred 15 minutes.Reduce the temperature to 30 ℃ and with 1 the crust C
2H
4Import reactor.The mixture high pressure N of the silica that 0.238g catalyst B and 0.725g TIBAL are handled then
2Injecting reactor.With C
2H
4Pressure remain on following 5 minutes of the pressure of 1 crust, then pressure is increased to fast 6.5 crust and temperature is increased to 80 ℃ fast.Then with H
2Import reactor with the 1-hexene.In all the other times of described test, temperature, C
2H
4Pressure and H
2And 1-hexene level all keeps constant.The total polymerization time is 116 minutes.At duration of test, average H
2/ C
2H
4Than being 0.0052, average 1-hexene/C
2H
4Ratio is 0.0049.With reactor emptying and cooling, reclaimed the 99g polymkeric substance, catalytic activity is 33.1g/g. hour. crust.Polymkeric substance M1
2.16Be 2.7 and density be 0.9185g/ml.The prepolymerization on the spot of embodiment 11 catalyst B
305g NaCl is joined in advance at 85 ℃, N
2In the dry phase reactor of the stirring of 2.5 liters of volumes that purge flow is dried down.The silica that 1.20g TIBAL is handled adds reactor and stirred 15 minutes.Reduce the temperature to 30 ℃ and with 1 the crust C
2H
4Import reactor.The mixture high pressure N of the silica that 0.231g catalyst B and 0.912g TIBAL are handled then
2Injecting reactor.With C
2H
4Pressure remain on following 5 minutes of the pressure of 1 crust, then pressure is increased to fast 6.5 crust and temperature is increased to 70 ℃ fast.Then with H
2Import reactor with the 1-hexene.In all the other times of described test, temperature, C
2H
4Pressure and H
2And 1-hexene level all keeps constant.The total polymerization time is 189 minutes.At duration of test, average H
2/ C
2H
4Than being 0.00395, average 1-hexene/C
2H
4Ratio is 0.0048.With reactor emptying and cooling, reclaimed the 168g polymkeric substance, catalytic activity is 35.5g/g. hour. crust.Polymkeric substance M1
216Be 1.7 and density be 0.9295g/ml.The comparative example 2
Except the pressure of the low temperature that omits beginning and startup, carry out according to the scheme of embodiment 9,10 and 11.Therefore, 344g NaCl is joined in advance at 85 ℃, N
2In the dry phase reactor of the stirring of 2.5 liters of volumes that purge flow is dried down.The silica that 1.30g TIBAL is handled adds reactor and stirred 15 minutes.With temperature of reactor drop to 70 ℃ and be pressurized to 6.5 the crust C
2H
4Then with H
2Import reactor with the 1-hexene.The mixture high pressure N of the silica that 0.213g catalyzer C and 0.781g TIBAL are handled
2Injecting reactor.In all the other times of described test, temperature, C
2H
4Pressure and H
2And 1-hexene level all keeps constant.At duration of test, average H
2/ C
2H
4Than being 0.0038, average 1-hexene/C
2H
4Ratio is 0.0053.With reactor emptying and cooling, reclaimed the 101g polymkeric substance, catalytic activity is 26.3g/g. hour. crust.
Embodiment 9,10 and 11 and comparative example 2 between comparison sheet be illustrated in the prepolymerization on the spot of stirring in the dry phase reactor and obtained higher copolymerization catalytic activity.The polymerization of the prepolymer of embodiment 12 catalyzer C
305g NaCl is joined in advance at 85 ℃, N
2In the dry phase reactor of the stirring of 2.5 liters of volumes that purge flow is dried down.The silica that 1.225g TIBAL is handled adds reactor and stirred 15 minutes.With temperature of reactor drop to 70 ℃ and be pressurized to 6.5 the crust C
2H
4With H
2Import reactor with the 1-hexene.The mixture high pressure N of the silica that the prepolymer of 0.956g catalyzer C and 0.745g TIBAL are handled
2Injecting reactor.In all the other times of described test, temperature, C
2H
4Pressure and H
2And 1-hexene level all keeps constant.The total polymerization time is 127 minutes.At duration of test, average H
2/ C
2H
4Than being 0.00415, average 1-hexene/C
2H
2Ratio is 0.0057.With reactor emptying and cooling, reclaimed the 250g polymkeric substance, activity is based on raw catalyst weight 28.8g/g. hour. crust.The polymerization of the prepolymer of embodiment 13 catalyzer E
292g NaCl is joined in advance at 85 ℃, N
2In the dry phase reactor of the stirring of 2.5 liters of volumes that purge flow is dried down.The silica that 1.223g TIBAL is handled adds reactor and stirred 15 minutes.With temperature of reactor drop to 70 ℃ and be pressurized to 6.5 the crust C
2H
4With H
2Import reactor with the 1-hexene.The mixture high pressure N of the silica that the prepolymer of 1.02g catalyzer E and 0.744g TIBAL are handled
2Injecting reactor.In all the other times of described test, temperature, C
2H
4Pressure and H
2And 1-hexene level all keeps constant.The total polymerization time is 127 minutes.At duration of test, average H
2/ C
2H
4Than being 0.0044, average 1-hexene/C
2H
4Ratio is 0.0048.With reactor emptying and cooling, reclaimed the 175g polymkeric substance, activity is based on raw catalyst weight 37.4g/g. hour. crust.The polymerization of the prepolymer of embodiment 14 catalyzer E
352g NaCl is joined in advance at 85 ℃, N
2In the dry phase reactor of the stirring of 2.5 liters of volumes that purge flow is dried down.The silica that 1.20g TIBAL is handled adds reactor and stirred 15 minutes.Reduce the temperature to 60 ℃ and also will be pressurized to 6.5 crust C
2H
4Then with H
2Import reactor with the 1-hexene.The mixture high pressure N of the silica that the prepolymer of 0.915g catalyzer E and 0.8g TIBAL are handled
2Injecting reactor.Temperature is promptly brought up to 70 ℃.In all the other times of described test, temperature, C
2H
4Pressure and H
2And 1-hexene level all keeps constant.The total polymerization time is 87 minutes.At duration of test, average H
2/ C
2H
4Than being 0.0044, average 1-hexene/C
2H
4Ratio is 0.0052.With reactor emptying and cooling, reclaimed the 128g polymkeric substance, activity is based on raw catalyst weight 44.5g/g. hour. crust.
Embodiment 13 uses identical basic catalyst composition to begin to carry out polymerization (referring to above) with 14 with comparative example 2.They have illustrated before with the catalyzer injecting reactor the prepolymerized effect improved catalytic activity of this catalyzer.
Claims (20)
1. method that is used at gas phase polymerising ethylene or copolymerization of ethylene and one or more alpha-olefins, this method comprises:
(1) in the fs, comprise on (a) a kind of carrier transition metal complex and (b) a kind of activator catalyst system in the presence of, pre-polymerization of ethylene or ethene and one or more alpha-olefins in the gas phase under 20-70 ℃ temperature,
(2) randomly, reclaim pre-polymerized catalyst and
(3) in subordinate phase, in the presence of described pre-polymerized catalyst, polymerising ethylene or ethene and one or more alpha-olefins in the gas phase under 65-100 ℃ temperature.
2. according to the process of claim 1 wherein that the described fs is to carry out under 25-40 ℃ temperature, and described subordinate phase is to carry out under 70-85 ℃ temperature.
3. according to the method for claim 1 or 2, the wherein said fs is to carry out under the pressure of 0.1-10 crust.
4. according to the method for above-mentioned arbitrary claim, the wherein said fs carries out in mutually in drying.
5. according to the method for claim 4, the wherein said fs stirs dry phase reactor and carries out with a kind of.
6. according to the method for above-mentioned arbitrary claim, wherein said two stages all carry out in a single Gas-phase reactor.
7. according to the method for above-mentioned arbitrary claim, wherein said transition metal complex is a kind of title complex of restriction geometrical shape of following formula:
Wherein:
R ' always is independently selected from hydrogen, alkyl, silyl, germyl, halo, cyano group and its combination, described R ' has 20 non-hydrogen atoms at the most and optional two R ' groups (wherein R ' is not hydrogen, halo or cyano group) form a kind of its divalent derivative together, and it links to each other with the consecutive position of cyclopentadienyl rings and forms a condensed ring structure;
X is one and has the neutral η of 30 non-hydrogen atoms at the most
4The diene group of-bonding, it and M form a kind of π-title complex;
Y is-O-,-S-,-NR
*-,-PR
*-;
M is+titanium or the zirconium of 2 form oxidation state;
Z
*Be SiR
2, CR
* 2, SiR
* 2SiR
* 2, CR
* 2CR
* 2, CR
*=CR
*, CR
2SiR
* 2Or GeR
* 2R wherein
*Always independently for hydrogen or for being selected from a member of alkyl, silyl, haloalkyl, halogenated aryl and its combination, described R
*Have 10 non-hydrogen atoms at the most, and choose two wantonly from Z
*(work as R
*When being not hydrogen) R
*Group or one are from Z
*R
*Group and a R from Y
*Group forms a loop systems.
8. according to the method for claim 7, wherein said title complex is:
(tertiary butyl amido) (tetramethyl--η
5-cyclopentadienyl) dimethylsilane titanium (II) 1,3-pentadiene.
9. according to the method for claim 1-6, wherein said transition metal complex has following general formula:
Wherein:
Cp
*Be a single η
5-cyclopentadienyl or η
5-the cyclopentadienyl group that replaces optionally is covalently bound to M by-Z-Y-and goes up and accord with following formula:
Wherein R is always hydrogen or for being selected from halogen, alkyl, aryl, haloalkyl, alkoxyl group, aryloxy, silyl and its part of the combination of 20 non-hydrogen atoms at the most, perhaps two or more R groups form a condensed ring system together;
M is with η
5Bonding scheme be attached to zirconium, titanium or the hafnium on cyclopentadienyl or the substituted cyclopentadienyl group and be in+3 or+4 valence state;
X be always hydride or for be selected from halo, alkyl, aryl, silyl, germyl, aryloxy, alkoxyl group, acid amides, siloxy-and have at the most 20 non-hydrogen atoms its combination (for example haloalkyl, halogenated aryl, halo silyl, alkaryl, aralkyl, silyl alkyl, aryloxy aryl and alkoxyalkyl, amidoalkyl, amido aryl) part and have the neutral Lewis base ligand of 20 non-hydrogen atoms at the most;
N is 1 or 2 according to the valence state of M;
Z is a divalent moiety, comprises a member of oxygen, boron or periodic table of elements family 14;
Y is a linking group that is covalently bound on the described metal, comprises nitrogen, phosphorus, oxygen or sulphur, or optional Z and Y form a fused rings system together.
10. according to the method for claim 9, wherein said title complex is (tertiary butyl amido) (tetramethyl--η
5-cyclopentadienyl) dimethylsilane dimethyl titanium.
11. according to the method for above-mentioned arbitrary claim, wherein said title complex is stated from the silica.
12. according to the method for claim 11, wherein said silica is pretreated with trialkyl aluminium compound.
13. according to the method for above-mentioned arbitrary claim, wherein said activator is three (pentafluorophenyl group) boron.
14. according to the method for above-mentioned arbitrary claim, the ratio of wherein said title complex and activator is 1: 10000 to 100: 1.
15. according to the method for claim 14, wherein said ratio is 1: 10 to 1: 1.
16. method for preparing pre-polymerized catalyst, this method is included in the transition metal complex that comprises on (a) a kind of carrier and (b) under a kind of existence of catalyst system of activator, pre-polymerization of ethylene or ethene and one or more alpha-olefins are to form pre-polymerized catalyst and to reclaim this pre-polymerized catalyst subsequently.
17. according to the method for claim 16, wherein this method is carried out in mutually in drying.
18. the method for a polymerising ethylene or ethene and one or more alpha-olefins, this method comprises:
(1) in the fs, comprise on (a) a kind of carrier transition metal complex and (b) a kind of activator catalyst system in the presence of, under-20 to+60 ℃ temperature, pre-polymerization of ethylene or ethene and one or more alpha-olefins are to form pre-polymerized catalyst;
(2) randomly, reclaim described pre-polymerized catalyst and
(3) in subordinate phase, in the presence of described pre-polymerized catalyst, in the gas phase under 65-100 ℃ temperature, polymerising ethylene or ethene and one or more alpha-olefins.
19. according to the method for claim 18, the wherein said fs carries out in slurry, dry phase or gas phase.
20. according to the method for above-mentioned arbitrary claim, wherein said alpha-olefin is 1-butylene, 1-hexene or 4-methyl-1-pentene.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 97182266 CN1259964A (en) | 1997-06-27 | 1997-06-27 | Process for polymerization olefins in gas phase |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 97182266 CN1259964A (en) | 1997-06-27 | 1997-06-27 | Process for polymerization olefins in gas phase |
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| Publication Number | Publication Date |
|---|---|
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ID=5178365
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|---|---|---|---|
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102443084A (en) * | 2005-02-21 | 2012-05-09 | 英尼奥斯欧洲有限公司 | Polymerization catalyst |
-
1997
- 1997-06-27 CN CN 97182266 patent/CN1259964A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102443084A (en) * | 2005-02-21 | 2012-05-09 | 英尼奥斯欧洲有限公司 | Polymerization catalyst |
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