KR19980082808A - Alpha olefin polymerization and copolymerization catalyst - Google Patents
Alpha olefin polymerization and copolymerization catalyst Download PDFInfo
- Publication number
- KR19980082808A KR19980082808A KR1019970017907A KR19970017907A KR19980082808A KR 19980082808 A KR19980082808 A KR 19980082808A KR 1019970017907 A KR1019970017907 A KR 1019970017907A KR 19970017907 A KR19970017907 A KR 19970017907A KR 19980082808 A KR19980082808 A KR 19980082808A
- Authority
- KR
- South Korea
- Prior art keywords
- catalyst
- magnesium
- compound
- carbon atoms
- alcohol
- Prior art date
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- 239000003054 catalyst Substances 0.000 title claims abstract description 114
- 238000006116 polymerization reaction Methods 0.000 title claims abstract description 41
- 238000007334 copolymerization reaction Methods 0.000 title claims abstract description 15
- 239000004711 α-olefin Substances 0.000 title description 7
- 239000002245 particle Substances 0.000 claims abstract description 58
- 239000011777 magnesium Substances 0.000 claims abstract description 55
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 55
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 42
- 150000002681 magnesium compounds Chemical class 0.000 claims abstract description 31
- 239000010936 titanium Substances 0.000 claims abstract description 30
- 239000007787 solid Substances 0.000 claims abstract description 29
- 150000001298 alcohols Chemical class 0.000 claims abstract description 21
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 18
- 150000004292 cyclic ethers Chemical class 0.000 claims abstract description 17
- 150000001336 alkenes Chemical class 0.000 claims abstract description 15
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims abstract description 13
- 150000001282 organosilanes Chemical class 0.000 claims abstract description 11
- 239000012046 mixed solvent Substances 0.000 claims abstract description 7
- 150000003623 transition metal compounds Chemical class 0.000 claims abstract description 7
- -1 magnesium halide Chemical class 0.000 claims description 49
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 37
- 238000000034 method Methods 0.000 claims description 26
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical group C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 22
- 125000004432 carbon atom Chemical group C* 0.000 claims description 20
- 150000003609 titanium compounds Chemical class 0.000 claims description 20
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical group CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 18
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 15
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 11
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 10
- 125000003545 alkoxy group Chemical group 0.000 claims description 8
- 229910052736 halogen Inorganic materials 0.000 claims description 7
- 150000002367 halogens Chemical class 0.000 claims description 7
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- 239000001257 hydrogen Substances 0.000 claims description 5
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 5
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 5
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 5
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 claims description 4
- 125000003118 aryl group Chemical group 0.000 claims description 4
- 150000004820 halides Chemical class 0.000 claims description 4
- PHTQWCKDNZKARW-UHFFFAOYSA-N isoamylol Chemical compound CC(C)CCO PHTQWCKDNZKARW-UHFFFAOYSA-N 0.000 claims description 4
- 125000001188 haloalkyl group Chemical group 0.000 claims description 3
- VXEGSRKPIUDPQT-UHFFFAOYSA-N 4-[4-(4-methoxyphenyl)piperazin-1-yl]aniline Chemical compound C1=CC(OC)=CC=C1N1CCN(C=2C=CC(N)=CC=2)CC1 VXEGSRKPIUDPQT-UHFFFAOYSA-N 0.000 claims description 2
- 150000004791 alkyl magnesium halides Chemical class 0.000 claims description 2
- 125000004104 aryloxy group Chemical group 0.000 claims description 2
- 239000005049 silicon tetrachloride Substances 0.000 claims description 2
- HBGGXOJOCNVPFY-UHFFFAOYSA-N diisononyl phthalate Chemical group CC(C)CCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCC(C)C HBGGXOJOCNVPFY-UHFFFAOYSA-N 0.000 claims 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 claims 1
- 229920000642 polymer Polymers 0.000 abstract description 32
- 238000009826 distribution Methods 0.000 abstract description 29
- 230000037048 polymerization activity Effects 0.000 abstract description 10
- 239000000243 solution Substances 0.000 description 35
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 21
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 17
- 238000002360 preparation method Methods 0.000 description 16
- 150000001875 compounds Chemical class 0.000 description 13
- 238000006243 chemical reaction Methods 0.000 description 11
- 238000004519 manufacturing process Methods 0.000 description 11
- 239000011148 porous material Substances 0.000 description 10
- 239000002904 solvent Substances 0.000 description 10
- 239000004743 Polypropylene Substances 0.000 description 9
- 229930195733 hydrocarbon Natural products 0.000 description 9
- 150000002430 hydrocarbons Chemical class 0.000 description 9
- 229920001155 polypropylene Polymers 0.000 description 9
- 239000004215 Carbon black (E152) Substances 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 7
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 7
- 239000011949 solid catalyst Substances 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- 150000001412 amines Chemical class 0.000 description 6
- 239000002685 polymerization catalyst Substances 0.000 description 6
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 6
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 6
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 5
- 239000005977 Ethylene Substances 0.000 description 5
- 150000002902 organometallic compounds Chemical class 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 4
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 4
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 description 4
- 238000012685 gas phase polymerization Methods 0.000 description 4
- 239000012299 nitrogen atmosphere Substances 0.000 description 4
- 150000003961 organosilicon compounds Chemical class 0.000 description 4
- 239000006228 supernatant Substances 0.000 description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 150000001299 aldehydes Chemical class 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 125000005843 halogen group Chemical group 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 3
- 150000007524 organic acids Chemical class 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910000077 silane Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 150000003377 silicon compounds Chemical class 0.000 description 3
- UQMOLLPKNHFRAC-UHFFFAOYSA-N tetrabutyl silicate Chemical compound CCCCO[Si](OCCCC)(OCCCC)OCCCC UQMOLLPKNHFRAC-UHFFFAOYSA-N 0.000 description 3
- 150000003606 tin compounds Chemical class 0.000 description 3
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 3
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 2
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 2
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 2
- WRMNZCZEMHIOCP-UHFFFAOYSA-N 2-phenylethanol Chemical compound OCCC1=CC=CC=C1 WRMNZCZEMHIOCP-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
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- UUGLJVMIFJNVFH-UHFFFAOYSA-N Hexyl benzoate Chemical compound CCCCCCOC(=O)C1=CC=CC=C1 UUGLJVMIFJNVFH-UHFFFAOYSA-N 0.000 description 2
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical group [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- XSIFPSYPOVKYCO-UHFFFAOYSA-N butyl benzoate Chemical compound CCCCOC(=O)C1=CC=CC=C1 XSIFPSYPOVKYCO-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 description 2
- SJJCABYOVIHNPZ-UHFFFAOYSA-N cyclohexyl-dimethoxy-methylsilane Chemical compound CO[Si](C)(OC)C1CCCCC1 SJJCABYOVIHNPZ-UHFFFAOYSA-N 0.000 description 2
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 2
- FLKPEMZONWLCSK-UHFFFAOYSA-N diethyl phthalate Chemical compound CCOC(=O)C1=CC=CC=C1C(=O)OCC FLKPEMZONWLCSK-UHFFFAOYSA-N 0.000 description 2
- MGWAVDBGNNKXQV-UHFFFAOYSA-N diisobutyl phthalate Chemical compound CC(C)COC(=O)C1=CC=CC=C1C(=O)OCC(C)C MGWAVDBGNNKXQV-UHFFFAOYSA-N 0.000 description 2
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- MTZQAGJQAFMTAQ-UHFFFAOYSA-N ethyl benzoate Chemical compound CCOC(=O)C1=CC=CC=C1 MTZQAGJQAFMTAQ-UHFFFAOYSA-N 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 150000008282 halocarbons Chemical class 0.000 description 2
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 2
- WVDDGKGOMKODPV-UHFFFAOYSA-N hydroxymethyl benzene Natural products OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- HQKMJHAJHXVSDF-UHFFFAOYSA-L magnesium stearate Chemical compound [Mg+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O HQKMJHAJHXVSDF-UHFFFAOYSA-L 0.000 description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
- QPJVMBTYPHYUOC-UHFFFAOYSA-N methyl benzoate Chemical compound COC(=O)C1=CC=CC=C1 QPJVMBTYPHYUOC-UHFFFAOYSA-N 0.000 description 2
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 2
- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 description 2
- 235000005985 organic acids Nutrition 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 2
- 230000000737 periodic effect Effects 0.000 description 2
- 150000003014 phosphoric acid esters Chemical class 0.000 description 2
- 125000005498 phthalate group Chemical class 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- ODLMAHJVESYWTB-UHFFFAOYSA-N propylbenzene Chemical compound CCCC1=CC=CC=C1 ODLMAHJVESYWTB-UHFFFAOYSA-N 0.000 description 2
- 230000001603 reducing effect Effects 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 description 1
- 125000003837 (C1-C20) alkyl group Chemical group 0.000 description 1
- KNKRKFALVUDBJE-UHFFFAOYSA-N 1,2-dichloropropane Chemical compound CC(Cl)CCl KNKRKFALVUDBJE-UHFFFAOYSA-N 0.000 description 1
- JTPNRXUCIXHOKM-UHFFFAOYSA-N 1-chloronaphthalene Chemical compound C1=CC=C2C(Cl)=CC=CC2=C1 JTPNRXUCIXHOKM-UHFFFAOYSA-N 0.000 description 1
- HYFLWBNQFMXCPA-UHFFFAOYSA-N 1-ethyl-2-methylbenzene Chemical compound CCC1=CC=CC=C1C HYFLWBNQFMXCPA-UHFFFAOYSA-N 0.000 description 1
- CMAOLVNGLTWICC-UHFFFAOYSA-N 2-fluoro-5-methylbenzonitrile Chemical compound CC1=CC=C(F)C(C#N)=C1 CMAOLVNGLTWICC-UHFFFAOYSA-N 0.000 description 1
- JWUJQDFVADABEY-UHFFFAOYSA-N 2-methyltetrahydrofuran Chemical compound CC1CCCO1 JWUJQDFVADABEY-UHFFFAOYSA-N 0.000 description 1
- DUAYDERMVQWIJD-UHFFFAOYSA-N 2-n,2-n,6-trimethyl-1,3,5-triazine-2,4-diamine Chemical compound CN(C)C1=NC(C)=NC(N)=N1 DUAYDERMVQWIJD-UHFFFAOYSA-N 0.000 description 1
- JEABIFHLYSDNRJ-UHFFFAOYSA-N 2-o-butyl 1-o-ethyl benzene-1,2-dicarboxylate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCC JEABIFHLYSDNRJ-UHFFFAOYSA-N 0.000 description 1
- OIGWAXDAPKFNCQ-UHFFFAOYSA-N 4-isopropylbenzyl alcohol Chemical compound CC(C)C1=CC=C(CO)C=C1 OIGWAXDAPKFNCQ-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- XBVQSAIISGFAAS-UHFFFAOYSA-N CC(C)O[Mg] Chemical compound CC(C)O[Mg] XBVQSAIISGFAAS-UHFFFAOYSA-N 0.000 description 1
- ZNEGVQGQHBETJB-UHFFFAOYSA-M CC=1C(=C(O[Mg])C=CC=1)C Chemical compound CC=1C(=C(O[Mg])C=CC=1)C ZNEGVQGQHBETJB-UHFFFAOYSA-M 0.000 description 1
- ZKCNZMISGOLOOY-UHFFFAOYSA-N CCCCCCCCO[Mg] Chemical compound CCCCCCCCO[Mg] ZKCNZMISGOLOOY-UHFFFAOYSA-N 0.000 description 1
- ZFAGXQVYYWOLNK-UHFFFAOYSA-N CCO[Mg] Chemical compound CCO[Mg] ZFAGXQVYYWOLNK-UHFFFAOYSA-N 0.000 description 1
- UYXLOULABOHUAJ-UHFFFAOYSA-N CO[SiH](OC)CCC1=CC=CC=C1 Chemical compound CO[SiH](OC)CCC1=CC=CC=C1 UYXLOULABOHUAJ-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 1
- NHTMVDHEPJAVLT-UHFFFAOYSA-N Isooctane Chemical compound CC(C)CC(C)(C)C NHTMVDHEPJAVLT-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- DHXVGJBLRPWPCS-UHFFFAOYSA-N Tetrahydropyran Chemical compound C1CCOCC1 DHXVGJBLRPWPCS-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 150000004996 alkyl benzenes Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- KYZHGEFMXZOSJN-UHFFFAOYSA-N benzoic acid isobutyl ester Natural products CC(C)COC(=O)C1=CC=CC=C1 KYZHGEFMXZOSJN-UHFFFAOYSA-N 0.000 description 1
- 235000019445 benzyl alcohol Nutrition 0.000 description 1
- SIPUZPBQZHNSDW-UHFFFAOYSA-N bis(2-methylpropyl)aluminum Chemical compound CC(C)C[Al]CC(C)C SIPUZPBQZHNSDW-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 238000012662 bulk polymerization Methods 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- VZGDMQKNWNREIO-UHFFFAOYSA-N carbon tetrachloride Substances ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001924 cycloalkanes Chemical class 0.000 description 1
- DQZKGSRJOUYVPL-UHFFFAOYSA-N cyclohexyl benzoate Chemical class C=1C=CC=CC=1C(=O)OC1CCCCC1 DQZKGSRJOUYVPL-UHFFFAOYSA-N 0.000 description 1
- 229930007927 cymene Natural products 0.000 description 1
- DIOQZVSQGTUSAI-NJFSPNSNSA-N decane Chemical compound CCCCCCCCC[14CH3] DIOQZVSQGTUSAI-NJFSPNSNSA-N 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229960002380 dibutyl phthalate Drugs 0.000 description 1
- ZFTFAPZRGNKQPU-UHFFFAOYSA-N dicarbonic acid Chemical compound OC(=O)OC(O)=O ZFTFAPZRGNKQPU-UHFFFAOYSA-N 0.000 description 1
- ZVMRWPHIZSSUKP-UHFFFAOYSA-N dicyclohexyl(dimethoxy)silane Chemical compound C1CCCCC1[Si](OC)(OC)C1CCCCC1 ZVMRWPHIZSSUKP-UHFFFAOYSA-N 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- YNLAOSYQHBDIKW-UHFFFAOYSA-M diethylaluminium chloride Chemical compound CC[Al](Cl)CC YNLAOSYQHBDIKW-UHFFFAOYSA-M 0.000 description 1
- AHUXYBVKTIBBJW-UHFFFAOYSA-N dimethoxy(diphenyl)silane Chemical compound C=1C=CC=CC=1[Si](OC)(OC)C1=CC=CC=C1 AHUXYBVKTIBBJW-UHFFFAOYSA-N 0.000 description 1
- NHYFIJRXGOQNFS-UHFFFAOYSA-N dimethoxy-bis(2-methylpropyl)silane Chemical compound CC(C)C[Si](OC)(CC(C)C)OC NHYFIJRXGOQNFS-UHFFFAOYSA-N 0.000 description 1
- VHPUZTHRFWIGAW-UHFFFAOYSA-N dimethoxy-di(propan-2-yl)silane Chemical compound CO[Si](OC)(C(C)C)C(C)C VHPUZTHRFWIGAW-UHFFFAOYSA-N 0.000 description 1
- CVQVSVBUMVSJES-UHFFFAOYSA-N dimethoxy-methyl-phenylsilane Chemical compound CO[Si](C)(OC)C1=CC=CC=C1 CVQVSVBUMVSJES-UHFFFAOYSA-N 0.000 description 1
- JVSWJIKNEAIKJW-UHFFFAOYSA-N dimethyl-hexane Natural products CCCCCC(C)C JVSWJIKNEAIKJW-UHFFFAOYSA-N 0.000 description 1
- LIKFHECYJZWXFJ-UHFFFAOYSA-N dimethyldichlorosilane Chemical compound C[Si](C)(Cl)Cl LIKFHECYJZWXFJ-UHFFFAOYSA-N 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- OANIYCQMEVXZCJ-UHFFFAOYSA-N ditert-butyl(dimethoxy)silane Chemical compound CO[Si](OC)(C(C)(C)C)C(C)(C)C OANIYCQMEVXZCJ-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- RSIHJDGMBDPTIM-UHFFFAOYSA-N ethoxy(trimethyl)silane Chemical compound CCO[Si](C)(C)C RSIHJDGMBDPTIM-UHFFFAOYSA-N 0.000 description 1
- BIHHBTVQFPVSTE-UHFFFAOYSA-N ethyl 2-bromobenzoate Chemical compound CCOC(=O)C1=CC=CC=C1Br BIHHBTVQFPVSTE-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- UAIZDWNSWGTKFZ-UHFFFAOYSA-L ethylaluminum(2+);dichloride Chemical compound CC[Al](Cl)Cl UAIZDWNSWGTKFZ-UHFFFAOYSA-L 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 150000005171 halobenzenes Chemical class 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000012456 homogeneous solution Substances 0.000 description 1
- 150000004678 hydrides Chemical group 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- OTCKOJUMXQWKQG-UHFFFAOYSA-L magnesium bromide Chemical compound [Mg+2].[Br-].[Br-] OTCKOJUMXQWKQG-UHFFFAOYSA-L 0.000 description 1
- 229910001623 magnesium bromide Inorganic materials 0.000 description 1
- ORUIBWPALBXDOA-UHFFFAOYSA-L magnesium fluoride Chemical compound [F-].[F-].[Mg+2] ORUIBWPALBXDOA-UHFFFAOYSA-L 0.000 description 1
- 229910001635 magnesium fluoride Inorganic materials 0.000 description 1
- BLQJIBCZHWBKSL-UHFFFAOYSA-L magnesium iodide Chemical compound [Mg+2].[I-].[I-] BLQJIBCZHWBKSL-UHFFFAOYSA-L 0.000 description 1
- 229910001641 magnesium iodide Inorganic materials 0.000 description 1
- 235000019359 magnesium stearate Nutrition 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Natural products C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- SWGQITQOBPXVRC-UHFFFAOYSA-N methyl 2-bromobenzoate Chemical compound COC(=O)C1=CC=CC=C1Br SWGQITQOBPXVRC-UHFFFAOYSA-N 0.000 description 1
- 229940095102 methyl benzoate Drugs 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- DIOQZVSQGTUSAI-UHFFFAOYSA-N n-butylhexane Natural products CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- 238000005457 optimization Methods 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 125000001181 organosilyl group Chemical group [SiH3]* 0.000 description 1
- HFPZCAJZSCWRBC-UHFFFAOYSA-N p-cymene Chemical compound CC(C)C1=CC=C(C)C=C1 HFPZCAJZSCWRBC-UHFFFAOYSA-N 0.000 description 1
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 description 1
- 229940067107 phenylethyl alcohol Drugs 0.000 description 1
- 125000004437 phosphorous atom Chemical group 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- UHZYTMXLRWXGPK-UHFFFAOYSA-N phosphorus pentachloride Chemical compound ClP(Cl)(Cl)(Cl)Cl UHZYTMXLRWXGPK-UHFFFAOYSA-N 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 229920013639 polyalphaolefin Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 150000004756 silanes Chemical class 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- HXLWJGIPGJFBEZ-UHFFFAOYSA-N tert-butyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C(C)(C)C HXLWJGIPGJFBEZ-UHFFFAOYSA-N 0.000 description 1
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 description 1
- XYJRNCYWTVGEEG-UHFFFAOYSA-N trimethoxy(2-methylpropyl)silane Chemical compound CO[Si](OC)(OC)CC(C)C XYJRNCYWTVGEEG-UHFFFAOYSA-N 0.000 description 1
- ZNOCGWVLWPVKAO-UHFFFAOYSA-N trimethoxy(phenyl)silane Chemical compound CO[Si](OC)(OC)C1=CC=CC=C1 ZNOCGWVLWPVKAO-UHFFFAOYSA-N 0.000 description 1
- 239000005051 trimethylchlorosilane Substances 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
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
- C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F110/04—Monomers containing three or four carbon atoms
- C08F110/06—Propene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- 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
- C08F2500/00—Characteristics or properties of obtained polyolefins; Use thereof
- C08F2500/16—Syndiotactic
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Abstract
본 발명은 ⅰ) 마그네슘 화합물을 환상에테르와 2종 이상의 알코올의 혼합용매에 용해시켜 마그네슘 용액을 제조하여 여기에 유기실란을 첨가하고, ⅱ) 마그네슘 용액을 전이금속 화합물과 반응시켜 고형의 입자를 재결정시킨 다음, ⅲ) 재결정된 고형의 입자를 전이금속 화합물 및 전자공여체와 반응시켜 제조되는 올레핀 중합 및 공중합용 고체착물 티타늄 촉매에 관한 것이다.The present invention provides a magnesium solution by dissolving a magnesium compound in a mixed solvent of cyclic ether and two or more alcohols, and adding an organosilane thereto, and ii) recrystallizing solid particles by reacting the magnesium solution with a transition metal compound. And (iii) a solid complex titanium catalyst for olefin polymerization and copolymerization prepared by reacting recrystallized solid particles with a transition metal compound and an electron donor.
본 발명의 촉매는 평균입자크기가 크고 좁은 입자 분포도를 가지며, 중합활성이 높고 생성된 중합체의 입체규칙성과 겉보기 밀도가 높다.The catalyst of the present invention has a large particle size distribution with a large average particle size, high polymerization activity and high stereoregularity and apparent density of the resulting polymer.
Description
본 발명은 α-올레핀 중합 및 공중합용 촉매에 관한 것으로서, 보다 상세하게는 마그네슘을 포함하는 담지체에 지지된 티타늄 고체 착물 촉매에 관한 것이다.The present invention relates to a catalyst for α-olefin polymerization and copolymerization, and more particularly, to a titanium solid complex catalyst supported on a support containing magnesium.
지금까지 많은 올레핀 중합 및 공중합용 촉매, 그리고 중합 공정이 보고되어 왔으나, 생성된 폴리머의 물성을 향상시키거나, 특수한 물성이 요구되는 폴리머를 생산하기 위해서는 촉매의 최적화가 바람직하므로, 더욱 개량된 촉매의 개발이 요구되고 있다.Although many catalysts for olefin polymerization and copolymerization and polymerization processes have been reported so far, the optimization of the catalyst is desirable in order to improve the physical properties of the produced polymer or to produce a polymer requiring special physical properties. Development is required.
마그네슘을 포함하는 올레핀 중합용 촉매는 매우 높은 촉매활성과 입체규칙성을 갖는 것으로 알려져 있으며 기상 중합용으로도 적합한 것으로 알려져 있다. 기상 중합용 촉매는 상업 공정의 운전성을 위해 촉매활성과 입체규칙성 이외에 촉매의 입자 모양, 크기 그리고 입자 분포도 등이 중요하다. 특히 작은 입자의 촉매는 촉매 이송 중에 문제를 일으킬 수 있기 때문에 입자 분포도가 좁은 촉매를 제조하는 것이 필요하다. 예를 들어, 폴리머의 평균 입자 크기가 1000 마이크론 정도인 높은 에틸렌 함량을 가진 에틸렌과 프로필렌의 내충격 공중합체를 생산하기 위해서는 촉매의 평균 입자크기가 30 내지 55 마이크론 정도인 공중합용 촉매가 필요하다. 그리고 이 공중합용 촉매는 촉매의 크기에 따른 촉매의 미세구조의 기공조직(pore structure)이 매우 발달되어 있는 것이 유리하다. 또한 촉매는 중합 공정상의 마모에 대한 기계적 성질이 우수하여야 하며 생성된 폴리머의 겉보기 밀도도 충분히 우수해야 된다. 그래서 공정이 간단하면서도, 촉매의 입자모양, 크기, 입자분포도를 조절할 수 있는 촉매의 제조방법의 개발은 중합 촉매 개발에 있어서 무엇보다도 중요하다고 하겠다.Catalysts for olefin polymerization containing magnesium are known to have very high catalytic activity and stereoregularity and are also suitable for gas phase polymerization. In addition to catalytic activity and stereoregularity, catalysts for gas phase polymerization are important in terms of particle shape, size and particle distribution. In particular, it is necessary to prepare a catalyst having a narrow particle distribution because catalysts of small particles may cause problems during catalyst transfer. For example, in order to produce an impact copolymer of ethylene and propylene having a high ethylene content having an average particle size of about 1000 microns of a polymer, a catalyst for copolymerization having an average particle size of about 30 to 55 microns is required. In addition, it is advantageous that the copolymer catalyst has a highly developed pore structure of the catalyst according to the size of the catalyst. In addition, the catalyst should have good mechanical properties against wear in the polymerization process and the apparent density of the resulting polymer should be good enough. Therefore, while the process is simple, the development of a catalyst production method that can control the particle shape, size, particle distribution of the catalyst is important to the development of the polymerization catalyst.
마그네슘을 포함하고 티타늄에 기초를 둔 많은 올레핀 중합 촉매 및 촉매 제조공정이 보고되어 왔다. 특히 위에서 언급한 입자형태가 조절된 올레핀 중합촉매를 얻기 위해 마그네슘 용액을 이용한 방법이 많이 알려져 있다. 탄화수소 용매 존재하에서 마그네슘 화합물을 알코올, 아민, 환상 에테르, 카르복시 산화물 등과 같은 전자공여체와 반응시켜 마그네슘 용액을 얻는 방법이 있는데, 알코올을 사용한 경우는 미국 특허 제4,330,649호, 제5,106,807호, 일본국 공개 특허 소58-83006호에 언급되어 있다. 그리고 미국 특허 제4,315,874호, 제4,399,054호, 제4,071,674호, 제4,439,540호에도 마그네슘 용액을 제조하는 방법이 보고되어 있다. 환상 에테르인 테트라하이드로퓨란은 염화 마그네슘 화합물(예를 들어, 미국 특허 제4,482,687호, 제4,277,372호, 제3,642,746호, 제3,642,772호, 유럽 특허 제131,832호)로, 조촉매의 첨가제(미국 특허 제4,158,642호, 제4,148,756호)로, 그리고 용매(미국특허 제4,477,639호, 제4,518,706호) 등으로 다양하게 이용되어 왔다.Many olefin polymerization catalysts and catalyst preparation processes based on titanium and based on titanium have been reported. In particular, the method using a magnesium solution to obtain the olefin polymerization catalyst of the above-mentioned particle shape is known a lot. There is a method of obtaining a magnesium solution by reacting a magnesium compound with an electron donor such as an alcohol, an amine, a cyclic ether, or a carboxy oxide in the presence of a hydrocarbon solvent. US Pat. Nos. 4,330,649, 5,106,807, and Japanese Patent Laid-Open Reference is made to SO 58-83006. In addition, U.S. Patent Nos. 4,315,874, 4,399,054, 4,071,674, and 4,439,540 also report methods for preparing magnesium solutions. Tetrahydrofuran, a cyclic ether, is a magnesium chloride compound (e.g., U.S. Pat. Nos. 4,482,687, 4,277,372, 3,642,746, 3,642,772, and European Patent 131,832). No. 4,148,756, and solvents (US Pat. Nos. 4,477,639, 4,518,706) and the like.
미국특허 제4,946,816호, 제4,866,022호, 제4,988,656호, 제5,013,702호, 제5,124,297호 들은 서로 연관성이 있으며, 이들 특허에 개시된 촉매 제조 공정은 먼저 (ⅰ) 마그네슘 카르복실레이트 마그네슘 알킬카보네이트로부터 마그네슘을 포함하는 용액을 만들고, (ⅱ) 마그네슘 용액을 전이 금속 할라이드와 유기실란 첨가제의 존재하에 침전을 시키고, (ⅲ) 다시 침전된 고형성분을 테트라하이드로퓨란을 포함하는 혼합용액을 사용하여 재침전시킨 다음, (ⅳ) 재침전된 입자들을 전이금속 성분과 전자공여체 화합물로 반응시켜 촉매 입자가 일정한 촉매를 제조하는 방법들이다. 그러나 이 방법은 촉매 제조 단계가 많고, 제조 공정이 복잡한 단점이 있다.U.S. Pat. Nos. 4,946,816, 4,866,022, 4,988,656, 5,013,702, and 5,124,297 are related to each other, and the catalyst preparation process disclosed in these patents first comprises magnesium from (i) magnesium carboxylate magnesium alkylcarbonate. (Ii) precipitating the magnesium solution in the presence of a transition metal halide and organosilane additive, and (i) reprecipitating the solid component precipitated again using a mixed solution containing tetrahydrofuran, (Iii) Reprecipitated particles are reacted with a transition metal component and an electron donor compound to prepare catalysts having a uniform catalyst particle. However, this method has a disadvantage in that there are many catalyst preparation steps and the manufacturing process is complicated.
일본국 공개 특허 소63-54004호, 미국특허 제4,330,649호들은 마그네슘 용액 제소시에 유기 탄화수소 용매 존재하에서 마그네슘 화합물을 알코올, 유기 카르복시산, 알데하이드, 아민중 한 성분 이상과 반응시켜 용액 상태로 제조하고, 최종 촉매성분은 이 용액을 티타늄 화합물과 전자 공여체와 반응시켜 제조하는 것으로 기술하고 있다.Japanese Patent Laid-Open Nos. 63-54004 and US Pat. No. 4,330,649 are prepared in a solution state by reacting a magnesium compound with at least one component of alcohol, organic carboxylic acid, aldehyde, and amine in the presence of an organic hydrocarbon solvent when the magnesium solution is filed. The final catalyst component is described as being prepared by reacting this solution with a titanium compound and an electron donor.
상기 인용된 특허들에서도 언급된 형상 조절제로서의 유기실란이 고체촉매 제조과정 중에 빈번히 이용되어 왔다. 이 형상 조절제의 사용은 미세 촉매 입자나 매우 큰 촉매 입자의 생성을 억제시켜 촉매의 입자 분포도를 조절하는데 유용하다. 이러한 유기실란은 RnSiR'4-n(n=0~4)의 일반적인 구조식을 가진 물질로서 R은 수소, 탄소수 1개 내지 10개의 알킬, 알콕시, 할로알킬 또는 아릴기이며, R'는 OR 또는 할로겐이다. 이 유기실란의 구체적인 예로는 트리메틸클로로실란, 트리메틸에톡시실란, 디메틸디클로로실란, 테트라에톡시실란, 테트라부톡시실란 등이 있다. 그러나 이 유기실란을 촉매의 다공성을 증가시키는데 적용한 결과는 보고되지 않았다.Organosilanes as shape control agents mentioned in the above cited patents have been frequently used during the preparation of solid catalysts. Use of this shape modifier is useful for controlling the particle distribution of the catalyst by suppressing the production of fine catalyst particles or very large catalyst particles. The organosilane is a substance having a general structure of R n SiR ' 4-n (n = 0 to 4), wherein R is hydrogen, alkyl having 1 to 10 carbon atoms, alkoxy, haloalkyl or aryl group, and R' is OR Or halogen. Specific examples of this organosilane include trimethylchlorosilane, trimethylethoxysilane, dimethyldichlorosilane, tetraethoxysilane, tetrabutoxysilane and the like. However, the results of applying this organosilane to increase the porosity of the catalyst have not been reported.
미국특허 제4,847,227호, 제4,816,433호, 제4,829,037호, 제4,970,186호, 제5,130,284호는 마그네슘 알콕사이드, 디알킬 프탈레이트, 프탈로일 클로라이드 등과 같은 전자공여체, 그리고 염화 티타늄 화합물을 반응시켜 우수한 올레핀 중합 촉매를 제조하는 것으로 보고하고 있다.U.S. Pat.Nos. 4,847,227, 4,816,433, 4,829,037, 4,970,186, 5,130,284 are known to provide excellent olefin polymerization catalysts by reacting electron donors such as magnesium alkoxides, dialkyl phthalates, phthaloyl chlorides, and titanium chloride compounds. It is reported to manufacture.
미국특허 제4,298,718호, 제4,476,289호, 제4,544,717호, 제4,636,486호는 활성 마그네슘 클로라이드와 티타늄 화합물을 반응시켜 중합 촉매를 제조하는 방법을 소개하고 있다.U.S. Patent Nos. 4,298,718, 4,476,289, 4,544,717, and 4,636,486 introduce methods for preparing polymerization catalysts by reacting titanium compounds with active magnesium chloride.
위에서 살펴본 바와 같이 제조 공정이 간단하면서도, 높은 중합 활성과 입체규칙성, 그리고 촉매 입자모양, 크기, 분포도 등이 조절되어 높은 폴리머 겉보기 밀도를 줄 수 있는 새로운 올레핀 중합 촉매의 개발이 요구되고 있다.As described above, while the manufacturing process is simple, it is required to develop a new olefin polymerization catalyst which can give high polymer apparent density by controlling high polymerization activity, stereoregularity, and catalyst particle shape, size and distribution.
따라서 본 발명에서는 간단한 제조 공정을 거쳐 촉매 입자모양이 조절되고 입자크기가 큰 촉매를 제조하는 방법을 제공하고자 한다. 그리고 본 발명에서 밝히고자 하는 구체적인 촉매 제조 단계나 공정들은 기존의 특허나 문헌에는 알려진 바가 없다.Therefore, the present invention is to provide a method for producing a catalyst having a controlled particle shape and a large particle size through a simple manufacturing process. In addition, specific catalyst preparation steps or processes to be disclosed in the present invention are not known in the existing patents or literature.
본 발명의 목적은 촉매활성와 입체규칙성이 매우 높고, 그리고 촉매 입자의 형태가 조절된 새로운 올레핀 중합 및 공중합용 고체 촉매 성분과 그 제조방법을 제공하는 것이다.It is an object of the present invention to provide a novel solid catalyst component for polymerization and copolymerization of olefins having a very high catalytic activity and stereoregularity and controlled catalyst particles, and a method for producing the same.
구체적으로는, 본 발명의 목적은 촉매 평균 입자크기가 크고 다공성이 큰 올레핀 중합 및 공중합용 고체 촉매 성분을 제공하는 것이다.Specifically, an object of the present invention is to provide a solid catalyst component for olefin polymerization and copolymerization having a large catalyst average particle size and a large porosity.
본 발명의 다른 목적은 촉매 평균 입자크기가 크고 다공성이 큰 올레핀 중합 및 공중합용 고체 촉매 성분을 제조하는 방법을 제공하는 것이다.Another object of the present invention is to provide a method for producing a solid catalyst component for olefin polymerization and copolymerization having a large catalyst average particle size and a high porosity.
또 다른 본 발명의 목적은 높은 에틸렌 함량과 높은 용융지수를 가진 내충격 에틸렌/프로필렌 공중합체를 생성할 수 있는 고체 촉매 성분과 고체 촉매 제조방법을 제공하는 것이다.Another object of the present invention is to provide a solid catalyst component and a method for preparing a solid catalyst capable of producing an impact ethylene / propylene copolymer having a high ethylene content and a high melt index.
본 발명의 다른 목적들과 유익성은 다음의 설명과 본 발명의 청구범위를 참조하면 더욱 명확해 질 것이다.Other objects and benefits of the present invention will become more apparent with reference to the following description and claims of the present invention.
본 발명에 따른 올레핀 중합 및 공중합용 촉매는 (ⅰ) 환원성이 없는 마그네슘 화합물로부터 마그네슘을 포함하는 용액을 제조하고, (ⅱ) 마그네슘 용액을 전이금속 화합물과 반응시켜 고형의 입자를 재결정시킨 다음, (ⅲ) 재결정된 고형의 입자를 티타늄 화합물 및 전자공여체와 반응시킨 다음, 탄화수소 용매로 세척후 입자 형태가 조절된 고형의 촉매 입자를 얻는 간단하면서도 효과적인 제조 공정으로 제조된다.The catalyst for olefin polymerization and copolymerization according to the present invention comprises (i) preparing a solution containing magnesium from a magnesium compound having no reducibility, (ii) reacting the magnesium solution with a transition metal compound to recrystallize solid particles, and then ( V) Recrystallized solid particles are reacted with a titanium compound and electron donor and then washed with a hydrocarbon solvent to obtain a simple and effective production process for obtaining solid catalyst particles with controlled particle morphology.
상기 (ⅰ) 단계에서 마그네슘을 포함하는 용액은 탄화수소 용매의 존재 또는 부재하에서 환상 에테르와 알코올의 혼합 용매를 사용하여 환원성이 없는 마그네슘 화합물을 용해시키고, 여기에 유기실란을 첨가하여 제조된다.The solution containing magnesium in the step (iii) is prepared by dissolving a non-reducing magnesium compound using a mixed solvent of cyclic ether and alcohol in the presence or absence of a hydrocarbon solvent and adding an organosilane thereto.
환원성이 없는 마그네슘 화합물의 종류로는 염화마그네슘, 요드화마그네슘, 불화마그네슘, 그리고 브롬화마그네슘과 같은 할로겐화마그네슘; 메틸마그네슘 할라이드, 에틸마그네슘 할라이드, 프로필마그네슘 할라이드, 부탈마그네슘 할라이드, 이소부틸마그네슘 할라이드, 헥실마그네슘 할라이드, 아밀마그네슘 할라이드, 이소프로폭시마그네슘 할라이드, 부톡시 마그네슘 할라이드, 그리고 옥톡시 마그네슘 할라이드와 같은 알콕시 마그네슘 할라이드; 페녹시 마그네슘 할라이드, 그리고 메틸페녹시 마그네슘 할라이드와 같은 아릴옥시 마그네슘 할라이드; 에톡시 마그네슘, 이소프로폭시 마그네슘, 부록시마그네슘, 그리고 옥톡시마그네슘과 같은 알콕시마그네슘; 페녹시마그네슘, 그리고 디메틸페녹시 마그네슘과 같은 아릴옥시 마그네슘; 라우릴마그네슘 및 스테아린산마그네슘과 같은 카르복시산 마그네슘염을 예로 들 수 있다. 상기 마그네슘 화합물 중 2종 이상의 혼합물로 사용되어도 무방하다. 또한, 마그네슘 화합물은 다른 금속과의 착화합물 형태로 사용되어도 효과적이다.Examples of magnesium compounds having no reducing properties include magnesium halides such as magnesium chloride, magnesium iodide, magnesium fluoride, and magnesium bromide; Alkoxy magnesium halides such as methylmagnesium halide, ethylmagnesium halide, propylmagnesium halide, butanemium halide, isobutylmagnesium halide, hexylmagnesium halide, amyl magnesium halide, isopropoxymagnesium halide, butoxy magnesium halide, and octoxy magnesium halide ; Aryloxy magnesium halides such as phenoxy magnesium halides, and methylphenoxy magnesium halides; Alkoxymagnesiums such as ethoxy magnesium, isopropoxy magnesium, appendixi magnesium, and octoxy magnesium; Aryloxy magnesium, such as phenoxyshima magnesium, and dimethylphenoxy magnesium; Magnesium carboxylate salts such as magnesium lauryl and magnesium stearate are exemplified. It may be used as a mixture of two or more kinds of the magnesium compounds. Magnesium compounds are also effective when used in the form of complexes with other metals.
위에서 열거한 화합물들은 간단한 화학식으로 나타낼 수 있으나. 어떤 경우에는 마그네슘 화합물의 제조방법에 따라 간단한 식으로 나타낼 수 없는 경우가 있다. 이런 경우에는 일반적으로 열거한 마그네슘 화합물의 혼합물로 간주할 수 있다. 예를 들어, 마그네슘 화합물을 폴리실록산 화합물, 할로겐 함유 실란 화합물, 에스테르, 알코올 등과 반응시켜 얻는 화합물; 마그네슘 금속을 할로 실란, 오염화인, 또는 염화티오닐 존재하에서 알코올, 페놀, 또는 에테르와 반응시켜 얻은 화합물들도 본 발명에 사용될 수 있다. 바람직한 마그네슘 화합물은 마그네슘 할라이드, 특히 마그네슘 클로라이드, 알킬 마그네슘 할라이드, 바람직하기로는 C1내지 C10알킬기를 갖는 것, 알콕시 마그네슘 할라이드, 바람직하기로는 C1내지 C10알콕시기를 갖는 것, 그리고 아랄옥시 마그네슘 할라이드, 바람직하기로는 C6내지 C20아릴옥시기를 갖는 것 또는 이들의 혼합물이 좋다.The compounds listed above may be represented by simple formulas. In some cases, depending on the method for producing the magnesium compound, it may not be represented by a simple formula. In this case, it can be regarded as a mixture of magnesium compounds listed generally. For example, the compound obtained by making a magnesium compound react with a polysiloxane compound, a halogen containing silane compound, ester, alcohol, etc .; Compounds obtained by reacting magnesium metal with an alcohol, phenol, or ether in the presence of halo silane, phosphorus pentachloride, or thionyl chloride can also be used in the present invention. Preferred magnesium compounds are magnesium halides, in particular magnesium chloride, alkyl magnesium halides, preferably having C 1 to C 10 alkyl groups, alkoxy magnesium halides, preferably having C 1 to C 10 alkoxy groups, and araloxy magnesium halides Preferably, those having C 6 to C 20 aryloxy groups or mixtures thereof are preferable.
상기 (ⅰ) 단계에서 마그네슘 용액제조시에 사용될 수 있는 탄화수소 용매의 종류로는 펜탄, 헥산, 헵탄, 옥탄, 데칸, 그리고 케로센과 같은 지방족 탄화수소, 시클로벤젠, 메틸시클로벤젠, 시클로헥산, 그리고 메틸시클로헥산과 같은 지환족 탄화수소, 벤젠, 톨루엔, 크실렌, 에틸벤젠, 큐멘, 그리고 시멘과 같은 방향족 탄화수소, 디클로로프로판, 디클로로에틸렌, 트리클로로에틸렌, 사염화탄소, 그리고 클로로벤젠과 같은 할로겐화 탄화수소를 예로 들 수 있다.Examples of hydrocarbon solvents that may be used in the preparation of the magnesium solution in step (iii) include aliphatic hydrocarbons such as pentane, hexane, heptane, octane, decane, and kerosene, cyclobenzene, methylcyclobenzene, cyclohexane, and methylcyclo Examples include alicyclic hydrocarbons such as hexane, aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, cumene, and cymene, and halogenated hydrocarbons such as dichloropropane, dichloroethylene, trichloroethylene, carbon tetrachloride, and chlorobenzene.
마그네슘 화합물을 마그네슘 용액으로 전환시 전술한 바와 같이 탄화수소의 존재 또는 부재하에서 환상에테르와 알코올의 혼합용매가 사용된다. 본 발명에 이용될 수 있는 환상에테르로는 테트라하이드로퓨란, 2-메틸 테트라하이드로퓨란, 테트라하이드로피란을 예로 들 수 있으나, 바람직한 환상에테르는 테트라하이드로퓨란이다. 알코올의 종류로는 메탄올, 에탄올, 프로판올, 부탄올, 펜탄올, 헥산올, 옥탄올, 도데칸올, 옥타데실알코올, 벤질알코올, 페닐에틸알코올, 이소프로필벤질알코올, 쿠밀알코올과 같은 1개 내지 20개의 탄소원자를 함유하는 알코올을 들 수 있고, 바람직한 알코올은 1개 내지 12개의 탄소원자를 포함하는 알코올이 좋다. 원하는 촉매 평균 입자크기, 입자분포도는 알코올과 환상에테르의 종류, 전체양, 알코올과 환상에테르의 비, 마그네슘 화합물의 종류, 마그네슘과 환상에테르의 비 등에 따라 변하지만, 마그네슘 용액을 얻기 위해서는 알코올과 환상에테르의 전체양은 마그네슘 화합물 1몰당 최소 0.5몰, 바람직하기로는 약 1.0몰 내지 20몰, 더욱 바람직하기로는 약 2.0몰 내지 10몰이 좋다. 그리고 알코올은 2종 이상이 사용되며, 환상에테르와 2종 이상의 알코올의 전체량의 몰비는 1:0.05 내지 1:0.95이다.When converting a magnesium compound into a magnesium solution, a mixed solvent of cyclic ether and alcohol is used in the presence or absence of a hydrocarbon as described above. Examples of the cyclic ether that can be used in the present invention include tetrahydrofuran, 2-methyl tetrahydrofuran and tetrahydropyran, but preferred cyclic ethers are tetrahydrofuran. Examples of the alcohol include 1 to 20 alcohols such as methanol, ethanol, propanol, butanol, pentanol, hexanol, octanol, dodecanol, octadecyl alcohol, benzyl alcohol, phenylethyl alcohol, isopropyl benzyl alcohol and cumyl alcohol. Alcohol containing a carbon atom is mentioned, Preferred alcohol is an alcohol containing 1-12 carbon atoms. The desired catalyst average particle size and particle distribution vary depending on the type of alcohol and the cyclic ether, the total amount, the ratio of the alcohol and the cyclic ether, the type of the magnesium compound, and the ratio of the magnesium and the cyclic ether. The total amount of ether is preferably at least 0.5 mol, preferably about 1.0 mol to 20 mol, more preferably about 2.0 mol to 10 mol, per mol of the magnesium compound. In addition, two or more kinds of alcohols are used, and the molar ratio of the total amount of the cyclic ether and the two or more kinds of alcohols is 1: 0.05 to 1: 0.95.
본 발명에서 사용되는 2종 이상의 알코올은 전체가 상기 (ⅰ) 단계에서 마그네슘 화합물을 용해시킬 때 이용될 수 있다. 또 다른 방법으로는 2종 이상의 알코올의 일부를 마그네슘 화합물을 용해시킬 때 이용하고, 나머지 일부는 마그네슘 화합물을 용해시킨 마그네슘 용액에 첨가할 수 있다. 그렇지만 상기 (ⅱ) 단계에서 마그네슘 용액을 전이금속 화합물과 반응시켜 고형의 입자를 재결정시킬 때 전술한 2종 이상의 알코올의 전체 함량은 유지되어야 한다.Two or more alcohols used in the present invention may be used when the whole dissolves the magnesium compound in the step (iii). In another method, a part of two or more alcohols may be used to dissolve the magnesium compound, and the other part may be added to the magnesium solution in which the magnesium compound is dissolved. However, when the magnesium solution is reacted with the transition metal compound in step (ii) to recrystallize the solid particles, the total content of the two or more alcohols described above must be maintained.
구체적으로, 2종 이상의 알코올은 상대적으로 분자량이 작은 1개 내지 3개의 탄소원자를 가진 알코올과 상대적으로 분자량이 큰 4개 내지 20개의 탄소원자를 가진 알코올로 이루어진다. 상대적으로 분자량이 큰 알코올과 상대적으로 분자량이 작은 알코올과의 몰비는 1:0.01 내지 1:0.40이며, 바람직하게는 1:0.01 내지 1:0.25 이다. 바람직한 상대적으로 분자량이 작은 알코올은 메탄올 혹은 에탄올이며, 상대적으로 분자량이 큰 알코올은 부탄올 혹은 이소아밀 알코올 혹은 2-에틸 헥산올이다.Specifically, the two or more alcohols consist of alcohols having 1 to 3 carbon atoms having a relatively low molecular weight and alcohols having 4 to 20 carbon atoms having a relatively high molecular weight. The molar ratio between the relatively high alcohol and the relatively low molecular weight alcohol is 1: 0.01 to 1: 0.40, preferably 1: 0.01 to 1: 0.25. Preferred relatively low molecular weight alcohols are methanol or ethanol, while relatively high molecular weight alcohols are butanol or isoamyl alcohol or 2-ethyl hexanol.
본 발명에서 2종 이상의 알코올을 사용하여 얻게 되는 이점은 (1) 평균 입자 크기가 크고, 입자 분포도가 좁고, 그리고 겉보기 밀도가 우수한 폴리머를 생성할 수 있는 평균 입자크기가 크고, 입자분포도가 좁은 촉매를 제조할 수 있고, (2) 미세 촉매 입자의 함량을 줄여서 생성된 폴리머 중의 미세입자의 함량을 줄일 수 있고, (3) 마그네슘 화합물을 마그네슘 용액으로 쉽게 전환할 수 있다는 것이다.Advantages of using two or more alcohols in the present invention are (1) a catalyst having a large average particle size and a narrow particle distribution that can produce a polymer having a large average particle size, a narrow particle distribution, and a good apparent density. It can be prepared, (2) to reduce the content of the fine catalyst particles to reduce the content of the fine particles in the resulting polymer, (3) it is easy to convert the magnesium compound into a magnesium solution.
상기 (ⅰ) 단계에서 마그네슘 용액의 제조시 마그네슘 화합물과 환상에테르와 알코올과의 혼합용매의 반응은 탄소수소 매질 중에서 수행하는 것이 바람직하며, 반응온도는 환상에테르와 알코올의 종류 및 양에 따라 다르지만, 최소 약 -25℃, 바람직하기로는 -10℃ 내지 200℃, 더욱 바람직하기로는 약 0℃ 내지 160℃에서 약 16분 내지 5시간, 바람직하기로는 약 30분 내지 3시간 동안 실시하는 것이 좋다.The reaction of the mixed solvent of the magnesium compound, the cyclic ether and the alcohol in the preparation of the magnesium solution in the step (iii) is preferably carried out in a carbon medium, and the reaction temperature depends on the type and amount of the cyclic ether and alcohol, It is preferably carried out for at least about -25 ° C, preferably at -10 ° C to 200 ° C, more preferably at about 0 ° C to 160 ° C for about 16 minutes to 5 hours, preferably about 30 minutes to 3 hours.
상기 (ⅰ) 단계에서 마그네슘용액 제조시에 첨가되는 유기실란은 RnSiR'4-n(여기서 R은 수소 또는 탄소수 1개 내지 10개의 알킬, 할로알킬, 아릴기 또는 탄소수 1개 내지 8개의 할로실릴, 할로실릴알킬기이며, R'는 OR 또는 할로겐, n=0~4이다)의 일반식을 갖는 것이 사용된다.The organosilane added in the preparation of the magnesium solution in step (iii) is R n SiR ′ 4-n (where R is hydrogen or alkyl having 1 to 10 carbon atoms, haloalkyl, aryl group or halo having 1 to 8 carbon atoms). Silyl and a halosilylalkyl group, R 'is OR or halogen, n = 0-4).
이와 같이 본 발명에서는 마그네슘 용액제조 단계에서 유기실란을 첨가함으로써 후술하는 실시예와 비교예에 나타난 바와 같이 촉매의 다공성을 증대시킬 수 있으며, 이러한 효과는 종래에는 전혀 보고된 바가 없다.As described above, in the present invention, by adding the organosilane in the magnesium solution preparation step, the porosity of the catalyst can be increased as shown in the following Examples and Comparative Examples, and this effect has not been reported in the prior art.
상기와 같이 제조된 마그네슘 화합물 용액은 전이금속 화합물, 예를 들어 액체상태의 일반식 Ti(OR)aX4-a의 티타늄 화합물(R은 탄화수소기, X는 할로겐원자, 그리고 a는 0≤a≤4의 수)과 반응시켜 일정한 입자모양을 가지며 입자크기가 크고, 그리고 입자분포도가 좁은 촉매입자로 재결정시킨다((ⅱ)단계). 상기 일반식중 R은 탄소원자 1개 내지 10개의 알킬기를 의미한다. 상기 일반식을 만족하는 티타늄 화합물의 종류로는 TiCl4, TiBr4, TiI4와 같은 사할로겐화 티타늄, Ti(OCH3)Cl3, Ti(OC2H5)Cl3, Ti(OC2H5)Br3, 그리고 Ti(O(i-C4H9)Br3와 같은 삼할로겐화 알콕시티타늄, Ti(OCH3)2Cl2, Ti(OC2H5)2Cl2, Ti(O(i-C4H9)2Cl2, 그리고 Ti(OC2H5)2Br2와 같은 이할로겐화 알콕시티타늄, Ti(OCH3)4, Ti(OC2H5)4, 그리고 Ti(OC4H9)4와 같은 테트라알콕시티타늄을 예를 들 수 있다. 또한 상기한 티티늄 화합물의 혼합물도 본 발명에 사용될 수 있다. 바람직한 티타늄 화합물은 할로겐 함유 티타늄 화합물이며, 더욱 바람직한 티타늄 화합물은 티타늄 테트라클로라이드이다.The magnesium compound solution prepared as described above is a transition metal compound, for example, a titanium compound of the general formula Ti (OR) a X 4-a in the liquid state (R is a hydrocarbon group, X is a halogen atom, and a is 0 ≦ a Number of? 4), and recrystallized into catalyst particles having a constant particle shape, a large particle size, and a narrow particle distribution (step (ii)). R in the general formula means an alkyl group of 1 to 10 carbon atoms. Types of titanium compounds satisfying the above general formula include titanium tetrahalides such as TiCl 4 , TiBr 4 , TiI 4 , Ti (OCH 3 ) Cl 3 , Ti (OC 2 H 5 ) Cl 3 , and Ti (OC 2 H 5 ) Br 3 , and trihalogenated alkoxytitanium such as Ti (O (iC 4 H 9 ) Br 3 , Ti (OCH 3 ) 2 Cl 2 , Ti (OC 2 H 5 ) 2 Cl 2 , Ti (O (iC 4 H) 9 ) dihalogenated alkoxytitanium such as 2 Cl 2 and Ti (OC 2 H 5 ) 2 Br 2 , Ti (OCH 3 ) 4 , Ti (OC 2 H 5 ) 4 , and Ti (OC 4 H 9 ) 4 The same tetraalkoxytitanium may be exemplified, and mixtures of the above-described titanium compounds may also be used in the present invention Preferred titanium compounds are halogen-containing titanium compounds, and more preferred titanium compounds are titanium tetrachloride.
마그네슘 화합물 용액은 또한 실리콘테르할라이드, 특히 실리콘 테트라클로라이드, 실리콘알킬할라이드, 주석테트라할라이드, 주석알킬할라이드, 주석하이드로할라이드 또는 이들의 혼합물이나, 이들 화합물과 티타늄테트라할라이드와의 혼합물을 사용하여 입자크기가 크고 입자분포가 좁은 고체 성분으로 재결정될 수 있다.Magnesium compound solutions may also contain silicon terhalides, in particular silicon tetrachloride, silicon alkyl halides, tin tetrahalides, tin alkyl halides, tin hydrohalides or mixtures thereof, or mixtures of these compounds with titanium tetrahalide Large and narrow particle distribution can be recrystallized into a solid component.
마그네슘 화합물 용액을 재결정시킬 때 사용하는 티타늄 화합물, 실리콘 화합물, 주석화합물, 그리고 이들의 혼합물의 양은 마그네슘 화합물 1몰당 0.1 내지 200몰이 적당하며, 바람직하게는 0.1몰 내지 100몰이고, 더욱 바람직하게는 0.2몰 내지 80몰이다. 마그네슘 화합물 용액과 티타늄 화합물, 실리콘 화합물, 주석 화합물 또는 이들의 혼합물을 반응시킬 때 반응조건에 따라 재결정된 고체 성분의 모양, 크기, 그리고 입자 분포가 많이 변화한다. 따라서 마그네슘 화합물 용액과 티타늄 화합물, 실리콘 화합물, 주석 화합물 또는 이들의 혼합물과의 반응은 충분히 낮은 온도에서 행하여, 고체생성물이 바로 생성되지 않도록 하고 반응 생성물을 가열하여 서서히 고체 성분을 생성시키는 것이 좋다. 바람직하게는 -70℃ 내지 70℃에서 접촉반응을 실시하는 것이 좋고, 더욱 바람직하기로는 -50℃ 내지 50℃에서 0.5시간 내지 5시간 동안 충분히 반응시킨다. 이렇게 함으로써, 입자 모양, 크기 및 분포가 우수한 담지체를 얻을 수 있다.The amount of titanium compound, silicon compound, tin compound, and mixtures thereof used to recrystallize the magnesium compound solution is suitably 0.1 to 200 moles per mole of magnesium compound, preferably 0.1 to 100 moles, more preferably 0.2 Moles to 80 moles. When the magnesium compound solution and the titanium compound, the silicon compound, the tin compound, or a mixture thereof are reacted, the shape, size, and particle distribution of the recrystallized solid component vary greatly depending on the reaction conditions. Therefore, the reaction of the magnesium compound solution with the titanium compound, the silicon compound, the tin compound, or a mixture thereof is preferably performed at a sufficiently low temperature so that the solid product is not immediately produced and the reaction product is heated to gradually produce the solid component. Preferably, the contact reaction is preferably performed at -70 ° C to 70 ° C, and more preferably at 0.5 ° C to 5 hours at -50 ° C to 50 ° C. By doing in this way, the support body excellent in particle shape, size, and distribution can be obtained.
생성된 담지체는 적절한 전자공여체의 존재하에서 티타늄 화합물과 반응시켜 촉매를 제조한다((ⅲ)단계). 이 반응은 전형적으로 두 단계로 진행되는데, 먼저 담지체를 티타늄 화합물과 반응시키거나 또는 담지체를 티타늄 화합물 및 적절한 전자공여체와 반응시킨 다음, 고체성분을 분리한 뒤 이 고체성분과 티타늄 화합물 및 전자공여체를 다시 한 번 반응시킨 후 고체성분을 분리하고 건조시켜 촉매를 얻는다. 다른 방법으로는 탄화수소, 할로겐화 탄화수소 용매의 존재 또는 부재하에서 티타늄 화합물과 일정시간 반응시킨후 전자공여체를 투입하여 반응시킬 수도 있다.The resulting carrier is reacted with a titanium compound in the presence of a suitable electron donor to prepare a catalyst (step (iii)). This reaction typically proceeds in two stages: first, the carrier is reacted with a titanium compound or the carrier is reacted with a titanium compound and an appropriate electron donor, and then the solid component is separated and then the solid component and the titanium compound and electron The donor is reacted once more, and then the solid component is separated and dried to obtain a catalyst. Alternatively, the reaction may be performed by introducing an electron donor after reacting the titanium compound for a predetermined time in the presence or absence of a hydrocarbon or a halogenated hydrocarbon solvent.
본 발명에서 얻은 담지체와의 반응에 유익한 티타늄 화합물은 티타늄 할라이드, 그리고 알콕시 관능기의 탄소수가 1개 내지 20개인 할로겐화알콕시 티타늄이다. 경우에 따라서는 이들의 혼합물도 사용할 수가 있다. 이들 중 바람직하기로는 티타늄 할라이드와 알콕시 관능기의 탄소수가 1개 내지 8개인 할로겐화알콕시 티타늄이 적절하며, 보다 바람직하기로는 티타늄 테트라할라이드, 특히 티타늄 테트라클로라이드가 적당하다.The titanium compound which is beneficial for the reaction with the support obtained in the present invention is a titanium halide and an alkoxy halide titanium having 1 to 20 carbon atoms of the alkoxy functional group. In some cases, mixtures thereof may also be used. Of these, titanium halides and alkoxy halide alkoxy titanium having 1 to 8 carbon atoms of the alkoxy functional group are preferable, and more preferably titanium tetrahalide, particularly titanium tetrachloride.
상기 (ⅲ) 단계에서 입체규칙성이 우수한 올레핀 중합용 촉매 제조에 적절한 전자공여체의 종류로는 산소, 질소, 황, 그리고 인을 포함하는 화합물을 들 수 있다. 이러한 화합물의 예는 유기산, 유기산 에스테르, 알코올, 에테르, 알데히드, 케톤, 아민, 아민옥사이드, 아마이드, 인산 에스테르, 그리고 이들의 혼합물들이 전자공여체로 사용될 수 있다. 본 발명에서 사용되는 바람직한 전자공여체는 방향족 에스테르이다. 더 자세하게는 메틸벤조에이트, 메틸브로모벤조에이트, 에틸벤조에이트, 에틸클로로벤조에이트, 에틸브로모벤조에이트, 부틸벤조에이트, 이소부틸벤조에이트, 헥실벤조에이트, 사이클로헥실벤조에이트와 같은 벤젠산알킬에스테르 및 할로벤젠산에스테르가 유용하며, 디이소부틸프탈레이트, 디에틸프탈레이트, 에틸부틸프탈레이트, 디부틸프탈레이트와 같은 탄소수 2개 내지 10개의 디알킬프탈레이트가 적절하다. 이들 전자공여체는 2종 또는 그 이상의 혼합물로 사용될 수 있으며, 다른 화합물의 부가물 또는 착화물 형태로 사용될 수도 있다. 사용되는 전자공여체의 양은 변화될 수 있으며, 마그네슘 화합물 1몰당 약 0.01몰 내지 10몰, 바람직하게는 약 0.01몰 내지 5몰, 더 바람직하게는 0.05몰 내지 2몰이다.Examples of the electron donor suitable for preparing the catalyst for olefin polymerization having excellent stereoregularity in the step (iii) include compounds including oxygen, nitrogen, sulfur, and phosphorus. Examples of such compounds are organic acids, organic acid esters, alcohols, ethers, aldehydes, ketones, amines, amine oxides, amides, phosphate esters, and mixtures thereof, as electron donors. Preferred electron donors used in the present invention are aromatic esters. More specifically, alkyl benzenes such as methyl benzoate, methyl bromo benzoate, ethyl benzoate, ethyl chloro benzoate, ethyl bromo benzoate, butyl benzoate, isobutyl benzoate, hexyl benzoate and cyclohexyl benzoate Esters and halobenzene acid esters are useful, and dialkyl phthalates having from 2 to 10 carbon atoms such as diisobutyl phthalate, diethyl phthalate, ethyl butyl phthalate, dibutyl phthalate are suitable. These electron donors can be used in mixtures of two or more, and can also be used in the form of adducts or complexes of other compounds. The amount of electron donor used can vary and is about 0.01 to 10 moles, preferably about 0.01 to 5 moles, more preferably 0.05 to 2 moles per mole of magnesium compound.
본 발명에서 제시된 방법에 의해 제조된 촉매는 에틸렌, 프로필렌과 같은 올레핀의 중합에 유익하게 사용된다. 특히 이 촉매는 프로필렌, 1-부텐, 1-펜텐, 4-메틸-1-펜텐, 1-헥센과 같은 탄소수 3개 이상의 α-올레핀의 입체규칙성 중합, 이들 상호간의 공중합, 에틸렌과 이들의 공중합, 프로필렌과 20몰 미만의 에틸렌 또는 다른 α-올레핀과의 공중합, 그리고 공액 또는 비공액 디엔류와 같은 폴리불포화 화합물을 가진 이들의 공중합에 적절하게 사용된다.The catalyst prepared by the process presented in the present invention is advantageously used for the polymerization of olefins such as ethylene, propylene. In particular, this catalyst is a stereoregular polymerization of α-olefins having 3 or more carbon atoms, such as propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, copolymerization of these mutually, copolymerization of ethylene and their copolymerization , Copolymerization of propylene with less than 20 moles of ethylene or other α-olefins, and copolymerization thereof with polyunsaturated compounds such as conjugated or unconjugated dienes.
본 발명의 촉매 존재하에서의 중합반응은 (a) 마그네슘, 티타늄, 할로겐, 그리고 내부 전자공여체로 이루어진 본 발명에 의한 고체 착물 티타늄 촉매와, (b) 주기율표 제Ⅱ족 및 제Ⅲ족 유기금속 화합물, 그리고 (c) 유기규소 화합물로 이루어진 외부전자공여체 성분으로 구성된 촉매계를 사용하여 수행된다.The polymerization reaction in the presence of the catalyst of the present invention comprises (a) a solid complex titanium catalyst according to the present invention consisting of magnesium, titanium, halogen, and an internal electron donor, (b) group II and III organometallic compounds of the periodic table, and (c) using a catalyst system consisting of an external electron donor component consisting of an organosilicon compound.
본 발명의 고체착물 티타늄 촉매 성분(a)은 중합반응에 사용되기 전에 α-올레핀으로 전중합하여 사용할 수 있다. 전중합은 헥산과 같은 탄화수소 용매의 존재하에서 충분히 낮은 온도와 α-올레핀 압력조건에서 상기의 촉매 성분과, 트리에틸알루미늄과 같은 유기알루미늄 화합물, 유기규소 화합물로 된 전자공여체의 존재 또는 부재하에서 행하여진다. 전중합은 촉매 입자를 폴리머로 둘러싸서 촉매 형상을 유기시켜 중합후에 생성된 폴리머의 형상을 좋게 하는데 도움을 준다. 또한 전중합을 행함으로써 촉매의 활성이나 입체규칙성이 증가하는 경우도 있다. 전중합후의 폴리머/촉매의 무게비는 대개 0.1:1 내지 20:1이다.The solid complex titanium catalyst component (a) of the present invention may be prepolymerized with an α-olefin before being used for polymerization. Prepolymerization is carried out in the presence or absence of an electron donor of the above catalyst component, an organoaluminum compound such as triethylaluminum, or an organosilicon compound at sufficiently low temperatures and α-olefin pressure conditions in the presence of a hydrocarbon solvent such as hexane. . Prepolymerization helps to improve the shape of the polymer produced after polymerization by enclosing the catalyst particles with a polymer to induce the catalyst shape. In addition, the prepolymerization may increase the activity and stereoregularity of the catalyst. The weight ratio of polymer / catalyst after prepolymerization is usually from 0.1: 1 to 20: 1.
본 발명의 촉매성분을 이용한 중합반응에 유익한 유기금속 화합물(b)은 MRn의 일반식으로 표기할 수 있는데 여기에서 M은 마그네슘, 칼슘, 아연, 보론, 알루미늄, 갈륨과 같은 주기율표 Ⅱ족 또는 ⅢA족 금속성분이며, R은 메틸, 에틸, 부틸, 헥실, 옥틸, 데실과 같은 탄소수 1개 내지 20개의 알킬기를 나타내며, n은 금속성분의 원자가를 표시한다. 보다 바람직한 유기금속 화합물로는 트리에틸알루미늄, 트리이소부틸알루미늄과 같은 탄소수 1개 내지 6개의 알킬기를 가진 트리알킬알루미늄과 이들의 혼합물이 유익하다. 경우에 따라서는 에틸알루미늄 디클로라이드, 디에틸알루미늄 클로라이드, 에틸알루미늄 세스퀴클로라이드, 디이소부틸알루미늄 히드리드와 같은 한 개 이상의 할로겐 또는 히드리드기를 유기알루미늄 화합물이 사용될 수 있다.The organometallic compound (b), which is beneficial for the polymerization reaction using the catalyst component of the present invention, may be represented by the general formula of MR n , wherein M is a periodic table of group II or IIIA such as magnesium, calcium, zinc, boron, aluminum, and gallium. It is a group metal component, R represents a C1-C20 alkyl group, such as methyl, ethyl, butyl, hexyl, octyl, and decyl, and n represents the valence of a metal component. As more preferable organometallic compound, trialkylaluminum having 1 to 6 carbon atoms, such as triethylaluminum and triisobutylaluminum, and a mixture thereof are advantageous. In some cases, an organoaluminum compound may be used for at least one halogen or hydride group such as ethylaluminum dichloride, diethylaluminum chloride, ethylaluminum sesquichloride, diisobutylaluminum hydride.
통상적으로 α-올레핀, 특히 프로필렌의 중합에 있어서 촉매의 활성 및 입체규칙성을 최적화하기 위해서 외부 전자공여체가 많이 쓰이고 있다. 이러한 전자공여체의 종류에는 유기산, 유기산 안하이드라이드, 유기산에스테르, 알코올, 에테르, 알데히드, 키톤, 실란, 아민, 아민옥사이드, 아마이드, 디올, 인산에스테르와 같은 산소, 규소, 질소, 황, 인 원자를 포함하는 유기화합물과 이들의 혼합물을 들 수 있다. 본 발명에 유익한 외부전자공여체는 유기규소 화합물이며, SiR4의 일반식으로 표기할 수 있는데, R은 R'나 OR'로 대표되며 R'는 1개 내지 20개의 탄소수를 갖는 알킬기이다. 이들의 종류에는 디페닐디메톡시실란, 페닐트리메톡시실란, 페닐에틸디메톡시실란, 페닐메틸디메톡시실란과 같은 아로마틱실란; 이소부틸트리메톡시실란, 디이소부틸디메톡시실란, 디이소프로필디메톡시실란, 디-t-부틸디메톡시실란, t-부틸트리메톡시실란, 시클로헥실메틸디메톡시실란, 디시클로펜틸디메톡시실란, 디시클로헥실디메톡시실란, 2-노르보르난트리에톡시실란, 2-노르보르난메틸디메톡시실란 등의 알리파틱실란; 그리고 이들의 혼합물 등이 있다.In general, in order to optimize the activity and stereoregularity of the catalyst in the polymerization of α-olefins, especially propylene, an external electron donor is frequently used. Examples of such electron donors include oxygen, silicon, nitrogen, sulfur, and phosphorus atoms such as organic acids, organic acid anhydrides, organic acid esters, alcohols, ethers, aldehydes, ketones, silanes, amines, amine oxides, amides, diols, and phosphate esters. The organic compound and mixtures thereof containing are mentioned. An external electron donor useful in the present invention is an organosilicon compound, which may be represented by the general formula of SiR 4 , wherein R is represented by R ′ or OR ′ and R ′ is an alkyl group having 1 to 20 carbon atoms. These types include aromatic silanes such as diphenyldimethoxysilane, phenyltrimethoxysilane, phenylethyldimethoxysilane and phenylmethyldimethoxysilane; Isobutyltrimethoxysilane, diisobutyldimethoxysilane, diisopropyldimethoxysilane, di-t-butyldimethoxysilane, t-butyltrimethoxysilane, cyclohexylmethyldimethoxysilane, dicyclopentyldimethoxy Aliphatic silanes such as silane, dicyclohexyldimethoxysilane, 2-norbornanetriethoxysilane and 2-norbornanemethyldimethoxysilane; And mixtures thereof.
중합반응은 유기용매 부재하에서의 기상 또는 벌크 중합이나 유기용매 존재하에서 액상 슬러리 중합 방법으로 가능하다. 이들 중합법은 산소, 물, 그리고 촉매독으로 작용할 수 있는 기타 화합물의 부재하에서 수행된다. 액상 슬러리 중합의 경우에 바람직한 고체착물 티타늄 촉매(a)의 중합 반응계상의 농도는 용제 1리터에 대하여 촉매의 티타늄원자로 약 0.001밀리몰 내지 5밀리몰, 바람직하게는 약 0.001밀리몰 내지 0.5밀리몰이다. 용제로는 펜탄, 헥산, 헵탄, n-옥탄, 이소옥탄, 시클로헥산, 메틸시클로헥산과 같은 알칸 또는 시클로알칸, 톨루엔, 자이렌, 에틸벤젠, 이소프로필벤젠, 에틸톨루엔, n-프로필벤젠, 디에틸벤젠과 같은 알킬아로마틱, 클로로벤젠, 클로로나프탈렌, 오소-디클로로벤젠과 같은 할로겐화 아로마틱, 그리고 이들의 혼합물이 유익하다. 기상중합의 경우 고체 착물 티타늄촉매(a)의 양은 중합대역 1리터에 대하여 촉매의 티타늄 원자로 약 0.001밀리몰 내지 5밀리몰, 바람직하게는 약 0.001밀리몰 내지 1.0밀리몰, 더욱 바람직하게로는 약 0.01밀리몰 내지 0.5밀리몰로 하는 것이 좋다. 유기 금속 화합물(b)의 바람직한 농도는 알루미늄 원자로 계산하여 촉매(a)중 티탄 원자의 몰당 약 1몰 내지 2000몰이며, 더욱 바람직하게는 약 5몰 내지 500몰이 유익하며, 유기 규소 화합물(c)의 바람직한 농도는 규소원자로 계산하여 유기 금속 화합물(b)중의 알루미늄 원자의 몰당 약 0.001몰 내지 40몰, 더욱 바람직하게는 약 0.05몰 내지 30몰이다.The polymerization reaction can be carried out by gas phase or bulk polymerization in the absence of an organic solvent or by liquid phase slurry polymerization in the presence of an organic solvent. These polymerization methods are carried out in the absence of oxygen, water and other compounds that can act as catalyst poisons. Preferred concentrations of the solid complex titanium catalyst (a) in the case of liquid phase slurry polymerization are about 0.001 to 5 mmol, preferably about 0.001 to 0.5 mmol, of titanium atoms of the catalyst with respect to 1 liter of solvent. Solvents include alkanes or cycloalkanes such as pentane, hexane, heptane, n-octane, isooctane, cyclohexane, methylcyclohexane, toluene, xylene, ethylbenzene, isopropylbenzene, ethyltoluene, n-propylbenzene, diethyl Alkylaromatics such as benzene, halogenated aromatics such as chlorobenzene, chloronaphthalene, ortho-dichlorobenzene, and mixtures thereof are advantageous. In the case of gas phase polymerization, the amount of the solid complex titanium catalyst (a) is about 0.001 to 5 mmol, preferably about 0.001 to 1.0 mmol, more preferably about 0.01 to 0.5 mmol, of titanium atoms of the catalyst per 1 liter of the polymerization zone. It is good to use millimoles. The preferred concentration of the organometallic compound (b) is about 1 to 2000 moles per mole of titanium atoms in the catalyst (a), calculated as aluminum atoms, more preferably about 5 to 500 moles, more preferably organosilicon compound (c) The preferred concentration of is about 0.001 to 40 moles, more preferably about 0.05 to 30 moles per mole of aluminum atoms in the organometallic compound (b), calculated as silicon atoms.
높은 중합속도를 얻기 위해 중합 반응은 중합 공정에 상관없이 충분히 높은 온도에서 수행된다. 일반적으로 약 20℃ 내지 200℃가 적당하며, 더욱 바람직하기로는 20℃ 내지 95℃가 좋다. 중합시의 단량체의 압력은 대기압 내지 100기압이 적절하며, 더욱 바람직하기로는 2기압 내지 50기압의 압력이 적당하다.In order to obtain a high polymerization rate, the polymerization reaction is carried out at a sufficiently high temperature regardless of the polymerization process. Generally, about 20 ° C to 200 ° C is suitable, and more preferably 20 ° C to 95 ° C. As for the pressure of the monomer at the time of superposition | polymerization, atmospheric pressure-100 atmospheres are suitable, More preferably, the pressure of 2 atmospheres-50 atmospheres is suitable.
경우에 따라서 생성되는 중합체의 분자량을 조절하기 위하여 첨가제를 쓸 수 있다. 대표적인 첨가제는 수소인데, 이의 사용은 통상적으로 알려진 바에 의하여 결정할 수 있다.In some cases, additives may be used to control the molecular weight of the resulting polymer. An exemplary additive is hydrogen, the use of which can be determined as commonly known.
본 발명의 촉매를 이용한 올레핀 중합방법에서 얻어진 생성물은 고체의 이소탁틱 폴리 α-올레핀이며, 중합체의 수율도 충분히 높아서 촉매 잔사의 제거가 필요하지 않고, 중합체의 입체규칙성도 우수하여 비입체규칙성 중합체의 분리가 필요하지 않다. 또한, 이 중합 생성물은 우수한 겉보기 밀도와 유동성을 갖고 있다.The product obtained in the olefin polymerization method using the catalyst of the present invention is a solid isotactic poly α-olefin, and the yield of the polymer is sufficiently high that no removal of catalyst residues is required, and the stereoregularity of the polymer is also excellent. No separation is required. This polymerization product also has excellent apparent density and fluidity.
본 발명을 다음의 실시예와 비교예를 통하여 더 상세히 설명한다. 그러나 본 발명은 이들예에 국한되지는 않는다.The present invention will be described in more detail with reference to the following examples and comparative examples. However, the present invention is not limited to these examples.
실시예 1Example 1
고체 착물 티타늄 촉매성분은 다음의 3단계의 과정을 통하여 제조되었다.The solid complex titanium catalyst component was prepared through the following three steps.
(ⅰ) 단계(Iii) step
마그네슘 용액의 제조Preparation of Magnesium Solution
질소분위기로 치환된, 기계식 교반기가 설치된 1.0ℓ 반응기에 MgCl215g, 톨루엔 450㎖의 혼합물을 넣고 400rpm으로 교반시킨 다음, 테트라하이드로퓨란 30㎖, 부탄올 28.0㎖와 메탄올 1.4㎖를 투입한 후, 온도를 105℃로 올린 다음 4시간 동안 반응시켰다. 반응후에 얻어진 균일용액을 상온으로 식힌 다음 실리콘 테트라에톡사이드 3.2㎖를 주입한 후 0.5시간 이상 교반하였다.15 g of MgCl 2 and a mixture of 450 ml of toluene were added to a 1.0 liter reactor equipped with a mechanical stirrer, which was replaced with a nitrogen atmosphere, stirred at 400 rpm. Then, 30 ml of tetrahydrofuran, 28.0 ml of butanol and 1.4 ml of methanol were added thereto. It was raised to 105 ℃ and reacted for 4 hours. After the reaction, the homogeneous solution was cooled to room temperature, and then 3.2 ml of silicon tetraethoxide was injected, followed by stirring for at least 0.5 hours.
(ⅱ) 단계(Ii) step
고체 담지체의 제조Preparation of Solid Support
반응기의 온도를 15~35℃로 유지시킨 1.6ℓ 반응기에 상기의 마그네슘 용액을 이송시켰다. 교반을 360rpm으로 유지시킨 다음, TiCl420㎖를 투입한 후 반응기의 온도를 90℃로 올렸다. 이 과정 동안에 고체 담지체가 생성되었다. 90℃에서 1시간 동안 반응을 시킨 다음 교반을 중지하고 생성된 고체성분이 가라앉도록 하였다. 상등액을 분리한 뒤 고체성분은 톨루엔 76㎖로 두번 세척하였다.The magnesium solution was transferred to a 1.6 L reactor in which the temperature of the reactor was maintained at 15 to 35 ° C. After stirring was maintained at 360rpm, 20ml of TiCl 4 was added thereto, and the temperature of the reactor was raised to 90 ° C. Solid carriers were produced during this process. The reaction was allowed to react at 90 ° C. for 1 hour, and then stirring was stopped to allow the resulting solid component to sink. After separating the supernatant, the solid component was washed twice with 76 ml of toluene.
(ⅲ) 단계(Iii) step
티타늄(Ⅳ) 화합물 처리Titanium (IV) Compound Treatment
고체성분에 톨루엔 100㎖와 TiCl4100㎖를 투입한 후 반응기의 온도를 110℃로 올린 다음 1시간 동안 가열하였다. 교반을 중지하고 고체성분을 가라앉힌 뒤 상등액을 분리제거하고 톨루엔 100㎖와 TiCl4100㎖를 투입한 뒤, 70℃에서 디이소프탈레이트 2.9㎖를 주입하였다. 반응기의 온도는 115℃로 올린 다음 1시간 동안 교반하였다. 교반을 중지한 뒤 상등액을 분리하고 톨루엔 100㎖를 주입한 후 반응기의 온도를 70℃로 내리고 30분 동안 교반하였다. 반응후 교반을 중지하고 상등액을 분리한 후 TiCl4100㎖를 주입한 후 70℃에서 30분 동안 교반하였다. 이렇게 제조된 촉매는 정제된 헥산 75㎖로 5번 세척하였다. 촉매는 질소 분위기에서 건조한 후 보관하였다.100 mL of toluene and 100 mL of TiCl 4 were added to the solid, and the temperature of the reactor was raised to 110 ° C., and then heated for 1 hour. After stirring was stopped, the solid component was allowed to settle, the supernatant was separated, 100 ml of toluene and 100 ml of TiCl 4 were added, and 2.9 ml of diisophthalate was injected at 70 ° C. The temperature of the reactor was raised to 115 ℃ and stirred for 1 hour. After the stirring was stopped, the supernatant was separated, 100 ml of toluene was injected, and the temperature of the reactor was lowered to 70 ° C. and stirred for 30 minutes. After the reaction, the stirring was stopped, the supernatant was separated, and 100 ml of TiCl 4 was injected, followed by stirring at 70 ° C. for 30 minutes. The catalyst thus prepared was washed five times with 75 ml of purified hexane. The catalyst was stored after drying in a nitrogen atmosphere.
촉매의 입자크기 분포도는 레이저 입자 분석기(Mastersizer X, Malvern Instrument)를 이용하여 측정하였으며, d10=31.2㎛, d50=51.9㎛, d90=92.7㎛의 분포도를 가지고 있었다. 여기서 d10, d50, d90은 10, 50, 90 퍼센트의 입자가 각각 31.2㎛, 51.9㎛, 92.7㎛보다 작은 입자를 가지고 있다는 의미이고, d50은 중간 입자크기로 정의된다.The particle size distribution of the catalyst was measured using a laser particle analyzer (Mastersizer X, Malvern Instrument), and had a distribution of d 10 = 31.2 μm, d 50 = 51.9 μm, and d 90 = 92.7 μm. Where d 10 , d 50 , d 90 means that 10, 50, 90 percent of the particles have particles smaller than 31.2 μm, 51.9 μm, and 92.7 μm, respectively, and d 50 is defined as the median particle size.
촉매의 총 기공 용량(pore volume, ㎖/g)은 mercury poresimeter(Micromeritics Autopore Ⅱ 9220)을 이용하여 측정하였다. 촉매 시료는 Glove Box내의 질소 분위기에서 다루어 가능한 공기와의 접촉을 피하였으며, 수은주입시의 압력은 30,000psi까지 상승시켰다. 이렇게 측정한 총 기공 용량은 1.54㎖/g이었다.The total pore volume (ml / g) of the catalyst was measured using mercury poresimeter (Micromeritics Autopore II 9220). The catalyst samples were handled in a nitrogen atmosphere in the Glove Box to avoid possible contact with air, and the pressure during mercury injection increased to 30,000 psi. The total pore capacity measured in this way was 1.54 ml / g.
중합polymerization
용량 2리터의 고압 반응기를 오븐에 말린후 뜨거운 상태로 조립하고, 촉매 38㎎이 담긴 유리 바이알을 반응기 안에 장착한 후 질소와 진공을 교대로 3회 가하여 반응기 안을 질소 분위기로 만들었다. n-헥산 1000㎖를 반응기에 주입한 후 트리에틸알루미늄 10밀리몰과 외부 전자공여체로 시클로헥실메틸디메톡시실란 1밀리몰을 투입하였다. 20psi의 프로필렌 압력을 가하고 교반기로 촉매 바이알을 깨뜨리고 630rpm으로 교반하면서 상온에서 5분동안 중합을 실시하였다. 수소 100㎖를 가한후 반응기의 온도를 70℃로 올리고 프로필렌 압력을 100psi로 조정한 다음 한 시간 동안 중합을 실시하였다. 중합이 끝난후 반응기의 온도를 상온으로 내리고, 중합 내용물에 과량의 에탄올 용액을 가하였다. 생성된 중합체는 분리수집하고 50℃의 진공오븐에서 최소한 6시간 동안 건조하여 백색 분말의 폴리프로필렌을 얻었다.The high-pressure reactor with a capacity of 2 liters was dried in an oven and assembled in a hot state. A glass vial containing 38 mg of catalyst was mounted in the reactor, and nitrogen and vacuum were alternately added three times to make the reactor into a nitrogen atmosphere. After 1000 ml of n-hexane was injected into the reactor, 10 mmol of triethylaluminum and 1 mmol of cyclohexylmethyldimethoxysilane were added as an external electron donor. Propylene pressure of 20 psi was added and the catalyst vial was broken by a stirrer and polymerization was performed at room temperature for 5 minutes while stirring at 630 rpm. After adding 100 ml of hydrogen, the temperature of the reactor was increased to 70 ° C., the propylene pressure was adjusted to 100 psi, and polymerization was performed for one hour. After completion of the polymerization, the temperature of the reactor was lowered to room temperature, and excess ethanol solution was added to the polymerization contents. The resulting polymer was collected separately and dried in a vacuum oven at 50 ° C. for at least 6 hours to obtain a polypropylene of white powder.
사용한 촉매의 무게(g)당 생성된 중합체의 무게(㎏)비로 계산한 중합 활성(㎏폴리프로필렌/g 촉매)은 4.8이었고, 3시간 내지 6시간 동안 끓는 n-헵탄에 추출되지 않는 중합체의 무게(g)비로 나타낸 중합체의 입체규칙성(%)은 97.3%이였다. 중합체의 겉보기 밀도(g/㎖)는 0.33로 측정되었다.The polymerization activity (kg polypropylene / g catalyst), calculated as the weight (kg) of polymer produced per weight (g) of catalyst used, was 4.8 and the weight of the polymer not extracted in boiling n-heptane for 3-6 hours The stereoregularity (%) of the polymer indicated by the ratio (g) was 97.3%. The apparent density (g / ml) of the polymer was determined to be 0.33.
실시예 2Example 2
실시예 1의 촉매제조 과정중 마그네슘 용액 제조시 테트라하이드로퓨란 30㎖, 부탄올 28㎖, 메탄올 0.6㎖ 및 실리콘테트라에톡사이드 3.2㎖를 사용하여 실시예 1에서와 같이 촉매를 제조하였고, 중합 반응도 실시예 1과 같은 방법으로 실시하였다.In preparing the magnesium solution of Example 1, a catalyst was prepared as in Example 1 using 30 ml of tetrahydrofuran, 28 ml of butanol, 0.6 ml of methanol, and 3.2 ml of silicon tetraethoxide. It carried out by the same method as Example 1.
얻어진 촉매의 입자 분포도는 d10=32.9㎛, d50=56.3㎛, d90=94.7㎛의 분포를 가지고 있었으며, 촉매의 총기공용량은 1.76㎖/g이었다. 그리고 중합 활성은 5.1㎏ 폴리프로필렌/g 촉매로 나타났고, 중합체의 입체규칙성은 97.1% 이었으며, 중합체의 겉보기 밀도는 0.32g/㎖이었다.The particle distribution of the catalyst thus obtained had a distribution of d 10 = 32.9 µm, d 50 = 56.3 µm, and d 90 = 94.7 µm, and the total pore capacity of the catalyst was 1.76 ml / g. The polymerization activity was found to be 5.1 kg polypropylene / g catalyst, the stereoregularity of the polymer was 97.1%, and the apparent density of the polymer was 0.32 g / ml.
실시예 3Example 3
실시예 1의 촉매 제조 과정중 마그네슘 용액 제조시 테트라하이드로퓨란 30㎖, 부탄올 28㎖, 에탄올 0.4㎖ 및 실리콘테트라에부톡사이드 5.1㎖를 사용하여 실시예 1에서와 같이 촉매를 제조하였고, 중합 반응도 실시예 1과 같은 방법으로 실시하였다.The catalyst was prepared as in Example 1 using 30 ml of tetrahydrofuran, 28 ml of butanol, 0.4 ml of ethanol and 5.1 ml of silicon tetrabutoxide when preparing a magnesium solution during the catalyst preparation of Example 1. The polymerization reaction was also carried out. It carried out by the same method as Example 1.
얻어진 촉매의 입자 분포도는 d10=26.4㎛, d50=53.2㎛, d90=89.8㎛의 분포를 가지고 있었으며 촉매의 총기공용량은 1.50㎖/g이었다. 그리고 중합 활성은 3.2㎏ 폴리프로필렌/g 촉매로 나타났고, 중합체의 입체규칙성은 97.1% 이었으며, 중합체의 겉보기 밀도는 0.35g/㎖이었다.The particle distribution of the catalyst obtained had a distribution of d 10 = 26.4 µm, d 50 = 53.2 µm, and d 90 = 89.8 µm, and the total pore capacity of the catalyst was 1.50 ml / g. The polymerization activity was found to be 3.2 kg polypropylene / g catalyst, the stereoregularity of the polymer was 97.1%, and the apparent density of the polymer was 0.35 g / ml.
실시예 4Example 4
실시예 1의 촉매제조 과정중 마그네슘 용액 제조시 테트라하이드로퓨란 30㎖, 부탄올 28㎖, 에탄올 0.6㎖ 및 실리콘테트라부톡사이드 5.1㎖를 사용하여 실시예 1에서와 같이 촉매를 제조하였고, 중합 반응도 실시예 1과 같은 방법으로 실시하였다.A catalyst was prepared as in Example 1 using 30 ml of tetrahydrofuran, 28 ml of butanol, 0.6 ml of ethanol, and 5.1 ml of silicon tetrabutoxide when preparing a magnesium solution during the preparation of the catalyst of Example 1. It carried out by the same method as 1.
얻어진 촉매의 입자 분포도는 d10=27.4㎛, d50=57.2㎛, d90=95.8㎛의 분포를 가지고 있었으며 촉매의 총기공용량은 1.57㎖/g이었다. 그리고 중합 활성은 3.4㎏ 폴리프로필렌/g 촉매로 나타났고, 중합체의 입체규칙성은 97.6%이었으며, 중합체의 겉보기 밀도는 0.35g/㎖이었다.The particle distribution of the catalyst obtained had a distribution of d 10 = 27.4 µm, d 50 = 57.2 µm, and d 90 = 95.8 µm, and the total pore capacity of the catalyst was 1.57 ml / g. The polymerization activity was 3.4 kg polypropylene / g catalyst, the stereoregularity of the polymer was 97.6%, and the apparent density of the polymer was 0.35 g / ml.
실시예 5Example 5
실시예 1의 촉매제조 과정중 마그네슘 용액 제조시 테트라하이드로퓨란 30㎖, 부탄올 28㎖, 에탄올 0.6㎖ 및 실리콘테트라에톡사이드 1.6㎖를 사용하여 실시예 1에서와 같이 촉매를 제조하였고, 중합 반응도 실시예 1과 같은 방법으로 실시하였다.The catalyst was prepared as in Example 1 using 30 ml of tetrahydrofuran, 28 ml of butanol, 0.6 ml of ethanol, and 1.6 ml of silicon tetraethoxide when preparing a magnesium solution during the preparation of the catalyst of Example 1. The polymerization reaction was also carried out. It carried out by the same method as Example 1.
얻어진 촉매의 입자 분포도는 d10=31.1㎛, d50=54.8㎛, d90=96.8㎛의 분포를 가지고 있었으며 촉매의 총기공용량은 1.52㎖/g이었다. 그리고 중합 활성은 4.3㎏ 폴리프로필렌/g 촉매로 나타났고, 중합체의 입체규칙성은 97.7%이었으며, 중합체의 겉보기 밀도는 0.34g/㎖이었다.The particle distribution of the catalyst obtained had a distribution of d 10 = 31.1 µm, d 50 = 54.8 µm, and d 90 = 96.8 µm, and the total pore capacity of the catalyst was 1.52 ml / g. The polymerization activity was found to be 4.3 kg polypropylene / g catalyst, the stereoregularity of the polymer was 97.7%, and the apparent density of the polymer was 0.34 g / ml.
실시예 6Example 6
실시예 1의 촉매제조 과정중 마그네슘 용액 제조시 테트라하이드로퓨란 30㎖, 부탄올 28㎖, 에탄올 0.6㎖ 및 실리콘테트라에톡사이드 4.8㎖를 사용하여 실시예 1에서와 같이 촉매를 제조하였고, 중합 반응도 실시예 1과 같은 방법으로 실시하였다.The catalyst was prepared as in Example 1 using 30 ml of tetrahydrofuran, 28 ml of butanol, 0.6 ml of ethanol, and 4.8 ml of silicon tetraethoxide when preparing the magnesium solution during the catalyst preparation of Example 1. The polymerization reaction was also carried out. It carried out by the same method as Example 1.
얻어진 촉매의 입자 분포도는 d10=31.4㎛, d50=68.1㎛, d90=92.6㎛의 분포를 가지고 있었으며 촉매의 총기공용량은 1.8㎖/g이었다. 그리고 중합 활성은 5.2㎏ 폴리프로필렌/g 촉매로 나타났고, 중합체의 입체규칙성은 97.4%이었으며, 중합체의 겉보기 밀도는 0.31g/㎖이었다.The particle size distribution of the catalyst thus obtained had a distribution of d 10 = 31.4 µm, d 50 = 68.1 µm, and d 90 = 92.6 µm, and the total pore capacity of the catalyst was 1.8 ml / g. The polymerization activity was found to be 5.2 kg polypropylene / g catalyst, the stereoregularity of the polymer was 97.4%, and the apparent density of the polymer was 0.31 g / ml.
비교예 1Comparative Example 1
실시예 1의 촉매제조 과정중 마그네슘 용액 제조시에 실리콘테트라에톡사이드를 사용하지 않고 마그네슘 용액을 제조하여 실시예 1에서와 같이 촉매를 제조하였고, 중합 반응도 실시예 1과 같은 방법으로 실시하였다.In preparing the magnesium solution of Example 1, a magnesium solution was prepared without using silicon tetraethoxide to prepare a catalyst as in Example 1, and a polymerization reaction was performed in the same manner as in Example 1.
얻어진 촉매의 입자 분포도는 d10=30.6㎛, d50=56.1㎛, d90=89.7㎛의 분포를 가지고 있었으며 촉매의 총기공용량은 1.14㎖/g이었다. 그리고 중합 활성은 2.3㎏ 폴리프로필렌/g 촉매로 나타났고, 중합체의 입체규칙성은 96.9% 이었으며, 중합체의 겉보기 밀도는 0.39g/㎖이었다.The particle distribution of the catalyst obtained had a distribution of d 10 = 30.6 µm, d 50 = 56.1 µm, and d 90 = 89.7 µm, and the total pore capacity of the catalyst was 1.14 ml / g. The polymerization activity was found to be 2.3 kg polypropylene / g catalyst, the stereoregularity of the polymer was 96.9%, and the apparent density of the polymer was 0.39 g / ml.
비교예 2Comparative Example 2
실시예 2의 촉매제조 과정중 마그네슘 용액 제조시에 실리콘테트라에톡사이드를 사용하지 않고 마그네슘 용액을 제조하여 실시예 2에서와 같이 촉매를 제조하였고, 중합 반응도 실시예 2과 같은 방법으로 실시하였다.In preparing the magnesium solution in Example 2, a magnesium solution was prepared without using silicon tetraethoxide to prepare a catalyst as in Example 2, and a polymerization reaction was performed in the same manner as in Example 2.
얻어진 촉매의 입자 분포도는 d10=32.7㎛, d50=54.3㎛, d90=89.3㎛의 분포를 가지고 있었으며, 촉매의 총기공용량은 1.17㎖/g이었다. 그리고 중합 활성은 3.4㎏ 폴리프로필렌/g 촉매로 나타났고, 입체규칙성은 97.6% 이었으며, 중합체의 겉보기 밀도는 0.42g/㎖이었다.The particle distribution of the catalyst obtained had distributions of d 10 = 32.7 µm, d 50 = 54.3 µm, and d 90 = 89.3 µm, and the total pore capacity of the catalyst was 1.17 ml / g. The polymerization activity was found to be 3.4 kg polypropylene / g catalyst, stereoregularity was 97.6%, and the apparent density of the polymer was 0.42 g / ml.
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| KR1019970017907A KR100430845B1 (en) | 1997-05-09 | 1997-05-09 | Catalyst having high catalytic activity, increased average particle size and narrow particle size distribution for alpha-olefin polymerization and copolymerization |
| GB9725453A GB2325004B (en) | 1997-05-09 | 1997-12-01 | A catalyst for polymerization and copolymerization of olefins |
| US08/989,292 US6034025A (en) | 1997-05-09 | 1997-12-11 | Catalyst for polymerization and copolymerization of olefins |
| IT98MI000103A IT1298174B1 (en) | 1997-05-09 | 1998-01-22 | CATALYST FOR THE POLYMERIZATION AND COPOLYMERIZATION OF OLEFINE |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2001040320A1 (en) * | 1999-12-01 | 2001-06-07 | Samsung General Chemicals Co., Ltd. | Catalyst for polymerization and co-polymerization of ethylene |
| WO2001081432A1 (en) * | 2000-04-24 | 2001-11-01 | Samsung General Chemicals Co., Ltd. | Catalyst for producing an ultra high molecular weight polyethylene and method for producing an ultra high molecular weight polyethylene using the same |
| WO2001092345A1 (en) * | 2000-05-31 | 2001-12-06 | Samsung General Chemicals Co., Ltd. | A method for producing ethylene homo- and co-polymer |
| WO2001096412A1 (en) * | 2000-06-15 | 2001-12-20 | Samsung General Chemicals Co. Ltd. | A catalyst for ethylene homo- and copolymerization |
| KR100371405B1 (en) * | 2000-02-16 | 2003-02-06 | 주식회사 엘지화학 | Method for preparing catalyst for polyolefin polymerization |
| KR100417257B1 (en) * | 1999-06-04 | 2004-02-05 | 주식회사 엘지화학 | Method of catalyst synthesis for polyolefin |
| KR100743912B1 (en) * | 2001-07-10 | 2007-07-30 | 삼성토탈 주식회사 | Catalysts for Ethylene Polymerization and Copolymerization |
| KR100771274B1 (en) * | 2005-12-20 | 2007-10-29 | 삼성토탈 주식회사 | Method for preparing a catalyst for producing polyolefin having a narrow molecular weight distribution |
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| KR101123523B1 (en) | 2009-11-09 | 2012-03-12 | 삼성토탈 주식회사 | A method for preparation of a solid catalyst for polymerization of propylene |
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| US4866022A (en) * | 1984-03-23 | 1989-09-12 | Amoco Corporation | Olefin polymerization catalyst |
| US5081090A (en) * | 1990-07-23 | 1992-01-14 | Amoco Corporation | Dry olefin polymerization catalyst |
| JP2935878B2 (en) * | 1990-08-22 | 1999-08-16 | チッソ株式会社 | Catalyst component for olefin polymerization |
| US5223466A (en) * | 1992-03-20 | 1993-06-29 | Amoco Corporation | Olefin polymerization and copolymerization catalyst |
| KR100219191B1 (en) * | 1997-05-07 | 1999-09-01 | 서갑석 | Method for producing solid catalyst for polyolefin production |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| KR100417257B1 (en) * | 1999-06-04 | 2004-02-05 | 주식회사 엘지화학 | Method of catalyst synthesis for polyolefin |
| WO2001040320A1 (en) * | 1999-12-01 | 2001-06-07 | Samsung General Chemicals Co., Ltd. | Catalyst for polymerization and co-polymerization of ethylene |
| KR100371405B1 (en) * | 2000-02-16 | 2003-02-06 | 주식회사 엘지화학 | Method for preparing catalyst for polyolefin polymerization |
| WO2001081432A1 (en) * | 2000-04-24 | 2001-11-01 | Samsung General Chemicals Co., Ltd. | Catalyst for producing an ultra high molecular weight polyethylene and method for producing an ultra high molecular weight polyethylene using the same |
| WO2001092345A1 (en) * | 2000-05-31 | 2001-12-06 | Samsung General Chemicals Co., Ltd. | A method for producing ethylene homo- and co-polymer |
| KR100353960B1 (en) * | 2000-05-31 | 2002-09-27 | 삼성종합화학주식회사 | A method for producing ethylene homo- and co-polymer |
| WO2001096412A1 (en) * | 2000-06-15 | 2001-12-20 | Samsung General Chemicals Co. Ltd. | A catalyst for ethylene homo- and copolymerization |
| KR100743912B1 (en) * | 2001-07-10 | 2007-07-30 | 삼성토탈 주식회사 | Catalysts for Ethylene Polymerization and Copolymerization |
| KR100771274B1 (en) * | 2005-12-20 | 2007-10-29 | 삼성토탈 주식회사 | Method for preparing a catalyst for producing polyolefin having a narrow molecular weight distribution |
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