TWI222980B - A process for the polymerisation of olefin in a gas phase reactor - Google Patents
A process for the polymerisation of olefin in a gas phase reactor Download PDFInfo
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- TWI222980B TWI222980B TW087100798A TW87100798A TWI222980B TW I222980 B TWI222980 B TW I222980B TW 087100798 A TW087100798 A TW 087100798A TW 87100798 A TW87100798 A TW 87100798A TW I222980 B TWI222980 B TW I222980B
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- 150000001336 alkenes Chemical class 0.000 title claims abstract description 9
- 238000000034 method Methods 0.000 title claims description 45
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 title description 2
- 239000003054 catalyst Substances 0.000 claims abstract description 28
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical group CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims abstract description 15
- 150000001335 aliphatic alkanes Chemical class 0.000 claims abstract description 15
- 239000012190 activator Substances 0.000 claims abstract description 11
- 239000007788 liquid Substances 0.000 claims abstract description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 35
- 229910052751 metal Inorganic materials 0.000 claims description 31
- 239000002184 metal Substances 0.000 claims description 31
- -1 hydrogen anion Chemical class 0.000 claims description 28
- 229910052739 hydrogen Inorganic materials 0.000 claims description 27
- 239000001257 hydrogen Substances 0.000 claims description 27
- 239000007789 gas Substances 0.000 claims description 17
- 229920000642 polymer Polymers 0.000 claims description 17
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 15
- 238000006116 polymerization reaction Methods 0.000 claims description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 13
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 claims description 12
- 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
- 125000000217 alkyl group Chemical group 0.000 claims description 10
- 125000004429 atom Chemical group 0.000 claims description 9
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 9
- 229910052799 carbon Inorganic materials 0.000 claims description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 7
- 229910052760 oxygen Inorganic materials 0.000 claims description 7
- 239000001301 oxygen Substances 0.000 claims description 7
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 7
- 125000003118 aryl group Chemical group 0.000 claims description 6
- 125000004122 cyclic group Chemical group 0.000 claims description 5
- 125000001183 hydrocarbyl group Chemical group 0.000 claims description 5
- 238000007254 oxidation reaction Methods 0.000 claims description 5
- 230000000379 polymerizing effect Effects 0.000 claims description 5
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 4
- 125000004104 aryloxy group Chemical group 0.000 claims description 4
- 229910052796 boron Inorganic materials 0.000 claims description 4
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 4
- 230000003647 oxidation Effects 0.000 claims description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 3
- 125000003545 alkoxy group Chemical group 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 claims description 3
- 150000007527 lewis bases Chemical class 0.000 claims description 3
- 230000007935 neutral effect Effects 0.000 claims description 3
- 229910052698 phosphorus Inorganic materials 0.000 claims description 3
- 239000011574 phosphorus Substances 0.000 claims description 3
- 239000002879 Lewis base Substances 0.000 claims description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 2
- 125000004171 alkoxy aryl group Chemical group 0.000 claims description 2
- 125000002877 alkyl aryl group Chemical group 0.000 claims description 2
- 125000003277 amino group Chemical group 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
- 125000001188 haloalkyl group Chemical group 0.000 claims description 2
- 125000005647 linker group Chemical group 0.000 claims description 2
- JQQSUOJIMKJQHS-UHFFFAOYSA-N pentaphenyl group Chemical group C1=CC=CC2=CC3=CC=C4C=C5C=CC=CC5=CC4=C3C=C12 JQQSUOJIMKJQHS-UHFFFAOYSA-N 0.000 claims description 2
- 150000003254 radicals Chemical class 0.000 claims description 2
- 125000005353 silylalkyl group Chemical group 0.000 claims description 2
- 229910052717 sulfur Inorganic materials 0.000 claims description 2
- 239000011593 sulfur Substances 0.000 claims description 2
- 125000001181 organosilyl group Chemical group [SiH3]* 0.000 claims 2
- PJANXHGTPQOBST-UHFFFAOYSA-N stilbene Chemical compound C=1C=CC=CC=1C=CC1=CC=CC=C1 PJANXHGTPQOBST-UHFFFAOYSA-N 0.000 claims 2
- 239000000126 substance Substances 0.000 claims 2
- 241000208340 Araliaceae Species 0.000 claims 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims 1
- 235000005035 Panax pseudoginseng ssp. pseudoginseng Nutrition 0.000 claims 1
- 235000003140 Panax quinquefolius Nutrition 0.000 claims 1
- PJANXHGTPQOBST-VAWYXSNFSA-N Stilbene Natural products C=1C=CC=CC=1/C=C/C1=CC=CC=C1 PJANXHGTPQOBST-VAWYXSNFSA-N 0.000 claims 1
- 125000001309 chloro group Chemical group Cl* 0.000 claims 1
- NYRMIXUCGSRWPT-UHFFFAOYSA-N cyclopenta[a]fluorene Chemical class C1=C2C=CC=CC2=C2C1=C1C=CC=C1C=C2 NYRMIXUCGSRWPT-UHFFFAOYSA-N 0.000 claims 1
- 229910000078 germane Inorganic materials 0.000 claims 1
- 229910052732 germanium Inorganic materials 0.000 claims 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 claims 1
- 235000008434 ginseng Nutrition 0.000 claims 1
- 230000000737 periodic effect Effects 0.000 claims 1
- 239000002689 soil Substances 0.000 claims 1
- 235000021286 stilbenes Nutrition 0.000 claims 1
- 125000002730 succinyl group Chemical group C(CCC(=O)*)(=O)* 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 27
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 21
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 21
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Natural products CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 20
- 239000005977 Ethylene Substances 0.000 description 19
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 18
- 238000011049 filling Methods 0.000 description 13
- 239000000377 silicon dioxide Substances 0.000 description 13
- 239000000203 mixture Substances 0.000 description 12
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 description 10
- ZSWFCLXCOIISFI-UHFFFAOYSA-N endo-cyclopentadiene Natural products C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 9
- 150000001993 dienes Chemical class 0.000 description 8
- 239000004575 stone Substances 0.000 description 7
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 6
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 5
- 238000011010 flushing procedure Methods 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- 125000003698 tetramethyl group Chemical group [H]C([H])([H])* 0.000 description 5
- 229910052723 transition metal Inorganic materials 0.000 description 5
- 150000003624 transition metals Chemical class 0.000 description 5
- PMJHHCWVYXUKFD-SNAWJCMRSA-N (E)-1,3-pentadiene Chemical compound C\C=C\C=C PMJHHCWVYXUKFD-SNAWJCMRSA-N 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 230000002079 cooperative effect Effects 0.000 description 4
- 125000005843 halogen group Chemical group 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- AQZWEFBJYQSQEH-UHFFFAOYSA-N 2-methyloxaluminane Chemical compound C[Al]1CCCCO1 AQZWEFBJYQSQEH-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 239000001273 butane Substances 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 229910052809 inorganic oxide Inorganic materials 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 239000011780 sodium chloride Substances 0.000 description 3
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-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
- 229910052693 Europium Inorganic materials 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- 240000007817 Olea europaea Species 0.000 description 2
- 150000001212 Plutonium Chemical class 0.000 description 2
- 125000002947 alkylene group Chemical group 0.000 description 2
- 239000004305 biphenyl Substances 0.000 description 2
- 150000001639 boron compounds Chemical class 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000003426 co-catalyst Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 2
- RMBPEFMHABBEKP-UHFFFAOYSA-N fluorene Chemical compound C1=CC=C2C3=C[CH]C=CC3=CC2=C1 RMBPEFMHABBEKP-UHFFFAOYSA-N 0.000 description 2
- 238000012685 gas phase polymerization Methods 0.000 description 2
- 229910052735 hafnium Chemical group 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- QWTDNUCVQCZILF-UHFFFAOYSA-N isopentane Chemical compound CCC(C)C QWTDNUCVQCZILF-UHFFFAOYSA-N 0.000 description 2
- 239000003446 ligand Substances 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N o-biphenylenemethane Natural products C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 description 2
- PMJHHCWVYXUKFD-UHFFFAOYSA-N piperylene Natural products CC=CC=C PMJHHCWVYXUKFD-UHFFFAOYSA-N 0.000 description 2
- 229920000098 polyolefin Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 229910052702 rhenium Inorganic materials 0.000 description 2
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical group [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 description 2
- 229910000077 silane Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- 239000004711 α-olefin Substances 0.000 description 2
- ZOICEQJZAWJHSI-UHFFFAOYSA-N (2,3,4,5,6-pentafluorophenyl)boron Chemical compound [B]C1=C(F)C(F)=C(F)C(F)=C1F ZOICEQJZAWJHSI-UHFFFAOYSA-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
- ZSLUVFAKFWKJRC-IGMARMGPSA-N 232Th Chemical compound [232Th] ZSLUVFAKFWKJRC-IGMARMGPSA-N 0.000 description 1
- LGLDSEPDYUTBNZ-UHFFFAOYSA-N 3-phenylbuta-1,3-dien-2-ylbenzene Chemical compound C=1C=CC=CC=1C(=C)C(=C)C1=CC=CC=C1 LGLDSEPDYUTBNZ-UHFFFAOYSA-N 0.000 description 1
- OQLZINXFSUDMHM-UHFFFAOYSA-N Acetamidine Chemical compound CC(N)=N OQLZINXFSUDMHM-UHFFFAOYSA-N 0.000 description 1
- 241000226585 Antennaria plantaginifolia Species 0.000 description 1
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 1
- FDYAUVYPZOQMFE-UHFFFAOYSA-N C1(CC=C(C=C1)C)(C)C=CC=C Chemical compound C1(CC=C(C=C1)C)(C)C=CC=C FDYAUVYPZOQMFE-UHFFFAOYSA-N 0.000 description 1
- 125000000041 C6-C10 aryl group Chemical group 0.000 description 1
- GWAGOKMZTSJCBP-UHFFFAOYSA-N C[SiH](C)[Ti] Chemical compound C[SiH](C)[Ti] GWAGOKMZTSJCBP-UHFFFAOYSA-N 0.000 description 1
- ZSKWAXZRJMKGQD-UHFFFAOYSA-N C[SiH](C)[Ti].CC=CC=C Chemical compound C[SiH](C)[Ti].CC=CC=C ZSKWAXZRJMKGQD-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- QMMFVYPAHWMCMS-UHFFFAOYSA-N Dimethyl sulfide Chemical compound CSC QMMFVYPAHWMCMS-UHFFFAOYSA-N 0.000 description 1
- 101100289061 Drosophila melanogaster lili gene Proteins 0.000 description 1
- ODVVNSKYSZIOAY-UHFFFAOYSA-N FC1=C(C(=C(C(=C1[B])F)F)F)F.[B] Chemical compound FC1=C(C(=C(C(=C1[B])F)F)F)F.[B] ODVVNSKYSZIOAY-UHFFFAOYSA-N 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- 206010061274 Malocclusion Diseases 0.000 description 1
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical class OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 1
- 229910052778 Plutonium Inorganic materials 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- 229910052776 Thorium Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- DDBPNGXQJHSBHE-UHFFFAOYSA-L [Cl-].[Cl-].[SiH3][Ti++] Chemical compound [Cl-].[Cl-].[SiH3][Ti++] DDBPNGXQJHSBHE-UHFFFAOYSA-L 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- YCOXTKKNXUZSKD-UHFFFAOYSA-N as-o-xylenol Natural products CC1=CC=C(O)C=C1C YCOXTKKNXUZSKD-UHFFFAOYSA-N 0.000 description 1
- JXLHNMVSKXFWAO-UHFFFAOYSA-N azane;7-fluoro-2,1,3-benzoxadiazole-4-sulfonic acid Chemical compound N.OS(=O)(=O)C1=CC=C(F)C2=NON=C12 JXLHNMVSKXFWAO-UHFFFAOYSA-N 0.000 description 1
- UORVGPXVDQYIDP-BJUDXGSMSA-N borane Chemical compound [10BH3] UORVGPXVDQYIDP-BJUDXGSMSA-N 0.000 description 1
- 229910000085 borane Inorganic materials 0.000 description 1
- XPQOWSUDVLKXTA-UHFFFAOYSA-N buta-1,3-dienyl(dimethyl)sulfanium Chemical compound C[S+](C)C=CC=C XPQOWSUDVLKXTA-UHFFFAOYSA-N 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 230000000875 corresponding effect Effects 0.000 description 1
- 210000004268 dentin Anatomy 0.000 description 1
- 125000004663 dialkyl amino group Chemical group 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
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical group [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 1
- 125000003106 haloaryl group Chemical group 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 239000012771 household material Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- SNHMUERNLJLMHN-UHFFFAOYSA-N iodobenzene Chemical compound IC1=CC=CC=C1 SNHMUERNLJLMHN-UHFFFAOYSA-N 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 239000006210 lotion Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- WWZKQHOCKIZLMA-UHFFFAOYSA-M octanoate Chemical compound CCCCCCCC([O-])=O WWZKQHOCKIZLMA-UHFFFAOYSA-M 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 125000004469 siloxy group Chemical group [SiH3]O* 0.000 description 1
- MKIAXBKOEOEQDD-UHFFFAOYSA-N silylmethanimidamide Chemical group C(N)(=N)[SiH3] MKIAXBKOEOEQDD-UHFFFAOYSA-N 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 239000001384 succinic acid Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-O tributylazanium Chemical compound CCCC[NH+](CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-O 0.000 description 1
- UORVGPXVDQYIDP-UHFFFAOYSA-N trihydridoboron Substances B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 150000003754 zirconium Chemical class 0.000 description 1
- 229910052726 zirconium Inorganic materials 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
-
- 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
- C08F2/00—Processes of polymerisation
- C08F2/34—Polymerisation in gaseous state
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Description
A7 -^ ___ B7 五、發明説明(丨) — 本發明係關於一種聚合方法,特別係關於使用一種包 括活化金屬辛錯合物之催化劑系統聚合婦煙之氣相方法。 基於金屬辛錯合物之催化劑廣泛用於烯烴之聚合。此 等用於催化劑系、統之錯合物典型包括威(環戍二婦基)過渡 金屬呈錯合物及一種輔催化劑。此種貳(Cp)過渡金屬錯合 物稱為金屬辛,典型係基於鈦或鍅金屬,使用時之鋁化合 物如鋁氧烷類輔助催化。用於氣相方法時,此種貳(cp)金 屬辛系統可支禮於氧化石夕。此種摧化劑系統述於Ep 及 EP206794。 更為晚近,另一型過渡金屬錯合物用於製備烯烴聚合 物。此種錯合物具有單個一環戊二烯基環配合基及雜原子 鍵結至金屬原子,也可與鋁氧烷合併使用。此等錯合物稱 為具有‘約束幾何’及述於EP420436及EP416815。 類似催化劑系統教示於EP418044及W092/00333。此 等系統中,催化劑系統包括單(環戊二烯基)雜原子金屬錯 合物及離子活化劑化合物,此種系統稱作離子性單(環戊 一嫦基)催化劑。此等系統之典型離子活化劑可以蝴酸鹽 代表。 經濟部中央標準局員工消費合作社印製 W095/00526敘述鈦或锆錯合物,其中過渡金屬為+2 克式1氧化態。錯合物也包括中性、共軛或非共軛二烯配 合基,其與金屬形成7Γ -錯合物。此種錯合物經由舉例如 銘氧燒硼烷類或硼酸鹽類之活化辅催化劑組合可變成催化 劑。用於氣相聚合法時,此種催化劑也適合支撐於氧化石夕 本紙張尺度適用中國國家標準(CNS ) A4規格(210X^97公釐) 1222980 A7 B7 五、發明説明(2 另一類型催化劑系統係述於W096/04290。此處金屬 辛錯合物以貳(Cp)錯合物表示但也包括共軛二烯,其可呈 7Γ -錯合物或σ -錯合物結合金屬。 金屬辛錯合物揭示為適用於氣相聚合烯烴方法。例如 ΕΡ206794 , ΕΡ696293 , ΕΡ719289 , ΕΡ802202 , ΕΡ659773 ,ΕΡ593083及ΕΡ739360揭示金屬辛錯合物用於氣相之用 途。 發明人今日出乎意外地發現於使用活化金屬辛催化劑 系統之氣相方法中,經由將惰性液體注入反應器内可獲得 催化活性改良。 特別發明人發現使用低碳烷類特別適合此種用途。 如此,根據本發明提供一種於氣相聚合烯烴之方法, 該方法係於包括(a)金屬辛及(b)活化劑之催化劑系統存在 下進行,而其特徵為低碳烷添加至氣相反應器。 烷較佳直接添加至反應器。 鈦(Π )或錘(Π )錯合物特別適用於本發明方法做為金 屬辛。此等錯合物揭示於前述W095/00526(併述於此以供 參考)。錯合物具有通式:
Y 經濟部中央標準局員工消費合作社印製 (請先閱讀背面之注意事項再填寫本頁) 其中: R’於各次出現時分別選自氫,烴基,矽烷基,鍺烷基 本紙張尺度適用中國國家標準(CNS ) A4規格(210X297公釐)
經濟部中央標準局員工消費合作社印掣 五、發明説明(3 ) ,齒原子,氰基及其組合,R,含至多2〇個非氫原子,及選 擇性兩個R’基(此處R,非為氫,函原子或氰基)共同形成二 4貝衍生物聯結至壞戊二烯基環之毗鄰位置而形成稠合環結 構; X為含至多30個非氫原子之"鍵結二烯基,其與M形 成7Γ -錯合物; Y為-0-,-S_,-NR*-,; Μ為呈二價正式氧化態之鈦或鍅; Ζ 為 SiR2,CR%,SiR*2SiR*2,CR*2CR*2,CR>CR*, CR2SiR 2 ’ 或 GeR*2 ;其中: R*於各次出現時分別為氫或選自烴基,矽烷基,齒化 絲,iS化芳基及其組合中之一者,R*含至多1〇個非氮原 子及選擇性兩個來自Z*的R*基(當R*非為氫時),或一個來 自Z*之R*基及一個來自丫的以*基形成環系。 最佳錯合物為醯胺基矽烷或醯胺基烷二基錯合物,其 中該金屬為鈦。 高度較佳二烯基為二苯基-:1,3-丁二烯,丨,3-戊二 稀,1,4-二千基-;ι,3_ 丁二烯,3_甲基」,3•戊二烯。 不例祝明但非限制性錯合物實例較佳為(第三丁基醯 胺基)(四甲基· β 5-環戊二稀基)二甲基石夕烧欽⑻i,心二苯 基-1,3-丁二稀。 (第三丁基醯胺基)(四曱基1、環戊二烯基)二甲基矽 烷鈦(Π )1,3-戊二烯。 (第三丁基醯胺基)(2-曱基節基)二?基石夕燒欽⑷M_ 本紙張尺度適用中國國家g準(CNS ) A4規格(210x797公一--'~ -- -6 - (請先閱讀背面之注意事項再填寫本頁)
1222980 經濟部中央標準局員工消費合作社印製 Α7 Β7 五、發明説明(4 ) 二苯基-1,3-丁二烯。 此等錯合物經由與活化輔催化劑組合可變成催化活性 。適當輔催化劑包含鋁氧烷類,特別甲基鋁氧烷(MA〇)或 強路易士酸例如叁(烴基)硼化合物或_化衍生物。 特佳活化劑為銮(五氟苯基)硼。 其它適用於本發明方法之錯合物為其中金屬係呈較高 價態者。此等錯合物揭示於EP416815&Ep491842(皆併述 於此以供參考)。錯合物具有通式:
其中:
Cp為單獨7? 5-環戊二稀基或?7 5-取代環戊二稀基 選擇性經由-Z-Y-共價鍵結至Μ及對應於式:
R
R 其中R於各次出現時為氫或選自鹵原子,烧基,芳基,齒 烷基,烷氧基,芳氧基,矽烧基及其組合之部分,含有至 多20個非氫原子,或兩個或多個R基共同形成稠合環系·, 本紙張尺度適用中國國家標準(CNS ) Α4規格(210X 297公釐) (請先閱讀背面之注意事項再填寫本頁)
1222980 A7 B7 五、發明説明(5 ) Μ為鍅、鈦或铪以▽ 5鍵結模式結合至環戊二烯基或 取代環戊二烯基且為+3或+4價態; X於各次出現時為氫陰離子或選自含至多2〇個非氫原 子之鹵原子,烷基,芳基,矽烷基,鍺烷基,芳氧基,烷 氧基,醯胺基,矽氧基及其組合(例如鹵烷基,齒芳基, 鹵矽烷基,烷芳基,芳烷基,矽烷基烷基,芳氧芳基及烷 氧芳基,醯胺基烷基,醯胺基芳基)之一部分及含至多2〇 個非氫原子之中性路易士鹼配合基; η為1或2,依Μ之價數而定; Ζ為包括氧,硼或元素周期表14族成員之二價部分; Υ為鍵聯基共價鍵結至包括氮,磷,氧或硫之金屬, 或選擇性Ζ與Υ共同形成稠合環系。 最佳錯合物為其中γ為對應於式-(NR,)或_(pR,)之含 氮或含磷基,其中11’為(:1-(:1()烷基或C6-C10芳基及其中冗為 SiR”2,cr”2,siR,,2siR,,2,或 GeR,,2,其中 R” 為氫或烴基。 最佳錯合物為其中Μ為鈦或錘。 經滴部中央標隼局員工消費合作社印製 不例說明但非限制性適當錯合物實例有(第三丁基醯 月女基)(四甲基-7; 環戊二烯基)二甲基矽烷鈦二甲基,(第 二丁基醯胺基)二苄基(四甲基1、環戊二烯基)矽烷錯二 苄基,(苄基醯胺基)二甲基(四甲基1、瓖戊二烯基)矽烷 鈦二氯化物,(苯基磷陰離子)二甲基(四甲基I、環戊二 烯基)矽烷錯二苄基等。 此等錯合物經由組合活性輔催化劑可變成催化活性。 本紙張尺度適用巾關家料(CNS) Α4規格公釐) 1222980 Μ Β7 五、發明説明(6 適·化劑為紹氧烷類,特別甲基鋁氧烷(ma〇)或強路 易士酸如叁(烴基)硼化合物或_化衍生物。 特別適合之活化劑為銮(五氟苯基)硼。 也適用於本發明方法者為具有如τ通式之金屬辛錯合 物:
Cp2MY2 或
Cp〆、 Z /MY2 Cp 或
CpMY' 其中 (請先閱讀背面之注意事項再填寫本頁)
經濟部中央標準局員工消費合作社印製 Μ為 Zr,Ti 或 Hf Y為一價配合基
Cp為無取代或取代環戊二婦基配合基,及 Z為橋連基。 典型Y基為鹵原子或烷基,環戊二烯基配合基可由烷 基取代,或兩個取代基可接合形成稠合環例如g卩基。 Z典型為伸烷基,二烷基矽烷基或二烷基鍺烷基橋連 基。 特別適當之錯合物例如為伸乙基貳(茚基)鍅二氯化物 或伸乙基貳(茚基)錯二甲基。 此等金屬辛錯合物典型係於鋁氧烷輔催化劑存在下使 用。 適用於本發明方法之金屬辛錯合物範例揭示於 EP129368 , EP206794及EP260130 。 貳(Cp)金屬辛錯合物當包括二烯配合基時也適用於本 本紙張尺度適用中國國家標準(CNS ) A4規格(210X297公釐) 9 1222980 A7 B7 五、發明説明( 發明方法。此類型錯合物述於W096/04290。 含有此種二烯配合基之貳(Cp)金屬辛錯合物可以下式 表示: (請先閱讀背面之注意事項再填寫本頁)
(R)
X
經濟部中央標率局員工消費合作社印製 其中 Μ為鈦、鍅或铪, D為安定共軛二烯,其選擇性以一或多個烴基,矽烷 基,烴基矽烷基,矽烷基烴基或其混合物取代,或可含有 路易士驗官能基,D含有4至40個非氫原子且與Μ形成7Γ-錯合物, Ζ為橋連基,包括含1-20個碳原子之伸烷基或二烷基 石夕烧基或錯烧基或烧基麟基或胺基’ R為氫或含1-10個碳原子之烷基及X為1-6。 本紙張尺度適用中國國家標準(CNS ) Α4規格(210X 297公釐) 10 1222980 經滴部中夾標準局員工消費合作社印製 Α7 Β7 五、發明説明(8 ) 此族之最佳金屬辛錯合物由X-光繞射或NMR證實, 低配合基係以7/ 3方式7Γ -鍵結至Μ原子,此等金屬辛錯合 物之特徵為Μ原子係呈+2氧化態。 較佳錯合物為其中Μ為鍅及Ζ為伸乙基(CH2CH2)。 D配合基最佳選自: s-反-π 4-1,4-二苯基-1,3-丁 二烯;s·反-4-3_ 曱基-1,3-戊一稀;s-反-;74-l,4-二千基-1,3-丁二婦;s-反-;74-2,4-己 二烯;s_反-77Μ,4·二甲苯基_1,3-丁二烯;s·反-7/Μ,4·貳 (二甲基石夕烧基)-1,3-丁二婦;s-順-?74-1,4-二苯基-1,3-丁 二烯;^順14-3-甲基-1,3-戊二烯;s-順-7^-2,4-己二烯 ;s·順-7/ 4-2,4-己二烯;s-順-π 戊二烯;以丨頁-β 4-1,4- 二甲苯基-1,3-丁二烯及s-順-々4_ 14-貳(三甲基矽烷基)_ 1,3-丁二烯,該s-順二烯基與金屬生成此處定義之π-錯合 物。 特別適合為外部取代二烯特別丨,4_二苯基取代丁二烯 〇 此等錯合物之製備徹底敘述以WO96/04290,也列舉 適用於本發明之代表例。 當二烯基D含有路易士鹼官能基時,可選自下列:
-NR2,-PR2,-A2R2,-〇R_,-SR 特佳此類型二烯為二烷基胺基取代、二烯如丨_苯基-4(N,N - 一乙基胺基苯基)-1,3-丁二稀。 特佳錯合物為伸乙基貳(茚基)锆(Π )1,4-二苯基丁二 婦0 本紙張尺度通用中國國家榡準(CNS ) A4規格(2l〇x 297公釐) (請先閲讀背面之注意事項再填寫本頁)
11 經濟部中央標準局員工消費合作社印製 !22298〇 A7 _____ B7 五、發明説明(9 ) ~ ' 本發明方法使用的錯合物對活化劑之莫耳比係於1 : 10000至100 · i之範圍。較佳範圍為i · 5〇⑼至i及最 佳為1. 1〇至1:〗之範圍。烷可選自包括丁烷,戊烷,異 戊烷或己烷之低碳烷。較佳烷為戊烷。 烧可於添加單體前添加至氣相反應器。較佳於室溫呈 液體添加且直接添加至反應器。另外,烧可於聚合過程中 連續添加至反應器。 根據本發明方法用於氣相之錯合物可經支撐。另外, 金屬辛錯合物可呈未支撐形式使用。 t經支撐時,撐體可為任—種有機絲機惰性固體, 特別多孔撐體如滑石,無機氧化物及含樹脂撐體材料如聚 烯烴類。有用的適當無機氧化物材料包含2,13,14或15 族金屬氧化物如氧切,氧㈣,氧切_氧化喊其混 合物。其它可單獨使用或與氧化石夕,氧化铭或氧化石广氧 化叙合併使用的無機氧化物為氧化鎮,氧化欽或氧化錯。 其它適當撐體材料可使用例如精細分割聚稀煙如聚乙婦。 最佳用於根據本發明方法之經支撐催化劑之材料 化矽。 ’ 較佳氧化石夕於使用前經乾燥,典型係於升高溫度例如 200至850°C加熱進行。 〜車父佳方案中,經支撐催化劑可經由添加活化劑於適當 f劑之溶液至以三烧基銘化物處理的活化氧化矽漿液,接 著加入金屬辛錯合物於相同溶劑之溶液製備。另外,錯合 物可於添加活化劑前添加至經三烷基鋁處理的氧化矽。口 本紙張尺度適用中國國家標準(CNS ) Α4規格(210;297公釐)— (請先閲讀背面之注意事項再填寫本頁)
、1T 12 1222980 A7 B7 五、發明説明(10 ) 製備經支撐催化劑之適當溶劑為甲苯。 適當三烷基鋁化合物為三烷基鋁(TMA),三乙基鋁 (TEA)或三異丁基鋁(TIBAL)。 根據本發明方法適用於聚合烯烴,特別用於乙烯之均 聚合或乙烯與其它α-烯烴之共聚合反應,特別含3至10碳 原子者。最佳α-烯烴為1-丁烯,1-己烯及4-甲基-1-戊烯 〇 本發明方法可於任何適當氣相方法進行。 例如傳統攪拌床反應器如US3256263及US4012573揭 示者適合使用。但本發明方法特別適用於包括流化床的氣 相方法。此種方法中,增長中的聚合物顆粒流化床支撐於 流化格柵上方。床使用流化介質維持於流化態,包括循環 氣流向上通過格柵。 特殊類型流化床作業利用循環氣流冷卻輔助冷卻流化 床。含夾帶液體之冷循環流返回流化格栅下方的流化床。 例如ΕΡ89691,ΕΡ699212及ΕΡ784637揭示此種氣相方法。 經濟部中央標準局員工消費合作社印製 (請先閱讀背面之注意事項再填寫本頁 另一類型氣相方法述於WO94/28032,其中循環氣流 冷卻及分離成氣流及液流。冷液體可為惰性液體或為可冷 凝單體。分離的液流直接引進流化床俾提供冷卻床。 此種流化床方法中,烷可藉任何適當手段添加至反應 器。例如烷可直接添加至反應器或可間接例如藉循環管路 ,催化劑注入系統等添加。 烷可於聚合過程中連續添加至流化床反應器。 至於氣相方法,特別流化床反應器,適用於本發明方 本紙張尺度適用中國國家標準(CNS ) Α4規格(21〇Χ29·7公釐) 13 經濟部中央標準局員工消費合作社印製 A^298〇 A7 B7 五、發明説明(U ) 法之稀數量,較佳以於穩態條件下烧對催化劑之重量比表 示。對催化劑之重量比大於或等於10。該重量比較佳於 10-10,000 之範圍。 另外’烷數量可以於穩態條件下反應器内之烷對聚合 物數量之重量比表示。烷對聚合物之最小重量比為〇.〇1〇 及烧對聚合物之重量比之較佳範圍為〇. 〇 1 〇至〇 · 5,及最佳 於0.018至0.5之範圍。 烧於低共聚單體濃度之聚合條件下特別有效。 使用根據本發明方法,聚合物可製備成具有密度於 0.905至0.960克/立方厘米之範圍,及熔體指數根據ASTM D1238條件Ε(2·16千克於190°C)於〇·1至20之範圍。 本發明將參照下列實例進一步說明。 實例1 經支撐催化劑1之製備 7.0千克Crosfield ES70氧化矽(於500°C活化)於11〇升 己烷調成漿液。加入9.32升0.976M TEA於己烷及漿液於 30°C攪動2小時。任氧化矽沈降及去除上清液己烷。氧化 石夕以己烧洗數次至洗液之銘濃度達小於1毫莫耳銘/升為止 。然後氧化矽於4(TC真空脫水。 50克經TEA處理的ES70氧化矽於250毫升無水甲苯調 成漿液。加入10.4毫升10· 7wt%(第三丁基醯胺基)(四甲基_ 7/ 5-環戊二婦基)二曱基石夕烧鈦戊-1,3-二稀於甲苯及混合 物激烈振搖。然後加入2 9.4亳升,7 · 8 5 wt%妻(五敗苯基) 硼於甲苯之溶液。混合物經徹底振搖,然後於4〇t真空去 本紙張尺度適用中國國家標準(CNS ) A4規格(210X 297公釐) (請先閱讀背面之注意事項再填寫本頁) —· 訂 -14 - 1222980 經濟部中央標率局員工消費合作社印製 A7 B7 五、發明説明(u ) 除溶劑獲得撖欖綠粉末。 實例2 里立·益劑之製備 2.5千克Crosfield ES70氧化矽(於5〇〇°C活化)於110升 己烷調成漿液。加入4.00升0.976M TEA於己烷及漿液於 30 C攪動2小時。任氧化矽沈降及去除上清液己烷。氧化 矽以己烷洗數次至洗液之鋁濃度達小於1亳莫耳鋁/升為止 。然後氧化矽於40°C真空脫水。 10克經TEA處理的ES70氧化矽於40毫升無水甲苯調 成漿液。加入2.1毫升10.7wt%(第三丁基醯胺基)(四甲基· β 5_環戊二烯基)二甲基矽烷鈦戊-1,3-二烯於甲苯及混合 物激烈振搖。然後加入5.9亳升,7_85 wt%妻(五氟苯基)硼 於曱苯之溶液。混合物經徹底振搖,然後於4〇°c真空去除 溶劑獲得撖欖綠粉末。 實例3 聚合 347克氯化鈉添加至2.5升容積經攪妥的無水相反應器 ’反應器事先於85 °C於N2沖洗下烘烤。反應器冷卻至 25°C及5毫升無水戊烷添加至反應器。反應器密封及溫度 升兩至85 C。1.19克經TIBAL處理的氧化矽添加至反應器 ,攪動15分鐘。反應器冷卻至70°C及加入6.5巴乙稀。然 後添加氫氣及1-己烯至反應器。0.309克實例1製備之催化 劑及0.912克經TIBAL處理之氧化矽混合物以高壓氮氣注 入反應器内。溫度,乙烯壓力及氫氣及1-己稀濃度於其餘 本紙張尺度適用中國國家標準(CNS ) A4規格(210X 297公嫠) n — ---衣—- (請先閲讀背面之注意事項再填寫本頁) 訂 -15 - 1222980 經濟部中央標準局員工消費合作社印製 A7 B7 五、發明説明(13 ) 試驗過程皆維持恆定。總聚合時間為233分鐘。試驗過程 中’平均氫/乙烯比為0 0038及平均丨_己烯/乙烯比為0 0062 。反應器通風及冷卻,洗滌鹽後回收262克聚合物獲得 33.6g/g cat.h.巴。聚合物密度為〇 9175克/毫升及M1(2 16) 為 2.10。 實例4 聚合 289克氣化鈉添加至2 5升容積經攪妥的無水相反應器 ’反應器事先於85 °C於N2沖洗下烘烤。反應器冷卻至 25°C及5亳升無水戊烷添加至反應器。反應器密封及溫度 升高至85°C。1.30克經TIBAL處理的氧化矽添加至反應器 ’授動15分鐘。反應器冷卻至7 〇它及加入6 · 5巴乙稀。然 後添加氫氣及1_己烯至反應器。〇.289克實例1製備之催化 劑及0.853克經TIBAL處理之氧化矽混合物以高壓氮氣注 入反應器内。溫度,乙烯壓力及氫氣及卜己烯濃度於其餘 試驗過程皆維持恆定。總聚合時間為1〇5分鐘。試驗過程 中,平均氫/乙稀比為0.0040及平均1-己婦/乙稀比為〇〇〇6〇 。反應為通風及冷卻,洗滌鹽後回收144克聚合物獲得 43.8g/g cat.h.巴。聚合物密度為〇·9175克/毫升及M1(2 16) 為3.10 。 實例5 (比較例) 344克氯化鈉添加至2.5升容積經攪妥的無水相反應器 ,反應态事先於85C於N2沖洗下烘烤。丨·3〇克經TIBAL處 本紙張尺度適用中國國家標準(CNS ) A4規格(210X 297公釐) "~· -16 - (請先閱讀背面之注意事項再填寫本頁) _
、1T B7 五、發明説明(14 ) (請先閱讀背面之注意事項再填寫本頁) 理之氧化石夕添加至反應器,及擾動15分鐘。反應器冷卻至 70 C及添加6.5巴乙稀。然後添加氫氣及己烯至反應器 。0.213克實例1製備之催化劑及0.781克經TIBAL處理之氧 化矽混合物以高壓氮氣注入反應器内。溫度,乙烯壓力及 氫氣及1-己烯濃度於其餘試驗過程皆維持恆定。總聚合時 間為166分鐘。試驗過程中,平均氫/乙烯比為〇 〇〇39及平 均1-己烯/乙烯比為0.0053。反應器通風及冷卻,洗滌鹽後 回收101克聚合物獲得26.3g/g cat.h.巴。 實例6 聚合 經濟部中央標準局員工消費合作社印製 273克氣化鈉添加至2.5升容積經攪妥的無水相反應器 ,反應器事先於85 °C於N2沖洗下烘烤。反應器冷卻至 25°C及5毫升無水戊烷添加至反應器。反應器密封及溫度 升高至85°C。1.21克經TIBAL處理的氧化矽添加至反應器 ,攪動15分鐘。反應器冷卻至70°C及加入6·5巴乙烯。然 後添加氫氣及1-己烯至反應器。0.217克實例2製備之催化 劑及0.755克經TIBAL處理之氧化矽混合物以高壓氮氣注 入反應器内。溫度,乙烯壓力及氫氣及1-己烯濃度於其餘 試驗過程皆維持恆定。總聚合時間為132分鐘。試驗過程 中,平均氫/乙烯比為0.0042及平均1-己烯/乙烯比為0.0044 。反應器通風及冷卻,洗滌鹽後回收122克聚合物獲得 39.3g/g cat.h.巴。聚合物密度為0.918克/亳升及Ml(2.16) 為 4.4。 實例7 本紙張尺度適用中國國家標準(CNS ) A4規格(210X 297公釐) 17 1222980 Α7 Β7 五、發明説明(15 ) (比較例) 322克氯化鈉添加至2.5升容積經攪妥的無水相反應器 ’反應裔事先於8 5 C於N2沖洗下烘烤。1.19克經τιb AL處 理之氧化矽添加至反應器,及攪動15分鐘。反應器冷卻至 70 C及添加6·5巴乙細。然後添加氫氣及1 _己稀至反應器 。0.220克實例2之催化劑及〇·75β·ΉΒΑ:ί處理之氧化矽 混合物以南壓氮氣注入反應器内。溫度,乙嫦壓力及氫氣 及1 -己烯濃度於其餘試驗過程皆維持恆定。總聚合時間為 123分鐘。試驗過程中,平均氫/乙烯比為〇.〇〇35及平均^ 己烯/乙烯比為0.0037。反應器通風及冷卻,洗滌鹽後回 收85克聚合物獲得29.0g/g cat.h.巴。聚合物密度為〇_919克 / 毫升及 Μ1(2·16)為 0.8。 (請先閱讀背面之注意事項再填寫本頁) 訂 經濟部中央標準局員工消費合作社印製 本紙張尺度適用中國國家標準(CNS ) A4規格(210X297公釐) 18 申請曰期 _K f、vj_— 案 號 類 別 (以上各欄由本局填註) C4
It /ν'- 1222980
第_98 II專利説明書H.〇7 -:名稱 中文 於氣相反應器聚合烯烴之方法 英 文 A PROCESS FOR THE POLYMERISATION OF OLEFIN IN A GAS phase REACTOR 姓 名 (1)彼特J.曼多克斯 ί2$彼# S.威廉斯 装 國 籍 英國 發明 創作> 住、居所 (1) 英國中塞克斯•杉伯瑞•泰晤河銜牛津排2號 (2) 法國愛辛普文斯•格拉西•莫利爾公館25號 姓 名 (名稱) 國 籍 英商·ΒΡ化學有限公司 英國 申請人 住、居所 (事務所) 英國倫敦芬斯堡廣場1號大不列顛宅 蘇珊J.戴伊 代表人 姓 名 紙張尺度賴中ϋΐΐ家襟準(CNS ) Α4· ( 2ΐ()χ297公釐)
Claims (1)
- 93. 1222980第87 100798號專利專利案中請專利範圍修正本 六、申請專利範圍 修正日期:93年6月 種;x非〜綾模式運作的氣相反應器中聚合烯烴之方法 /方法係於包括(a)_金屬辛(metall〇cene)& (b)一活化劑 之催化劑系統的存在下進行,該方法之特徵為一選自於丁 烧、戊院、異錢或己院所組成之群組中的低碳炫被添加 至氣相反應器内; 其中該金屬辛具有化學式其中: 於各人出現知分別選自於氫、烴基、石夕烧基、鍺烷· 基' i原子、氰基及此等之組合’ R’含有至多2〇個非氯原 子’及選擇性地兩個R,美Γ R J 暴(此處R非為氫、齒原子或氰基) 共同形成它的一個被聯結至毗鄰環戍二烯基環之位置的二 價衍生物,俾以形成一個稠合環結構; X為一個含有至多3〇個非窬 似乔虱原子之π -鍵結的二烯基 ’其與Μ形成一個π-錯合物; Υ為-0-、-S-、-NR'、; Μ為呈二價正式氧化態之鈦或錯; Ζ*為 SiR2、CR%、ςίρ * A 2 SlR 2SlR 2、CR*2CR*2、cr* = cr' CR^SiR 2 或 GeR 2 ’ 其中: 1222980六、申請專利範圍 R於各次出現時分別為氫或選自於烴基、矽烷基、鹵 化烷基、齒化芳基及此等之組合中之一者,r*含有至多Μ 個非氫原子;及 其中該金屬辛係被支撐於氧化矽上。。 2·如申凊專利範圍第i項之方法,其中該金屬辛具有化學式: Z \ (X), Cp> 其中: P為個單獨環戊二烯基或7/、取代環戊二嫦芙 選擇性經由被共價地鍵結至Μ且對應於下式:土:基、齒烷基、烷氧基、芳氧基、矽烷基及此等之組合之 部分,R含有至多2G個非氫原子,或兩個或多個 成一個稠合環系; Μ為錯、鈦或給,其以鍵結模式被 基或取代環戊二稀基且呈+3或+4價態; 衣戍-知 X於各次出現時為氫陰離子或一個選自於含有至多2〇 個非氫原子之齒原子、院基、芳基、石夕烧基、鍺烧基、芳 氧基、烧氧基、酿胺、石夕惫其 女矽虱基及此等之組合(例如齒烷基、 -2- 1222980 六、申請專利範圍 ~~ ' '一 - i芳基、鹵矽烷基、烷芳基、芳烷基、矽烷基烷基、芳氧 芳基,以及烷氧芳基、醯胺基烷基、醯胺基芳基)之部分, 以及含有至多20個非氫原子之中性路易士鹼配合基; η為1或2,依Μ之價數而定; ζ為一個包括氧、硼或元素周期表第14族之一成員之二 價部分; Υ為一個鍵聯基被共價地鍵結至包含有氮、磷、氧或 硫之金屬,或選擇性地2與丫共同形成稠合環系。 3·如申請專利範圍第巧之方法,其中該活化劑為參(五氣苯 基)硼。 4. 如申請專利範圍第巧之方法,其中該低碳烷為戊烷。 5. 如申明專利範圍第丨項之方法,其中該低碳烷係被直接添加· 至反應器内。 ^ 6. 如申請專利範圍第丄項之方法,其中該低碳烧係如同一液體 被添加至反應器内。 7. 如申請專利範圍第13:員之方法,其中於穩態條件下該低碳烷 對催化劑之重量比係在丨〇_ i 〇,〇〇〇之範圍内。 8 ·如申請專利範圍第i項之方法,其中於穩態條件下,低碳烧 對反應益内聚合物之重量比係在〇 〇1〇至〇 〇2之範圍内。 9·如申請專利範圍第8項之方法,其中該低碳烧對反應器内聚 合物之重量比係在〇_〇18至〇〇2之範圍。 1〇·如申請專利範圍第1項之方法,其中該聚合方法係於-流化 1222980 六、申請專利範圍 床反應器内進行者。 1 1.如申請專利範圍第1 0項之方法,其中該低碳烷係被連續地 添加至流化床反應器内。
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EP97430001A EP0853091A1 (en) | 1997-01-13 | 1997-01-13 | Polymerisation process |
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JP (1) | JP4104667B2 (zh) |
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DE10139477A1 (de) | 2001-08-10 | 2003-02-20 | Basell Polyolefine Gmbh | Optimierung der Wärmeabfuhr im Gasphasenwirbelschichtverfahren |
EP1348719B2 (en) † | 2002-03-25 | 2010-11-17 | Mitsui Chemicals, Inc. | Process for producing polyolefin |
SG106681A1 (en) | 2002-03-29 | 2004-10-29 | Mitsui Chemicals Inc | Olefinic polymer and process for producing the same |
EP1380602A1 (en) * | 2002-07-11 | 2004-01-14 | BP Lavéra SNC | Process for the (co-)polymerisation of olefins in the gas phase |
US7157531B2 (en) * | 2004-06-21 | 2007-01-02 | Univation Technologies, Llc | Methods for producing polymers with control over composition distribution |
US8318872B2 (en) | 2007-12-18 | 2012-11-27 | Univation Technologies, Llc | Method for controlling bimodal catalyst activity during polymerization |
RU2612555C2 (ru) * | 2011-11-30 | 2017-03-09 | Юнивейшн Текнолоджиз, Ллк | Способы и системы доставки катализатора |
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NZ235032A (en) | 1989-08-31 | 1993-04-28 | Dow Chemical Co | Constrained geometry complexes of titanium, zirconium or hafnium comprising a substituted cyclopentadiene ligand; use as olefin polymerisation catalyst component |
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KR20000070143A (ko) | 2000-11-25 |
BR9806744A (pt) | 2000-03-14 |
DE69826832T2 (de) | 2005-02-10 |
NO993432L (no) | 1999-09-13 |
ZA98225B (en) | 1999-07-12 |
EP0952993B1 (en) | 2004-10-06 |
CA2277907A1 (en) | 1998-07-16 |
PL334549A1 (en) | 2000-03-13 |
DE69826832D1 (de) | 2004-11-11 |
TR199901588T2 (xx) | 1999-09-21 |
JP2001508098A (ja) | 2001-06-19 |
EP0952993A1 (en) | 1999-11-03 |
ES2229467T3 (es) | 2005-04-16 |
ID21882A (id) | 1999-08-05 |
HUP0000776A2 (en) | 2000-07-28 |
JP4104667B2 (ja) | 2008-06-18 |
EP0853091A1 (en) | 1998-07-15 |
HUP0000776A3 (en) | 2000-11-28 |
EG22048A (en) | 2002-06-30 |
AU5565798A (en) | 1998-08-03 |
AU747055B2 (en) | 2002-05-09 |
NO993432D0 (no) | 1999-07-12 |
ATE278716T1 (de) | 2004-10-15 |
CN1249762A (zh) | 2000-04-05 |
US6437062B1 (en) | 2002-08-20 |
AR014339A1 (es) | 2001-02-28 |
NZ336639A (en) | 2001-11-30 |
WO1998030605A1 (en) | 1998-07-16 |
SK93699A3 (en) | 2000-05-16 |
KR100580902B1 (ko) | 2006-05-17 |
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