KR20210012543A - Dinuclear metallocene compound, catalyst composition and method for preparing olein polymer using the same - Google Patents
Dinuclear metallocene compound, catalyst composition and method for preparing olein polymer using the same Download PDFInfo
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- KR20210012543A KR20210012543A KR1020190090449A KR20190090449A KR20210012543A KR 20210012543 A KR20210012543 A KR 20210012543A KR 1020190090449 A KR1020190090449 A KR 1020190090449A KR 20190090449 A KR20190090449 A KR 20190090449A KR 20210012543 A KR20210012543 A KR 20210012543A
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- 150000001875 compounds Chemical class 0.000 title claims abstract description 86
- 239000003054 catalyst Substances 0.000 title claims abstract description 41
- 238000000034 method Methods 0.000 title claims abstract description 15
- 239000000203 mixture Substances 0.000 title claims description 34
- 229920000642 polymer Polymers 0.000 title description 16
- PHYFQTYBJUILEZ-IUPFWZBJSA-N triolein Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OCC(OC(=O)CCCCCCC\C=C/CCCCCCCC)COC(=O)CCCCCCC\C=C/CCCCCCCC PHYFQTYBJUILEZ-IUPFWZBJSA-N 0.000 title 1
- 229920000098 polyolefin Polymers 0.000 claims abstract description 30
- 238000004519 manufacturing process Methods 0.000 claims abstract description 19
- 239000000126 substance Substances 0.000 claims abstract description 9
- 125000004432 carbon atom Chemical group C* 0.000 claims description 86
- -1 cationic Lewis acid Chemical class 0.000 claims description 25
- 125000003118 aryl group Chemical group 0.000 claims description 23
- 229910052782 aluminium Inorganic materials 0.000 claims description 21
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 19
- 125000000217 alkyl group Chemical group 0.000 claims description 19
- 229910052796 boron Inorganic materials 0.000 claims description 19
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 18
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 14
- 239000000178 monomer Substances 0.000 claims description 14
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 claims description 12
- 150000001336 alkenes Chemical class 0.000 claims description 11
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 11
- 229910052799 carbon Inorganic materials 0.000 claims description 9
- 125000001424 substituent group Chemical group 0.000 claims description 9
- 125000001931 aliphatic group Chemical group 0.000 claims description 8
- 229910052736 halogen Inorganic materials 0.000 claims description 8
- 125000003342 alkenyl group Chemical group 0.000 claims description 6
- 125000002877 alkyl aryl group Chemical group 0.000 claims description 6
- 125000000304 alkynyl group Chemical group 0.000 claims description 6
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 6
- 125000005843 halogen group Chemical group 0.000 claims description 6
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 6
- ZGEGCLOFRBLKSE-UHFFFAOYSA-N 1-Heptene Chemical compound CCCCCC=C ZGEGCLOFRBLKSE-UHFFFAOYSA-N 0.000 claims description 4
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 claims description 4
- CRSBERNSMYQZNG-UHFFFAOYSA-N 1-dodecene Chemical compound CCCCCCCCCCC=C CRSBERNSMYQZNG-UHFFFAOYSA-N 0.000 claims description 4
- GQEZCXVZFLOKMC-UHFFFAOYSA-N 1-hexadecene Chemical compound CCCCCCCCCCCCCCC=C GQEZCXVZFLOKMC-UHFFFAOYSA-N 0.000 claims description 4
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 claims description 4
- HFDVRLIODXPAHB-UHFFFAOYSA-N 1-tetradecene Chemical compound CCCCCCCCCCCCC=C HFDVRLIODXPAHB-UHFFFAOYSA-N 0.000 claims description 4
- DCTOHCCUXLBQMS-UHFFFAOYSA-N 1-undecene Chemical compound CCCCCCCCCC=C DCTOHCCUXLBQMS-UHFFFAOYSA-N 0.000 claims description 4
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 claims description 4
- 150000002367 halogens Chemical class 0.000 claims description 4
- 125000001072 heteroaryl group Chemical group 0.000 claims description 4
- 239000000155 melt Substances 0.000 claims description 4
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 claims description 4
- 230000000379 polymerizing effect Effects 0.000 claims description 4
- 125000003545 alkoxy group Chemical group 0.000 claims description 3
- 239000002841 Lewis acid Substances 0.000 claims description 2
- 125000004104 aryloxy group Chemical group 0.000 claims description 2
- 229910052795 boron group element Inorganic materials 0.000 claims description 2
- 229940069096 dodecene Drugs 0.000 claims description 2
- 125000001183 hydrocarbyl group Chemical group 0.000 claims description 2
- 230000007935 neutral effect Effects 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 26
- 238000006116 polymerization reaction Methods 0.000 description 22
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 21
- 238000002360 preparation method Methods 0.000 description 20
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 18
- 239000002904 solvent Substances 0.000 description 14
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 12
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 11
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 11
- 239000003446 ligand Substances 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 229910052751 metal Inorganic materials 0.000 description 9
- 239000002184 metal Substances 0.000 description 9
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 8
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 7
- 239000005977 Ethylene Substances 0.000 description 7
- 238000009826 distribution Methods 0.000 description 7
- 239000007789 gas Substances 0.000 description 7
- 230000000704 physical effect Effects 0.000 description 7
- 239000007787 solid Substances 0.000 description 7
- 239000004711 α-olefin Substances 0.000 description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- DLEDOFVPSDKWEF-UHFFFAOYSA-N lithium butane Chemical compound [Li+].CCC[CH2-] DLEDOFVPSDKWEF-UHFFFAOYSA-N 0.000 description 6
- MZRVEZGGRBJDDB-UHFFFAOYSA-N n-Butyllithium Substances [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- IMFACGCPASFAPR-UHFFFAOYSA-O tributylazanium Chemical compound CCCC[NH+](CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-O 0.000 description 6
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 5
- DXQXWMYUGOTNGJ-UHFFFAOYSA-N [4-(trifluoromethyl)phenyl]boron Chemical compound [B]C1=CC=C(C(F)(F)F)C=C1 DXQXWMYUGOTNGJ-UHFFFAOYSA-N 0.000 description 5
- 238000007334 copolymerization reaction Methods 0.000 description 5
- 239000000706 filtrate Substances 0.000 description 5
- 150000002736 metal compounds Chemical class 0.000 description 5
- ZMANZCXQSJIPKH-UHFFFAOYSA-O triethylammonium ion Chemical compound CC[NH+](CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-O 0.000 description 5
- YFTHZRPMJXBUME-UHFFFAOYSA-N tripropylamine Chemical compound CCCN(CCC)CCC YFTHZRPMJXBUME-UHFFFAOYSA-N 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 4
- GGSUCNLOZRCGPQ-UHFFFAOYSA-O diethyl(phenyl)azanium Chemical compound CC[NH+](CC)C1=CC=CC=C1 GGSUCNLOZRCGPQ-UHFFFAOYSA-O 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 239000012968 metallocene catalyst Substances 0.000 description 4
- 150000002739 metals Chemical class 0.000 description 4
- 239000012044 organic layer Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- VKMQKNJWQNCEQV-UHFFFAOYSA-N (4-methylphenyl)boron Chemical compound [B]C1=CC=C(C)C=C1 VKMQKNJWQNCEQV-UHFFFAOYSA-N 0.000 description 3
- PBKONEOXTCPAFI-UHFFFAOYSA-N 1,2,4-trichlorobenzene Chemical compound ClC1=CC=C(Cl)C(Cl)=C1 PBKONEOXTCPAFI-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 3
- 125000005234 alkyl aluminium group Chemical group 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000001569 carbon dioxide Substances 0.000 description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical compound C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 description 3
- 239000002685 polymerization catalyst Substances 0.000 description 3
- 150000003623 transition metal compounds Chemical class 0.000 description 3
- RIOQSEWOXXDEQQ-UHFFFAOYSA-O triphenylphosphanium Chemical compound C1=CC=CC=C1[PH+](C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-O 0.000 description 3
- LWNGJAHMBMVCJR-UHFFFAOYSA-N (2,3,4,5,6-pentafluorophenoxy)boronic acid Chemical compound OB(O)OC1=C(F)C(F)=C(F)C(F)=C1F LWNGJAHMBMVCJR-UHFFFAOYSA-N 0.000 description 2
- GWUXLTRGPPIDJA-UHFFFAOYSA-N (4-methylphenyl)alumane Chemical compound CC1=CC=C([AlH2])C=C1 GWUXLTRGPPIDJA-UHFFFAOYSA-N 0.000 description 2
- LBUJPTNKIBCYBY-UHFFFAOYSA-N 1,2,3,4-tetrahydroquinoline Chemical compound C1=CC=C2CCCNC2=C1 LBUJPTNKIBCYBY-UHFFFAOYSA-N 0.000 description 2
- NQSVLUNXRDDHQD-UHFFFAOYSA-N 8-(2,3,4,5-tetramethylcyclopenta-1,3-dien-1-yl)-1,2,3,4-tetrahydroquinoline Chemical compound CC1C(C)=C(C)C(C)=C1C1=CC=CC2=C1NCCC2 NQSVLUNXRDDHQD-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 2
- PGTKVMVZBBZCKQ-UHFFFAOYSA-N Fulvene Chemical compound C=C1C=CC=C1 PGTKVMVZBBZCKQ-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- SHPVKUQHCZKKRP-UHFFFAOYSA-N [B+2]C(C(F)=C(C(F)=C1F)F)=C1F.[B+2]C(C(F)=C(C(F)=C1F)F)=C1F.[B+2]C(C(F)=C(C(F)=C1F)F)=C1F.[B+2]C(C(F)=C(C(F)=C1F)F)=C1F.CCCCN(CCCC)CCCC Chemical compound [B+2]C(C(F)=C(C(F)=C1F)F)=C1F.[B+2]C(C(F)=C(C(F)=C1F)F)=C1F.[B+2]C(C(F)=C(C(F)=C1F)F)=C1F.[B+2]C(C(F)=C(C(F)=C1F)F)=C1F.CCCCN(CCCC)CCCC SHPVKUQHCZKKRP-UHFFFAOYSA-N 0.000 description 2
- XIBZTAIPROXEDH-UHFFFAOYSA-N [B+2]C(C(F)=C(C(F)=C1F)F)=C1F.[B+2]C(C(F)=C(C(F)=C1F)F)=C1F.[B+2]C(C(F)=C(C(F)=C1F)F)=C1F.[B+2]C(C(F)=C(C(F)=C1F)F)=C1F.CCN(CC)C1=CC=CC=C1 Chemical compound [B+2]C(C(F)=C(C(F)=C1F)F)=C1F.[B+2]C(C(F)=C(C(F)=C1F)F)=C1F.[B+2]C(C(F)=C(C(F)=C1F)F)=C1F.[B+2]C(C(F)=C(C(F)=C1F)F)=C1F.CCN(CC)C1=CC=CC=C1 XIBZTAIPROXEDH-UHFFFAOYSA-N 0.000 description 2
- RPXNIXOOFOQCKJ-UHFFFAOYSA-N [B+2]C(C(F)=C(C(F)=C1F)F)=C1F.[B+2]C(C(F)=C(C(F)=C1F)F)=C1F.[B+2]C(C(F)=C(C(F)=C1F)F)=C1F.[B+2]C(C(F)=C(C(F)=C1F)F)=C1F.CCNCC Chemical compound [B+2]C(C(F)=C(C(F)=C1F)F)=C1F.[B+2]C(C(F)=C(C(F)=C1F)F)=C1F.[B+2]C(C(F)=C(C(F)=C1F)F)=C1F.[B+2]C(C(F)=C(C(F)=C1F)F)=C1F.CCNCC RPXNIXOOFOQCKJ-UHFFFAOYSA-N 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 239000012190 activator Substances 0.000 description 2
- 229940100198 alkylating agent Drugs 0.000 description 2
- 239000002168 alkylating agent Substances 0.000 description 2
- 230000029936 alkylation Effects 0.000 description 2
- 238000005804 alkylation reaction Methods 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 235000011089 carbon dioxide Nutrition 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical group C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 2
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- BHNGKNROBJWJDN-UHFFFAOYSA-L dimagnesium;pentane;dibromide Chemical compound [Mg+2].[Mg+2].[Br-].[Br-].[CH2-]CCC[CH2-] BHNGKNROBJWJDN-UHFFFAOYSA-L 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229920001519 homopolymer Polymers 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- SKVWXDRVFXUPJX-UHFFFAOYSA-M lithium;carbamate Chemical compound [Li+].NC([O-])=O SKVWXDRVFXUPJX-UHFFFAOYSA-M 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- VAMFXQBUQXONLZ-UHFFFAOYSA-N n-alpha-eicosene Natural products CCCCCCCCCCCCCCCCCCC=C VAMFXQBUQXONLZ-UHFFFAOYSA-N 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 2
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 description 2
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 description 2
- YWWDBCBWQNCYNR-UHFFFAOYSA-O trimethylphosphanium Chemical compound C[PH+](C)C YWWDBCBWQNCYNR-UHFFFAOYSA-O 0.000 description 2
- 238000010626 work up procedure Methods 0.000 description 2
- WCFQIFDACWBNJT-UHFFFAOYSA-N $l^{1}-alumanyloxy(2-methylpropyl)aluminum Chemical compound CC(C)C[Al]O[Al] WCFQIFDACWBNJT-UHFFFAOYSA-N 0.000 description 1
- MPPPKRYCTPRNTB-UHFFFAOYSA-N 1-bromobutane Chemical compound CCCCBr MPPPKRYCTPRNTB-UHFFFAOYSA-N 0.000 description 1
- 229940106006 1-eicosene Drugs 0.000 description 1
- FIKTURVKRGQNQD-UHFFFAOYSA-N 1-eicosene Natural products CCCCCCCCCCCCCCCCCC=CC(O)=O FIKTURVKRGQNQD-UHFFFAOYSA-N 0.000 description 1
- YVSMQHYREUQGRX-UHFFFAOYSA-N 2-ethyloxaluminane Chemical compound CC[Al]1CCCCO1 YVSMQHYREUQGRX-UHFFFAOYSA-N 0.000 description 1
- RXNYJUSEXLAVNQ-UHFFFAOYSA-N 4,4'-Dihydroxybenzophenone Chemical compound C1=CC(O)=CC=C1C(=O)C1=CC=C(O)C=C1 RXNYJUSEXLAVNQ-UHFFFAOYSA-N 0.000 description 1
- SKHRLNSNVBBGOG-UHFFFAOYSA-N 4,4,5,5-tetramethylcyclopent-2-yn-1-one Chemical compound CC1(C(C#CC1=O)(C)C)C SKHRLNSNVBBGOG-UHFFFAOYSA-N 0.000 description 1
- JFZKLFKSJQUIBS-UHFFFAOYSA-N 77308-48-6 Chemical compound CC1(C)CCC(C)(C)C2=C1C=C1C(C=C3C(C)(C)CCC(C3=C3)(C)C)=C3CC1=C2 JFZKLFKSJQUIBS-UHFFFAOYSA-N 0.000 description 1
- 241000349731 Afzelia bipindensis Species 0.000 description 1
- PLGVIJOQDDMWAO-UHFFFAOYSA-N CCCCN(CCCC)CCCC.FC(C(F)=C(C([Al+2])=C1F)F)=C1F.FC(C(F)=C(C([Al+2])=C1F)F)=C1F.FC(C(F)=C(C([Al+2])=C1F)F)=C1F.FC(C(F)=C(C([Al+2])=C1F)F)=C1F Chemical compound CCCCN(CCCC)CCCC.FC(C(F)=C(C([Al+2])=C1F)F)=C1F.FC(C(F)=C(C([Al+2])=C1F)F)=C1F.FC(C(F)=C(C([Al+2])=C1F)F)=C1F.FC(C(F)=C(C([Al+2])=C1F)F)=C1F PLGVIJOQDDMWAO-UHFFFAOYSA-N 0.000 description 1
- 239000004831 Hot glue Substances 0.000 description 1
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 1
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- BULLHRADHZGONG-UHFFFAOYSA-N [cyclopenta-2,4-dien-1-ylidene(phenyl)methyl]benzene Chemical compound C1=CC=CC1=C(C=1C=CC=CC=1)C1=CC=CC=C1 BULLHRADHZGONG-UHFFFAOYSA-N 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 239000003849 aromatic solvent Substances 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- YHTBNARIMXSJKH-UHFFFAOYSA-N bis(4-butoxyphenyl)methanone Chemical compound C1=CC(OCCCC)=CC=C1C(=O)C1=CC=C(OCCCC)C=C1 YHTBNARIMXSJKH-UHFFFAOYSA-N 0.000 description 1
- 238000009529 body temperature measurement Methods 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 238000004581 coalescence Methods 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 238000010960 commercial process Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- MYBJXSAXGLILJD-UHFFFAOYSA-N diethyl(methyl)alumane Chemical compound CC[Al](C)CC MYBJXSAXGLILJD-UHFFFAOYSA-N 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-O diethylammonium Chemical compound CC[NH2+]CC HPNMFZURTQLUMO-UHFFFAOYSA-O 0.000 description 1
- JGHYBJVUQGTEEB-UHFFFAOYSA-M dimethylalumanylium;chloride Chemical compound C[Al](C)Cl JGHYBJVUQGTEEB-UHFFFAOYSA-M 0.000 description 1
- MWNKMBHGMZHEMM-UHFFFAOYSA-N dimethylalumanylium;ethanolate Chemical compound CCO[Al](C)C MWNKMBHGMZHEMM-UHFFFAOYSA-N 0.000 description 1
- DQYBDCGIPTYXML-UHFFFAOYSA-N ethoxyethane;hydrate Chemical compound O.CCOCC DQYBDCGIPTYXML-UHFFFAOYSA-N 0.000 description 1
- SHGOGDWTZKFNSC-UHFFFAOYSA-N ethyl(dimethyl)alumane Chemical compound CC[Al](C)C SHGOGDWTZKFNSC-UHFFFAOYSA-N 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- RMBPEFMHABBEKP-UHFFFAOYSA-N fluorene Chemical compound C1=CC=C2C3=C[CH]C=CC3=CC2=C1 RMBPEFMHABBEKP-UHFFFAOYSA-N 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 229910052735 hafnium Inorganic materials 0.000 description 1
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 150000004678 hydrides Chemical class 0.000 description 1
- UBJFKNSINUCEAL-UHFFFAOYSA-N lithium;2-methylpropane Chemical compound [Li+].C[C-](C)C UBJFKNSINUCEAL-UHFFFAOYSA-N 0.000 description 1
- IHLVCKWPAMTVTG-UHFFFAOYSA-N lithium;carbanide Chemical compound [Li+].[CH3-] IHLVCKWPAMTVTG-UHFFFAOYSA-N 0.000 description 1
- BQBCXNQILNPAPX-UHFFFAOYSA-N methoxy(dimethyl)alumane Chemical compound [O-]C.C[Al+]C BQBCXNQILNPAPX-UHFFFAOYSA-N 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- ZCYXXKJEDCHMGH-UHFFFAOYSA-N nonane Chemical compound CCCC[CH]CCCC ZCYXXKJEDCHMGH-UHFFFAOYSA-N 0.000 description 1
- BKIMMITUMNQMOS-UHFFFAOYSA-N normal nonane Natural products CCCCCCCCC BKIMMITUMNQMOS-UHFFFAOYSA-N 0.000 description 1
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N o-biphenylenemethane Natural products C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- NDUUEFPGQBSFPV-UHFFFAOYSA-N tri(butan-2-yl)alumane Chemical compound CCC(C)[Al](C(C)CC)C(C)CC NDUUEFPGQBSFPV-UHFFFAOYSA-N 0.000 description 1
- SQBBHCOIQXKPHL-UHFFFAOYSA-N tributylalumane Chemical compound CCCC[Al](CCCC)CCCC SQBBHCOIQXKPHL-UHFFFAOYSA-N 0.000 description 1
- CMHHITPYCHHOGT-UHFFFAOYSA-N tributylborane Chemical compound CCCCB(CCCC)CCCC CMHHITPYCHHOGT-UHFFFAOYSA-N 0.000 description 1
- PYLGJXLKFZZEBJ-UHFFFAOYSA-N tricyclopentylalumane Chemical compound C1CCCC1[Al](C1CCCC1)C1CCCC1 PYLGJXLKFZZEBJ-UHFFFAOYSA-N 0.000 description 1
- LALRXNPLTWZJIJ-UHFFFAOYSA-N triethylborane Chemical compound CCB(CC)CC LALRXNPLTWZJIJ-UHFFFAOYSA-N 0.000 description 1
- ORYGRKHDLWYTKX-UHFFFAOYSA-N trihexylalumane Chemical compound CCCCCC[Al](CCCCCC)CCCCCC ORYGRKHDLWYTKX-UHFFFAOYSA-N 0.000 description 1
- WXRGABKACDFXMG-UHFFFAOYSA-N trimethylborane Chemical compound CB(C)C WXRGABKACDFXMG-UHFFFAOYSA-N 0.000 description 1
- LFXVBWRMVZPLFK-UHFFFAOYSA-N trioctylalumane Chemical compound CCCCCCCC[Al](CCCCCCCC)CCCCCCCC LFXVBWRMVZPLFK-UHFFFAOYSA-N 0.000 description 1
- JOJQVUCWSDRWJE-UHFFFAOYSA-N tripentylalumane Chemical compound CCCCC[Al](CCCCC)CCCCC JOJQVUCWSDRWJE-UHFFFAOYSA-N 0.000 description 1
- JQPMDTQDAXRDGS-UHFFFAOYSA-N triphenylalumane Chemical compound C1=CC=CC=C1[Al](C=1C=CC=CC=1)C1=CC=CC=C1 JQPMDTQDAXRDGS-UHFFFAOYSA-N 0.000 description 1
- CNWZYDSEVLFSMS-UHFFFAOYSA-N tripropylalumane Chemical compound CCC[Al](CCC)CCC CNWZYDSEVLFSMS-UHFFFAOYSA-N 0.000 description 1
- ZMPKTELQGVLZTD-UHFFFAOYSA-N tripropylborane Chemical compound CCCB(CCC)CCC ZMPKTELQGVLZTD-UHFFFAOYSA-N 0.000 description 1
- XDSSGQHOYWGIKC-UHFFFAOYSA-N tris(2-methylpropyl)borane Chemical compound CC(C)CB(CC(C)C)CC(C)C XDSSGQHOYWGIKC-UHFFFAOYSA-N 0.000 description 1
- WSITXTIRYQMZHM-UHFFFAOYSA-N tris(4-methylphenyl)alumane Chemical compound C1=CC(C)=CC=C1[Al](C=1C=CC(C)=CC=1)C1=CC=C(C)C=C1 WSITXTIRYQMZHM-UHFFFAOYSA-N 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F17/00—Metallocenes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/62—Refractory metals or compounds thereof
- C08F4/64—Titanium, zirconium, hafnium or compounds thereof
- C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
- C08F4/65912—Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with an organoaluminium compound
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/62—Refractory metals or compounds thereof
- C08F4/64—Titanium, zirconium, hafnium or compounds thereof
- C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
- C08F4/6592—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring
- C08F4/65922—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring containing at least two cyclopentadienyl rings, fused or not
- C08F4/65927—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring containing at least two cyclopentadienyl rings, fused or not two cyclopentadienyl rings being mutually bridged
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2500/00—Characteristics or properties of obtained polyolefins; Use thereof
- C08F2500/12—Melt flow index or melt flow ratio
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Abstract
Description
본 발명은 이핵 메탈로센 화합물, 촉매 조성물 및 이를 이용한 올레핀 중합체의 제조방법에 관한 것이다.The present invention relates to a dinuclear metallocene compound, a catalyst composition, and a method for preparing an olefin polymer using the same.
올레핀 중합 촉매계는 지글러 나타 및 메탈로센 촉매계로 분류할 수 있으며, 이 두 가지의 고활성 촉매계는 각각의 특징에 맞게 발전되어 왔다. 지글러 나타 촉매는 50년대 발명된 이래 기존의 상업 프로세스에 널리 적용되어 왔으나, 활성점이 여러 개 혼재하는 다활성점 촉매(multi-site catalyst)이기 때문에, 중합체의 분자량 분포가 넓은 것이 특징이며, 공단량체의 조성 분포가 균일하지 않아 원하는 물성 확보에 한계가 있다는 문제점이 있다.The olefin polymerization catalyst system can be classified into a Ziegler Natta and a metallocene catalyst system, and these two highly active catalyst systems have been developed according to their respective characteristics. Ziegler Natta catalysts have been widely applied to conventional commercial processes since their invention in the 1950s, but since they are multi-site catalysts with multiple active points, they are characterized by a wide molecular weight distribution of polymers. There is a problem in that there is a limit to securing desired physical properties because the composition distribution of is not uniform.
한편, 메탈로센 촉매는 전이금속 화합물이 주성분인 주촉매와 알루미늄이 주성분인 유기 금속 화합물인 조촉매의 조합으로 이루어지고, 이와 같은 촉매는 균일계 착체 촉매로 단일 활성점 촉매(single site catalyst)이며, 단일 활성점 특성에 따라 분자량 분포가 좁고 공단량체의 조성 분포가 균일한 고분자가 얻어지며, 촉매의 리간드 구조 변형 및 중합 조건의 변경에 따라 고분자의 입체 규칙도, 공중합 특성, 분자량, 결정화도 등을 변화시킬 수 있는 특성을 가지고 있다.On the other hand, the metallocene catalyst is composed of a combination of a main catalyst composed of a transition metal compound and a cocatalyst composed of an organometallic compound composed mainly of aluminum. Such a catalyst is a homogeneous complex catalyst and is a single site catalyst. A polymer with a narrow molecular weight distribution and a uniform comonomer composition distribution is obtained according to the single active point characteristics, and the stereoregularity, copolymerization characteristics, molecular weight, crystallinity, etc. of the polymer according to the modification of the ligand structure of the catalyst and the change of polymerization conditions It has a characteristic that can change it.
하지만, 상기 방법들을 이용하게 되면, 이전에 보고된 바이페닐렌 브릿지를 가지는 4족 금속 메탈로센 촉매의 경우 치환기의 첨가 및 구조의 변경에 문제가 있으므로, 올레핀 제조에 유용한 새로운 메탈로센 촉매의 개발이 필요한 실정이다.However, when the above methods are used, in the case of the previously reported Group 4 metal metallocene catalyst having a biphenylene bridge, there is a problem in adding a substituent and changing the structure, so that a new metallocene catalyst useful for olefin production It is in need of development.
일반적으로, 용액 중합에 있어서는 고온에서 중합을 행하는 것이 생산성의 향상으로 이어지기 때문에 바람직하다고 여겨진다. 즉, 생성된 올레핀 중합체를 포함하는 중합 용액의 점도가 고온에서는 저하되기 때문에, 저온 중합 시에 비하여 중합기 내의 올레핀 중합체의 농도를 올리는 것이 가능해져, 결과적으로 중합기당의 생산성이 향상된다. 또한 올레핀 중합은 발열 반응이기 때문에, 중합 온도를 원하는 값으로 유지하기 위해서, 통상은 중합열을 제열(除熱)할 필요가 있다. 고온 중합에 있어서는 제열하는 열량이 저온 중합에 비하여 적기 때문에, 제열 비용의 저감이라는 이점도 얻어진다. 한편으로, 중합 온도의 상승에 수반하여 생성되는 올레핀 중합체의 분자량은 저하되는 것이 당해 업자에게 있어 주지이다. 이로부터, 원하는 분자량의 올레핀 중합체를 제조하기 위해서, 중합 온도의 상한이 제약된다는 문제가 많이 생기고 있다. In general, in solution polymerization, it is considered preferable to perform polymerization at a high temperature because it leads to an improvement in productivity. That is, since the viscosity of the polymerization solution containing the resulting olefin polymer decreases at high temperature, it becomes possible to increase the concentration of the olefin polymer in the polymerization reactor compared to the low temperature polymerization, and as a result, the productivity per polymerization reactor is improved. Further, since olefin polymerization is an exothermic reaction, it is usually necessary to remove the heat of polymerization in order to maintain the polymerization temperature at a desired value. In high-temperature polymerization, since the amount of heat to be heat-removed is smaller than that of low-temperature polymerization, an advantage of reducing heat removal cost is also obtained. On the other hand, it is well known to those skilled in the art that the molecular weight of the olefin polymer produced decreases with an increase in the polymerization temperature. From this, in order to produce an olefin polymer of a desired molecular weight, many problems arise that the upper limit of the polymerization temperature is restricted.
이 문제를 해소하기 위한 수단으로서, 고분자량의 올레핀 중합체를 생성하는 중합 촉매가 요구되고 있다. 이와 같은 올레핀 중합 촉매를 이용하는 것에 의해, 고온 중합에 있어서 생성되는 올레핀 중합체의 분자량을 원하는 높은 값으로 유지하는 것이 가능해져 생산성의 향상, 생산 비용의 저감이라는 이점이 얻어진다.As a means for solving this problem, a polymerization catalyst for producing an olefin polymer having a high molecular weight is required. By using such an olefin polymerization catalyst, it becomes possible to maintain the molecular weight of the olefin polymer produced in high-temperature polymerization at a desired high value, thereby obtaining advantages of improving productivity and reducing production cost.
상기와 같이 고분자량의 올레핀 중합체를 생성하는 촉매, 및 그를 구성하는 메탈로센 화합물에 관한 개량이 계속해서 검토되고 있는 실정이다.As described above, the catalyst for producing the olefin polymer of high molecular weight and the improvement of the metallocene compound constituting the catalyst are continuously being studied.
본 발명의 목적은 신규한 구조의 이핵 메탈로센 화합물을 제공하는 것이다.It is an object of the present invention to provide a dinuclear metallocene compound having a novel structure.
본 발명의 다른 목적은 상기 이핵 메탈로센 화합물을 포함하는 촉매 조성물을 제공하는 것이다.Another object of the present invention is to provide a catalyst composition comprising the dinuclear metallocene compound.
본 발명의 다른 목적은 상기 촉매 조성물을 이용한 올레핀 중합체의 제조방법을 제공하는 것이다.Another object of the present invention is to provide a method for producing an olefin polymer using the catalyst composition.
본 발명의 일 실시예는 하기 화학식 1로 표시되는 이핵 메탈로센 화합물을제공한다:An embodiment of the present invention provides a dinuclear metallocene compound represented by Formula 1:
[화학식 1][Formula 1]
상기 화학식 1에서,In Formula 1,
Y는 탄소 원자이고, R1 내지 R12는 각각 독립적으로 수소 원자; 탄소수 1 내지 20의 알킬기; 탄소수 2 내지 20의 알케닐기; 탄소수 2 내지 20의 알키닐기; 탄소수 6 내지 20의 아릴기; 탄소수 7 내지 20의 알킬아릴기; 또는 탄소수 7 내지 20의 아릴알킬기이고, 상기 R1 내지 R12 중 인접하는 2개는 서로 연결되어 1개 이상의 치환 또는 비치환된 지방족 고리, 또는 치환 또는 비치환된 방향족 고리를 형성할 수 있고, R13 및 R14는 각각 독립적으로 치환 또는 비치환된 탄소수 6 내지 20의 아릴기; 또는 치환 또는 비치환된 탄소수 4 내지 20의 헤테로 아릴기이고, X는 할로겐 원자이고, n은 1 내지 10의 정수이다.Y is a carbon atom, and R 1 to R 12 are each independently a hydrogen atom; An alkyl group having 1 to 20 carbon atoms; An alkenyl group having 2 to 20 carbon atoms; Alkynyl group having 2 to 20 carbon atoms; Aryl group having 6 to 20 carbon atoms; An alkylaryl group having 7 to 20 carbon atoms; Or an arylalkyl group having 7 to 20 carbon atoms, and two adjacent two of R 1 to R 12 may be linked to each other to form one or more substituted or unsubstituted aliphatic rings, or substituted or unsubstituted aromatic rings, R 13 and R 14 are each independently a substituted or unsubstituted aryl group having 6 to 20 carbon atoms; Or a substituted or unsubstituted C 4 to C 20 hetero aryl group, X is a halogen atom, and n is an integer of 1 to 10.
본 발명의 다른 실시예는 상기 화학식 1로 표시되는 이핵 메탈로센 화합물을 포함하는 촉매 조성물을 제공한다.Another embodiment of the present invention provides a catalyst composition comprising a dinuclear metallocene compound represented by Chemical Formula 1.
본 발명의 또 다른 실시예는 상기 촉매 조성물의 존재 하에 올레핀계 단량체를 중합하는 단계;를 포함하는, 올레핀 중합체의 제조방법을 제공한다.Another embodiment of the present invention provides a method for producing an olefin polymer comprising; polymerizing an olefin-based monomer in the presence of the catalyst composition.
본 발명에 따른 이핵 메탈로센 화합물은 신규한 구조의 이핵 메탈로센 화합물로서, 원하는 물성과 분자량 분포를 가지는 올레핀 중합체의 생산이 가능하다. 또한, 촉매 활성이 우수하며 높은 분자량을 갖는 올레핀 중합체의 제조에 유용하게 사용될 수 있다.The dinuclear metallocene compound according to the present invention is a dinuclear metallocene compound having a novel structure, and it is possible to produce an olefin polymer having a desired physical property and molecular weight distribution. In addition, it is excellent in catalytic activity and can be usefully used in the production of an olefin polymer having a high molecular weight.
본 명세서 및 청구범위에서 사용된 용어나 단어는 통상적이거나 사전적인 의미로 한정해서 해석되어서는 아니 되며, 발명자는 그 자신의 발명을 가장 최선의 방법으로 설명하기 위해 용어의 개념을 적절하게 정의할 수 있다는 원칙에 입각하여 본 발명의 기술적 사상에 부합하는 의미와 개념으로 해석되어야만 한다.The terms or words used in the specification and claims should not be construed as being limited to their usual or dictionary meanings, and the inventor may appropriately define the concept of terms in order to describe his own invention in the best way. It should be interpreted as a meaning and concept consistent with the technical idea of the present invention based on the principle that there is.
이하, 본 발명을 자세히 설명한다.Hereinafter, the present invention will be described in detail.
이핵 메탈로센 화합물Dinuclear metallocene compounds
본 발명의 이핵 메탈로센 화합물은 하기 화학식 1로 표시되는 것을 특징으로 한다.The dinuclear metallocene compound of the present invention is characterized by represented by the following formula (1).
[화학식 1][Formula 1]
상기 화학식 1에서,In Formula 1,
Y는 탄소 원자이고,Y is a carbon atom,
R1 내지 R12는 각각 독립적으로 수소 원자; 탄소수 1 내지 20의 알킬기; 탄소수 2 내지 20의 알케닐기; 탄소수 2 내지 20의 알키닐기; 탄소수 6 내지 20의 아릴기; 탄소수 7 내지 20의 알킬아릴기; 또는 탄소수 7 내지 20의 아릴알킬기이고,R 1 to R 12 are each independently a hydrogen atom; An alkyl group having 1 to 20 carbon atoms; An alkenyl group having 2 to 20 carbon atoms; Alkynyl group having 2 to 20 carbon atoms; Aryl group having 6 to 20 carbon atoms; An alkylaryl group having 7 to 20 carbon atoms; Or an arylalkyl group having 7 to 20 carbon atoms,
상기 R1 내지 R12 중 인접하는 2개는 서로 연결되어 1개 이상의 치환 또는 비치환된 지방족 고리, 또는 치환 또는 비치환된 방향족 고리를 형성할 수 있고Two of the adjacent R 1 to R 12 may be linked to each other to form one or more substituted or unsubstituted aliphatic rings, or substituted or unsubstituted aromatic rings, and
R13 및 R14는 각각 독립적으로 치환 또는 비치환된 탄소수 6 내지 20의 아릴기; 또는 치환 또는 비치환된 탄소수 4 내지 20의 헤테로 아릴기이고,R 13 and R 14 are each independently a substituted or unsubstituted aryl group having 6 to 20 carbon atoms; Or a substituted or unsubstituted C 4 to C 20 hetero aryl group,
X는 할로겐 원자이고,X is a halogen atom,
n은 1 내지 10의 정수이다.n is an integer from 1 to 10.
바람직하게는, 상기 화학식 1의 이핵 메탈로센 화합물에서, 상기 R1, R4, R5, 및 R8 내지 R12는 각각 독립적으로 수소 원자; 탄소수 1 내지 20의 알킬기; 또는 탄소수 6 내지 20의 아릴기; 탄소수 7 내지 20의 알킬아릴기; 또는 탄소수 7 내지 20의 아릴알킬기이고, 상기 R2과 R3, 및 R6과 R7은 서로 연결되어 치환 또는 비치환된 지방족 고리를 형성하고, 상기 R13 및 R14는 각각 독립적으로 치환 또는 비치환된 탄소수 6 내지 20의 아릴기일 수 있다.Preferably, in the dinuclear metallocene compound of Formula 1, R 1 , R 4 , R 5 , and R 8 to R 12 are each independently a hydrogen atom; An alkyl group having 1 to 20 carbon atoms; Or an aryl group having 6 to 20 carbon atoms; An alkylaryl group having 7 to 20 carbon atoms; Or an arylalkyl group having 7 to 20 carbon atoms, wherein R 2 and R 3 , and R 6 and R 7 are connected to each other to form a substituted or unsubstituted aliphatic ring, and R 13 and R 14 are each independently substituted or It may be an unsubstituted aryl group having 6 to 20 carbon atoms.
보다 바람직하게는, 상기 화학식 1의 이핵 메탈로센 화합물에서, 상기 R1, R4, R5, 및 R8 내지 R12는 수소 원자이고, 상기 R2과 R3, 및 R6과 R7은 서로 연결되어 탄소수 1 내지 12의 알킬로 치환된 탄소수 1 내지 20의 지방족 고리를 형성하고, 상기 R13 및 R14는 각각 독립적으로 치환 또는 비치환된 탄소수 6 내지 20의 아릴기일 수 있다.More preferably, in the dinuclear metallocene compound of Formula 1, R 1 , R 4 , R 5 , and R 8 to R 12 are hydrogen atoms, and R 2 and R 3 , and R 6 and R 7 Are connected to each other to form an aliphatic ring having 1 to 20 carbon atoms substituted with an alkyl having 1 to 12 carbon atoms, and R 13 and R 14 may each independently be a substituted or unsubstituted aryl group having 6 to 20 carbon atoms.
상기 치환기는 탄소수 1 내지 10의 알킬기; 탄소수 3 내지 20의 사이클로알킬기; 탄소수 6 내지 20의 아릴기; 및 탄소수 1 내지 10의 알콕시기로 이루어진 군에서 선택될 수 있다.The substituent is an alkyl group having 1 to 10 carbon atoms; A cycloalkyl group having 3 to 20 carbon atoms; Aryl group having 6 to 20 carbon atoms; And it may be selected from the group consisting of an alkoxy group having 1 to 10 carbon atoms.
본 발명의 화학식 1로 표시되는 이핵 메탈로센 화합물은 구조 내에 중심 금속으로 2개의 하프늄(Hr)을 포함하고, 각각 중심 금속에 연결된 리간드는 2개의 사이클로펜타디엔 골격이 브릿지(bridge)로 연결되어 있는 구조의 신규한 화합물이며, 이에 포함된 리간드 구조는 사이클로펜타디에닐 또는 이의 유도체 골격을 포함한다.The dinuclear metallocene compound represented by Chemical Formula 1 of the present invention contains two hafnium (Hr) as the central metal in the structure, and the ligands each connected to the central metal have two cyclopentadiene skeletons connected by a bridge. It is a novel compound having a structure, and the ligand structure contained therein includes a backbone of cyclopentadienyl or a derivative thereof.
상기 이핵 메탈로센 화합물은 2개의 중심 금속 사이의 상호 작용을 감소시키기 위해 중심 금속 사이에 알킬 체인으로 간격을 부여하였고, 2개의 메탈로센 화합물의 중심 금속(Hf)을 연결하는 알킬 체인은 각 메탈로센 화합물의 중심 금속을 연결하는 링커(linker)의 역할을 하며 금속 사이의 불필요한 상호 작용을 감소시킬 수 있어, 이핵 메탈로센 화합물의 안정성을 높일 수 있으며 리간드 구조를 용이하게 변형할 수 있는 특징이 있다.The dinuclear metallocene compound was provided with an alkyl chain between the central metals to reduce the interaction between the two central metals, and the alkyl chains connecting the central metals (Hf) of the two metallocene compounds are each It acts as a linker connecting the central metal of the metallocene compound and can reduce unnecessary interactions between metals, thereby increasing the stability of the dinuclear metallocene compound and easily modifying the ligand structure. There are features.
상기 이핵 메탈로센 화합물을 메틸알루미녹산과 같은 조촉매와 반응시켜 활성화하고 올레핀 단량체의 중합 반응에 촉매로서 적용할 경우, 높은 중합 온도에서도 고활성, 고분자량의 특징을 갖는 올레핀 중합체를 생성하는 것이 가능하다. 특히, 이핵 메탈로센 화합물의 구조적인 특징상 낮은 용융 지수를 갖는 올레핀 중합체의 제조에도 이용될 수 있으며, 알파-올레핀을 도입하여 에틸렌/알파-올레핀 공중합체와 같은 공중합 반응에도 유용하게 활용할 수 있다. When the dinuclear metallocene compound is activated by reacting with a cocatalyst such as methylaluminoxane and applied as a catalyst to the polymerization reaction of an olefin monomer, it is possible to produce an olefin polymer having high activity and high molecular weight characteristics even at a high polymerization temperature. It is possible. In particular, it can be used to prepare an olefin polymer having a low melt index due to the structural characteristics of the dinuclear metallocene compound, and it can be usefully used for copolymerization reactions such as ethylene/alpha-olefin copolymers by introducing alpha-olefins. .
상기 이핵 메탈로센 화합물은 하기 화학식 1a 또는 1b로 표시되는 것일 수 있다.The dinuclear metallocene compound may be represented by the following Formula 1a or 1b.
[화학식 1a][Formula 1a]
상기 화학식 1a에서,In Formula 1a,
Y는 탄소 원자이고,Y is a carbon atom,
R15 내지 R22는 각각 독립적으로 수소 원자; 또는 탄소수 1 내지 12의 알킬기이고,R 15 to R 22 are each independently a hydrogen atom; Or an alkyl group having 1 to 12 carbon atoms,
n은 1 내지 10의 정수이고,n is an integer from 1 to 10,
[화학식 1b][Formula 1b]
상기 화학식 1b에서, In Formula 1b,
Y는 탄소 원자이고,Y is a carbon atom,
R15 내지 R22는 각각 독립적으로 수소 원자; 또는 탄소수 1 내지 12의 알킬기이고,R 15 to R 22 are each independently a hydrogen atom; Or an alkyl group having 1 to 12 carbon atoms,
R23은 탄소수 1 내지 20의 알킬기; 탄소수 2 내지 20의 알케닐기; 탄소수 2 내지 20의 알키닐기; 또는 탄소수 6 내지 20의 아릴기이고,R 23 is an alkyl group having 1 to 20 carbon atoms; An alkenyl group having 2 to 20 carbon atoms; Alkynyl group having 2 to 20 carbon atoms; Or an aryl group having 6 to 20 carbon atoms,
n은 1 내지 10의 정수이다.n is an integer from 1 to 10.
구체적인 실시예로서, 상기 화학식 1로 표시되는 이핵 메탈로센 화합물은 하기 구조의 화합물일 수 있으나, 이에 제한되지 않는다.As a specific embodiment, the dinuclear metallocene compound represented by Formula 1 may be a compound having the following structure, but is not limited thereto.
본 발명에서, 상기 화학식 1의 이핵 메탈로센 화합물은 하기 화학식 2로 표시되는 일핵 메탈로센 화합물과 하기 화학식 3으로 표시되는 링커(linker) 화합물을 1 : 0.5 내지 1 : 1의 몰 비율로 반응시켜, 화학식 2로 표시되는 화합물의 중심 금속(Hf)을 알킬 체인으로 연결시키는 방법으로 제조될 수 있다.In the present invention, the dinuclear metallocene compound of Formula 1 is reacted with a mononuclear metallocene compound represented by Formula 2 and a linker compound represented by Formula 3 in a molar ratio of 1: 0.5 to 1: 1. Thus, it can be prepared by connecting the central metal (Hf) of the compound represented by Chemical Formula 2 with an alkyl chain.
[화학식 2][Formula 2]
[화학식 3][Formula 3]
상기 화학식 2에서, 치환기의 정의는 화학식 1에서 정의한 바와 동일하다.In Formula 2, the definition of the substituent is the same as defined in Formula 1.
상기 화학식 3에서, Z는 Cl 또는 Br이고, n은 1 내지 10의 정수이다.In Formula 3, Z is Cl or Br, and n is an integer from 1 to 10.
상기 화학식 1의 이핵 메탈로센 화합물의 제조를 위한 반응은 이 기술 분야에 잘 알려진 통상의 유기 합성 방법을 사용할 수 있으므로, 그 조건이 특별히 제한되지 않는다. The reaction for the preparation of the dinuclear metallocene compound of Formula 1 may use a conventional organic synthesis method well known in the art, and thus the conditions are not particularly limited.
촉매 조성물Catalyst composition
본 발명의 촉매 조성물은 상기 화학식 1로 표시되는 이핵 메탈로센 화합물을 포함하는 것을 특징으로 한다. 또한, 상기 촉매 조성물은 1종 이상의 조촉매를 더 포함할 수 있다. The catalyst composition of the present invention is characterized in that it contains a dinuclear metallocene compound represented by Chemical Formula 1. In addition, the catalyst composition may further include one or more cocatalysts.
본 발명에서, 상기 "조성물"이란 해당 조성물의 재료로부터 형성된 반응 생성물 및 분해 생성물뿐만 아니라 해당 조성물을 포함하는 재료들의 혼합물을 포함한다. In the present invention, the "composition" includes reaction products and decomposition products formed from materials of the composition, as well as mixtures of materials including the composition.
본 발명에서, 상기 "촉매 조성물"이란 화학식 1로 표시되는 이핵 메탈로센 화합물 및 조촉매의 2성분이 동시에 또는 임의의 순서로 혼합되거나, 상기 화학식 2로 표시되는 일핵 메탈로센 화합물, 화학식 3으로 표시되는 링커 화합물 및 조촉매의 3성분이 동시에 또는 임의의 순서로 혼합됨으로써, 활성이 있는 조성물로 수득될 수 있는 상태를 의미한다.In the present invention, the "catalyst composition" is a dinuclear metallocene compound represented by Formula 1 and two components of a cocatalyst are mixed simultaneously or in any order, or a mononuclear metallocene compound represented by Formula 2, Formula 3 It means a state in which the three components of the linker compound and cocatalyst represented by are mixed simultaneously or in any order, thereby obtaining an active composition.
상기 조촉매는 하기 화학식 4 내지 6 중에서 선택되는 하나 이상을 포함할 수 있으나, 이에 제한되지 않는다.The cocatalyst may include one or more selected from Formulas 4 to 6, but is not limited thereto.
[화학식 4][Formula 4]
-[Al(R24)-O]a- - [Al (R 24) -O ] a -
상기 화학식 4에서,In Chemical Formula 4,
R24은 각각 독립적으로 할로겐 라디칼; 탄소수 1 내지 20의 하이드로카르빌 라디칼; 또는 할로겐으로 치환된 탄소수 1 내지 20의 하이드로카르빌 라디칼이고,Each R 24 is independently a halogen radical; A hydrocarbyl radical having 1 to 20 carbon atoms; Or a hydrocarbyl radical having 1 to 20 carbon atoms substituted with a halogen,
a는 2 이상의 정수이고,a is an integer of 2 or more,
[화학식 5][Formula 5]
D(R24)3 D(R 24 ) 3
상기 화학식 5에서,In Chemical Formula 5,
D는 알루미늄 또는 보론이고,D is aluminum or boron,
R24은 각각 독립적으로 할로겐 라디칼; 탄소수 1 내지 20의 하이드로카르빌 라디칼; 또는 할로겐으로 치환된 탄소수 1 내지 20의 하이드로카르빌 라디칼이고,Each R 24 is independently a halogen radical; A hydrocarbyl radical having 1 to 20 carbon atoms; Or a hydrocarbyl radical having 1 to 20 carbon atoms substituted with a halogen,
[화학식 6][Formula 6]
[L-H]+[Z(A)4]- 또는 [L]+[Z(A)4]- [LH] + [Z (A ) 4] - or [L] + [Z (A ) 4] -
상기 화학식 6에서,In Formula 6,
L은 중성 또는 양이온성 루이스 산이고,L is a neutral or cationic Lewis acid,
H는 수소 원자이고,H is a hydrogen atom,
Z는 13족 원소이고,Z is a group 13 element,
A는 각각 독립적으로 1 이상의 수소 원자가 치환기로 치환될 수 있는 탄소수 6 내지 20의 아릴; 또는 1 이상의 수소 원자가 치환기로 치환될 수 있는 탄소수 1 내지 20의 알킬이고,Each A is independently aryl having 6 to 20 carbon atoms in which one or more hydrogen atoms may be substituted with a substituent; Or at least one hydrogen atom is an alkyl having 1 to 20 carbon atoms which may be substituted with a substituent,
상기 A의 치환기는 할로겐 원자, 탄소수 1 내지 20의 하이드로카빌기, 탄소수 1 내지 20의 알콕시기 또는 탄소수 6 내지 20의 아릴옥시기이다. The substituent of A is a halogen atom, a hydrocarbyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or an aryloxy group having 6 to 20 carbon atoms.
본 발명에서, 상기 촉매 조성물은 화학식 1로 표시되는 이핵 메탈로센 화합물과 상기 화학식 4 또는 화학식 5로 표시되는 화합물을 접촉시켜 혼합물을 얻는 단계; 및 상기 혼합물에 화합물 6으로 표시되는 화합물을 첨가하는 단계;를 포함하는 제조방법으로 제조된 것일 수 있다. In the present invention, the catalyst composition comprises: obtaining a mixture by contacting a dinuclear metallocene compound represented by Formula 1 with a compound represented by Formula 4 or Formula 5; And adding the compound represented by compound 6 to the mixture.
이 때, 상기 화학식 1로 표시되는 이핵 메탈로센 화합물 대비 상기 화학식 4 또는 화학식 5로 표시되는 화합물의 몰비는 1 : 2 내지 1 : 5,000일 수 있고, 바람직하게는 1 : 10 내지 1 : 1,000, 보다 바람직하게는 1 : 20 내지 1 : 500일 수 있다. In this case, the molar ratio of the compound represented by Formula 4 or Formula 5 to the dinuclear metallocene compound represented by Formula 1 may be 1: 2 to 1: 5,000, preferably 1: 10 to 1: 1,000, More preferably, it may be 1: 20 to 1: 500.
상기 화학식 1로 표시되는 이핵 메탈로센 화합물 대비 상기 화학식 4 또는 화학식 5로 표시되는 화합물의 몰비가 1 : 2 미만일 경우에는 알킬화제의 양이 매우 작아 금속 화합물의 알킬화가 완전히 진행되지 못하는 문제가 있고 1 : 5,000 초과인 경우에는 금속 화합물의 알킬화는 이루어지지만, 남아있는 과량의 알킬화제와 상기 화학식 6으로 표시되는 화합물인 활성화제 간의 부반응으로 인하여 알킬화된 금속 화합물의 활성화가 완전히 이루어지지 못하는 문제가 있다.When the molar ratio of the compound represented by Formula 4 or Formula 5 to the dinuclear metallocene compound represented by Formula 1 is less than 1:2, the amount of the alkylating agent is very small, so that the alkylation of the metal compound does not proceed completely. : When the amount exceeds 5,000, the alkylation of the metal compound is performed, but there is a problem in that the activation of the alkylated metal compound is not completely achieved due to a side reaction between the remaining excess alkylating agent and the activating agent, which is a compound represented by Formula 6.
또한, 상기 촉매 조성물은 화학식 1로 표시되는 이핵 메탈로센 화합물과 상기 화학식 6으로 표시되는 화합물을 접촉시키는 단계;를 포함하는 제조방법으로 제조된 것일 수 있다. In addition, the catalyst composition may be prepared by a method comprising: contacting the dinuclear metallocene compound represented by Formula 1 with the compound represented by Formula 6.
이 때, 상기 화학식 1로 표시되는 이핵 메탈로센 화합물 대비 상기 화학식 6으로 표시되는 화합물의 몰비는 1 : 1 내지 1 : 25일 수 있고, 바람직하게는 1 : 1 내지 1 : 10, 보다 바람직하게는 1 : 1 내지 1 : 5일 수 있다.At this time, the molar ratio of the compound represented by Formula 6 to the dinuclear metallocene compound represented by Formula 1 may be 1:1 to 1:25, preferably 1:1 to 1:10, more preferably May be 1:1 to 1:5.
상기 화학식 1로 표시되는 이핵 메탈로센 화합물 대비 상기 화학식 6으로 표시되는 화합물의 몰비가 1 : 1 미만일 경우에는 활성화제의 양이 상대적으로 적어 금속 화합물의 활성화가 완전히 이루어지지 못해 생성되는 촉매 조성물의 활성도가 떨어지는 문제가 있고 1 : 25 초과인 경우에는 금속 화합물의 활성화가 완전히 이루어지지만, 남아 있는 과량의 활성화제로 촉매 조성물의 단가가 경제적으로 못하거나 생성되는 고분자의 순도가 떨어지는 문제가 있다.When the molar ratio of the compound represented by Formula 6 to the dinuclear metallocene compound represented by Formula 1 is less than 1: 1, the amount of the activator is relatively small, so that the metal compound cannot be completely activated. There is a problem in that the activity is inferior, and if it exceeds 1:25, the activation of the metal compound is completely achieved, but there is a problem that the unit cost of the catalyst composition is not economically or the purity of the resulting polymer is poor with the remaining excess activator.
상기 촉매 조성물의 제조 시에 반응 용매로서 펜탄, 헥산, 헵탄 등과 같은 탄화수소계 용매나, 벤젠, 톨루엔 등과 같은 방향족계 용매가 사용될 수 있으나, 반드시 이에 한정되지는 않으며 당해 기술 분야에서 사용 가능한 모든 용매가 사용될 수 있다.When preparing the catalyst composition, a hydrocarbon-based solvent such as pentane, hexane, or heptane, or an aromatic solvent such as benzene and toluene may be used as the reaction solvent, but is not limited thereto, and all solvents available in the art are Can be used.
상기 화학식 4로 표시되는 화합물은 알킬알루미녹산이라면 특별히 제한되지 않는다. 바람직한 예로는 메틸알루미녹산, 에틸알루미녹산, 이소부틸알루미녹산, 부틸알루미녹산 등이 있으며, 특히 바람직한 화합물은 메틸알루미녹산이다.The compound represented by Formula 4 is not particularly limited as long as it is an alkylaluminoxane. Preferred examples include methylaluminoxane, ethylaluminoxane, isobutylaluminoxane, butylaluminoxane, and the like, and a particularly preferred compound is methylaluminoxane.
상기 화학식 5로 표시되는 화합물은 특별히 제한되지 않으나 바람직한 예로는 트리메틸알루미늄, 트리에틸알루미늄, 트리이소부틸알루미늄, 트리프로필알루미늄, 트리부틸알루미늄, 디메틸클로로알루미늄, 트리이소프로필알루미늄, 트리-s-부틸알루미늄, 트리사이클로펜틸알루미늄, 트리펜틸알루미늄, 트리이소펜틸알루미늄, 트리헥실알루미늄, 트리옥틸알루미늄, 에틸디메틸알루미늄, 메틸디에틸알루미늄, 트리페닐알루미늄, 트리-p-톨릴알루미늄, 디메틸알루미늄메톡시드, 디메틸알루미늄에톡시드, 트리메틸보론, 트리에틸보론, 트리이소부틸보론, 트리프로필보론, 트리부틸보론 등이 포함되며, 특히 바람직한 화합물은 트리메틸알루미늄, 트리에틸알루미늄, 트리이소부틸알루미늄 중에서 선택된다.The compound represented by Formula 5 is not particularly limited, but preferred examples include trimethyl aluminum, triethyl aluminum, triisobutyl aluminum, tripropyl aluminum, tributyl aluminum, dimethyl chloro aluminum, triisopropyl aluminum, tri-s-butyl aluminum. , Tricyclopentyl aluminum, tripentyl aluminum, triisopentyl aluminum, trihexyl aluminum, trioctyl aluminum, ethyl dimethyl aluminum, methyl diethyl aluminum, triphenyl aluminum, tri-p-tolyl aluminum, dimethyl aluminum methoxide, dimethyl aluminum Ethoxide, trimethyl boron, triethyl boron, triisobutyl boron, tripropyl boron, tributyl boron, etc. are included, and particularly preferred compounds are selected from trimethyl aluminum, triethyl aluminum, and triisobutyl aluminum.
상기 화학식 6으로 표시되는 화합물의 예로는 트리에틸암모니움테트라페닐보론, 트리부틸암모니움테트라페닐보론, 트리메틸암모니움테트라페닐보론, 트리프로필암모니움테트라페닐보론, 트리메틸암모니움테트라(p-톨릴)보론, 트리메틸암모니움테트라(o,p-디메틸페닐)보론, 트리부틸암모니움테트라(p-트리플루오로메틸페닐)보론, 트리메틸암모니움테트라(p-트리플루오로메틸페닐)보론, 트리부틸암모니움테트라펜타플루오로페닐보론, N,N-디에틸아닐리디움테트라페틸보론, N,N-디에틸아닐리디움테트라페닐보론, N,N-디에틸아닐리니움테트라펜타플루오로페닐보론, 디에틸암모니움테트라펜타플루오로페닐보론, 트리페닐포스포늄테트라페닐보론, 트리메틸포스포늄테트라페닐보론, 트리에틸암모니움테트라페닐알루미늄, 트리부틸암모니움테트라페닐알루미늄, 트리메틸암모니움테트라페닐알루미늄, 트리프로필암모니움테트라페닐알루미늄, 트리메틸암모니움테트라(p-톨릴)알루미늄, 트리프로필암모니움테트라(p-톨릴)알루미늄, 트리에틸암모니움테트라(o,p-디메틸페닐)알루미늄, 트리부틸암모니움테트라(p-트리플루오로메틸페닐)알루미늄, 트리메틸암모니움테트라(p-트리플루오로메틸페닐)알루미늄, 트리부틸암모니움테트라펜타플루오로페닐알루미늄, N,N-디에틸아닐리니움테트라페닐알루미늄, N,N-디에틸아닐리니움테트라페닐알루미늄, N,N-디에틸아닐리니움테트라펜타플루오로페닐알루미늄, 디에틸암모니움테트라펜타텐트라페닐알루미늄, 트리페닐포스포늄테트라페닐알루미늄, 트리메틸포스포늄테트라페닐알루미늄, 트리에틸암모니움테트라페닐알루미늄, 트리부틸암모니움테트라페닐알루미늄, 트리메틸암모니움테트라페닐보론, 트리프로필암모니움테트라페닐보론, 트리메틸암모니움테트라(p-톨릴)보론,트리프로필암모니움테트라(p-톨릴)보론, 트리에틸암모니움테트라(o,p-디메틸페닐)보론, 트리메틸암모니움테트라(o,p-디메틸페닐)보론, 트리부틸암모니움테트라(p-트리플루오로메틸페닐)보론, 트리메틸암모니움테트라(p-트리플루오로메틸페닐)보론, 트리부틸암모니움테트라펜타플루오로페닐보론, N,N-디에틸아닐리니움테트라페닐보론, N,N-디에틸아닐리니움테트라페닐보론, N,N-디에틸아닐리니움테트라펜타플루오로페닐보론, 디에틸암모니움테트라펜타플루오로페닐보론, 트리페닐포스포늄테트라페닐보론, 트리페닐카보니움테트라(p-트리플루오로메틸페닐)보론, 트리페닐카보니움테트라펜타플루오로페닐보론 등이 있다.Examples of the compound represented by Formula 6 include triethyl ammonium tetraphenyl boron, tributyl ammonium tetraphenyl boron, trimethyl ammonium tetraphenyl boron, tripropyl ammonium tetraphenyl boron, trimethyl ammonium tetra (p-tolyl) Boron, trimethylammonium tetra (o,p-dimethylphenyl) boron, tributyl ammonium tetra (p-trifluoromethylphenyl) boron, trimethyl ammonium tetra (p-trifluoromethylphenyl) boron, tributyl ammonium tetra Pentafluorophenyl boron, N,N-diethylanilideum tetrafetyl boron, N,N-diethylanilideum tetraphenyl boron, N,N-diethylanilinium tetrapentafluorophenyl boron, diethyl Ammonium tetrapentafluorophenyl boron, triphenylphosphonium tetraphenyl boron, trimethyl phosphonium tetraphenyl boron, triethyl ammonium tetraphenyl aluminum, tributyl ammonium tetraphenyl aluminum, trimethyl ammonium tetraphenyl aluminum, tripropyl ammonium Um tetraphenyl aluminum, trimethyl ammonium tetra (p-tolyl) aluminum, tripropyl ammonium tetra (p-tolyl) aluminum, triethyl ammonium tetra (o,p-dimethylphenyl) aluminum, tributyl ammonium tetra (p -Trifluoromethylphenyl) aluminum, trimethylammonium tetra (p-trifluoromethylphenyl) aluminum, tributylammonium tetrapentafluorophenyl aluminum, N,N-diethylanilinium tetraphenylaluminum, N,N- Diethylanilinium tetraphenylaluminum, N,N-diethylaniliniumtetrapentafluorophenylaluminum, diethylammonium tetrapentatentraphenylaluminum, triphenylphosphonium tetraphenylaluminum, trimethylphosphonium tetraphenylaluminum , Triethyl ammonium tetraphenyl aluminum, tributyl ammonium tetraphenyl aluminum, trimethyl ammonium tetraphenyl boron, tripropyl ammonium tetraphenyl boron, trimethyl ammonium tetra (p-tolyl) boron, tripropyl ammonium tetra (p -Tolyl) boron, triethylammonium tetra (o,p-dimethylphenyl) boron, trimethylammonium tetra (o,p-dimethylphenyl) boron, tributylammonium tetra (p-trifluoromethylphenyl) boron, trimethyl Ammonium tetra (p-trifluoromethylphenyl) boron, tributyl ammonium tetrapentafluorophenyl boron, N,N-diethylanilinium tetraphenyl boron, N,N-diethylani Linium tetraphenyl boron, N,N-diethylanilinium tetrapentafluorophenyl boron, diethylammonium tetrapentafluorophenyl boron, triphenylphosphonium tetraphenyl boron, triphenylcarbonium tetra (p- Trifluoromethylphenyl) boron, triphenylcarbonium tetrapentafluorophenyl boron, and the like.
본 발명에서, 화학식 1로 표시되는 이핵 메탈로센 화합물, 화학식 2로 표시되는 일핵 메탈로센 화합물, 조촉매는 필요에 따라 담체에 담지된 형태로 이용할 수 있고, 담체로는 실리카 또는 알루미나가 사용될 수 있다.In the present invention, the dinuclear metallocene compound represented by Formula 1, the mononuclear metallocene compound represented by Formula 2, and the cocatalyst may be used in a form supported on a carrier as needed, and silica or alumina may be used as the carrier. I can.
올레핀 중합체의 제조방법Method for producing olefin polymer
본 발명의 올레핀 중합체의 제조방법은 상기 촉매 조성물의 존재 하에 올레핀계 단량체를 중합하는 단계;를 포함하는 것을 특징으로 한다.The method for producing an olefin polymer of the present invention is characterized by including a step of polymerizing an olefin-based monomer in the presence of the catalyst composition.
본 발명에서, 상기 "중합체"란 동일 혹은 상이한 종류의 단량체들을 중합함으로써 제조된 중합체 화합물을 지칭한다. 이와 같이 해서 일반 용어 중합체는, 단지 1종의 단량체로부터 제조된 중합체를 지칭하는데 통상 이용되는 단독중합체란 용어, 및 이하에 규정된 바와 같은 혼성중합체(interpolymer)란 용어를 망라한다.In the present invention, the "polymer" refers to a polymer compound prepared by polymerizing monomers of the same or different types. The generic term polymer in this way encompasses the term homopolymer, which is commonly used to refer to polymers made from only one monomer, and the term interpolymer as defined below.
본 발명에서, 상기 올레핀계 단량체는 에틸렌, 프로필렌, 1-부텐, 1-펜텐, 4-메틸-1-펜텐, 1-헥센, 1-헵텐, 1-옥텐, 1-데센, 1-운데센, 1-도데센, 1-테트라데센, 1-헥사데센 및 1-에이코센으로 이루어진 군으로부터 선택된 1종 이상일 수 있으나, 이에 제한되지 않는다.In the present invention, the olefinic monomer is ethylene, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-undecene, It may be one or more selected from the group consisting of 1-dodecene, 1-tetradecene, 1-hexadecene, and 1-eicosene, but is not limited thereto.
구체적으로, 본 발명의 올레핀 중합체는 올레핀계 단량체의 종류에 따라 올레핀 호모중합체일 수 있고, 올레핀/알파-올레핀 공중합체일 수 있으며, 바람직하게는 에틸렌/알파-올레핀 공중합체일 수 있다. 이 경우 공단량체인 알파-올레핀계 단량체의 함량은 올레핀 중합체의 용도, 목적 등에 따라 통상의 기술자가 적절히 선택할 수 있고, 약 1 내지 99 몰%일 수 있다.Specifically, the olefin polymer of the present invention may be an olefin homopolymer, an olefin/alpha-olefin copolymer, and preferably an ethylene/alpha-olefin copolymer, depending on the type of the olefin-based monomer. In this case, the content of the alpha-olefin-based monomer as a comonomer may be appropriately selected by a person skilled in the art depending on the use and purpose of the olefin polymer, and may be about 1 to 99 mol%.
상기 촉매 조성물은 올레핀계 단량체의 중합 공정에 적합한 탄소수 5 내지 12의 지방족 탄화수소 용매, 예를 들면 펜탄, 헥산, 헵탄, 노난, 데칸, 및 이들의 이성질체와 톨루엔, 벤젠과 같은 방향족 탄화수소 용매, 디클로로메탄, 클로로벤젠과 같은 염소원자로 치환된 탄화수소 용매 등에 용해하거나 희석하여 주입 가능하다. 여기에 사용되는 용매는 소량의 알킬알루미늄 처리함으로써 촉매 독으로 작용하는 소량의 물 또는 공기 등을 제거하여 사용하는 것이 바람직하며, 조촉매를 더 사용하여 실시하는 것도 가능하다.The catalyst composition is an aliphatic hydrocarbon solvent having 5 to 12 carbon atoms suitable for the polymerization process of an olefinic monomer, such as pentane, hexane, heptane, nonane, decane, and isomers thereof, and an aromatic hydrocarbon solvent such as toluene and benzene, and dichloromethane. , It can be dissolved or diluted in a hydrocarbon solvent substituted with a chlorine atom such as chlorobenzene and injected. The solvent used here is preferably used after removing a small amount of water or air acting as a catalyst poison by treatment with a small amount of alkyl aluminum, and it is possible to further use a cocatalyst.
본 발명에서, 상기 올레핀 중합체의 제조방법은 화학식 1로 표시되는 이핵 메탈로센 화합물이 포함된 촉매 조성물을 사용함으로써, 90 ℃ 이상의 높은 반응온도에서도 에틸렌과 1-옥텐과 같은 입체적 장애가 큰 단량체의 공중합 반응에서 높은 분자량을 가지는 특징을 가진다.In the present invention, the method for preparing the olefin polymer uses a catalyst composition containing a dinuclear metallocene compound represented by Formula 1, so that the copolymerization of a monomer having a large steric hindrance such as ethylene and 1-octene even at a high reaction temperature of 90° C. or higher. It has the characteristic of having a high molecular weight in the reaction.
본 발명에서, 상기 제조방법으로 제조된 올레핀 중합체의 190 ℃, 2.16 kg 하중 조건에서의 용융 지수(dg/min)는 0.05 내지 2, 구체적으로는 0.1 내지 1.5, 0.1 내지 1, 0.1 내지 0.5, 0.1 내지 0.15이고, 190 ℃, 10 kg 하중 조건에서의 용융 지수(dg/min)는 0.5 내지 10.0, 0.5 내지 5.0, 0.5 내지 2.0, 구체적으로는 0.5 내지 1, 또는 0.7 내지 1일 수 있다. In the present invention, the melt index (dg/min) of the olefin polymer prepared by the above manufacturing method at 190° C. and 2.16 kg load condition is 0.05 to 2, specifically 0.1 to 1.5, 0.1 to 1, 0.1 to 0.5, 0.1 To 0.15, and a melt index (dg/min) under the condition of 190°C and 10 kg load may be 0.5 to 10.0, 0.5 to 5.0, 0.5 to 2.0, specifically 0.5 to 1, or 0.7 to 1.
본 발명에서, 상기 제조방법으로 제조된 올레핀 중합체의 중량평균 분자량은 약 5,000 내지 약 500,000, 바람직하게는 약 10,000 내지 약 300,000, 또는 90,000 내지 300,000일 수 있다. 또한 상기 올레핀 중합체의 분자량 분포(Mw/Mn)는 약 1.8 내지 15, 또는 1.8 내지 10, 1.8 내지 5, 1.8 내지 3일 수 있다.In the present invention, the weight average molecular weight of the olefin polymer prepared by the above production method may be about 5,000 to about 500,000, preferably about 10,000 to about 300,000, or 90,000 to 300,000. In addition, the molecular weight distribution (Mw/Mn) of the olefin polymer may be about 1.8 to 15, or 1.8 to 10, 1.8 to 5, and 1.8 to 3.
이와 같이, 본 발명의 올레핀 중합체는 용융 지수가 낮고 분자량이 높기 때문에 인장 강도, 파단 신율 등 물성이 개선되었으며 핫멜트 접착제, 컴파운드, 필름 등에 적용하여 상당히 우수한 물성을 구현할 수 있다.As described above, since the olefin polymer of the present invention has a low melt index and a high molecular weight, physical properties such as tensile strength and elongation at break have been improved, and it can be applied to hot melt adhesives, compounds, films, etc. to realize quite excellent physical properties.
상기 중합은 하나의 연속식 슬러리 중합 반응기, 루프 슬러리 반응기, 기상 반응기 또는 용액 반응기를 이용하여, 하나의 올레핀계 단량체로 호모중합하거나 또는 2종 이상의 올레핀계 단량체로 공중합하여 진행할 수 있다.The polymerization may be performed by homopolymerization with one olefinic monomer or by copolymerization with two or more olefinic monomers using one continuous slurry polymerization reactor, loop slurry reactor, gas phase reactor or solution reactor.
또한, 상기 중합반응 시에는 반응기 내의 수분을 제거하기 위한 유기 알루미늄 화합물이 더욱 투입되어, 이의 존재 하에 중합 반응이 진행될 수 있다. 이러한 유기 알루미늄 화합물의 구체적인 예로는, 트리알킬알루미늄, 디알킬 알루미늄 할라이드, 알킬 알루미늄 디할라이드, 알루미늄 디알킬 하이드라이드 또는 알킬 알루미늄 세스퀴 할라이드 등을 들 수 있으며, 이의 보다 구체적인 예로는, Al(C2H5)3, Al(C2H5)2H, Al(C3H7)3, Al(C3H7)2H, Al(i-C4H9)2H, Al(C8H17)3, Al(C12H25)3, Al(C2H5)(C12H25)2, Al(i-C4H9)(C12H25)2, Al(i-C4H9)2H, Al(i-C4H9)3, (C2H5)2AlCl, (i-C3H9)2AlCl 또는 (C2H5)3Al2Cl3 등을 들 수 있다. 이러한 유기 알루미늄 화합물은 반응기에 연속적으로 투입될 수 있고, 적절한 수분 제거를 위해 반응기에 투입되는 반응 매질의 1kg 당 약 0.1 내지 10몰의 비율로 투입될 수 있다.In addition, during the polymerization reaction, an organic aluminum compound for removing moisture in the reactor is further added, so that the polymerization reaction may proceed in the presence of the organic aluminum compound. Specific examples of such an organoaluminum compound include trialkyl aluminum, dialkyl aluminum halide, alkyl aluminum dihalide, aluminum dialkyl hydride or alkyl aluminum sesqui halide, and more specific examples thereof, Al(C 2 H 5 ) 3 , Al(C 2 H 5 ) 2 H, Al(C 3 H 7 ) 3 , Al(C 3 H 7 ) 2 H, Al(iC 4 H 9 ) 2 H, Al(C 8 H 17 ) 3 , Al(C 12 H 25 ) 3 , Al(C 2 H 5 )(C 12 H 25 ) 2 , Al(iC 4 H 9 )(C 12 H 25 ) 2 , Al(iC 4 H 9 ) 2 H, Al(iC 4 H 9 ) 3 , (C 2 H 5 ) 2 AlCl, (iC 3 H 9 ) 2 AlCl, or (C 2 H 5 ) 3 Al 2 Cl 3 . These organoaluminum compounds may be continuously introduced into the reactor, and may be added in a ratio of about 0.1 to 10 moles per 1 kg of the reaction medium introduced into the reactor for proper moisture removal.
본 발명의 일 실시예에 따르면, 상기 올레핀 중합체의 중합은 약 80 내지 200 ℃의 온도, 구체적으로는 약 90 내지 200 ℃의 온도, 또는 약 130 내지 200 ℃의 온도와, 약 20 내지 100 bar의 압력, 구체적으로는 약 20 내지 50 bar의 압력, 또는 약 20 내지 40 bar의 압력 조건에서, 약 8분 내지 2시간 동안 반응시켜 수행할 수 있다. According to an embodiment of the present invention, the polymerization of the olefin polymer is performed at a temperature of about 80 to 200 °C, specifically, a temperature of about 90 to 200 °C, or a temperature of about 130 to 200 °C, and a temperature of about 20 to 100 bar. It can be carried out by reacting for about 8 minutes to 2 hours under pressure, specifically, a pressure of about 20 to 50 bar, or a pressure of about 20 to 40 bar.
실시예Example
이하, 하기 실시예에 의거하여 본 발명을 보다 구체적으로 설명한다. 이들 실시예는 본 발명의 이해를 돕기 위한 것으로서 본 발명의 범위가 이들에 의해 한정되는 것은 아니다.Hereinafter, the present invention will be described in more detail based on the following examples. These examples are intended to aid understanding of the present invention, and the scope of the present invention is not limited thereto.
<제조예: 화합물의 제조><Production Example: Preparation of compound>
제조예 1Manufacturing Example 1
1) 리간드 화합물의 제조1) Preparation of Ligand Compound
1,1,4,4,7,7,10,10-octamethyl-2,3,4,7,8,9,10,12-octahydro-1H-dibenzo [b,h]fluorine (10g, 25.87mmol, 1eq)에 MTBE (129ml, 0.2M)를 투입하고, n-BuLi (10.87ml, 27.16mmol,1.05eq)를 -20℃에서 투입한 후 실온에서 밤새도록 반응하였다. 반응 후 -20℃로 냉각하고 diphenyl fulvene (6.55g, 28.46mmol, 1.1eq)을 MTBE (71.15ml, 0.4M)에 녹인 용액을 transfer하였다. 실온까지 승온한 후 50℃로 가열하고 밤새도록 교반하였다. MTBE와 물로 워크업(work-up)하여 유기층을 추출하고 용매를 진공 건조하여 수득한 후, MeOH 침전으로 깨끗한 리간드 화합물을 수득하였다(백색 고체, 14.04g, 수율 88%).1,1,4,4,7,7,10,10-octamethyl-2,3,4,7,8,9,10,12-octahydro-1H-dibenzo [b,h]fluorine (10g, 25.87mmol , 1eq) was added to MTBE (129ml, 0.2M), and n-BuLi (10.87ml, 27.16mmol, 1.05eq) was added at -20°C, followed by reaction at room temperature overnight. After the reaction, the mixture was cooled to -20°C, and a solution in which diphenyl fulvene (6.55g, 28.46mmol, 1.1eq) was dissolved in MTBE (71.15ml, 0.4M) was transferred. After the temperature was raised to room temperature, it was heated to 50° C. and stirred overnight. After work-up with MTBE and water to extract the organic layer and vacuum drying the solvent, a clean ligand compound was obtained by precipitation of MeOH (white solid, 14.04 g, yield 88%).
- 1H NMR (CDCl3, 500 MHz) : δ7.4-6.2 (m, 18H), 5.44 (m, 2H), 1.64 (m, 1H), 1.28 (m, 24H) -1 H NMR (CDCl 3 , 500 MHz): δ7.4-6.2 (m, 18H), 5.44 (m, 2H), 1.64 (m, 1H), 1.28 (m, 24H)
2) 이핵 메탈로센 화합물의 제조2) Preparation of dinuclear metallocene compound
상기에서 제조한 12-(cyclopenta-2,4-dien-1-yldiphenylmethyl)-1,1,4,4,7,7,10,10-octamethyl-2,3,4,7,8,9,10,12-octahydro-1H-dibenzo[b,h]fluorine 리간드 화합물 (2.5g, 4.052mmol, 1eq)에 톨루엔/THF (37ml/3.7ml)를 투입하였다. -20℃에서 n-BuLi (3.40ml, 8.509mmol, 2.1eq)를 투입한 후 실온으로 승온하였다. 밤새도록 반응을 진행하고, -20℃로 냉각한 뒤 HfCl4 (1.43g, 4.457mmol, 1.1eq)를 투입하였다. 실온으로 승온한 후 60℃에서 가열하였다. 반응이 진행되었음을 확인한 후 -20℃에서 Pentamethylenebis(magnesium bromide) 용액 (4.86ml, 2.43mmol, 0.6eq)을 투입하였다. 60℃로 가열한 후 밤새도록 반응시켜 상기 이핵 메탈로센 화합물을 수득하였다.12-(cyclopenta-2,4-dien-1-yldiphenylmethyl)-1,1,4,4,7,7,10,10-octamethyl-2,3,4,7,8,9 prepared above, Toluene/THF (37ml/3.7ml) was added to the 10,12-octahydro-1H-dibenzo[b,h]fluorine ligand compound (2.5g, 4.052mmol, 1eq). After adding n-BuLi (3.40ml, 8.509mmol, 2.1eq) at -20°C, the temperature was raised to room temperature. The reaction was carried out overnight, and after cooling to -20°C, HfCl 4 (1.43g, 4.457mmol, 1.1eq) was added. After raising the temperature to room temperature, it was heated at 60°C. After confirming that the reaction proceeded, a Pentamethylenebis (magnesium bromide) solution (4.86ml, 2.43mmol, 0.6eq) was added at -20°C. After heating to 60 ℃ reacted overnight to obtain the dinuclear metallocene compound.
- 1H NMR (CDCl3, 500 MHz) : δ 8.05-7.87 (m, 28H), 6.25-5.43 (m, 8H), 1.62 (m, 16H), 1.49 (s, 12H), 1.43 (s, 12H), 1.3 (m, 10H), 0.97 (m, 12H), 0.86 (m, 12H) -1 H NMR (CDCl 3 , 500 MHz): δ 8.05-7.87 (m, 28H), 6.25-5.43 (m, 8H), 1.62 (m, 16H), 1.49 (s, 12H), 1.43 (s, 12H) ), 1.3 (m, 10H), 0.97 (m, 12H), 0.86 (m, 12H)
제조예 2Manufacturing Example 2
1) 리간드 화합물의 제조1) Preparation of Ligand Compound
(ⅰ) 4,4-bis(4-butoxyphenyl)methanone의 합성(I) Synthesis of 4,4-bis(4-butoxyphenyl)methanone
bis(4-hydroxyphenyl)methanone (10g, 46.68mol, 1eq)과 1-bromobutane (93.4ml, 0.5M), K2CO3 (19.35g, 140.04mmol, 3eq)를 혼합하고 아세톤 (93.4ml)을 투입한 후, 실온에서 반응시키다가 환류하였다. 황색+백색 용액 반응이 끝난 것을 확인한 후 300ml 물과 디에틸에테르 (100ml X 3)로 추출하였다. 유기층을 MgSO4로 건조하고, MC 세척한 후 헥산 세척하고 여과하여 생성물을 수득하였다(백색 고체, 13.7g, 수율 90%).Mix bis(4-hydroxyphenyl)methanone (10g, 46.68mol, 1eq), 1-bromobutane (93.4ml, 0.5M), K 2 CO 3 (19.35g, 140.04mmol, 3eq), and add acetone (93.4ml). Then, it was reacted at room temperature and then refluxed. After confirming that the reaction of the yellow + white solution was complete, extraction was performed with 300 ml of water and diethyl ether (100 ml X 3). The organic layer was dried over MgSO 4 , washed with MC, washed with hexane, and filtered to obtain a product (white solid, 13.7 g, yield 90%).
- 1H NMR (THF_ d8, 500 MHz) : δ 7.73 (d, 4H), 6.97 (d, 4H), 4.06 (t, 4H), 1.78 (m, 4H), 1.53 (m, 4H), 0.99 (t, 6H) -1 H NMR (THF_ d8, 500 MHz): δ 7.73 (d, 4H), 6.97 (d, 4H), 4.06 (t, 4H), 1.78 (m, 4H), 1.53 (m, 4H), 0.99 ( t, 6H)
(ⅱ) 4,4'-(cyclopenta-2,4-dien-1-ylidenemethylene) bis(butoxybenzene)의 합성(Ii) Synthesis of 4,4'-(cyclopenta-2,4-dien-1-ylidenemethylene) bis(butoxybenzene)
bis(4-butoxyphenyl)methanone (12g, 36.76mol, 1eq)에 AlCl3 (2.941g, 22.06mmol, 0.6eq)를 넣고 0℃에서 교반한 후 THF (72ml)를 투입하고, 실온에서 1시간 동안 교반하였다. 다른 플라스크에 CpLi (5.3g, 73.52mmol, 2.0eq)을 투입하고 0℃에서 벤조페논을 transfer하였다. 50℃ 이하에서 30분 동안 교반하고 반응이 종결됨을 확인하였다. 이어서, 10% HCl (aq)를 투입하고 에테르로 워크업을 한 후 NaHCO3 수용액을 투입하고 NaCl (aq)를 넣고 워크업하여 생성물을 수득하였다(붉은색 오일, 14.96g, 정량수율).AlCl 3 (2.941g, 22.06mmol, 0.6eq) was added to bis(4-butoxyphenyl)methanone (12g, 36.76mol, 1eq), stirred at 0℃, and THF (72ml) was added, followed by stirring at room temperature for 1 hour. I did. CpLi (5.3g, 73.52mmol, 2.0eq) was added to another flask, and benzophenone was transferred at 0°C. It was stirred at 50° C. or lower for 30 minutes, and it was confirmed that the reaction was complete. Then, 10% HCl (aq) was added and worked up with ether, NaHCO 3 aqueous solution was added, NaCl (aq) was added and work up to obtain a product (red oil, 14.96 g, quantitative yield).
- 1H NMR (CDCl3, 500 MHz) : δ 7.25 (d, 4H), 6.90 (d, 4H), 6.58 (d, 2H), 6.32 (d, 2H), 4.01 (t, 4H), 1.78 (m, 4H), 1.52 (m, 4H), 0.99 (t, 6H) -1 H NMR (CDCl 3 , 500 MHz): δ 7.25 (d, 4H), 6.90 (d, 4H), 6.58 (d, 2H), 6.32 (d, 2H), 4.01 (t, 4H), 1.78 ( m, 4H), 1.52 (m, 4H), 0.99 (t, 6H)
(ⅲ) 12-(bis(4-butoxyphenyl)(cyclopenta-2,4-dien-1-yl)methyl)-1,1,4,4,7,7,10,10-octamethyl-2,3,4,7,8,9,10,12-octahydro-1H-dibenzo[b,h] fluorene의 합성(Iii) 12-(bis(4-butoxyphenyl)(cyclopenta-2,4-dien-1-yl)methyl)-1,1,4,4,7,7,10,10-octamethyl-2,3, Synthesis of 4,7,8,9,10,12-octahydro-1H-dibenzo[b,h] fluorene
1,1,4,4,7,7,10,10-octamethyl-2,3,4,7,8,9,10,12-octahydro-1H-dibenzo[b,h]fluorene (9.52g, 24.63mmol, 1eq)를 톨루엔/THF (164.2ml, 0.1M)에 투입하고 -20℃에서 n-BuLi (11.38ml, 28.457mmol, 2.1eq)를 투입한 후 실온으로 승온하였다. 밤새도록 반응시킨 후 다른 플라스크에 풀벤(fulvene) (10.15g, 27.10mmol, 1.1eq)을 넣고 톨루엔으로 용해하였다. -10℃에서 냉각해서 풀벤을 Li 쪽으로 transfer하였다. 70℃로 가열하고 밤새도록 교반한 후 톨루엔으로 워크업하여 생성물을 수득하였다(황색 고체, 9.83g, 수율 52.4%).1,1,4,4,7,7,10,10-octamethyl-2,3,4,7,8,9,10,12-octahydro-1H-dibenzo[b,h]fluorene (9.52g, 24.63 mmol, 1eq) was added to toluene/THF (164.2ml, 0.1M), n-BuLi (11.38ml, 28.457mmol, 2.1eq) was added at -20°C, and the temperature was raised to room temperature. After reacting overnight, fulvene (10.15g, 27.10mmol, 1.1eq) was added to another flask and dissolved with toluene. After cooling at -10°C, fulven was transferred to Li. After heating to 70° C. and stirring overnight, the product was obtained by working up with toluene (yellow solid, 9.83 g, yield 52.4%).
- 1H NMR (CDCl3, 500 MHz) : δ 7.33-6.12 (m, 16H), 5.30 (m, 2H), 3.94 (m, 8H), 1.77 (m, 8H), 1.74 (m, 10H), 1.28 (m, 24H) -1 H NMR (CDCl 3 , 500 MHz): δ 7.33-6.12 (m, 16H), 5.30 (m, 2H), 3.94 (m, 8H), 1.77 (m, 8H), 1.74 (m, 10H), 1.28 (m, 24H)
2) 이핵 메탈로센 화합물의 제조2) Preparation of dinuclear metallocene compound
상기에서 제조한 리간드 화합물 (1.2g, 1.577mmol, 1eq)에 톨루엔 (14.3ml), THF (1.43ml)를 넣고 녹인 후 -20℃에서 n-BuLi (1.324ml, 3.311mmol, 2.1eq)를 투입하였다. 실온으로 승온한 뒤 밤새도록 반응시켰다. HfCl4 (0.556g, 1.735mmol, 1.1eq)를 -20℃에서 투입한 후 60℃로 가열하였다. -20℃에서 Pentamethylene bis(magnesium bromide) 용액 (1.892ml, 0.946mmol, 0.6eq)을 투입한 후 실온에서 밤새도록 반응시켜 상기 이핵 메탈로센 화합물을 수득하였다.Toluene (14.3ml), THF (1.43ml) was added and dissolved in the ligand compound (1.2g, 1.577mmol, 1eq) prepared above, and then n-BuLi (1.324ml, 3.311mmol, 2.1eq) was added at -20°C. I did. After raising the temperature to room temperature, the reaction was carried out overnight. HfCl 4 (0.556g, 1.735mmol, 1.1eq) was added at -20℃ and then heated to 60℃. Pentamethylene bis (magnesium bromide) solution (1.892ml, 0.946mmol, 0.6eq) was added at -20°C and reacted overnight at room temperature to obtain the dinuclear metallocene compound.
- 1H NMR (CDCl3, 500 MHz) : δ 7.4-6.86 (m, 32H), 4.09 (m, 16H), 2.0 (m, 16H), 1.84-1.74 (m, 18H), 1.4 (m, 12H), 1.08 (m, 48H) -1 H NMR (CDCl 3 , 500 MHz): δ 7.4-6.86 (m, 32H), 4.09 (m, 16H), 2.0 (m, 16H), 1.84-1.74 (m, 18H), 1.4 (m, 12H) ), 1.08 (m, 48H)
비교 제조예 1Comparative Preparation Example 1
1) 리간드 화합물의 제조1) Preparation of Ligand Compound
(ⅰ) 리튬 카바메이트의 제조(I) Preparation of lithium carbamate
1,2,3,4-테트라히드로퀴놀린 (13.08 g, 98.24 mmol)과 디에틸에테르 (150 mL)를 쉬렝크 플라스크에 넣었다. 드라이아이스와 아세톤으로 만든 -78 ℃저온조에 상기 쉬렝크 플라스크를 담궈 30분간 교반하였다. 이어서, n-BuLi (39.3 mL, 2.5 M, 98.24 mmol)을 질소 분위기 하에 주사기로 투입하였고, 연한 노란색의 슬러리가 형성되었다. 이어서, 플라스크를 2시간 동안 교반한 후에, 생성된 부탄 가스를 제거하면서 상온으로 플라스크의 온도를 올렸다. 플라스크를 다시 -78 ℃저온조에 담가 온도를 낮춘 후 이산화탄소 가스를 투입하였다. 이산화탄소 가스를 투입함에 따라 슬러리가 없어지면서 투명한 용액이 되었다. 플라스크를 버블러(bubbler)에 연결하여 이산화탄소 가스를 제거하면서 온도를 상온으로 올렸다. 그 후에, 진공 하에서 여분의 CO2 가스와 용매를 제거하였다. 드라이박스로 플라스크를 옮긴 후 펜탄을 가하고 심하게 교반한 후 여과하여 흰색 고체 화합물인 리튬 카바메이트를 얻었다. 상기 흰색 고체 화합물은 디에틸에테르가 배위결합 되어있다. 이때 수율은 100% 이다.1,2,3,4-tetrahydroquinoline (13.08 g, 98.24 mmol) and diethyl ether (150 mL) were added to a Schlenk flask. The Schlenk flask was immersed in a -78°C low temperature bath made of dry ice and acetone and stirred for 30 minutes. Then, n-BuLi (39.3 mL, 2.5 M, 98.24 mmol) was injected into a syringe under a nitrogen atmosphere, and a pale yellow slurry was formed. Then, after the flask was stirred for 2 hours, the temperature of the flask was raised to room temperature while removing the generated butane gas. The flask was again immersed in a -78 °C low temperature bath to lower the temperature, and then carbon dioxide gas was added. As the carbon dioxide gas was added, the slurry disappeared, resulting in a transparent solution. The flask was connected to a bubbler and the temperature was raised to room temperature while removing carbon dioxide gas. After that, excess CO 2 gas and solvent were removed under vacuum. After moving the flask to a dry box, pentane was added, stirred vigorously, and filtered to obtain a white solid compound, lithium carbamate. The white solid compound is coordinated with diethyl ether. At this time, the yield is 100%.
- 1H NMR(C6D6, 500 MHz) : δ 1.90 (t, J = 7.2 Hz, 6H, ether), 1.50 (br s, 2H, quin-CH2), 2.34 (br s, 2H, quin-CH2), 3.25 (q, J = 7.2 Hz, 4H, ether), 3.87 (br, s, 2H, quin-CH2), 6.76 (br d, J = 5.6 Hz, 1H, quin-CH) ppm -1 H NMR(C 6 D 6 , 500 MHz): δ 1.90 (t, J = 7.2 Hz, 6H, ether), 1.50 (br s, 2H, quin-CH 2 ), 2.34 (br s, 2H, quin -CH 2 ), 3.25 (q, J = 7.2 Hz, 4H, ether), 3.87 (br, s, 2H, quin-CH 2 ), 6.76 (br d, J = 5.6 Hz, 1H, quin-CH) ppm
- 13C NMR(C6D6, 500 MHz) : δ 24.24, 28.54, 45.37, 65.95, 121.17, 125.34, 125.57, 142.04, 163.09(C=O) ppm -13 C NMR (C 6 D 6 , 500 MHz): δ 24.24, 28.54, 45.37, 65.95, 121.17, 125.34, 125.57, 142.04, 163.09 (C=O) ppm
(ⅱ) 8-(2,3,4,5-테트라메틸-1,3-시클로펜타디에닐)-1,2,3,4-테트라하이드로퀴놀린 (8-(2,3,4,5-Tetramethyl-1,3-cyclopentadienyl)-1,2,3,4-tetrahydroquinoline)의 제조(Ii) 8-(2,3,4,5-tetramethyl-1,3-cyclopentadienyl)-1,2,3,4-tetrahydroquinoline (8-(2,3,4,5- Preparation of Tetramethyl-1,3-cyclopentadienyl)-1,2,3,4-tetrahydroquinoline)
상기 단계 (ⅰ)에서 제조된 리튬 카바메이트 화합물 (8.47 g, 42.60 mmol)을 쉬렝크 플라스크에 넣었다. 이어서, 테트라히드로퓨란 (4.6 g, 63.9 mmol)과 디에틸에테르 45 mL를 차례로 넣었다. 아세톤과 소량의 드라이 아이스로 만든 -20 ℃ 저온조에 상기 쉬렝크 플라스크를 담가 30분간 교반한 후, t-BuLi (25.1 mL, 1.7 M, 42.60 mmol)을 넣었다. 이때 반응 혼합물의 색깔이 붉은색으로 변했다. -20 ℃를 계속 유지하면서 6시간 동안 교반하였다. 테트라히드로퓨란에 녹아있는 CeCl3·2LiCl 용액 (129 mL, 0.33 M, 42.60 mmol)과 테트라메틸씨클로펜티논 (5.89 g, 42.60 mmol)을 주사기 안에서 섞어준 다음, 질소 분위기하에서 플라스크로 투입하였다. 플라스크의 온도를 상온으로 천천히 올리다가 1시간 후에 항온조를 제거하고 온도를 상온으로 유지하였다. 이어서, 상기 플라스크에 물 (15 mL)을 첨가한 후, 에틸아세테이트를 넣고 여과해서 여액을 얻었다. 그 여액을 분별 깔때기에 옮긴 후에 염산 (2 N, 80 mL)을 넣어서 12분간 흔들어주었다. 그리고, 포화 탄산수소나트륨 수용액 (160 mL)를 넣어서 중화한 후에 유기층을 추출하였다. 이 유기층에 무수황산마그네슘을 넣어 수분을 제거하고 여과한 후, 그 여액을 취하고 용매를 제거하였다. 얻어진 여액을 헥산과 에틸아세테이트 (v/v, 10 : 1) 용매를 사용하여 컬럼 크로마토그래피 방법으로 정제하여 노란색 오일을 얻었다. 수율은 40% 이었다.The lithium carbamate compound (8.47 g, 42.60 mmol) prepared in step (i) was put into a Schlenk flask. Then, tetrahydrofuran (4.6 g, 63.9 mmol) and 45 mL of diethyl ether were sequentially added. After immersing the Schlenk flask in a -20 °C low temperature bath made of acetone and a small amount of dry ice and stirring for 30 minutes, t-BuLi (25.1 mL, 1.7 M, 42.60 mmol) was added. At this time, the color of the reaction mixture turned red. The mixture was stirred for 6 hours while maintaining -20°C. CeCl 3 ·2LiCl solution (129 mL, 0.33 M, 42.60 mmol) dissolved in tetrahydrofuran and tetramethylcyclopentinone (5.89 g, 42.60 mmol) were mixed in a syringe, and then introduced into a flask under a nitrogen atmosphere. The temperature of the flask was slowly raised to room temperature, and after 1 hour, the thermostat was removed and the temperature was maintained at room temperature. Then, after adding water (15 mL) to the flask, ethyl acetate was added thereto, followed by filtration to obtain a filtrate. After the filtrate was transferred to a separatory funnel, hydrochloric acid (2 N, 80 mL) was added and shaken for 12 minutes. Then, a saturated aqueous sodium hydrogen carbonate solution (160 mL) was added to neutralize and the organic layer was extracted. Anhydrous magnesium sulfate was added to the organic layer to remove moisture and filtered. The filtrate was taken and the solvent was removed. The obtained filtrate was purified by column chromatography using hexane and ethyl acetate (v/v, 10: 1) solvent to obtain a yellow oil. The yield was 40%.
2) 전이금속 화합물의 제조2) Preparation of transition metal compound
(ⅰ) [(1,2,3,4-테트라하이드로퀴놀린-8-일)테트라메틸사이클로펜타디에닐 - η 5, κ-N]디리튬 화합물의 제조(I) [(1,2,3,4-tetrahydroquinolin-8-yl)tetramethylcyclopentadienyl- η 5 , κ-N] Preparation of dilithium compound
드라이 박스 안에서 상기 제조된 8-(2,3,4,5-테트라메틸-1,3-시클로펜타디에닐)-1,2,3,4-테트라하이드로퀴놀린 (8.07 g, 32.0 mmol)과 디에틸 에테르 140 mL를 둥근 플라스크에 넣은 후, -30℃로 온도를 낮추고, n-BuLi (17.7 g, 2.5 M, 64.0 mmol)을 교반하면서 천천히 넣었다. 온도를 상온으로 올리면서 6시간 동안 반응시켰다. 그 후에, 디에틸 에테르로 여러번 씻어내면서 여과하여 고체를 얻었다. 진공을 걸어 남아 있는 용매를 제거하여 노란색 고체인 디리튬 화합물을 수득하였다 (9.83 g, 수율 95%). 8-(2,3,4,5-tetramethyl-1,3-cyclopentadienyl)-1,2,3,4-tetrahydroquinoline (8.07 g, 32.0 mmol) and di After putting 140 mL of ethyl ether into a round flask, the temperature was lowered to -30°C, and n-BuLi (17.7 g, 2.5 M, 64.0 mmol) was slowly added while stirring. It was reacted for 6 hours while raising the temperature to room temperature. After that, it was filtered while washing several times with diethyl ether to obtain a solid. Vacuum was applied to remove the remaining solvent to obtain a yellow solid dilithium compound (9.83 g, yield 95%).
- 1H NMR(C6D6, 500 MHz) : δ 2.38 (br s, 2H, quin-CH2), 2.53 (br s, 12H, Cp-CH3), 3.48 (br s, 2H, quin-CH2), 4.19 (br s, 2H, quin-CH2), 6.77 (t, J = 6.8 Hz, 2H, quin-CH), 7.28 (br s, 1H, quin-CH), 7.75 (brs, 1H, quin-CH) ppm -1 H NMR (C 6 D 6 , 500 MHz): δ 2.38 (br s, 2H, quin-CH 2 ), 2.53 (br s, 12H, Cp-CH 3 ), 3.48 (br s, 2H, quin- CH 2 ), 4.19 (br s, 2H, quin-CH 2 ), 6.77 (t, J = 6.8 Hz, 2H, quin-CH), 7.28 (br s, 1H, quin-CH), 7.75 (brs, 1H , quin-CH) ppm
(ⅱ) (1,2,3,4-테트라하이드로퀴놀린-8-일)테트라메틸사이클로펜타디에닐-η 5,κ-N]티타늄 디메틸 ([(1,2,3,4-Tetrahydroquinolin-8-yl)tetramethylcyclopentadienyl-eta5,kapa-N]titanium dimethyl)의 제조(Ii) (1,2,3,4-tetrahydroquinolin-8-yl)tetramethylcyclopentadienyl- η 5 ,κ-N] titanium dimethyl ([(1,2,3,4-Tetrahydroquinolin-8 Preparation of -yl)tetramethylcyclopentadienyl-eta5,kapa-N]titanium dimethyl)
드라이 박스 안에서 TiCl4·DME (4.41 g, 15.76 mmol)와 디에틸 에테르 (150 mL)를 둥근 플라스크에 넣고 -30℃에서 교반하면서 MeLi (21.7 mL, 31.52 mmol, 1.4 M)을 천천히 넣었다. 15분 동안 교반한 후에 상기 제조된 [(1,2,3,4-테트라하이드로퀴놀린-8-일)테트라메틸사이클로펜타디에닐 - η 5, κ-N]디리튬 화합물 (5.30 g, 15.76 mmol)을 플라스크에 넣었다. 온도를 상온으로 올리면서 3시간 동안 교반하였다. 반응이 끝난 후, 진공을 걸어 용매를 제거하고, 펜탄에 녹인 후 여과하여 여액을 취하였다. 진공을 걸어 펜탄을 제거하여 진한 갈색의 화합물을 수득하였다 (3.70 g, 수율 71.3%).In a dry box, TiCl 4 ·DME (4.41 g, 15.76 mmol) and diethyl ether (150 mL) were added to a round flask, and MeLi (21.7 mL, 31.52 mmol, 1.4 M) was slowly added while stirring at -30°C. After stirring for 15 minutes, the prepared [(1,2,3,4-tetrahydroquinolin-8-yl)tetramethylcyclopentadienyl- η 5 , κ-N]dilithium compound (5.30 g, 15.76 mmol) ) Into the flask. The mixture was stirred for 3 hours while raising the temperature to room temperature. After the reaction was completed, vacuum was applied to remove the solvent, dissolved in pentane, and filtered to obtain a filtrate. Pentane was removed by applying vacuum to obtain a dark brown compound (3.70 g, 71.3% yield).
- 1H NMR(C6D6, 500 MHz) : δ 0.59 (s, 6H, Ti-CH3), 1.66 (s, 6H, Cp-CH3), 1.69 (br t, J = 6.4 Hz, 2H, quin-CH2), 2.05 (s, 6H, Cp-CH3), 2.47 (t, J = 6.0 Hz, 2H, quin-CH2), 4.53 (m, 2H, quin-CH2), 6.84 (t, J = 7.2 Hz, 1H, quin-CH), 6.93 (d, J =7.6 Hz, quin-CH), 7.01 (d, J =6.8 Hz, quin-CH) ppm -1 H NMR (C 6 D 6 , 500 MHz): δ 0.59 (s, 6H, Ti-CH 3 ), 1.66 (s, 6H, Cp-CH 3 ), 1.69 (br t, J = 6.4 Hz, 2H , quin-CH 2 ), 2.05 (s, 6H, Cp-CH 3 ), 2.47 (t, J = 6.0 Hz, 2H, quin-CH 2 ), 4.53 (m, 2H, quin-CH 2 ), 6.84 ( t, J = 7.2 Hz, 1H, quin-CH), 6.93 (d, J =7.6 Hz, quin-CH), 7.01 (d, J =6.8 Hz, quin-CH) ppm
- 13C NMR(C6D6, 500 MHz) : δ 12.12, 23.08, 27.30, 48.84, 51.01, 119.70, 119.96, 120.95, 126.99, 128.73, 131.67, 136.21 ppm -13 C NMR (C 6 D 6 , 500 MHz): δ 12.12, 23.08, 27.30, 48.84, 51.01, 119.70, 119.96, 120.95, 126.99, 128.73, 131.67, 136.21 ppm
<실시예: 에틸렌/알파-올레핀 공중합체의 제조><Example: Preparation of ethylene/alpha-olefin copolymer>
실시예 1Example 1
2L 오토클레이브 반응기에 헥산 용매와 1-옥텐을 총 합이 1.2L가 되도록 헥산 용매 900 mL와 1-옥텐 300 mL를 가한 후, 반응기의 온도를 150 ℃로 예열하였다. 그와 동시에 반응기의 압력을 에틸렌 (35bar)으로 미리 채워 놓았다. 촉매 0.75 umol과 촉매 대비 10 eq의 디메틸아닐리늄 테트라키스(펜타플루오로페닐) 보레이트(AB) 조촉매를 차례로 고압 아르곤 압력을 가하여 반응기에 넣었다. 이어서, 공중합 반응을 8분간 진행하였다. 다음으로, 남은 에틸렌 가스를 빼내고 고분자 용액을 과량의 에탄올에 가하여 침전을 유도하였다. 침전된 고분자를 에탄올으로 2회 내지 3회 세척한 후, 90 ℃ 진공 오븐에서 12시간 이상 건조한 후 물성을 측정하였다.900 mL of hexane solvent and 300 mL of 1-octene were added to a 2L autoclave reactor so that the total sum of hexane solvent and 1-octene became 1.2 L, and then the temperature of the reactor was preheated to 150 °C. At the same time, the pressure in the reactor was pre-filled with ethylene (35 bar). 0.75 umol of the catalyst and 10 eq of dimethylanilinium tetrakis (pentafluorophenyl) borate (AB) cocatalyst were sequentially added to the reactor by applying high pressure argon pressure. Then, the copolymerization reaction was performed for 8 minutes. Next, the remaining ethylene gas was removed and the polymer solution was added to excess ethanol to induce precipitation. The precipitated polymer was washed 2 to 3 times with ethanol, and then dried in a vacuum oven at 90° C. for 12 hours or more, and then the physical properties were measured.
실시예 2Example 2
제조예 1의 화합물 대신 제조예 2의 화합물을 사용하고 촉매의 함량을 하기 표 1과 같이 변경한 것을 제외하고는, 상기 실시예 1과 동일한 방법으로 공중합체를 제조하였다.A copolymer was prepared in the same manner as in Example 1, except that the compound of Preparation Example 2 was used instead of the compound of Preparation Example 1 and the content of the catalyst was changed as shown in Table 1 below.
비교예 1Comparative Example 1
1-옥텐 함량을 170 mL 사용하면서, 제조예 1의 화합물 대신 비교 제조예 1의 화합물을 사용하고 촉매의 함량을 하기 표 1과 같이 변경한 것을 제외하고는, 상기 실시예 1과 동일한 방법으로 공중합체를 제조하였다.While using 170 mL of 1-octene, the compound of Comparative Preparation 1 was used instead of the compound of Preparation Example 1, and the content of the catalyst was changed as shown in Table 1 below. The coalescence was prepared.
<실험예: 에틸렌/알파-올레핀 공중합체의 물성 분석><Experimental Example: Analysis of physical properties of ethylene/alpha-olefin copolymer>
상기 실시예 및 비교예에서 제조한 각 공중합체의 물성을 비교 분석하였다. 측정 조건 및 방법은 하기와 같으며, 측정 결과는 표 2에 정리하여 나타내었다.The physical properties of each copolymer prepared in Examples and Comparative Examples were compared and analyzed. Measurement conditions and methods are as follows, and the measurement results are summarized in Table 2.
- 중량평균 분자량 (MW) 및 분자량 분포 (MWD): PL-SP260을 이용하여 BHT 0.0125% 포함된 1,2,4-Trichlorobenzene에서 160 ℃, 3시간 동안 녹여 전처리하고, PL-GPC220을 이용하여 측정 온도 160 ℃에서 Mw(중량평균 분자량), Mz(Z-평균 분자량) 및 Mn(수평균 분자량)을 각각 측정하였다. 이 때 각각의 분자량은 폴리스티렌으로 표준화하여 측정하였으며, 측정한 Mw 값 및 Mn 값을 이용하여 Mw 값을 Mn 값으로 나누어 MWD를 계산하였다.-Weight average molecular weight (M W ) and molecular weight distribution (MWD): Pretreat by dissolving in 1,2,4-Trichlorobenzene containing 0.0125% BHT for 3 hours using PL-SP260 at 160°C for 3 hours, and using PL-GPC220 Mw (weight average molecular weight), Mz (Z-average molecular weight), and Mn (number average molecular weight) were measured at a measurement temperature of 160°C. At this time, each molecular weight was measured by standardizing it with polystyrene, and MWD was calculated by dividing the Mw value by the Mn value using the measured Mw and Mn values.
- 밀도 (Density, g/cm3): ASTM D-792에 따라 샘플을 180℃ 프레스 몰드(Press Mold)로 두께 3 mm, 반지름 2 cm 의 시트를 제작하고 10℃/min으로 냉각하여 메틀러(Mettler) 저울에서 측정하였다.-Density (Density, g/cm 3 ): According to ASTM D-792, the sample was made into a 180℃ press mold with a thickness of 3 mm and a radius of 2 cm, and cooled at 10℃/min. Mettler) balance.
- 용융 지수 (Melt Index, MI2.16): ASTM D-1238 (조건 E, 190℃, 2.16 Kg 하중)로 측정하였다.-Melt Index (MI 2.16 ): Measured by ASTM D-1238 (condition E, 190°C, 2.16 Kg load).
- 용융 지수 (Melt Index, MI10): ASTM D-1238 (조건 E, 190℃, 10 Kg 하중)로 측정하였다.-Melt Index (MI 10 ): Measured by ASTM D-1238 (Condition E, 190°C, 10 Kg load).
- 용융 흐름비 (MFRR (Melt Flow Rate Ratio), MI10/MI2.16): 상기와 같이 측정한 두 용융 지수 MI10 및 MI2.16의 비율로 나타내었다.-Melt Flow Rate Ratio (MFRR (Melt Flow Rate Ratio), MI 10 /MI 2.16 ): expressed as the ratio of the two melt indices MI 10 and MI 2.16 measured as above.
- 용융 온도 (Tm, ℃): 시차주사열량계(Differential Scanning Calorimeter, DSC, 장치명: DSC 2920, 제조사: TA instrument)를 이용하여 중합체의 용융 온도를 측정하였다. 구체적으로는 중합체를 150 ℃까지 가열한 후 5분 동안 유지하고, -100 ℃까지 온도를 내린 후 다시 온도를 증가시켰다. 이때 온도의 상승 속도와 하강속도는 각각 10 ℃/min으로 조절하였다. 용융 온도는 두 번째 온도가 상승하는 구간에서 측정한 흡열 피크의 최대 지점으로 하였다.-Melting temperature (T m , ℃): The melting temperature of the polymer was measured using a differential scanning calorimeter (DSC, device name: DSC 2920, manufacturer: TA instrument). Specifically, the polymer was heated to 150° C. and held for 5 minutes, and the temperature was lowered to -100° C. and then the temperature was increased again. At this time, the rate of rise and fall of the temperature were adjusted to 10 °C/min, respectively. The melting temperature was taken as the maximum point of the endothermic peak measured in the section where the second temperature rises.
- 결정화 온도 (Tc, ℃): DSC를 이용하여 용융 온도 측정시와 동일한 방법으로 수행하고, 온도를 감소시키면서 나타나는 곡선으로부터 발열 피크의 최대 지점을 결정화 온도로 하였다.-Crystallization temperature (T c , ℃): It was carried out in the same manner as the melting temperature measurement using DSC, and the maximum point of the exothermic peak from the curve appearing while decreasing the temperature was taken as the crystallization temperature.
상기 표 2에 나타낸 바와 같이, 본 발명의 실시예에 따라 촉매를 합성하여 중합체를 제조한 실시예 1 및 2의 경우 분자량이 높은 공중합체가 제조되었으며, 이와 함께 밀도 및 용융 지수 또한 낮게 나타난 것을 알 수 있었다. 또한, 밀도가 낮게 나타남에 따라 실시예 1 및 2의 공중합체는 Tm 온도 또한 낮게 나타났다.As shown in Table 2, in Examples 1 and 2, in which a polymer was prepared by synthesizing a catalyst according to an example of the present invention, a copolymer having a high molecular weight was prepared, and the density and melt index were also low. Could In addition, as the density was low, the copolymers of Examples 1 and 2 also showed a low T m temperature.
반면, 종래의 전이금속 화합물인 비교 제조예 1을 촉매로 사용한 비교예 1의 경우 중합체의 분자량이 낮게 나타났으며, 밀도 및 용융 지수는 높게 나타났다.On the other hand, in the case of Comparative Example 1 using Comparative Preparation Example 1, which is a conventional transition metal compound, as a catalyst, the molecular weight of the polymer was low, and the density and melt index were high.
즉, 본 발명의 화학식 1로 표시되는 화합물을 촉매로 사용함으로써, 고분자량의 중합체를 효율적으로 중합할 수 있음을 확인하였다.That is, it was confirmed that by using the compound represented by Formula 1 of the present invention as a catalyst, a polymer having a high molecular weight can be efficiently polymerized.
Claims (10)
[화학식 1]
상기 화학식 1에서,
Y는 탄소 원자이고,
R1 내지 R12는 각각 독립적으로 수소 원자; 탄소수 1 내지 20의 알킬기; 탄소수 2 내지 20의 알케닐기; 탄소수 2 내지 20의 알키닐기; 탄소수 6 내지 20의 아릴기; 탄소수 7 내지 20의 알킬아릴기; 또는 탄소수 7 내지 20의 아릴알킬기이고,
상기 R1 내지 R12 중 인접하는 2개는 서로 연결되어 1개 이상의 치환 또는 비치환된 지방족 고리, 또는 치환 또는 비치환된 방향족 고리를 형성할 수 있고,
R13 및 R14는 각각 독립적으로 치환 또는 비치환된 탄소수 6 내지 20의 아릴기; 또는 치환 또는 비치환된 탄소수 4 내지 20의 헤테로 아릴기이고,
X는 할로겐 원자이고,
n은 1 내지 10의 정수이다.
Dinuclear metallocene compound represented by the following formula (1):
[Formula 1]
In Formula 1,
Y is a carbon atom,
R 1 to R 12 are each independently a hydrogen atom; An alkyl group having 1 to 20 carbon atoms; An alkenyl group having 2 to 20 carbon atoms; Alkynyl group having 2 to 20 carbon atoms; Aryl group having 6 to 20 carbon atoms; An alkylaryl group having 7 to 20 carbon atoms; Or an arylalkyl group having 7 to 20 carbon atoms,
Two adjacent two of R 1 to R 12 may be linked to each other to form one or more substituted or unsubstituted aliphatic rings, or substituted or unsubstituted aromatic rings,
R 13 and R 14 are each independently a substituted or unsubstituted aryl group having 6 to 20 carbon atoms; Or a substituted or unsubstituted C 4 to C 20 hetero aryl group,
X is a halogen atom,
n is an integer from 1 to 10.
상기 R1, R4, R5, 및 R8 내지 R12는 각각 독립적으로 수소 원자; 탄소수 1 내지 20의 알킬기; 또는 탄소수 6 내지 20의 아릴기; 탄소수 7 내지 20의 알킬아릴기; 또는 탄소수 7 내지 20의 아릴알킬기이고,
상기 R2과 R3, 및 R6과 R7은 서로 연결되어 치환 또는 비치환된 지방족 고리를 형성하고,
상기 R13 및 R14는 각각 독립적으로 치환 또는 비치환된 탄소수 6 내지 20의 아릴기인, 이핵 메탈로센 화합물.
The method according to claim 1,
R 1 , R 4 , R 5 , and R 8 to R 12 are each independently a hydrogen atom; An alkyl group having 1 to 20 carbon atoms; Or an aryl group having 6 to 20 carbon atoms; An alkylaryl group having 7 to 20 carbon atoms; Or an arylalkyl group having 7 to 20 carbon atoms,
The R 2 and R 3 , and R 6 and R 7 are connected to each other to form a substituted or unsubstituted aliphatic ring,
The R 13 and R 14 are each independently a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, a dinuclear metallocene compound.
상기 R1, R4, R5, 및 R8 내지 R12는 수소 원자이고,
상기 R2과 R3, 및 R6과 R7은 서로 연결되어 치환 또는 비치환된 탄소수 1 내지 20의 지방족 고리를 형성하고,
상기 R13 및 R14는 각각 독립적으로 치환 또는 비치환된 탄소수 6 내지 20의 아릴기인, 이핵 메탈로센 화합물.
The method according to claim 1,
Wherein R 1 , R 4 , R 5 , and R 8 to R 12 are hydrogen atoms,
The R 2 and R 3 , and R 6 and R 7 are connected to each other to form a substituted or unsubstituted aliphatic ring having 1 to 20 carbon atoms,
The R 13 and R 14 are each independently a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, a dinuclear metallocene compound.
상기 이핵 메탈로센 화합물은 하기 화학식 1a 또는 1b로 표시되는 것인, 이핵 메탈로센 화합물:
[화학식 1a]
상기 화학식 1a에서,
Y는 탄소 원자이고,
R15 내지 R22는 각각 독립적으로 수소 원자; 또는 탄소수 1 내지 12의 알킬기이고,
n은 1 내지 10의 정수이고,
[화학식 1b]
상기 화학식 1b에서,
Y는 탄소 원자이고,
R15 내지 R22는 각각 독립적으로 수소 원자; 또는 탄소수 1 내지 12의 알킬기이고,
R23은 탄소수 1 내지 20의 알킬기; 탄소수 2 내지 20의 알케닐기; 탄소수 2 내지 20의 알키닐기; 또는 탄소수 6 내지 20의 아릴기이고,
n은 1 내지 10의 정수이다.
The method according to claim 1,
The dinuclear metallocene compound is represented by the following formula 1a or 1b, a dinuclear metallocene compound:
[Formula 1a]
In Formula 1a,
Y is a carbon atom,
R 15 to R 22 are each independently a hydrogen atom; Or an alkyl group having 1 to 12 carbon atoms,
n is an integer from 1 to 10,
[Formula 1b]
In Formula 1b,
Y is a carbon atom,
R 15 to R 22 are each independently a hydrogen atom; Or an alkyl group having 1 to 12 carbon atoms,
R 23 is an alkyl group having 1 to 20 carbon atoms; An alkenyl group having 2 to 20 carbon atoms; Alkynyl group having 2 to 20 carbon atoms; Or an aryl group having 6 to 20 carbon atoms,
n is an integer from 1 to 10.
[화학식 1]
상기 화학식 1에서,
Y는 탄소 원자이고,
R1 내지 R12는 각각 독립적으로 수소 원자; 탄소수 1 내지 20의 알킬기; 탄소수 2 내지 20의 알케닐기; 탄소수 2 내지 20의 알키닐기; 탄소수 6 내지 20의 아릴기; 탄소수 7 내지 20의 알킬아릴기; 또는 탄소수 7 내지 20의 아릴알킬기이고,
상기 R1 내지 R12 중 인접하는 2개는 서로 연결되어 1개 이상의 치환 또는 비치환된 지방족 고리, 또는 치환 또는 비치환된 방향족 고리를 형성할 수 있고,
R13 및 R14는 각각 독립적으로 치환 또는 비치환된 탄소수 6 내지 20의 아릴기; 또는 치환 또는 비치환된 탄소수 4 내지 20의 헤테로 아릴기이고,
X는 할로겐 원자이고,
n은 1 내지 10의 정수이다.
A catalyst composition comprising a dinuclear metallocene compound represented by the following Formula 1:
[Formula 1]
In Formula 1,
Y is a carbon atom,
R 1 to R 12 are each independently a hydrogen atom; An alkyl group having 1 to 20 carbon atoms; An alkenyl group having 2 to 20 carbon atoms; Alkynyl group having 2 to 20 carbon atoms; Aryl group having 6 to 20 carbon atoms; An alkylaryl group having 7 to 20 carbon atoms; Or an arylalkyl group having 7 to 20 carbon atoms,
Two adjacent two of R 1 to R 12 may be linked to each other to form one or more substituted or unsubstituted aliphatic rings, or substituted or unsubstituted aromatic rings,
R 13 and R 14 are each independently a substituted or unsubstituted aryl group having 6 to 20 carbon atoms; Or a substituted or unsubstituted C 4 to C 20 hetero aryl group,
X is a halogen atom,
n is an integer from 1 to 10.
상기 촉매 조성물은 1종 이상의 조촉매를 더 포함하는 것인, 촉매 조성물.
The method of claim 5,
The catalyst composition further comprises at least one cocatalyst.
상기 조촉매는 하기 화학식 4 내지 6 중에서 선택되는 하나 이상을 포함하는 것인, 촉매 조성물:
[화학식 4]
-[Al(R24)-O]a-
상기 화학식 4에서,
R24은 각각 독립적으로 할로겐 라디칼; 탄소수 1 내지 20의 하이드로카르빌 라디칼; 또는 할로겐으로 치환된 탄소수 1 내지 20의 하이드로카르빌 라디칼이고,
a는 2 이상의 정수이고,
[화학식 5]
D(R24)3
상기 화학식 5에서,
D는 알루미늄 또는 보론이고,
R24은 각각 독립적으로 할로겐 라디칼; 탄소수 1 내지 20의 하이드로카르빌 라디칼; 또는 할로겐으로 치환된 탄소수 1 내지 20의 하이드로카르빌 라디칼이고,
[화학식 6]
[L-H]+[Z(A)4]- 또는 [L]+[Z(A)4]-
상기 화학식 6에서,
L은 중성 또는 양이온성 루이스 산이고,
H는 수소 원자이고,
Z는 13족 원소이고,
A는 각각 독립적으로 1 이상의 수소 원자가 치환기로 치환될 수 있는 탄소수 6 내지 20의 아릴; 또는 1 이상의 수소 원자가 치환기로 치환될 수 있는 탄소수 1 내지 20의 알킬이고,
상기 A의 치환기는 할로겐 원자, 탄소수 1 내지 20의 하이드로카빌기, 탄소수 1 내지 20의 알콕시기 또는 탄소수 6 내지 20의 아릴옥시기이다.
The method of claim 6,
The cocatalyst is one comprising at least one selected from the following formulas 4 to 6, the catalyst composition:
[Formula 4]
- [Al (R 24) -O ] a -
In Chemical Formula 4,
Each R 24 is independently a halogen radical; A hydrocarbyl radical having 1 to 20 carbon atoms; Or a hydrocarbyl radical having 1 to 20 carbon atoms substituted with a halogen,
a is an integer of 2 or more,
[Formula 5]
D(R 24 ) 3
In Chemical Formula 5,
D is aluminum or boron,
Each R 24 is independently a halogen radical; A hydrocarbyl radical having 1 to 20 carbon atoms; Or a hydrocarbyl radical having 1 to 20 carbon atoms substituted with a halogen,
[Formula 6]
[LH] + [Z (A ) 4] - or [L] + [Z (A ) 4] -
In Formula 6,
L is a neutral or cationic Lewis acid,
H is a hydrogen atom,
Z is a group 13 element,
Each A is independently aryl having 6 to 20 carbon atoms in which one or more hydrogen atoms may be substituted with a substituent; Or at least one hydrogen atom is an alkyl having 1 to 20 carbon atoms which may be substituted with a substituent,
The substituent of A is a halogen atom, a hydrocarbyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or an aryloxy group having 6 to 20 carbon atoms.
A method for producing an olefin polymer comprising; polymerizing an olefin-based monomer in the presence of the catalyst composition of any one of claims 5 to 7.
상기 올레핀계 단량체는 에틸렌, 프로필렌, 1-부텐, 1-펜텐, 4-메틸-1-펜텐, 1-헥센, 1-헵텐, 1-옥텐, 1-데센, 1-운데센, 1-도데센, 1-테트라데센, 1-헥사데센 및 1-에이코센으로 이루어진 군으로부터 선택된 1종 이상인, 올레핀 중합체의 제조방법.
The method of claim 8,
The olefinic monomer is ethylene, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-undecene, 1-dodecene , 1-tetradecene, 1-hexadecene, and 1-eicocene, at least one selected from the group consisting of, a method for producing an olefin polymer.
상기 올레핀 중합체의 190 ℃, 2.16 kg 하중 조건에서의 용융 지수(dg/min)는 0.05 내지 2이고, 190 ℃, 10 kg 하중 조건에서의 용융 지수(dg/min)는 0.5 내지 10.0인, 올레핀 중합체의 제조방법.The method of claim 8,
The olefin polymer has a melt index (dg/min) of 0.05 to 2 under a load condition of 190°C and 2.16 kg, and a melt index (dg/min) of 0.5 to 10.0 under a load of 190°C and 10 kg, olefin polymer Method of manufacturing.
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