KR20170075529A - Transition metal compound, catalyst composition comprising the same, and method for preparing olefin polymer using the same - Google Patents
Transition metal compound, catalyst composition comprising the same, and method for preparing olefin polymer using the same Download PDFInfo
- Publication number
- KR20170075529A KR20170075529A KR1020150185300A KR20150185300A KR20170075529A KR 20170075529 A KR20170075529 A KR 20170075529A KR 1020150185300 A KR1020150185300 A KR 1020150185300A KR 20150185300 A KR20150185300 A KR 20150185300A KR 20170075529 A KR20170075529 A KR 20170075529A
- Authority
- KR
- South Korea
- Prior art keywords
- carbon atoms
- group
- transition metal
- metal compound
- alkyl
- Prior art date
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 58
- 150000003623 transition metal compounds Chemical class 0.000 title claims abstract description 49
- 239000000203 mixture Substances 0.000 title claims abstract description 34
- 229920000098 polyolefin Polymers 0.000 title claims abstract description 34
- 238000000034 method Methods 0.000 title claims abstract description 15
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims abstract description 23
- 150000001336 alkenes Chemical class 0.000 claims abstract description 21
- 230000008569 process Effects 0.000 claims abstract description 10
- 125000004432 carbon atom Chemical group C* 0.000 claims description 125
- 125000000217 alkyl group Chemical group 0.000 claims description 46
- -1 cationic Lewis base Chemical class 0.000 claims description 41
- 125000001183 hydrocarbyl group Chemical group 0.000 claims description 27
- 229910052736 halogen Inorganic materials 0.000 claims description 23
- 150000002367 halogens Chemical class 0.000 claims description 23
- 229910052739 hydrogen Inorganic materials 0.000 claims description 21
- 239000001257 hydrogen Substances 0.000 claims description 21
- 239000000178 monomer Substances 0.000 claims description 21
- 229910052723 transition metal Inorganic materials 0.000 claims description 19
- 150000003624 transition metals Chemical class 0.000 claims description 19
- 125000003342 alkenyl group Chemical group 0.000 claims description 15
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 14
- 125000003118 aryl group Chemical group 0.000 claims description 13
- 125000001424 substituent group Chemical group 0.000 claims description 12
- 150000001875 compounds Chemical class 0.000 claims description 10
- 125000002877 alkyl aryl group Chemical group 0.000 claims description 9
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 9
- GQEZCXVZFLOKMC-UHFFFAOYSA-N 1-hexadecene Chemical compound CCCCCCCCCCCCCCC=C GQEZCXVZFLOKMC-UHFFFAOYSA-N 0.000 claims description 8
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 8
- 150000002431 hydrogen Chemical class 0.000 claims description 7
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 claims description 7
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 claims description 6
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 claims description 6
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 6
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 6
- SVSARCCKBMZNMR-UHFFFAOYSA-N [1-[2-[methyl-[2-[4-(oxoazaniumylmethylidene)pyridin-1-yl]ethyl]amino]ethyl]pyridin-4-ylidene]methyl-oxoazanium;dichloride Chemical compound [Cl-].[Cl-].C1=CC(=C[NH+]=O)C=CN1CCN(C)CCN1C=CC(=C[NH+]=O)C=C1 SVSARCCKBMZNMR-UHFFFAOYSA-N 0.000 claims description 6
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 claims description 6
- 125000005842 heteroatom Chemical group 0.000 claims description 5
- 239000002879 Lewis base Substances 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 4
- 239000000377 silicon dioxide Substances 0.000 claims description 4
- HMDQPBSDHHTRNI-UHFFFAOYSA-N 1-(chloromethyl)-3-ethenylbenzene Chemical compound ClCC1=CC=CC(C=C)=C1 HMDQPBSDHHTRNI-UHFFFAOYSA-N 0.000 claims description 3
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 3
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 claims description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 3
- 229910052796 boron Inorganic materials 0.000 claims description 3
- 229910052795 boron group element Inorganic materials 0.000 claims description 3
- 229910052747 lanthanoid Inorganic materials 0.000 claims description 3
- 150000002602 lanthanoids Chemical class 0.000 claims description 3
- 239000000395 magnesium oxide Substances 0.000 claims description 3
- 230000007935 neutral effect Effects 0.000 claims description 3
- 230000000379 polymerizing effect Effects 0.000 claims description 3
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 claims description 2
- HFDVRLIODXPAHB-UHFFFAOYSA-N 1-tetradecene Chemical compound CCCCCCCCCCCCC=C HFDVRLIODXPAHB-UHFFFAOYSA-N 0.000 claims 2
- OJOWICOBYCXEKR-KRXBUXKQSA-N (5e)-5-ethylidenebicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(=C/C)/CC1C=C2 OJOWICOBYCXEKR-KRXBUXKQSA-N 0.000 claims 1
- CRSBERNSMYQZNG-UHFFFAOYSA-N 1 -dodecene Natural products CCCCCCCCCCC=C CRSBERNSMYQZNG-UHFFFAOYSA-N 0.000 claims 1
- UDMMZSJNHAWYKX-UHFFFAOYSA-N 4-phenylbicyclo[2.2.1]hept-2-ene Chemical compound C1C(C=C2)CCC21C1=CC=CC=C1 UDMMZSJNHAWYKX-UHFFFAOYSA-N 0.000 claims 1
- INYHZQLKOKTDAI-UHFFFAOYSA-N 5-ethenylbicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(C=C)CC1C=C2 INYHZQLKOKTDAI-UHFFFAOYSA-N 0.000 claims 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 claims 1
- 229940069096 dodecene Drugs 0.000 claims 1
- SJYNFBVQFBRSIB-UHFFFAOYSA-N norbornadiene Chemical compound C1=CC2C=CC1C2 SJYNFBVQFBRSIB-UHFFFAOYSA-N 0.000 claims 1
- JFNLZVQOOSMTJK-KNVOCYPGSA-N norbornene Chemical compound C1[C@@H]2CC[C@H]1C=C2 JFNLZVQOOSMTJK-KNVOCYPGSA-N 0.000 claims 1
- 238000006116 polymerization reaction Methods 0.000 abstract description 20
- 230000003197 catalytic effect Effects 0.000 abstract description 14
- 230000000694 effects Effects 0.000 abstract description 7
- 230000001747 exhibiting effect Effects 0.000 abstract description 6
- 230000000704 physical effect Effects 0.000 abstract description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 30
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 23
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 22
- 239000000243 solution Substances 0.000 description 22
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 21
- 239000011541 reaction mixture Substances 0.000 description 19
- 238000002360 preparation method Methods 0.000 description 17
- 238000005481 NMR spectroscopy Methods 0.000 description 15
- 239000003446 ligand Substances 0.000 description 15
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 14
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 13
- 239000005977 Ethylene Substances 0.000 description 13
- 238000006243 chemical reaction Methods 0.000 description 13
- 238000004519 manufacturing process Methods 0.000 description 12
- 239000007795 chemical reaction product Substances 0.000 description 11
- 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 11
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 9
- 239000012044 organic layer Substances 0.000 description 9
- 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 7
- 238000007334 copolymerization reaction Methods 0.000 description 6
- JLTDJTHDQAWBAV-UHFFFAOYSA-O dimethyl(phenyl)azanium Chemical compound C[NH+](C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-O 0.000 description 6
- 238000009826 distribution Methods 0.000 description 6
- 229920001519 homopolymer Polymers 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- KXYGKDBONOVZOM-UHFFFAOYSA-N 1h-cyclopenta[a]naphthalene Chemical compound C1=CC=CC2=C3CC=CC3=CC=C21 KXYGKDBONOVZOM-UHFFFAOYSA-N 0.000 description 5
- 239000012968 metallocene catalyst Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 0 C*C1(*C)C(*(C)C)=C(*C)C(C)=C1C Chemical compound C*C1(*C)C(*(C)C)=C(*C)C(C)=C1C 0.000 description 4
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 4
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical group C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 4
- OPRLLAPOGFQRMV-UHFFFAOYSA-N dichloromethyl-[6-[(2-methylpropan-2-yl)oxy]hexyl]silane Chemical compound C(C)(C)(C)OCCCCCC[SiH2]C(Cl)Cl OPRLLAPOGFQRMV-UHFFFAOYSA-N 0.000 description 4
- 239000000706 filtrate Substances 0.000 description 4
- 239000005457 ice water Substances 0.000 description 4
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YSSHVZSQQGCSMS-UHFFFAOYSA-N N-[chloro-methyl-[6-[(2-methylpropan-2-yl)oxy]hexyl]silyl]-2-methylpropan-2-amine Chemical compound C(C)(C)(C)OCCCCCC[Si](NC(C)(C)C)(C)Cl YSSHVZSQQGCSMS-UHFFFAOYSA-N 0.000 description 3
- 229910004298 SiO 2 Inorganic materials 0.000 description 3
- 125000003277 amino group Chemical group 0.000 description 3
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 125000003454 indenyl group Chemical group C1(C=CC2=CC=CC=C12)* 0.000 description 3
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical compound C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 229910052719 titanium Inorganic materials 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- RURFJXKOXIWFJX-UHFFFAOYSA-N (2,3,4,6-tetrafluorophenoxy)boronic acid Chemical compound OB(O)OC1=C(F)C=C(F)C(F)=C1F RURFJXKOXIWFJX-UHFFFAOYSA-N 0.000 description 2
- PMJHHCWVYXUKFD-SNAWJCMRSA-N (E)-1,3-pentadiene Chemical compound C\C=C\C=C PMJHHCWVYXUKFD-SNAWJCMRSA-N 0.000 description 2
- PMMZKEMRDBTRNX-UHFFFAOYSA-N 1,2-dihydrocyclopenta[a]naphthalen-3-one Chemical compound C1=CC2=CC=CC=C2C2=C1C(=O)CC2 PMMZKEMRDBTRNX-UHFFFAOYSA-N 0.000 description 2
- CLILMZOQZSMNTE-UHFFFAOYSA-N 1-chloro-6-[(2-methylpropan-2-yl)oxy]hexane Chemical compound CC(C)(C)OCCCCCCCl CLILMZOQZSMNTE-UHFFFAOYSA-N 0.000 description 2
- OILJRBUAWLPLRD-UHFFFAOYSA-N 2,3-dihydro-1h-cyclopenta[a]naphthalen-3-ol Chemical compound C1=CC2=CC=CC=C2C2=C1C(O)CC2 OILJRBUAWLPLRD-UHFFFAOYSA-N 0.000 description 2
- YPYDTDWNFCCRCH-UHFFFAOYSA-N 2-methyl-1,2-dihydrocyclopenta[a]naphthalen-3-one Chemical compound C1=CC=C2C(CC(C3=O)C)=C3C=CC2=C1 YPYDTDWNFCCRCH-UHFFFAOYSA-N 0.000 description 2
- NJHHIOOKFSESTG-UHFFFAOYSA-N 2-methyl-1h-cyclopenta[a]naphthalene Chemical compound C1=CC=CC2=C(CC(C)=C3)C3=CC=C21 NJHHIOOKFSESTG-UHFFFAOYSA-N 0.000 description 2
- RUBFEGSKABOQBU-UHFFFAOYSA-N 2-methyl-2,3-dihydro-1h-cyclopenta[a]naphthalen-3-ol Chemical compound C1=CC=C2C(CC(C3O)C)=C3C=CC2=C1 RUBFEGSKABOQBU-UHFFFAOYSA-N 0.000 description 2
- BOPNREWBDVBOKN-UHFFFAOYSA-N 3-chloro-1-naphthalen-2-ylpropan-1-one Chemical compound C1=CC=CC2=CC(C(=O)CCCl)=CC=C21 BOPNREWBDVBOKN-UHFFFAOYSA-N 0.000 description 2
- NGNVPXGUUCHTCV-UHFFFAOYSA-N 3-chloro-2-methyl-1-naphthalen-2-ylpropan-1-one Chemical compound ClCC(C(=O)C1=CC2=CC=CC=C2C=C1)C NGNVPXGUUCHTCV-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 229910007926 ZrCl Inorganic materials 0.000 description 2
- 239000012190 activator Substances 0.000 description 2
- 125000002178 anthracenyl group Chemical group C1(=CC=CC2=CC3=CC=CC=C3C=C12)* 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- UORVGPXVDQYIDP-UHFFFAOYSA-N borane Chemical compound B UORVGPXVDQYIDP-UHFFFAOYSA-N 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
- 229920001577 copolymer Polymers 0.000 description 2
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 2
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 229910052735 hafnium Inorganic materials 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 229910001092 metal group alloy Inorganic materials 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000001624 naphthyl group Chemical group 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 125000005373 siloxane group Chemical group [SiH2](O*)* 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- YBRBMKDOPFTVDT-UHFFFAOYSA-N tert-butylamine Chemical compound CC(C)(C)N YBRBMKDOPFTVDT-UHFFFAOYSA-N 0.000 description 2
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- 229910052726 zirconium Inorganic materials 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
- IIYJCOKOQWJTHO-PKNBQFBNSA-N (e)-hexadec-5-ene Chemical compound CCCCCCCCCC\C=C\CCCC IIYJCOKOQWJTHO-PKNBQFBNSA-N 0.000 description 1
- PAAZPARNPHGIKF-UHFFFAOYSA-N 1,2-dibromoethane Chemical compound BrCCBr PAAZPARNPHGIKF-UHFFFAOYSA-N 0.000 description 1
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 1
- 125000001637 1-naphthyl group Chemical group [H]C1=C([H])C([H])=C2C(*)=C([H])C([H])=C([H])C2=C1[H] 0.000 description 1
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- YVSMQHYREUQGRX-UHFFFAOYSA-N 2-ethyloxaluminane Chemical compound CC[Al]1CCCCO1 YVSMQHYREUQGRX-UHFFFAOYSA-N 0.000 description 1
- REBZXOIBOIJEAU-UHFFFAOYSA-N 3-chloro-2-methylpropanoyl chloride Chemical compound ClCC(C)C(Cl)=O REBZXOIBOIJEAU-UHFFFAOYSA-N 0.000 description 1
- INUNLMUAPJVRME-UHFFFAOYSA-N 3-chloropropanoyl chloride Chemical compound ClCCC(Cl)=O INUNLMUAPJVRME-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- GKTIJCCNDGIEOE-UHFFFAOYSA-N CCCCCCCCCCCCCCCCN(C)C.FC(C(F)=C1F)=C(C(C=CC=C2)=C2[N+](C(C(F)=C(C(F)=C2F)F)=C2F)(C(C(F)=C(C(F)=C2F)F)=C2F)C(C(F)=C(C(F)=C2F)F)=C2F)C(F)=C1F Chemical compound CCCCCCCCCCCCCCCCN(C)C.FC(C(F)=C1F)=C(C(C=CC=C2)=C2[N+](C(C(F)=C(C(F)=C2F)F)=C2F)(C(C(F)=C(C(F)=C2F)F)=C2F)C(C(F)=C(C(F)=C2F)F)=C2F)C(F)=C1F GKTIJCCNDGIEOE-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 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
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- MBDHLQKZIVIDEY-UHFFFAOYSA-N Olivin Natural products COc1cc(C=C(C)/C(=O)c2c(O)cc(O)cc2O)ccc1O MBDHLQKZIVIDEY-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- QQZWQOQLMGMKDC-UHFFFAOYSA-N [4-[tert-butyl(dimethyl)silyl]-2,3,5,6-tetrafluorophenoxy]boronic acid Chemical compound CC(C)(C)[Si](C)(C)C1=C(F)C(F)=C(OB(O)O)C(F)=C1F QQZWQOQLMGMKDC-UHFFFAOYSA-N 0.000 description 1
- SBDDCRVWXZUWON-UHFFFAOYSA-L [Cl-].[Cl-].[Ti+2].C1(C=CC=2C1=C1C=CC=CC1=CC2)[Si](C)(CCCCCCOC(C)(C)C)NC(C)(C)C Chemical compound [Cl-].[Cl-].[Ti+2].C1(C=CC=2C1=C1C=CC=CC1=CC2)[Si](C)(CCCCCCOC(C)(C)C)NC(C)(C)C SBDDCRVWXZUWON-UHFFFAOYSA-L 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 125000005024 alkenyl aryl group Chemical group 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000005370 alkoxysilyl group Chemical group 0.000 description 1
- 125000005234 alkyl aluminium group Chemical group 0.000 description 1
- 125000000304 alkynyl group Chemical group 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 125000004104 aryloxy group Chemical group 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 125000002619 bicyclic group Chemical group 0.000 description 1
- 229910000085 borane Inorganic materials 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 238000012662 bulk polymerization Methods 0.000 description 1
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 1
- 125000004369 butenyl group Chemical group C(=CCC)* 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- DOBRDRYODQBAMW-UHFFFAOYSA-N copper(i) cyanide Chemical compound [Cu+].N#[C-] DOBRDRYODQBAMW-UHFFFAOYSA-N 0.000 description 1
- 125000006165 cyclic alkyl group Chemical group 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 125000003113 cycloheptyloxy group Chemical group C1(CCCCCC1)O* 0.000 description 1
- 125000000596 cyclohexenyl group Chemical group C1(=CCCCC1)* 0.000 description 1
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- UWGIJJRGSGDBFJ-UHFFFAOYSA-N dichloromethylsilane Chemical compound [SiH3]C(Cl)Cl UWGIJJRGSGDBFJ-UHFFFAOYSA-N 0.000 description 1
- JGHYBJVUQGTEEB-UHFFFAOYSA-M dimethylalumanylium;chloride Chemical compound C[Al](C)Cl JGHYBJVUQGTEEB-UHFFFAOYSA-M 0.000 description 1
- ORVACBDINATSAR-UHFFFAOYSA-N dimethylaluminum Chemical compound C[Al]C ORVACBDINATSAR-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000002474 experimental method 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
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 125000002510 isobutoxy group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])O* 0.000 description 1
- 125000003253 isopropoxy group Chemical group [H]C([H])([H])C([H])(O*)C([H])([H])[H] 0.000 description 1
- 150000007527 lewis bases Chemical class 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- BQBCXNQILNPAPX-UHFFFAOYSA-N methoxy(dimethyl)alumane Chemical compound [O-]C.C[Al+]C BQBCXNQILNPAPX-UHFFFAOYSA-N 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 125000002950 monocyclic group Chemical group 0.000 description 1
- JZBZLRKFJWQZHU-UHFFFAOYSA-N n,n,2,4,6-pentamethylaniline Chemical compound CN(C)C1=C(C)C=C(C)C=C1C JZBZLRKFJWQZHU-UHFFFAOYSA-N 0.000 description 1
- 125000006606 n-butoxy group Chemical group 0.000 description 1
- UWHRNIXHZAWBMF-UHFFFAOYSA-N n-dodecyl-n-methyldodecan-1-amine Chemical compound CCCCCCCCCCCCN(C)CCCCCCCCCCCC UWHRNIXHZAWBMF-UHFFFAOYSA-N 0.000 description 1
- 125000003136 n-heptyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001298 n-hexoxy group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])O* 0.000 description 1
- 125000003506 n-propoxy group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])O* 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
- PIHTXGRVQBTVRE-KFYAXVMHSA-N olivin Chemical compound OC1=CC(O)=C2C(O)=C(C(=O)[C@H]([C@H]([C@H](OC)C(=O)[C@@H](O)[C@@H](C)O)C3)O)C3=CC2=C1 PIHTXGRVQBTVRE-KFYAXVMHSA-N 0.000 description 1
- 125000001181 organosilyl group Chemical group [SiH3]* 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 125000000538 pentafluorophenyl group Chemical group FC1=C(F)C(F)=C(*)C(F)=C1F 0.000 description 1
- 125000002255 pentenyl group Chemical group C(=CCCC)* 0.000 description 1
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 1
- 125000004344 phenylpropyl group Chemical group 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 125000004368 propenyl group Chemical group C(=CC)* 0.000 description 1
- LISFMEBWQUVKPJ-UHFFFAOYSA-N quinolin-2-ol Chemical compound C1=CC=C2NC(=O)C=CC2=C1 LISFMEBWQUVKPJ-UHFFFAOYSA-N 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- SQBBHCOIQXKPHL-UHFFFAOYSA-N tributylalumane Chemical compound CCCC[Al](CCCC)CCCC SQBBHCOIQXKPHL-UHFFFAOYSA-N 0.000 description 1
- DWAWYEUJUWLESO-UHFFFAOYSA-N trichloromethylsilane Chemical compound [SiH3]C(Cl)(Cl)Cl DWAWYEUJUWLESO-UHFFFAOYSA-N 0.000 description 1
- ZMANZCXQSJIPKH-UHFFFAOYSA-O triethylammonium ion Chemical compound CC[NH+](CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-O 0.000 description 1
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 description 1
- 125000000025 triisopropylsilyl group Chemical group C(C)(C)[Si](C(C)C)(C(C)C)* 0.000 description 1
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 description 1
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 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
- ANEFWEBMQHRDLH-UHFFFAOYSA-N tris(2,3,4,5,6-pentafluorophenyl) borate Chemical compound FC1=C(F)C(F)=C(F)C(F)=C1OB(OC=1C(=C(F)C(F)=C(F)C=1F)F)OC1=C(F)C(F)=C(F)C(F)=C1F ANEFWEBMQHRDLH-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
- 150000003682 vanadium compounds Chemical class 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 239000004711 α-olefin Substances 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
-
- C07F7/006—
-
- 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
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/28—Titanium compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/02—Carriers therefor
- C08F4/025—Metal oxides
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Abstract
본 발명에 따르면, 올레핀 중합 반응에서 높은 활성을 나타낼 수 있을 뿐만 아니라, 합성되는 올레핀 중합체의 물성을 용이하게 조절할 수 있는 전이 금속 화합물, 이를 포함하는 촉매 조성물 및 상기 촉매 조성물을 이용한 올레핀 중합체의 제조 방법이 제공될 수 있다. 상기 전이 금속 화합물을 이용하면 높은 촉매 활성을 나타내면서 다양한 분자량 범위 내에서 높은 겉보기 밀도를 갖는 올레핀 중합체를 제공할 수 있다.According to the present invention, there can be provided a transition metal compound capable of exhibiting high activity in the olefin polymerization reaction and easily controlling the physical properties of the synthesized olefin polymer, a catalyst composition containing the same, and a process for producing an olefin polymer using the catalyst composition Can be provided. When the transition metal compound is used, it is possible to provide an olefin polymer having a high apparent density within various molecular weight ranges while exhibiting a high catalytic activity.
Description
본 발명은 전이 금속 화합물, 상기 전이 금속 화합물을 포함하는 촉매 조성물 및 상기 촉매 조성물을 이용한 올레핀 중합체의 제조 방법에 관한 것이다. The present invention relates to a transition metal compound, a catalyst composition comprising the transition metal compound, and a process for preparing an olefin polymer using the catalyst composition.
기존의 폴리올레핀의 상업적 제조 과정에는 티타늄 또는 바나듐 화합물의 지글러-나타 촉매가 널리 사용되어 왔는데, 상기 지글러-나타 촉매는 높은 활성을 갖지만, 다활성점 촉매이기 때문에 생성 고분자의 분자량 분포가 넓으며 공단량체의 조성 분포가 균일하지 않아 원하는 물성 확보에 한계가 있었다.Ziegler-Natta catalysts of titanium or vanadium compounds have been widely used for the commercial production of polyolefins. Although the Ziegler-Natta catalysts have high activity, they have a wide molecular weight distribution of the produced polymers because of their high activity, The uniformity of the composition is not uniform and there is a limit in ensuring desired physical properties.
이에 따라, 최근에는 티타늄, 지르코늄, 하프늄 등의 전이 금속과 사이클로펜타디엔 작용기를 포함하는 리간드가 결합된 메탈로센 촉매가 개발되어 널리 사용되고 있다. 메탈로센 화합물은 일반적으로 알루미녹산, 보레인, 보레이트 또는 다른 활성화제를 이용하여 활성화시켜 사용한다. 예를 들어, 사이클로펜타다이에닐기를 포함한 리간드와 두 개의 시그마 클로라이드 리간드를 갖는 메탈로센 화합물은 알루미녹산을 활성화제로 사용한다. 이러한 메탈로센 촉매는 한 종류의 활성점을 가진 단일 활성점 촉매로 생성 중합체의 분자량 분포가 좁은 특징이 있다. 이에 따라, 올레핀 중합체의 분자량, 분자량 분포, 공단량체의 조성 등의 특성을 용이하게 조절할 수 있는 다양한 메탈로센 촉매의 개발이 요구되고 있다. Accordingly, recently, a metallocene catalyst in which a transition metal such as titanium, zirconium, or hafnium and a ligand containing a cyclopentadiene functional group are bonded has been developed and widely used. The metallocene compound is generally activated by using aluminoxane, borane, borate or other activator. For example, a metallocene compound having a ligand containing a cyclopentadienyl group and two sigma chloride ligands uses aluminoxane as an activator. These metallocene catalysts are characterized by a narrow molecular weight distribution of the resulting polymer as a single active site catalyst having one kind of active site. Accordingly, development of a variety of metallocene catalysts capable of easily controlling the molecular weight, molecular weight distribution, composition of the comonomer, and the like of the olefin polymer has been demanded.
본 발명은 뛰어난 촉매 활성을 나타내며 다양한 분자량 범위 내에서 높은 겉보기 밀도를 갖는 올레핀 중합체를 제공할 수 있는 전이 금속 화합물을 제공한다. The present invention provides a transition metal compound which exhibits excellent catalytic activity and can provide an olefin polymer having a high apparent density in various molecular weight ranges.
또한, 본 발명은 상기 전이 금속 화합물을 포함하는 촉매 조성물과 상기 촉매 조성물을 이용한 올레핀 중합체의 제조 방법을 제공한다. The present invention also provides a catalyst composition comprising the transition metal compound and a process for preparing an olefin polymer using the catalyst composition.
발명의 일 구현예에 따르면, 하기 화학식 1로 표시되는 전이 금속 화합물이 제공된다. According to one embodiment of the invention, there is provided a transition metal compound represented by the following formula (1).
[화학식 1][Chemical Formula 1]
상기 화학식 1에서,In Formula 1,
M1은 3족 전이 금속, 4족 전이 금속, 5족 전이 금속, 란타나이드 계열의 전이 금속 및 악타나이드 계열의 전이 금속 중 어느 하나이고,M 1 is any one of a Group 3 transition metal, a Group 4 transition metal, a Group 5 transition metal, a lanthanide series transition metal, and an ethanide series transition metal,
X1 및 X2는 서로 동일하거나 상이하며 각각 독립적으로 할로겐 및 탄소수 1 내지 20의 알킬 중 어느 하나이고,X 1 and X 2 are the same or different from each other and are each independently any one of halogen and alkyl of 1 to 20 carbon atoms,
A는 14족의 원소 중 어느 하나이며, n은 1 내지 20 사이의 정수이고,A is any one of the elements of Group 14, n is an integer of 1 to 20,
R1은 탄소수 1 내지 20의 알킬, 탄소수 2 내지 20의 알케닐, 탄소수 7 내지 30의 알킬아릴, 탄소수 7 내지 30의 아릴알킬 및 탄소수 6 내지 30의 아릴 중 어느 하나이며,R 1 is any one of alkyl having 1 to 20 carbon atoms, alkenyl having 2 to 20 carbon atoms, alkylaryl having 7 to 30 carbon atoms, arylalkyl having 7 to 30 carbon atoms, and aryl having 6 to 30 carbon atoms,
R2는 수소, 탄소수 1 내지 20의 알킬, 탄소수 2 내지 20의 알케닐, 탄소수 7 내지 30의 알킬아릴, 탄소수 7 내지 30의 아릴알킬 및 탄소수 6 내지 30의 아릴 중 어느 하나이고,R 2 is any one of hydrogen, alkyl having 1 to 20 carbon atoms, alkenyl having 2 to 20 carbon atoms, alkylaryl having 7 to 30 carbon atoms, arylalkyl having 7 to 30 carbon atoms, and aryl having 6 to 30 carbon atoms,
R3 및 R4는 각각 독립적으로 수소, 헤테로 원자로 치환되거나 치환되지 않은 탄소수 1 내지 20의 알킬 중 어느 하나이고, R 3 and R 4 are each independently hydrogen or alkyl having 1 to 20 carbon atoms which is optionally substituted with a heteroatom,
C1은 -NR5-, 
상기 R5는 탄소수 1 내지 20의 알킬 중 어느 하나이고, R 5 is any of alkyl having 1 to 20 carbon atoms,
상기 R6 내지 R21은 각각 독립적으로 수소 및 탄소수 1 내지 20의 알킬 중 어느 하나이다.Each of R 6 to R 21 is independently hydrogen or alkyl having 1 to 20 carbon atoms.
구체적으로, 상기 화학식 1에서 R3 및 R4는 각각 독립적으로 수소 및 탄소수 1 내지 5의 직쇄 알킬 중 어느 하나일 수 있다. 상기 화학식 1에서 C1은 -NR5-이고, R5는 탄소수 4 내지 8의 분지쇄 알킬 중 어느 하나일 수 있다. 상기 화학식 1에서 C1은 
한편, 발명의 다른 구현예에 따르면, 상기 화학식 1로 표시되는 전이 금속 화합물을 포함하는 촉매 조성물이 제공된다. According to another embodiment of the present invention, there is provided a catalyst composition comprising the transition metal compound represented by the general formula (1).
상기 촉매 조성물은 하기 화학식 2 내지 4로 표시되는 화합물로 이루어진 군에서 선택된 1 종 이상의 조촉매를 포함할 수 있다.The catalyst composition may include at least one cocatalyst selected from the group consisting of compounds represented by the following general formulas (2) to (4).
[화학식 2](2)
R23-[Al(R22)-O]m-R24 R 23 - [Al (R 22 ) -O] m -R 24
상기 화학식 2에서, In Formula 2,
R22, R23 및 R24는 각각 독립적으로 수소, 할로겐, 탄소수 1 내지 20의 하이드로카빌기 및 할로겐으로 치환된 탄소수 1 내지 20의 하이드로카빌기 중 어느 하나이고,R 22 , R 23 and R 24 are each independently any one of hydrogen, halogen, hydrocarbyl group having 1 to 20 carbon atoms and hydrocarbyl group having 1 to 20 carbon atoms substituted with halogen,
m은 2 이상의 정수이며,m is an integer of 2 or more,
[화학식 3](3)
D(R25)3 D (R 25) 3
상기 화학식 3에서, In Formula 3,
D는 알루미늄 또는 보론이고,D is aluminum or boron,
R25는 각각 독립적으로 할로겐, 탄소수 1 내지 20의 하이드로카빌기, 탄소수 1 내지 20의 하이드로카빌옥시기 및 할로겐으로 치환된 탄소수 1 내지 20의 하이드로카빌기 중 어느 하나이며,R 25 is each independently any one of halogen, a hydrocarbyl group having 1 to 20 carbon atoms, a hydrocarbyloxy group having 1 to 20 carbon atoms, and a hydrocarbyl group having 1 to 20 carbon atoms substituted with halogen,
[화학식 4][Chemical Formula 4]
[L-H]+[W(J)4]- 또는 [L]+[W(J)4]- [LH] + [W (J ) 4] - or [L] + [W (J ) 4] -
상기 화학식 4에서,In Formula 4,
L은 중성 또는 양이온성 루이스 염기이고, L is a neutral or cationic Lewis base,
W는 13족 원소이며, J는 각각 독립적으로 탄소수 1 내지 20의 하이드로카빌기; 탄소수 1 내지 20의 하이드로카빌옥시기; 및 이들 치환기의 1 이상의 수소 원자가 할로겐, 탄소수 1 내지 20의 하이드로카빌옥시기 및 탄소수 1 내지 20의 하이드로카빌(옥시)실릴기 중 1 이상의 치환기로 치환된 치환기들 중 어느 하나이다.W is a Group 13 element, J is independently a hydrocarbyl group having 1 to 20 carbon atoms; A hydrocarbyloxy group having 1 to 20 carbon atoms; And substituents in which at least one hydrogen atom of these substituents is substituted with at least one substituent selected from halogen, a hydrocarbyloxy group having 1 to 20 carbon atoms and a hydrocarbyl (oxy) silyl group having 1 to 20 carbon atoms.
한편, 상기 촉매 조성물은 상기 전이 금속 화합물을 담지하는 담체를 추가로 포함할 수 있다. 상기 담체로는 실리카, 알루미나, 마그네시아 또는 이들의 혼합물이 사용될 수 있다. On the other hand, the catalyst composition may further include a carrier that supports the transition metal compound. As the carrier, silica, alumina, magnesia, or a mixture thereof may be used.
상기 촉매 조성물은 상기 화학식 1의 전이 금속 화합물의 특유한 입체 구조로 인해, 높은 촉매 활성과 다양한 분자량 범위 내에서 높은 겉보기 밀도를 갖는 올레핀 중합체를 제공할 수 있다. The catalyst composition can provide an olefin polymer having a high catalytic activity and a high apparent density in various molecular weight ranges due to the peculiar stereostructure of the transition metal compound of the formula (1).
한편, 발명의 또 다른 구현예에 따르면, 상기 촉매 조성물 존재 하에, 올레핀 단량체를 중합 반응시키는 단계를 포함하는 올레핀 중합체의 제조 방법이 제공된다. According to another embodiment of the present invention, there is provided a process for producing an olefin polymer comprising the step of polymerizing an olefin monomer in the presence of the catalyst composition.
상기 올레핀 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, 1-아이토센, 노보넨, 노보나디엔, 에틸리덴노보덴, 페닐노보덴, 비닐노보덴, 디사이클로펜타디엔, 1,4-부타디엔, 1,5-펜타디엔, 1,6-헥사디엔, 스티렌, 알파-메틸스티렌, 디비닐벤젠 및 3-클로로메틸스티렌으로 이루어진 군으로부터 선택되는 1종 이상을 포함할 수 있다. The olefin monomers may be selected from the group consisting of ethylene, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, Butadiene, 1,5-hexadecene, 1-hexadecene, 1-hexadecene, 1-hexadecene, And at least one member selected from the group consisting of pentadiene, 1,6-hexadiene, styrene, alpha-methylstyrene, divinylbenzene and 3-chloromethylstyrene.
본 발명에 따르면, 올레핀 중합 반응에서 높은 활성을 나타낼 수 있을 뿐만 아니라, 합성되는 올레핀 중합체의 물성을 용이하게 조절할 수 있는 전이 금속 화합물, 이를 포함하는 촉매 조성물 및 상기 촉매 조성물을 이용한 올레핀 중합체의 제조 방법이 제공될 수 있다. 상기 전이 금속 화합물을 이용하면 높은 촉매 활성을 나타내면서 다양한 분자량 범위 내에서 높은 겉보기 밀도를 갖는 올레핀 중합체를 제공할 수 있다.According to the present invention, there can be provided a transition metal compound capable of exhibiting high activity in the olefin polymerization reaction and easily controlling the physical properties of the synthesized olefin polymer, a catalyst composition containing the same, and a process for producing an olefin polymer using the catalyst composition Can be provided. When the transition metal compound is used, it is possible to provide an olefin polymer having a high apparent density within various molecular weight ranges while exhibiting a high catalytic activity.
이하 발명의 구체적인 구현예에 따른 전이 금속 화합물, 이를 포함하는 촉매 조성물 및 상기를 이용하여 올레핀 중합체를 제조하는 방법 등에 대해 설명하기로 한다. Hereinafter, a transition metal compound, a catalyst composition containing the same, and a method for producing an olefin polymer using the catalyst will be described.
발명의 일 구현예에 따르면, 하기 화학식 1로 표시되는 전이 금속 화합물이 제공된다. According to one embodiment of the invention, there is provided a transition metal compound represented by the following formula (1).
[화학식 1][Chemical Formula 1]
상기 화학식 1에서,In Formula 1,
M1은 3족 전이 금속, 4족 전이 금속, 5족 전이 금속, 란타나이드 계열의 전이 금속 및 악타나이드 계열의 전이 금속 중 어느 하나이고,M 1 is any one of a Group 3 transition metal, a Group 4 transition metal, a Group 5 transition metal, a lanthanide series transition metal, and an ethanide series transition metal,
X1 및 X2는 서로 동일하거나 상이하며 각각 독립적으로 할로겐 및 탄소수 1 내지 20의 알킬 중 어느 하나이고,X 1 and X 2 are the same or different from each other and are each independently any one of halogen and alkyl of 1 to 20 carbon atoms,
A는 14족의 원소 중 어느 하나이며, n은 1 내지 20 사이의 정수이고,A is any one of the elements of Group 14, n is an integer of 1 to 20,
R1은 탄소수 1 내지 20의 알킬, 탄소수 2 내지 20의 알케닐, 탄소수 7 내지 30의 알킬아릴, 탄소수 7 내지 30의 아릴알킬 및 탄소수 6 내지 30의 아릴 중 어느 하나이며,R 1 is any one of alkyl having 1 to 20 carbon atoms, alkenyl having 2 to 20 carbon atoms, alkylaryl having 7 to 30 carbon atoms, arylalkyl having 7 to 30 carbon atoms, and aryl having 6 to 30 carbon atoms,
R2는 수소, 탄소수 1 내지 20의 알킬, 탄소수 2 내지 20의 알케닐, 탄소수 7 내지 30의 알킬아릴, 탄소수 7 내지 30의 아릴알킬 및 탄소수 6 내지 30의 아릴 중 어느 하나이고,R 2 is any one of hydrogen, alkyl having 1 to 20 carbon atoms, alkenyl having 2 to 20 carbon atoms, alkylaryl having 7 to 30 carbon atoms, arylalkyl having 7 to 30 carbon atoms, and aryl having 6 to 30 carbon atoms,
R3 및 R4는 각각 독립적으로 수소, 헤테로 원자로 치환되거나 치환되지 않은 탄소수 1 내지 20의 알킬 중 어느 하나이고, R 3 and R 4 are each independently hydrogen or alkyl having 1 to 20 carbon atoms which is optionally substituted with a heteroatom,
C1은 -NR5-, 
상기 R5는 탄소수 1 내지 20의 알킬 중 어느 하나이고,R 5 is any of alkyl having 1 to 20 carbon atoms,
상기 R6 내지 R21은 각각 독립적으로 수소 및 탄소수 1 내지 20의 알킬 중 어느 하나이다. Each of R 6 to R 21 is independently hydrogen or alkyl having 1 to 20 carbon atoms.
본 명세서에서 특별한 제한이 없는 한 다음 용어는 하기와 같이 정의될 수 있다. Unless defined otherwise herein, the following terms may be defined as follows.
할로겐(halogen)은 불소(F), 염소(Cl), 브롬(Br) 또는 요오드(I)일 수 있다.The halogen may be fluorine (F), chlorine (Cl), bromine (Br) or iodine (I).
탄소수 1 내지 20의 알킬은 직쇄, 분지쇄 또는 고리형 알킬일 수 있다. 구체적으로, 탄소수 1 내지 20의 알킬은 탄소수 1 내지 20의 직쇄 알킬; 탄소수 1 내지 10의 직쇄 알킬; 탄소수 1 내지 5의 직쇄 알킬; 탄소수 3 내지 20의 분지쇄 또는 고리형 알킬; 탄소수 3 내지 15의 분지쇄 또는 고리형 알킬; 또는 탄소수 3 내지 10의 분지쇄 또는 고리형 알킬일 수 있다. 보다 구체적으로, 탄소수 1 내지 20의 알킬은 메틸기, 에틸기, n-프로필기, iso-프로필기, n-부틸기, iso-부틸기, tert-부틸기, n-펜틸기, iso-펜틸기 또는 사이클로헥실기 등일 수 있다.The alkyl having 1 to 20 carbon atoms may be straight chain, branched chain or cyclic alkyl. Specifically, alkyl of 1 to 20 carbon atoms is straight chain alkyl of 1 to 20 carbon atoms; Straight chain alkyl having 1 to 10 carbon atoms; Straight chain alkyl of 1 to 5 carbon atoms; Branched or cyclic alkyl having 3 to 20 carbon atoms; Branched or cyclic alkyl having 3 to 15 carbon atoms; Or branched or cyclic alkyl having 3 to 10 carbon atoms. More specifically, the alkyl having 1 to 20 carbon atoms is preferably a methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, Cyclohexyl group and the like.
헤테로 원자로 치환된 탄소수 1 내지 20의 알킬은 하나 이상의 -CH2-가 헤테로 원자들이 직접 연결되지 않도록 -O-, -NH- -S-로 대체된 라디칼 혹은 하나 이상의 H가 할로겐으로 치환된 라디칼이다.Alkyl having 1 to 20 carbon atoms substituted with a heteroatom is a radical in which at least one -CH 2 - is replaced by -O-, -NH- -S- or one or more H is substituted with halogen, so that the heteroatoms are not directly connected .
탄소수 2 내지 20의 알케닐은 직쇄, 분지쇄 또는 고리형 알케닐일 수 있다. 구체적으로, 탄소수 2 내지 20의 알케닐은 탄소수 2 내지 20의 직쇄 알케닐, 탄소수 2 내지 10의 직쇄 알케닐, 탄소수 2 내지 5의 직쇄 알케닐, 탄소수 3 내지 20의 분지쇄 알케닐, 탄소수 3 내지 15의 분지쇄 알케닐, 탄소수 3 내지 10의 분지쇄 알케닐, 탄소수 5 내지 20의 고리형 알케닐 또는 탄소수 5 내지 10의 고리형 알케닐일 수 있다. 보다 구체적으로, 탄소수 2 내지 20의 알케닐은 에테닐, 프로페닐, 부테닐, 펜테닐 또는 사이클로헥세닐 등일 수 있다.The alkenyl having 2 to 20 carbon atoms may be straight-chain, branched-chain or cyclic alkenyl. Specific examples of the alkenyl having 2 to 20 carbon atoms include straight chain alkenyl having 2 to 20 carbon atoms, straight chain alkenyl having 2 to 10 carbon atoms, straight chain alkenyl having 2 to 5 carbon atoms, branched alkenyl having 3 to 20 carbon atoms, Branched chain alkenyl having 3 to 10 carbon atoms, cyclic alkenyl having 5 to 20 carbon atoms, or cyclic alkenyl having 5 to 10 carbon atoms. More specifically, the alkenyl having 2 to 20 carbon atoms can be ethenyl, propenyl, butenyl, pentenyl or cyclohexenyl, and the like.
탄소수 6 내지 30의 아릴은 모노사이클릭, 바이사이클릭 또는 트라이사이클릭 방향족 탄화수소를 의미할 수 있다. 구체적으로, 탄소수 6 내지 30의 아릴은 페닐기, 나프틸기 또는 안트라세닐기 등일 수 있다.The aryl having from 6 to 30 carbon atoms may mean a monocyclic, bicyclic or tricyclic aromatic hydrocarbon. Specifically, aryl having 6 to 30 carbon atoms may be a phenyl group, a naphthyl group, or an anthracenyl group.
탄소수 7 내지 30의 알킬아릴은 아릴의 1 이상의 수소가 알킬에 의하여 치환된 치환기를 의미할 수 있다. 구체적으로, 탄소수 7 내지 30의 알킬아릴은 메틸페닐, 에틸페닐, n-프로필페닐, iso-프로필페닐, n-부틸페닐, iso-부틸페닐, tert-부틸페닐 또는 사이클로헥실페닐 등일 수 있다. Alkylaryl having 7 to 30 carbon atoms can mean a substituent wherein at least one hydrogen of the aryl is substituted by alkyl. Specifically, the alkylaryl having 7 to 30 carbon atoms may be methylphenyl, ethylphenyl, n-propylphenyl, isopropylphenyl, n-butylphenyl, iso-butylphenyl, tert-butylphenyl or cyclohexylphenyl.
탄소수 7 내지 30의 아릴알킬은 알킬의 1 이상의 수소가 아릴에 의하여 치환된 치환기를 의미할 수 있다. 구체적으로, 탄소수 7 내지 30의 아릴알킬은 벤질기, 페닐프로필 또는 페닐헥실 등일 수 있다.Arylalkyl having 7 to 30 carbon atoms can mean a substituent wherein at least one hydrogen of the alkyl is substituted by aryl. Specifically, arylalkyl having 7 to 30 carbon atoms may be a benzyl group, phenylpropyl, phenylhexyl, or the like.
상기 화학식 1로 표시되는 전이 금속 화합물은 벤조인데닐기와, 아미노기, 플루오레닐기, 인데닐기 또는 사이클로펜타디엔기로 조합된 리간드로 포함하고, 상기 2개의 리간드를 연결하는 브릿지 그룹(bridge group)에 산소-주게(oxygen-donor)로서 루이스 염기의 역할을 할 수 있는 작용기가 포함된 구조를 가진다. 일 예로, 이러한 특정 구조를 가지는 전이 금속 화합물을 적절한 방법으로 활성화시켜 올레핀 단량체의 중합 촉매로 이용하면, 높은 촉매 활성을 나타내며, 다양한 분자량 범위 내에서 높은 겉보기 밀도를 갖는 올레핀 중합체를 제조할 수 있다. The transition metal compound represented by the general formula (1) comprises a benzoindenyl group and a ligand combined with an amino group, a fluorenyl group, an indenyl group or a cyclopentadiene group, and a bridge group connecting the two ligands includes oxygen - It has an oxygen-donor structure containing a functional group capable of acting as a Lewis base. For example, when a transition metal compound having such a specific structure is activated by an appropriate method and used as a polymerization catalyst for olefin monomers, an olefin polymer having high catalytic activity and having a high apparent density in various molecular weight ranges can be produced.
구체적으로, 상기 화학식 1로 표시되는 전이 금속 화합물에서, 벤조인데닐 리간드는 치환되지 않거나 혹은 입체 장애가 적은 치환기로 치환될 수 있다. 이에 따라, 양호한 촉매 활성을 나타내면서 목적하는 입체 구조의 올레핀 중합체를 용이하게 제조할 수 있다. 일 예로, 상기 화학식 1의 R3 및 R4는 각각 독립적으로 수소 및 탄소수 1 내지 5의 직쇄 알킬 중 어느 하나일 수 있다.Specifically, in the transition metal compound represented by the general formula (1), the benzoindenyl ligand may be substituted with a substituent which is not substituted or is less sterically hindered. As a result, an olefin polymer having a desired stereoregular structure can be easily produced while exhibiting good catalytic activity. For example, R 3 and R 4 in Formula 1 may each independently be hydrogen or straight chain alkyl having 1 to 5 carbon atoms.
상기 벤조인데닐 리간드는 아미노기, 플루오레닐기, 인데닐기 또는 사이클로펜타디엔기와 조합될 수 있다. 일 예로, 상기 화학식 1로 표시되는 전이 금속 화합물에서, C1은 -NR5-이고, R5는 탄소수 4 내지 8의 분지쇄 알킬 중 어느 하나일 수 있다. 이러한 구조를 가지는 전이 금속 화합물은 고분자량의 올레핀 중합체를 제공하는데 적합하며, 높은 공중합성을 나타낼 수 있다. The benzoindenyl ligand may be combined with an amino group, a fluorenyl group, an indenyl group or a cyclopentadiene group. For example, in the transition metal compound represented by Formula 1, C 1 is -NR 5 - and R 5 is any of branched alkyl having 4 to 8 carbon atoms. The transition metal compound having such a structure is suitable for providing a high molecular weight olefin polymer and can exhibit high copolymerization.
또한, 다른 일 예로, C1은 
그리고, 상기 화학식 1에서 벤조인데닐 리간드와 아미노기, 플루오레닐기, 인데닐기 또는 사이클로펜타디엔기를 연결하는 브릿지 그룹은 전이 금속 화합물의 촉매 활성 및 담지 안정성에 영향을 미칠 수 있다. 일 예로, 보다 개선된 촉매 활성 및 담지 효율을 위해 화학식 1의 R1은 탄소수 4 내지 6의 분지쇄 알킬 중 어느 하나이고, n은 4 내지 8 사이의 정수일 수 있다. 그리고, 화학식 1의 R2는 탄소수 1 내지 6의 직쇄 알킬 중 어느 하나일 수 있고, A는 C 또는 Si일 수 있다. The bridge group connecting the benzoindenyl ligand and the amino group, the fluorenyl group, the indenyl group or the cyclopentadiene group in the above formula (1) may affect the catalytic activity and the deposition stability of the transition metal compound. For example, R 1 in formula (1) may be any of branched chain alkyl having 4 to 6 carbon atoms and n may be an integer between 4 and 8 for improved catalytic activity and supporting efficiency. R 2 in the formula (1) may be any one of straight chain alkyl having 1 to 6 carbon atoms, and A may be C or Si.
특히, 본 발명자들의 실험 결과, 우수한 촉매 효율을 발현하며 다양한 분자량 범위 내에서 높은 겉보기 밀도를 갖는 올레핀 중합체를 제조하며, 화학식 1의 범위 내에서 리간드의 변화를 통해 올레핀 중합체의 용이한 물성 변화를 구현하기 위해서는, 화학식 1과 같이, 상술한 구조의 리간드가 상술한 구조의 브릿지 그룹으로 연결되어야 함이 확인되었다. 즉, 상술한 구조의 리간드를 포함하더라도 상기 리간드가 상술한 구조의 브릿지 그룹으로 연결되지 않은 전이 금속 화합물을 통해서는 본 발명에서 목적하는 올레핀 중합체가 제조될 수 없음이 확인되었다. Particularly, as a result of experiments conducted by the present inventors, it has been found that an olefin polymer exhibiting excellent catalytic efficiency and having a high apparent density within a wide range of molecular weights can be prepared, and the change in ligand within the range of the general formula It has been confirmed that the ligand of the above-mentioned structure should be linked to the bridge group of the above-mentioned structure, as shown in the general formula (1). That is, it has been confirmed that the olefin polymer of the present invention can not be prepared through the transition metal compound in which the ligand is not connected to the bridge group of the above-mentioned structure even though the ligand is included in the structure described above.
한편, 상기 화학식 1의 M1으로는 4족 전이 금속 중 어느 하나; 혹은 Ti, Zr 및 Hf 중 어느 하나를 사용하여 금속 착물의 보관 안정성을 향상시킬 수 있다. 그리고, X1 및 X2는 서로 동일하거나 상이하며, 각각 독립적으로 할로겐 및 탄소수 1 내지 20의 알킬 중 어느 하나이거나; 혹은 각각 독립적으로 할로겐 및 탄소수 1 내지 10의 알킬 중 어느 하나이거나; 혹은 각각 독립적으로 할로겐 중 어느 하나일 수 있다. Meanwhile, M 1 in the above formula (1) represents any one of the Group 4 transition metals; Or the storage stability of the metal complex can be improved by using any one of Ti, Zr and Hf. And X < 1 > and X < 2 > are the same or different from each other, and are each independently any one of halogen and alkyl having 1 to 20 carbon atoms; Or independently of each other, halogen and alkyl having 1 to 10 carbon atoms; Or independently of each other, halogen.
상기 화학식 1로 표시되는 전이 금속 화합물은 공지의 반응들을 응용하여 합성될 수 있으며, 보다 상세한 합성 방법은 후술하는 제조예 1 등을 참고할 수 있다. The transition metal compound represented by the formula (1) can be synthesized by applying known reactions, and a more detailed synthesis method can be referred to Preparation Example 1 described later.
한편, 발명의 다른 구현예에 따르면, 상기 화학식 1로 표시되는 전이 금속 화합물을 포함하는 촉매 조성물이 제공된다. According to another embodiment of the present invention, there is provided a catalyst composition comprising the transition metal compound represented by the general formula (1).
상기 촉매 조성물은 전이 금속 화합물을 활성화시킬 수 있는 조촉매를 추가로 포함할 수 있다. 이러한 조촉매로는 본 발명이 속하는 기술분야에서 통상적으로 사용하는 것을 특별한 제한 없이 사용할 수 있다. 비제한적인 예로, 상기 조촉매는 하기 화학식 2 내지 4로 표시되는 화합물로 이루어진 군에서 선택되는 1종 이상의 화합물일 수 있다. The catalyst composition may further comprise a cocatalyst capable of activating the transition metal compound. As such a promoter, those conventionally used in the art to which the present invention belongs can be used without any particular limitation. As a non-limiting example, the cocatalyst may be at least one compound selected from the group consisting of compounds represented by the following general formulas (2) to (4).
[화학식 2](2)
R23-[Al(R22)-O]m-R24 R 23 - [Al (R 22 ) -O] m -R 24
상기 화학식 2에서, In Formula 2,
R22, R23 및 R24는 각각 독립적으로 수소, 할로겐, 탄소수 1 내지 20의 하이드로카빌기 및 할로겐으로 치환된 탄소수 1 내지 20의 하이드로카빌기 중 어느 하나이고,R 22 , R 23 and R 24 are each independently any one of hydrogen, halogen, hydrocarbyl group having 1 to 20 carbon atoms and hydrocarbyl group having 1 to 20 carbon atoms substituted with halogen,
m은 2 이상의 정수이며,m is an integer of 2 or more,
[화학식 3](3)
D(R25)3 D (R 25) 3
상기 화학식 3에서, In Formula 3,
D는 알루미늄 또는 보론이고,D is aluminum or boron,
R25는 각각 독립적으로 할로겐, 탄소수 1 내지 20의 하이드로카빌기, 탄소수 1 내지 20의 하이드로카빌옥시기 및 할로겐으로 치환된 탄소수 1 내지 20의 하이드로카빌기 중 어느 하나이며,R 25 is each independently any one of halogen, a hydrocarbyl group having 1 to 20 carbon atoms, a hydrocarbyloxy group having 1 to 20 carbon atoms, and a hydrocarbyl group having 1 to 20 carbon atoms substituted with halogen,
[화학식 4][Chemical Formula 4]
[L-H]+[W(J)4]- 또는 [L]+[W(J)4]- [LH] + [W (J ) 4] - or [L] + [W (J ) 4] -
상기 화학식 4에서,In Formula 4,
L은 중성 또는 양이온성 루이스 염기이고, L is a neutral or cationic Lewis base,
W는 13족 원소이며, J는 각각 독립적으로 탄소수 1 내지 20의 하이드로카빌기; 탄소수 1 내지 20의 하이드로카빌옥시기; 및 이들 치환기의 1 이상의 수소 원자가 할로겐, 탄소수 1 내지 20의 하이드로카빌옥시기 및 탄소수 1 내지 20의 하이드로카빌(옥시)실릴기 중 1 이상의 치환기로 치환된 치환기들 중 어느 하나이다.W is a Group 13 element, J is independently a hydrocarbyl group having 1 to 20 carbon atoms; A hydrocarbyloxy group having 1 to 20 carbon atoms; And substituents in which at least one hydrogen atom of these substituents is substituted with at least one substituent selected from halogen, a hydrocarbyloxy group having 1 to 20 carbon atoms and a hydrocarbyl (oxy) silyl group having 1 to 20 carbon atoms.
본 명세서에서 특별한 제한이 없는 한 다음 용어는 하기와 같이 정의될 수 있다. Unless defined otherwise herein, the following terms may be defined as follows.
하이드로카빌기는 하이드로카본으로부터 수소 원자를 제거한 형태의 1가 작용기로서, 알킬기, 알케닐기, 알키닐기, 아릴기, 아르알킬기, 아르알케닐기, 아르알키닐기, 알킬아릴기, 알케닐아릴기 및 알키닐아릴기 등을 포함할 수 있다. 그리고, 탄소수 1 내지 20의 하이드로카빌기는 탄소수 1 내지 15 또는 탄소수 1 내지 10의 하이드로카빌기일 수 있다. 구체적으로, 탄소수 1 내지 20의 하이드로카빌기는 메틸기, 에틸기, n-프로필기, iso-프로필기, n-부틸기, iso-부틸기, tert-부틸기, n-펜틸기, n-헥실기, n-헵틸기, 사이클로헥실기 등의 직쇄, 분지쇄 또는 고리형 알킬기; 또는 페닐기, 나프틸기, 또는 안트라세닐기 등의 아릴기일 수 있다. The hydrocarbyl group is a monovalent functional group having a hydrogen atom removed from a hydrocarbon and is an alkyl group, an alkenyl group, an alkynyl group, an aryl group, an aralkyl group, an aralkenyl group, an aralkynyl group, an alkylaryl group, an alkenylaryl group, Aryl group, and the like. The hydrocarbyl group having 1 to 20 carbon atoms may be a hydrocarbyl group having 1 to 15 carbon atoms or 1 to 10 carbon atoms. Specifically, the hydrocarbyl group having 1 to 20 carbon atoms is preferably a methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, , an n-heptyl group, a cyclohexyl group, and other straight, branched or cyclic alkyl groups; Or an aryl group such as a phenyl group, a naphthyl group, or an anthracenyl group.
하이드로카빌옥시기는 하이드로카빌기가 산소에 결합한 작용기이다. 구체적으로, 탄소수 1 내지 20의 하이드로카빌옥시기는 탄소수 1 내지 15 또는 탄소수 1 내지 10의 하이드로카빌옥시기일 수 있다. 보다 구체적으로, 탄소수 1 내지 20의 하이드로카빌옥시기는 메톡시기, 에톡시기, n-프로폭시기, iso-프로폭시기, n-부톡시기, iso-부톡시기, tert-부톡시기, n-펜톡시기, n-헥톡시기, n-헵톡시기, 사이클로헥톡시기 등의 직쇄, 분지쇄 또는 고리형 알콕시기; 또는 페녹시기 또는 나프탈렌옥시(naphthalenoxy)기 등의 아릴옥시기일 수 있다. The hydrocarbyloxy group is a functional group in which the hydrocarbyl group is bonded to oxygen. Specifically, the hydrocarbyloxy group having 1 to 20 carbon atoms may be a hydrocarbyloxy group having 1 to 15 carbon atoms or 1 to 10 carbon atoms. More specifically, the hydrocarbyloxy group having 1 to 20 carbon atoms is preferably a methoxy group, an ethoxy group, an n-propoxy group, an iso-propoxy group, a n-butoxy group, an iso-butoxy group, , an n-hexoxy group, an n-heptoxy group, a cycloheptoxy group, and other straight-chain, branched-chain or cyclic alkoxy groups; Or an aryloxy group such as a phenoxy group or a naphthalenoxy group.
하이드로카빌(옥시)실릴기는 -SiH3의 1 내지 3개의 수소가 1 내지 3개의 하이드로카빌기 또는 하이드로카빌옥시기로 치환된 작용기이다. 구체적으로, 탄소수 1 내지 20의 하이드로카빌(옥시)실릴기는, 탄소수 1 내지 15, 탄소수 1 내지 10 또는 탄소수 1 내지 5의 하이드로카빌(옥시)실릴기일 수 있다. 보다 구체적으로, 탄소수 1 내지 20의 하이드로카빌(옥시)실릴기는 메틸실릴기, 다이메틸실릴기, 트라이메틸실릴기, 다이메틸에틸실릴기, 다이에틸메틸실릴기 및 다이메틸프로필실릴기 등의 알킬실릴기; 메톡시실릴기, 다이메톡시실릴기, 트라이메톡시실릴기 및 다이메톡시에톡시실릴기 등의 알콕시실릴기; 메톡시다이메틸실릴기, 다이에톡시메틸실릴기 및 다이메톡시프로필실릴기 등의 알콕시알킬실릴기 등일 수 있다.Hydrocarbyl (oxy) group is a silyl functional group is substituted with one to three of the hydrogen -SiH 3 group one to three dihydro car invoke or hydrocarbyl oxy. Specifically, the hydrocarbyl (oxy) silyl group having 1 to 20 carbon atoms may be a hydrocarbyl (oxy) silyl group having 1 to 15 carbon atoms, 1 to 10 carbon atoms, or 1 to 5 carbon atoms. More specifically, the hydrocarbyl (oxy) silyl group having 1 to 20 carbon atoms is preferably an alkyl group such as a methylsilyl group, a dimethylsilyl group, a trimethylsilyl group, a dimethylethylsilyl group, a diethylmethylsilyl group and a dimethylpropylsilyl group Silyl group; Alkoxysilyl groups such as a methoxysilyl group, a dimethoxysilyl group, a trimethoxysilyl group, and a dimethoxyethoxysilyl group; An alkoxyalkylsilyl group such as a methoxydimethylsilyl group, a diethoxymethylsilyl group, and a dimethoxypropylsilyl group.
상기에서 화학식 2로 표시되는 화합물의 비제한적인 예로는 메틸알루미녹산, 에틸알루미녹산, 이소부틸알루미녹산 또는 tert-부틸알루미녹산 등을 들 수 있다. 그리고, 화학식 3으로 표시되는 화합물의 비제한적인 예로는 트리메틸알루미늄, 트리에틸알루미늄, 트리이소부틸알루미늄, 트리프로필알루미늄, 트리부틸알루미늄, 디메틸클로로알루미늄, 트리이소프로필알루미늄, 트리-sec-부틸알루미늄, 트리사이클로펜틸알루미늄, 트리펜틸알루미늄, 트리이소펜틸알루미늄, 트리헥실알루미늄, 트리옥틸알루미늄, 에틸디메틸알루미늄, 메틸디에틸알루미늄, 트리페닐알루미늄, 트리-p-톨릴알루미늄, 디메틸알루미늄메톡시드 또는 디메틸알루미늄에톡시드 등을 들 수 있다. 마지막으로, 화학식 4로 표시되는 화합물의 비제한적인 예로는 트리메틸암모늄 테트라키스(펜타플루오로페닐)보레이트, 트리에틸암모늄 테트라키스(펜타플루오로페닐)보레이트, N,N-디메틸아닐리늄 테트라키스(펜타플루오로페닐)보레이트, N,N-디메틸아닐리늄 n-부틸트리스(펜타플루오로페닐)보레이트, N,N-디메틸아닐리늄 벤질트리스(펜타플루오로페닐)보레이트, N,N-디메틸아닐리늄 테트라키스(4-(t-부틸디메틸실릴)-2,3,5,6-테트라플루오로페닐)보레이트, N,N-디메틸아닐리늄 테트라키스(4-(트리이소프로필실릴)-2,3,5,6-테트라플루오로페닐)보레이트, N,N-디메틸아닐리늄 펜타플루오로페녹시트리스(펜타플루오로페닐)보레이트, N,N-디메틸-2,4,6-트리메틸아닐리늄 테트라키스(펜타플루오로페닐)보레이트, 트리메틸암모늄 테트라키스(2,3,4,6-테트라플루오로페닐)보레이트, N,N-디메틸아닐리늄 테트라키스(2,3,4,6-테트라플루오로페닐)보레이트, 헥사데실디메틸암모늄 테트라키스(펜타플루오로페닐)보레이트, N-메틸-N-도데실아닐리늄 테트라키스(펜타플루오로페닐)보레이트 또는 메틸디(도데실)암모늄 테트라키스(펜타플루오로페닐)보레이트 등을 들 수 있다. Non-limiting examples of the compound represented by the formula (2) include methyl aluminoxane, ethyl aluminoxane, isobutyl aluminoxane, and tert-butyl aluminoxane. Non-limiting examples of the compound represented by the formula (3) include trimethyl aluminum, triethyl aluminum, triisobutyl aluminum, tripropyl aluminum, tributyl aluminum, dimethyl chloro aluminum, triisopropyl aluminum, Triphenylaluminum, tri-p-tolylaluminum, dimethylaluminum methoxide, or dimethylaluminum in the presence of a catalyst such as a catalyst, Tosid and the like. Finally, non-limiting examples of the compound represented by Formula 4 include trimethylammonium tetrakis (pentafluorophenyl) borate, triethylammonium tetrakis (pentafluorophenyl) borate, N, N-dimethylanilinium tetrakis N, N-dimethylanilinium benzyltris (pentafluorophenyl) borate, N, N-dimethylanilinium n-butyltris (pentafluorophenyl) Tetrakis (4- (t-butyldimethylsilyl) -2,3,5,6-tetrafluorophenyl) borate, N, N-dimethylanilinium tetrakis (4- (triisopropylsilyl) , 5,6-tetrafluorophenyl) borate, N, N-dimethylanilinium pentafluorophenoxy tris (pentafluorophenyl) borate, N, N-dimethyl- 2,4,6- trimethylanilinium tetrakis (Pentafluorophenyl) borate, trimethylammonium tetrakis (2,3,4,6-tetrafluorophenyl ) Borate, N, N-dimethylanilinium tetrakis (2,3,4,6-tetrafluorophenyl) borate, hexadecyldimethylammonium tetrakis (pentafluorophenyl) Anilinium tetrakis (pentafluorophenyl) borate or methyldi (dodecyl) ammonium tetrakis (pentafluorophenyl) borate, and the like.
상기 촉매 조성물은 상술한 전이 금속 화합물이 담체에 담지된 담지 촉매일 수 있다. 상기 화학식 1로 표시되는 전이 금속 화합물은 상술한 구조적 특징을 가져 담체에 안정적으로 담지될 수 있다. 또한, 이러한 전이 금속 화합물이 담지된 담지 촉매는 올레핀 중합에 높은 활성을 나타내며, 다양한 분자량 범위 내에서 높은 겉보기 밀도를 갖는 올레핀 중합체를 용이하게 제공할 수 있다. The catalyst composition may be a supported catalyst in which the above-mentioned transition metal compound is supported on a carrier. The transition metal compound represented by Formula 1 has the above-described structural characteristics and can be stably supported on the carrier. In addition, the supported catalyst carrying such a transition metal compound exhibits high activity in olefin polymerization and can easily provide an olefin polymer having a high apparent density within various molecular weight ranges.
상기 담체로는 표면에 하이드록시기 또는 실록산기를 함유하는 담체를 사용할 수 있다. 구체적으로, 상기 담체로는 고온에서 건조하여 표면에 수분을 제거함으로써 반응성이 큰 하이드록시기 또는 실록산기를 함유하는 담체를 사용할 수 있다. 보다 구체적으로, 상기 담체로는 실리카, 알루미나, 마그네시아 또는 이들의 혼합물 등을 사용할 수 있다. 상기 담체는 고온에서 건조된 것일 수 있고, 이들은 통상적으로 Na2O, K2CO3, BaSO4 및 Mg(NO3)2 등의 산화물, 탄산염, 황산염, 질산염 성분을 포함할 수 있다.As the carrier, a carrier containing a hydroxyl group or a siloxane group on its surface can be used. Specifically, as the carrier, a carrier containing a hydroxyl group or a siloxane group having high reactivity by removing moisture on the surface by drying at a high temperature may be used. More specifically, examples of the carrier include silica, alumina, magnesia, and mixtures thereof. The carrier may be one which has been dried at elevated temperatures and these may typically comprise oxides, carbonates, sulphates and nitrate components such as Na 2 O, K 2 CO 3 , BaSO 4 and Mg (NO 3 ) 2 .
상술한 촉매 조성물은 올레핀 단량체의 중합 반응에 사용되어 높은 촉매 활성을 나타내며, 다양한 분자량 범위 내에서 높은 겉보기 밀도를 갖는 올레핀 중합체를 제공할 수 있다. The above-mentioned catalyst composition can be used for the polymerization reaction of olefin monomers to exhibit high catalytic activity and can provide an olefin polymer having a high apparent density in various molecular weight ranges.
한편, 발명의 다른 구현예에 따르면, 상기 촉매 조성물의 존재 하에, 올레핀 단량체를 중합 반응시키는 단계를 포함하는 올레핀 중합체의 제조 방법이 제공된다.On the other hand, according to another embodiment of the present invention, there is provided a process for producing an olefin polymer comprising the step of polymerizing an olefin monomer in the presence of the catalyst composition.
상술한 바와 같이, 상기 촉매 조성물은 특정 구조로 인하여 기존의 메탈로센 촉매를 이용하여 중합되는 폴리올레핀에 비하여 다양한 분자량 범위 내에서 높은 겉보기 밀도를 갖는 올레핀 중합체를 제공하며, 올레핀 단량체의 중합시 더 높은 활성을 나타낼 수 있다. As described above, the catalyst composition provides an olefin polymer having a high apparent density in various molecular weight ranges as compared with a polyolefin polymerized by using a conventional metallocene catalyst due to its specific structure. Activity.
상기 촉매 조성물로 중합 가능한 올레핀 단량체의 예로는 에틸렌, 알파-올레핀, 사이클릭 올레핀 등이 있으며, 이중 결합을 2개 이상 가지고 있는 다이엔 올레핀계 단량체 또는 트라이엔 올레핀계 단량체 등도 중합 가능하다. 상기 단량체의 구체적인 예로는 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, 1-아이토센, 노보넨, 노보나디엔, 에틸리덴노보넨, 페닐노보넨, 비닐노보넨, 디사이클로펜타디엔, 1,4-부타디엔, 1,5-펜타디엔, 1,6-헥사디엔, 스티렌, 알파-메틸스티렌, 디비닐벤젠, 3-클로로메틸스티렌 등이 있으며, 이들 단량체를 2 종 이상 혼합하여 공중합할 수도 있다. Examples of the olefin monomer polymerizable with the catalyst composition include ethylene, alpha-olefin, cyclic olefin, and the like. Dioene olefin-based monomers or triene olefin-based monomers having two or more double bonds can also be polymerized. Specific examples of the monomer include ethylene, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, Butene, dicyclopentadiene, 1,4-butadiene, 1,4-butadiene, 1,3-butadiene, 1,3-butadiene, Pentadiene, 1,6-hexadiene, styrene, alpha-methylstyrene, divinylbenzene, 3-chloromethylstyrene and the like. These two or more monomers may be mixed and copolymerized.
상기 올레핀 단량체의 중합 반응을 위하여, 연속식 용액 중합 공정, 벌크 중합 공정, 현탁 중합 공정, 슬러리 중합 공정 또는 유화 중합 공정 등 올레핀 단량체의 중합 반응으로 알려진 다양한 중합 공정을 채용할 수 있다.Various polymerization processes known as polymerization of olefin monomers such as a continuous solution polymerization process, a bulk polymerization process, a suspension polymerization process, a slurry polymerization process, or an emulsion polymerization process can be employed for the polymerization reaction of the olefin monomer.
구체적으로, 상기 중합 반응은 약 50 내지 110℃ 또는 약 60 내지 100℃의 온도와 약 1 내지 100kgf/cm2의 압력 하에서 수행될 수 있다.Specifically, the polymerization may be carried out at a temperature of about 50 to 110 DEG C or about 60 to 100 DEG C and a pressure of about 1 to 100 kgf / cm < 2 >.
또한, 상기 중합 반응에서, 상기 촉매 조성물는 펜탄, 헥산, 헵탄, 노난, 데칸, 톨루엔, 벤젠, 디클로로메탄, 클로로벤젠 등과 같은 용매에 용해 또는 희석된 상태로 이용될 수 있다. 이때, 상기 용매를 소량의 알킬알루미늄 등으로 처리함으로써, 촉매에 악영향을 줄 수 있는 소량의 물 또는 공기 등을 미리 제거할 수 있다. Further, in the above polymerization reaction, the catalyst composition may be used in a state of being dissolved or diluted in a solvent such as pentane, hexane, heptane, nonane, decane, toluene, benzene, dichloromethane, chlorobenzene and the like. At this time, by treating the solvent with a small amount of alkylaluminum or the like, a small amount of water or air that can adversely affect the catalyst can be removed in advance.
상기와 같은 방법으로 제조되는 올레핀 중합체는 전술한 촉매 조성물을 이용하여 제조됨에 따라 다양한 분자량 범위 내에서 높은 겉보기 밀도를 나타낼 수 있다. The olefin polymer prepared by the above-mentioned method can exhibit high apparent density within various molecular weight ranges as it is produced using the above-described catalyst composition.
이하 발명의 구체적인 실시예를 통해 발명의 작용, 효과를 보다 구체적으로 설명하기로 한다. 다만, 이는 발명의 예시로서 제시된 것으로 이에 의해 발명의 권리범위가 어떠한 의미로든 한정되는 것은 아니다. BRIEF DESCRIPTION OF THE DRAWINGS The above and other objects, features and advantages of the present invention will be more apparent from the following detailed description taken in conjunction with the accompanying drawings, in which: FIG. However, this is provided as an example of the invention, and the scope of the invention is not limited thereto in any sense.
제조예Manufacturing example 1: 전이 금속 화합물 및 담지 촉매의 제조 1: Preparation of transition metal compound and supported catalyst
1 단계: 1H-사이클로펜타[a]나프탈렌의 제조Step 1: Preparation of 1H-cyclopenta [a] naphthalene
나프탈렌 10mmol을 메틸렌 클로라이드(MC)에 용해시켜 나프탈렌 용액을 준비하였다. AlCl3 10mmol을 MC에 분산시키고, 얻어진 AlCl3 용액을 냉각하였다. 냉각된 AlCl3 용액에 상기 나프탈렌 용액과 3-클로로프로파노일 클로라이드 10mmol을 주입하였다. 얻어진 반응 혼합물의 온도를 상온으로 서서히 올린 후 밤새 교반하였다. 10 mmol of naphthalene was dissolved in methylene chloride (MC) to prepare a naphthalene solution. 10 mmol of AlCl 3 was dispersed in MC, and the resulting AlCl 3 solution was cooled. 10 mmol of the above naphthalene solution and 3-chloropropanoyl chloride were injected into the cooled AlCl 3 solution. The temperature of the obtained reaction mixture was gradually raised to room temperature and then stirred overnight.
그리고, 밤새 교반한 반응 혼합물에 얼음물을 넣어 반응을 종료하고 에테르로 유기층을 추출하여 3-클로로-1-(나프탈렌-2-일)프로판-1-온을 100%의 수율로 얻었다. Then, ice was added to the reaction mixture which was stirred overnight, and the reaction was terminated. The organic layer was extracted with ether to obtain 3-chloro-1- (naphthalen-2-yl) propan-1-one in a yield of 100%.
1H NMR (500 MHz, CDCl3): 3.54 (2H, t), 3.97 (2H, t), 7.50~8.65 (7H, m) 1 H NMR (500 MHz, CDCl 3): 3.54 (2H, t), 3.97 (2H, t), 7.50 ~ 8.65 (7H, m)
3-클로로-1-(나프탈렌-2-일)프로판-1-온 10mmol을 H2SO4 50mL에 용해시켜 90℃에서 5 시간 동안 반응시켰다. 그리고, 얻어진 반응 생성물에 얼음물을 넣어 반응을 종료하고 에테르로 유기층을 추출하여 1,2-디하이드로-3H-사이클로펜타[a]나프탈렌-3-온을 80%의 수율로 얻었다(isomer 존재).10 mmol of 3-chloro-1- (naphthalen-2-yl) propan-1-one was dissolved in 50 mL of H 2 SO 4 and reacted at 90 ° C. for 5 hours. The obtained reaction product was added with ice water to terminate the reaction, and the organic layer was extracted with ether to obtain 1,2-dihydro-3H-cyclopenta [a] naphthalen-3-one in an 80% yield (isomer existence).
1H NMR (500 MHz, CDCl3): 2.79 (1H, t), 2.84 (2H, t), 3.45 (1H, t), 3.74 (2H, t), 7.50~9.15 (6H, m) 1 H NMR (500 MHz, CDCl 3): 2.79 (1H, t), 2.84 (2H, t), 3.45 (1H, t), 3.74 (2H, t), 7.50 ~ 9.15 (6H, m)
1,2-디하이드로-3H-사이클로펜타[a]나프탈렌-3-온 10mmol을 메탄올에 용해시킨 후 냉각하였다. 냉각된 용액에 NaBH4 25mmol을 천천히 적가하고 2 시간 동안 교반하였다. 그리고, 얻어진 반응 생성물에 얼음물을 넣어 반응을 종료하고 에테르로 유기층을 추출하여 2,3-디하이드로-1H-사이클로펜타[a]나프탈렌-3-올을 100%의 수율로 얻었다(isomer 존재).10 mmol of 1,2-dihydro-3H-cyclopenta [a] naphthalene-3-one was dissolved in methanol and then cooled. 25 mmol of NaBH 4 was slowly added dropwise to the cooled solution and stirred for 2 hours. The obtained reaction product was added with ice water to terminate the reaction, and the organic layer was extracted with ether to obtain 2,3-dihydro-1H-cyclopenta [a] naphthalene-3-ol in a yield of 100% (presence of isomer).
1H NMR (500 MHz, CDCl3): 2.12 (1H, m), 2.18 (1H, m), 2.59 (1H, m), 2.67 (1H, m), 2.97 (1H, m), 3.12 (1H, m), 3.27 (1H, m), 3.43 (1H, m), 5.43 (1H, s), 5.78 (1H, s), 7.37~8.16 (12H, m) 1 H NMR (500 MHz, CDCl 3): 2.12 (1H, m), 2.18 (1H, m), 2.59 (1H, m), 2.67 (1H, m), 2.97 (1H, m), 3.12 (1H, m), 3.27 (1H, m), 3.43 (1H, s), 5.78
2,3-디하이드로-1H-사이클로펜타[a]나프탈렌-3-올을 THF에 용해시킨 후 1N HCl 용액을 적가하였다. 이렇게 얻어진 반응 혼합물을 2 시간 동안 환류 교반하였다. 그리고, 얻어진 반응 생성물에 물을 넣어 반응을 종료하고 에테르로 유기층을 추출하여 1H-사이클로펜타[a]나프탈렌을 70%의 수율로 얻었다(isomer 존재).2,3-Dihydro-1H-cyclopenta [a] naphthalen-3-ol was dissolved in THF and a 1N HCl solution was added dropwise. The reaction mixture thus obtained was refluxed and stirred for 2 hours. Water was added to the obtained reaction product to terminate the reaction. The organic layer was extracted with ether to obtain 1H-cyclopenta [a] naphthalene in a yield of 70% (presence of isomer).
1H NMR (500 MHz, CDCl3): 3.56 (2H, s), 3.71 (1H, s), 6.64 (0.5H, d), 6.73 (1H, d), 6.97 (0.5H, d), 7.36~8.13 (9H, m) 1 H NMR (500 MHz, CDCl 3): 3.56 (2H, s), 3.71 (1H, s), 6.64 (0.5H, d), 6.73 (1H, d), 6.97 (0.5H, d), 7.36 ~ 8.13 (9H, m)
2 단계: (6-t-부톡시헥실)디클로로메틸실란의 제조Step 2: Preparation of (6-t-butoxyhexyl) dichloromethylsilane
1L 플라스크에 Mg 95g을 넣고, 1.0M HCl로 3회 MeOH로 3회, 아세톤으로 3회 세척한 후, 25℃에서 3 시간 동안 감압 건조하였다. 건조한 Mg가 담긴 반응기에, THF 1.0L, 1,2-DBE (1,2-dibromoethane) 5.0mL를 순차적으로 투입하고, 이를 교반하였다. Dropping funnel에 t-부톡시헥실 클로라이드 500g을 투입한 후, 이중 약 5% 가량을 상기 반응기에 5 분간 투입하였다. 이후, 반응기의 온도를 70℃로 올리고, 반응 혼합물을 30 분간 교반하였다. 이어서, 나머지 함량의 t-부톡시헥실 클로라이드를 약 3 시간에 걸쳐 상기 반응기에 서서히 투입하고, 반응 혼합물을 70℃의 온도에서 약 15 시간 동안 교반하였다. 이후, 상기 반응기의 온도를 25℃로 냉각시키고, 반응 혼합물을 여과하여 과량의 Mg를 제거하고, 여액을 3L 플라스크로 이송시켰다. 95 g of Mg was added to a 1 L flask, washed three times with 1.0 M HCl three times with MeOH, three times with acetone, and then dried under reduced pressure at 25 DEG C for 3 hours. To a reactor containing dry Mg, 1.0 L of THF and 5.0 mL of 1,2-DBE (1,2-dibromoethane) were sequentially added and stirred. After dropping funnel was charged with 500 g of t-butoxyhexyl chloride, about 5% of the funnel was added to the reactor for 5 minutes. The temperature of the reactor was then raised to 70 캜 and the reaction mixture was stirred for 30 minutes. Subsequently, the remaining amount of t-butoxyhexyl chloride was slowly added to the reactor over a period of about 3 hours, and the reaction mixture was stirred at a temperature of 70 DEG C for about 15 hours. The temperature of the reactor was then cooled to 25 DEG C and the reaction mixture was filtered to remove excess Mg and the filtrate was transferred to a 3 L flask.
한편, 반응기를 세척 및 감압 건조한 후, 상기 반응기에 트리클로로메틸실란 583g과 THF 3.3L를 투입하고, 반응기의 온도를 -15℃로 냉각시켰다. 이후, 상기 반응기에 상기에서 제조한 여액을 2 시간 동안 -5℃로 유지시키며 서서히 적가하였다. 반응기의 온도를 25℃로 올리고, 16 시간 동안 약 130rpm으로 교반하였다. 이후, 반응 혼합물을 25℃에서 감압 증류하고, 헥산 4.3L에 분산시킨 다음, 30분간 교반하였다. 이후, 반응 혼합물로부터 고체를 여과한 다음, 헥산 1.0L로 추가 세척 및 여과하고, 여액을 25℃에서 감압 증류하여 85%의 수율로 (6-t-부톡시헥실)디클로로메틸실란을 얻었다. On the other hand, after the reactor was washed and dried under reduced pressure, 583 g of trichloromethylsilane and 3.3 L of THF were added to the reactor, and the temperature of the reactor was cooled to -15 캜. Then, the filtrate prepared above was slowly dropped to the reactor while maintaining the temperature at -5 ° C for 2 hours. The temperature of the reactor was raised to 25 DEG C and stirred at about 130 rpm for 16 hours. Thereafter, the reaction mixture was distilled under reduced pressure at 25 캜, dispersed in 4.3 L of hexane, and stirred for 30 minutes. Thereafter, the solid was filtered from the reaction mixture, and further washed with 1.0 L of hexane and filtered. The filtrate was distilled under reduced pressure at 25 캜 to obtain (6-t-butoxyhexyl) dichloromethylsilane in 85% yield.
1H NMR (500 MHz, CDCl3, 7.24 ppm): 0.76 (3H, s), 1.11 (2H, t), 1.18 (9H, s), 1.32~1.55 (8H, m), 3.33 (2H, t) 1 H NMR (500 MHz, CDCl 3, 7.24 ppm): 0.76 (3H, s), 1.11 (2H, t), 1.18 (9H, s), 1.32 ~ 1.55 (8H, m), 3.33 (2H, t)
3 단계: 1-(6-(t-부톡시)헥실)-N-(t-부틸)-1-클로로-1-메틸실란아민의 제조Step 3: Preparation of 1- (6- (t-butoxy) hexyl) -N- (t-butyl) -1-chloro-1-methylsilanamine
250mL schlenk flask에 t-부틸아민 120mmol과 에테르 용매 20mL를 넣고, 상기 flask와 다른 250mL schlenk flask에 (6-t-부톡시헥실)디클로로메틸실란 60mmol과 에테르 용매 40mL를 넣어 t-부틸아민 용액 및 (6-t-부톡시헥실)디클로로메틸실란 용액을 각각 준비하였다. 그리고, 상기 t-부틸아민 용액을 -78℃로 냉각한 다음, 냉각된 용액에 (6-t-부톡시헥실)디클로로메틸실란 용액을 천천히 주입하고, 이를 상온에서 약 2 시간 동안 교반하였다. 생성된 white suspension을 여과하여 아이보리(ivory) 색상을 띄며, 액상인 1-(6-(t-부톡시)헥실)-N-(t-부틸)-1-클로로-1-메틸실란아민을 얻었다.120 mmol of t-butylamine and 20 mL of an ether solvent were placed in a 250 mL schlenk flask and 60 mmol of (6-t-butoxyhexyl) dichloromethylsilane and 40 mL of an ether solvent were added to a 250 mL schlenk flask different from the above flask to prepare a t- 6-t-butoxyhexyl) dichloromethylsilane solution was prepared. Then, the t-butylamine solution was cooled to -78 deg. C, and then a solution of (6-t-butoxyhexyl) dichloromethylsilane was slowly poured into the cooled solution, which was then stirred at room temperature for about 2 hours. The resulting white suspension was filtered to obtain 1- (6- (t-butoxy) hexyl) -N- (t-butyl) -1-chloro-1-methylsilanamine which was ivory .
1H NMR (CDCl3): 3.29 (t, 2H), 1.52-1.29 (m, 10H), 1.20 (s, 9H), 1.16 (s, 9H), 0.40 (s, 3H) 1 H NMR (CDCl 3 ): 3.29 (t, 2H), 1.52-1.29 (m, 10H), 1.20 (s, 9H)
4 단계: 1-(6-(t-부톡시)헥실)-N-(t-부틸)-1-(1H-사이클로펜타[a]나프탈렌-1-일)-1-메틸실란아민의 제조 Step 4: Preparation of 1- (6- (t-butoxy) hexyl) -N- (t-butyl) -1- (1H-cyclopenta [a] naphthalen-
1H-사이클로펜타[a]나프탈렌 8.6mmol을 톨루엔 101mL와 THF 10.1mL의 혼합 용매에 녹였다. 이후, 상기 반응 혼합물을 -25℃로 냉각하고, 상기 반응 혼합물에 n-부틸리튬 용액 (2.5M solution in hexane) 3.6mL (9.1mmol)를 천천히 적가하였다. 이어서, 얻어지는 반응 혼합물을 상온에서 3 시간 동안 교반하였다. 그리고, CuCN 9.9mg을 소량의 톨루엔에 녹여 슬러리 형태로 상기 반응 혼합물에 첨가하고 30 분간 교반하였다. 이어서, 상기 반응 혼합물에 앞서 제조한 1-(6-(t-부톡시)헥실)-N-(t-부틸)-1-클로로-1-메틸실란아민을 첨가하고, 얻어지는 반응 혼합물을 상온에서 하루 동안 교반하였다. 이후, 얻어진 반응 생성물로부터 물과 에테르를 이용하여 유기층을 추출하고, 건조하여 1-(6-(t-부톡시)헥실)-N-(t-부틸)-1-(1H-사이클로펜타[a]나프탈렌-1-일)-1-메틸실란아민을 얻었다. 8.6 mmol of 1H-cyclopenta [a] naphthalene was dissolved in a mixed solvent of 101 mL of toluene and 10.1 mL of THF. Thereafter, the reaction mixture was cooled to -25 캜, and 3.6 mL (9.1 mmol) of a n-butyllithium solution (2.5 M solution in hexane) was slowly added dropwise to the reaction mixture. The resulting reaction mixture was then stirred at ambient temperature for 3 hours. Then 9.9 mg of CuCN was dissolved in a small amount of toluene and added to the reaction mixture in the form of a slurry, followed by stirring for 30 minutes. Subsequently, to the reaction mixture was added 1- (6- (t-butoxy) hexyl) -N- (t-butyl) -1-chloro-1-methylsilanamine prepared above, And stirred for one day. Then, an organic layer was extracted from the obtained reaction product using water and ether and dried to obtain 1- (6- (t-butoxy) hexyl) -N- (t-butyl) ] Naphthalen-1-yl) -1-methylsilanamine.
1H NMR (500 MHz, CDCl3, 7.24 ppm): 0.14 (3H, s), 1.15 (9H, s), 1.24 (9H, s), 0.60~1.49 (10H, m), 3.30 (2H, t), 3.56 (1H, s), 6.47 (1H, d), 6.96 (1H, d), 7.32~7.86 (6H, m) 1 H NMR (500 MHz, CDCl 3, 7.24 ppm): 0.14 (3H, s), 1.15 (9H, s), 1.24 (9H, s), 0.60 ~ 1.49 (10H, m), 3.30 (2H, t) , 3.56 (1H, s), 6.47 (1H, d), 6.96 (1H, d), 7.32-7.86
5 단계: (1H-사이클로펜타[a]나프탈렌-1-일)(t-부틸아미노)(6-(t-부톡시)헥실)(메틸)실란 티타늄 디클로라이드의 제조 Step 5: Preparation of (1H-cyclopenta [a] naphthalen-1-yl) (t-butylamino) (6- (t- butoxy) hexyl) (methyl) silane titanium dichloride
앞서 제조한 1-(6-(t-부톡시)헥실)-N-(t-부틸)-1-(1H-사이클로펜타[a]나프탈렌-1-일)-1-메틸실란아민 8.6mmol을 톨루엔 14mL와 n-헥산 1.7mL에 녹인 후, -78℃에서 상기 용액에 n-부틸리튬 용액 (2.5M solution in hexane) 7.3mL (18mmol)를 천천히 적가하였다. 이후, 얻어지는 반응 혼합물을 상온에서 약 12 시간 동안 교반하였다. 그리고, TiCl4(THF)2 8.6mmol이 담긴 반응 용기에 상기 반응 혼합물을 -78℃에서 첨가하고 상온에서 하루 동안 교반하였다. 이후, 반응 혼합물을 건조하여 용매를 제거한 후 톨루엔을 주입하였다. 그리고, 얻어진 혼합 용액을 여과하고 여액을 건조하여 하기 화학식 1a로 표시되는 전이 금속 화합물을 얻었다. 8.6 mmol of 1- (6- (t-butoxy) hexyl) -N- (t-butyl) -1- (1H- cyclopenta [a] naphthalen- After dissolving in 14 mL of toluene and 1.7 mL of n-hexane, 7.3 mL (18 mmol) of n-butyllithium solution (2.5 M solution in hexane) was slowly added dropwise to the solution at -78 ° C. Then, the resulting reaction mixture was stirred at room temperature for about 12 hours. Then, the reaction mixture was added to a reaction vessel containing 8.6 mmol of TiCl 4 (THF) 2 at -78 ° C and stirred at room temperature for one day. Then, the reaction mixture was dried to remove the solvent, and then toluene was injected. Then, the obtained mixed solution was filtered and the filtrate was dried to obtain a transition metal compound represented by the following formula (1a).
[화학식 1a][Formula 1a]
1H NMR (500 MHz, CDCl3, 7.24 ppm): 1.16 (9H, s), 1.35 (9H, s), 1.49 (3H, s), 0.79~1.83 (10H, m), 3.32 (2H, t), 6.39 (1H, d), 6.58 (1H, d), 7.39~7.92 (6H, m). 1 H NMR (500 MHz, CDCl 3, 7.24 ppm): 1.16 (9H, s), 1.35 (9H, s), 1.49 (3H, s), 0.79 ~ 1.83 (10H, m), 3.32 (2H, t) , 6.39 (1H, d), 6.58 (1H, d), 7.39-7.92 (6H, m).
6 단계: 담지 촉매의 제조Step 6: Preparation of supported catalyst
실리카 9.1g이 담긴 쉬링크 플라스크에 메틸알루미녹산(MAO) 8 mmol/gSiO2를 넣어 60℃에서 12 시간 동안 반응시켰다. 반응 종료 후, 반응 생성물이 가라 앉으면, 상층부 용액은 제거하고 남은 침전물을 톨루엔으로 1 회 세척하였다. 그리고, 상기 플라스크에 상기에서 제조한 전이 금속 화합물 0.1 mmol/gSiO2를 톨루엔에 용해시켜 주입하고, 40℃에서 2 시간 동안 반응시켰다. 반응 종료 후, 반응 생성물이 가라 앉으면, 상층부 용액은 제거하고 남은 침전물을 톨루엔으로 1회 세척하였다. 이후, 상기 플라스크에 디메틸아닐리니윰 테트라키스(펜타플루오로페닐)보레이트 0.15 mmol/gSiO2를 넣고, 50℃에서 5 시간 동안 반응시켰다. 반응 종료 후, 톨루엔으로 세척하고, 헥산으로 재차 세척한 후 진공 건조하여 고체 입자 형태의 실리카 담지 메탈로센 촉매를 얻었다.Methyl aluminoxane (MAO) 8 mmol / g SiO 2 was added to a shrinkage flask containing 9.1 g of silica and reacted at 60 ° C for 12 hours. After the completion of the reaction, when the reaction product had settled down, the upper layer solution was removed and the remaining precipitate was washed once with toluene. Then, the above-prepared transition metal compound, 0.1 mmol / g SiO 2 , was dissolved in toluene and injected into the flask, followed by reaction at 40 ° C for 2 hours. After the completion of the reaction, when the reaction product had settled down, the upper layer solution was removed and the remaining precipitate was washed once with toluene. Then, 0.15 mmol / g SiO 2 of dimethylanilinium tetrakis (pentafluorophenyl) borate was added to the flask, and the reaction was carried out at 50 ° C for 5 hours. After completion of the reaction, the reaction product was washed with toluene, washed again with hexane and then vacuum-dried to obtain a silica-supported metallocene catalyst in the form of solid particles.
제조예Manufacturing example 2: 전이 금속 화합물 및 담지 촉매의 제조 2: Preparation of transition metal compound and supported catalyst
상기 제조예 1의 3 단계에서 t-부틸아민 대신 플루오렌을 사용하여 1-(6-(t-부톡시)헥실)-1-(9H-플루오렌-9-일)-1-클로로-1-메틸아민을 제조하고, 5 단계에서 TiCl4(THF)2 대신 ZrCl4(THF)2를 사용한 것을 제외하고 제조예 1과 동일한 방법으로 하기 화학식 1b의 전이 금속 화합물과 담지 촉매를 제조하였다. (9H-fluoren-9-yl) -1-chloro-1 (1 H) -quinolinone was obtained by using fluorene in place of t- -Methylamine and ZrCl 4 (THF) 2 was used instead of TiCl 4 (THF) 2 in Step 5, a transition metal compound of the following Formula 1b and a supported catalyst were prepared.
[화학식 1b][Chemical Formula 1b]
1H NMR (500 MHz, CDCl3, 7.24 ppm): 1.10 (9H, m), 0.60~1.52 (10H, m), 3.31 (2H, m), 6.21 (1H, d), 6.52 (1H, d), 7.08~7.85 (6H, m). 1 H NMR (500 MHz, CDCl 3 , 7.24 ppm): 1.10 (9H, m), 0.60-1. 52 (10H, m), 3.31 , 7.08-7.85 (6H, m).
제조예Manufacturing example 3: 전이 금속 화합물 및 담지 촉매의 제조 3: Preparation of transition metal compound and supported catalyst
상기 제조예 1의 1 단계(1H-사이클로펜타[a]나프탈렌의 제조)를 하기 기재된 1 단계(2-메틸-1H-사이클로펜타[a]나프탈렌의 제조)로 대체하여 2-메틸-1H-사이클로펜타[a]나프탈렌을 제조하고, 이를 이용해 제조예 1의 2 내지 6 단계와 동일한 방법으로 하기 화학식 1c의 전이 금속 화합물과 담지 촉매를 제조하였다. A) Preparation of 1H-cyclopenta [a] naphthalene by the same procedure as described in Preparation Example 1 was used instead of 2-methyl-1H-cyclohexane Penta [a] naphthalene was prepared, and the transition metal compound of the following formula (1c) and the supported catalyst were prepared in the same manner as in steps 2 to 6 of Preparation Example 1.
[화학식 1c][Chemical Formula 1c]
1H NMR (500 MHz, CDCl3, 7.24 ppm): 1.16 (9H, s), 1.35 (9H, s), 1.41 (3H, s), 0.55~1.45 (10H, m), 1.92 (3H, s), 3.29 (2H, t), 7.14 (1H, d), 7.39~7.92 (6H, m). 1 H NMR (500 MHz, CDCl 3 , 7.24 ppm): 1.16 (9H, s), 1.35 (9H, s), 1.41 (3H, s), 0.55-1.45 , 3.29 (2H, t), 7.14 (1H, d), 7.39-7.92 (6H, m).
1 단계: 2-메틸-1H-사이클로펜타[a]나프탈렌의 제조Step 1: Preparation of 2-methyl-1H-cyclopenta [a] naphthalene
나프탈렌 10mmol을 메틸렌 클로라이드(MC)에 용해시켜 나프탈렌 용액을 준비하였다. AlCl3 10mmol을 MC에 분산시키고, 얻어진 AlCl3 용액을 냉각하였다. 냉각된 AlCl3 용액 상기 나프탈렌 용액과 3-클로로-2-메틸프로파노일 클로라이드 10mmol을 주입하였다. 얻어진 반응 혼합물의 온도를 상온으로 서서히 올린 후 밤새 교반하였다. 그리고, 밤새 교반한 반응 혼합물에 얼음물을 넣고 에테르로 유기층을 추출하여 3-클로로-2-메틸-1-(나프탈렌-2-일)프로판-1-온을 얻었다. 10 mmol of naphthalene was dissolved in methylene chloride (MC) to prepare a naphthalene solution. 10 mmol of AlCl 3 was dispersed in MC, and the resulting AlCl 3 solution was cooled. Cooled AlCl 3 solution The above naphthalene solution and 10 mmol of 3-chloro-2-methylpropanoyl chloride were introduced. The temperature of the obtained reaction mixture was gradually raised to room temperature and then stirred overnight. The ice water was added to the reaction mixture which was stirred overnight, and the organic layer was extracted with ether to obtain 3-chloro-2-methyl-1- (naphthalen-2-yl) propan-1-one.
1H NMR (500 MHz, CDCl3): 1.25 (3H, d), 3.20 (2H, m), 3.45 (1H, m), 7.60~8.60 (7H, m) 1 H NMR (500 MHz, CDCl 3): 1.25 (3H, d), 3.20 (2H, m), 3.45 (1H, m), 7.60 ~ 8.60 (7H, m)
3-클로로-2-메틸-1-(나프탈렌-2-일)프로판-1-온 10mmol을 H2SO4 50ml에 용해시켜 90℃에서 5 시간 동안 반응시켰다. 그리고, 얻어진 반응 생성물에 얼음물을 넣고 에테르로 유기층을 추출하여 2-메틸-1,2-디하이드로-3H-사이클로펜타[a]나프탈렌-3-온을 얻었다.10 mmol of 3-chloro-2-methyl-1- (naphthalen-2-yl) propan-1-one was dissolved in 50 ml of H 2 SO 4 and reacted at 90 ° C for 5 hours. Then, the obtained reaction product was poured into ice water and the organic layer was extracted with ether to obtain 2-methyl-1,2-dihydro-3H-cyclopenta [a] naphthalen-3-one.
1H NMR (500 MHz, CDCl3): 1.30 (3H, d), 3.28 (2H, d), 3.50 (1H, m), 7.50~9.20 (6H, m) 1 H NMR (500 MHz, CDCl 3 ): 1.30 (3H, d), 3.28 (2H, d), 3.50 (1H, m), 7.50-9.20
2-메틸-1,2-디하이드로-3H-사이클로펜타[a]나프탈렌-3-온 10mmol을 메탄올에 용해시킨 후 냉각하였다. 냉각된 용액에 NaBH4 25mmol을 천천히 적가하고 2 시간 동안 교반하였다. 그리고, 얻어진 반응 생성물에 물을 넣고 에테르로 유기층을 추출하여 2-메틸-2,3-디하이드로-1H-사이클로펜타[a]나프탈렌-3-올을 얻었다.10 mmol of 2-methyl-1,2-dihydro-3H-cyclopenta [a] naphthalen-3-one was dissolved in methanol and then cooled. 25 mmol of NaBH 4 was slowly added dropwise to the cooled solution and stirred for 2 hours. Water was added to the obtained reaction product and the organic layer was extracted with ether to obtain 2-methyl-2,3-dihydro-1H-cyclopenta [a] naphthalene-3-ol.
1H NMR (500 MHz, CDCl3): 1.27 (3H, d), 3.22 (2H, m), 3.48 (1H, s), 7.27~8.20 (6H, m) 1 H NMR (500 MHz, CDCl 3): 1.27 (3H, d), 3.22 (2H, m), 3.48 (1H, s), 7.27 ~ 8.20 (6H, m)
2-메틸-2,3-디하이드로-1H-사이클로펜타[a]나프탈렌-3-올 10mmol을 톨루엔에 용해시킨 후 p-돌루엔술폰산 1mmol을 적가하였다. 이렇게 얻어진 반응 혼합물을 2 시간 동안 환류 교반하였다. 그리고, 얻어진 반응 생성물에 물을 넣고 에테르로 유기층을 추출하여 2-메틸-1H-사이클로펜타[a]나프탈렌을 얻었다.10 mmol of 2-methyl-2,3-dihydro-1H-cyclopenta [a] naphthalene-3-ol was dissolved in toluene and 1 mmol of p-doluenesulfonic acid was added dropwise. The reaction mixture thus obtained was refluxed and stirred for 2 hours. Water was added to the obtained reaction product and the organic layer was extracted with ether to obtain 2-methyl-1H-cyclopenta [a] naphthalene.
1H NMR (500 MHz, CDCl3): 2.27 (3H, s), 3.45 (2H, s), 7.08 (1H, s), 7.40~8.05 (6H, m). 1 H NMR (500 MHz, CDCl 3 ): 2.27 (3H, s), 3.45 (2H, s), 7.08 (1H, s), 7.40 ~ 8.05 (6H, m).
제조예Manufacturing example 4: 전이 금속 화합물 및 담지 촉매의 제조 4: Preparation of transition metal compound and supported catalyst
상기 제조예 3의 3 단계에서 t-부틸아민 대신 플루오렌을 사용하여 1-(6-(t-부톡시)헥실)-1-(9H-플루오렌-9-일)-1-클로로-1-메틸아민을 제조하고, 5 단계에서 TiCl4(THF)2 대신 ZrCl4(THF)2를 사용한 것을 제외하고 제조예 3과 동일한 방법으로 하기 화학식 1d의 전이 금속 화합물과 담지 촉매를 제조하였다. (9H-fluoren-9-yl) -1-chloro-1 (4-fluorobenzyloxy) -1- -Methylamine and ZrCl 4 (THF) 2 was used instead of TiCl 4 (THF) 2 in Step 5, a transition metal compound of the following Formula 1d and a supported catalyst were prepared.
[화학식 1d]≪ RTI ID = 0.0 &
1H NMR (500 MHz, CDCl3, 7.24 ppm): 1.05 (9H, m), 0.72~1.61 (10H, m), 1.38 (3H, s), 3.21 (2H, m), 5.88 (2H, d), 6.96~7.85 (6H, m). 1 H NMR (500 MHz, CDCl 3, 7.24 ppm): 1.05 (9H, m), 0.72 ~ 1.61 (10H, m), 1.38 (3H, s), 3.21 (2H, m), 5.88 (2H, d) , 6.96-7.85 (6H, m).
실시예Example 1: 올레핀 단량체의 중합 1: Polymerization of olefin monomers
기계식 교반기가 장착되어 있으며, 온도 조절이 가능하고, 고압의 반응에 사용될 수 있는 600mL 금속 합금 반응기를 준비하였다. A 600 mL metal alloy reactor equipped with a mechanical stirrer and capable of temperature control and for high pressure reaction was prepared.
한편, 상기 제조예 1에서 제조한 담지 촉매를 드라이 박스에서 정량하여 50mL의 유리병에 담은 후, 상기 유리병의 입구를 고무 격막으로 밀봉하였다.Meanwhile, the supported catalyst prepared in Preparation Example 1 was quantified in a dry box and placed in a 50 mL glass bottle, and then the inlet of the glass bottle was sealed with a rubber septum.
그리고, 상기 600mL 금속 합금 반응기에 1.0mmol의 트라이에틸알루미늄이 함유된 헥산 400mL와 앞서 준비한 담지 촉매를 공기 접촉 없이 투입하였다. 이어서, 상기 반응기의 온도를 약 80℃로 올리고, 상기 반응기에 에틸렌 가스를 주입하여 약 1 시간 동안 에틸렌을 중합하였다. 이때, 에틸렌 가스는 반응기의 압력이 약 9 kgf/cm2 정도로 유지되도록 계속 주입되었다. Then, 400 mL of hexane containing 1.0 mmol of triethylaluminum and the above-prepared supported catalyst were added to the 600 mL metal alloy reactor without air contact. Then, the temperature of the reactor was raised to about 80 DEG C, and ethylene was injected into the reactor to polymerize ethylene for about 1 hour. At this time, the ethylene gas was continuously injected so that the pressure of the reactor was maintained at about 9 kgf / cm 2 .
이후, 에틸렌이 목적하는 수준으로 중합되면, 반응기의 교반을 멈추고, 미반응 에틸렌 가스를 배기시켜 제거하였다. 그리고, 반응 생성물에서 용매를 제거하고 얻어진 고체를 약 80℃의 진공 오븐에서 약 4 시간 동안 건조시켜 에틸렌 단독 중합체를 얻었다. Thereafter, when ethylene was polymerized to the desired level, stirring of the reactor was stopped, and unreacted ethylene gas was removed by evacuation. Then, the solvent was removed from the reaction product, and the obtained solid was dried in a vacuum oven at about 80 캜 for about 4 hours to obtain an ethylene homopolymer.
실시예Example 2: 올레핀 단량체의 중합 2: Polymerization of olefin monomers
실시예 1에서 제조예 2의 담지 촉매를 사용한 것을 제외하고, 실시예 1과 동일한 방법으로 에틸렌 단독 중합체를 얻었다. An ethylene homopolymer was obtained in the same manner as in Example 1, except that the supported catalyst of Production Example 2 was used in Example 1.
실시예Example 3: 올레핀 단량체의 중합 3: Polymerization of olefin monomers
실시예 1에서 제조예 3의 담지 촉매를 사용한 것을 제외하고, 실시예 1과 동일한 방법으로 에틸렌 단독 중합체를 얻었다. An ethylene homopolymer was obtained in the same manner as in Example 1, except that the supported catalyst of Production Example 3 was used in Example 1.
실시예Example 4: 올레핀 단량체의 중합 4: Polymerization of olefin monomers
실시예 1에서 제조예 4의 담지 촉매를 사용한 것을 제외하고, 실시예 1과 동일한 방법으로 에틸렌 단독 중합체를 얻었다. An ethylene homopolymer was obtained in the same manner as in Example 1, except that the supported catalyst of Production Example 4 was used in Example 1.
비교예Comparative Example 1: 올레핀 단량체의 중합 1: Polymerization of olefin monomers
하기 화학식 P-1으로 표시되는 전이 금속 화합물을 이용하여 제조예 1의 6 단계와 동일한 방법으로 담지 촉매를 제조하였다.A supported catalyst was prepared in the same manner as in the step 6 of Preparation Example 1 using the transition metal compound represented by the following formula (P-1).
[화학식 P-1][Formula P-1]
실시예 1에서 상기 화학식 P-1의 담지 촉매를 사용한 것을 제외하고, 실시예 1과 동일한 방법으로 에틸렌 단독 중합체를 얻었다. An ethylene homopolymer was obtained in the same manner as in Example 1 except that the supported catalyst of the above formula (P-1) was used in Example 1.
비교예Comparative Example 2: 올레핀 단량체의 중합 2: Polymerization of olefin monomers
하기 화학식 P-2로 표시되는 전이 금속 화합물을 이용하여 제조예 1의 6 단계와 동일한 방법으로 담지 촉매를 제조하였다.A supported catalyst was prepared in the same manner as in the step 6 of Production Example 1 using the transition metal compound represented by the following formula (P-2).
[화학식 P-2][Formula P-2]
실시예 1에서 상기 화학식 P-2의 담지 촉매를 사용한 것을 제외하고, 실시예 1과 동일한 방법으로 에틸렌 단독 중합체를 얻었다. An ethylene homopolymer was obtained in the same manner as in Example 1, except that the supported catalyst of the above formula (P-2) was used in Example 1.
시험예Test Example : : 올리핀Olivin 중합체의 물성 평가 Evaluation of physical properties of polymer
상기 실시예 1 내지 4 및 비교예 1 내지 2에서 제조한 올레핀 중합체의 물성을 다음과 같이 평가하고 그 결과를 하기 표 1에 나타내었다. The properties of the olefin polymers prepared in Examples 1 to 4 and Comparative Examples 1 and 2 were evaluated as follows, and the results are shown in Table 1 below.
(1) 촉매 활성: 중합 반응에 이용된 촉매의 질량과 상기 반응으로부터 시간당 산출된 고분자의 질량을 측정하여 각 실시예 및 비교예들에서 사용한 촉매의 활성(activity)를 산출하였다. (1) Catalytic activity: The activity of the catalyst used in each of the examples and the comparative examples was calculated by measuring the mass of the catalyst used in the polymerization reaction and the mass of the polymer calculated per hour from the reaction.
(2) 중량평균분자량 및 분자량 분포: 각 실시예 및 비교예들에서 제조한 고분자에서 10 mg을 샘플로 취하여 GPC 분석을 통해 중량평균분자량(Mw)과 분자량 분포(PDI)를 산출하였다. (2) Weight average molecular weight and molecular weight distribution: The weight average molecular weight (Mw) and the molecular weight distribution (PDI) were calculated by GPC analysis taking 10 mg as a sample from the polymer prepared in each of Examples and Comparative Examples.
(3) 겉보기 밀도(Bulk Density): IPT model 1132를 이용하여 100 mL 용기에 들어가는 올레핀 중합체의 무게(g)를 측정하여 구하였다.(3) Bulk Density: The weight (g) of an olefin polymer introduced into a 100 mL container was measured using an IPT model 1132.
(4) 공중합성: 상기 실시예 1 내지 4의 각각의 중합 반응에 에틸렌 가스를 주입하기 전 1-hexene 5 mL를 주입하여 공중합 반응을 실시하였다. 이러한 공중합 반응을 통해 제조한 에틸렌-1-헥센 공중합체에 포함된 1-헥센 유래의 반복 단위(branch)의 함량을 1H-NMR 및 13C-NMR을 통하여 산출하여 촉매의 공중합 반응 촉진 정도를 평가하였다. 전체 공중합체 몰수 대비 1-헥센 유래의 반복 단위(branch) 함량을 하기 표 1에 나타내었다. (4) Copolymerization: 5 ml of 1-hexene was injected into the polymerization reaction of each of Examples 1 to 4 before injecting ethylene gas to perform copolymerization reaction. The content of the repeating unit derived from 1-hexene contained in the ethylene-1-hexene copolymer produced through the copolymerization reaction was calculated by 1 H-NMR and 13 C-NMR, Respectively. The content of repeating units derived from 1-hexene with respect to the total number of moles of copolymer is shown in Table 1 below.
[kgPol./(gCat.*hr)]Catalytic activity
[kgPol./(gCat.*hr)]
[g/cm3]Apparent density
[g / cm 3]
[1-hexene 몰%]Copolymerization
[1-hexene mol%]
상기 표 1을 참조하면, 비교예 1 및 2에 따른 올레핀 단량체의 중합 반응에서는 매우 낮은 촉매 활성이 나타나는데 반해 실시예 1 내지 4의 중합 반응에 사용된 촉매는 매우 우수한 촉매 활성을 나타냈다. Referring to Table 1, the catalysts used in the polymerization reactions of Examples 1 to 4 exhibited very good catalytic activity while the polymerization of olefin monomers according to Comparative Examples 1 and 2 exhibited very low catalytic activity.
또한, 실시예 1 내지 4를 참조하면, 본 발명의 일 구현예에 따른 전이 금속 화합물을 이용하면, 화학식 1의 C1 리간드를 달리하여 올레핀 중합체의 분자량을 용이하게 조절할 수 있고, 다양한 분자량 범위에서 높은 bulk density를 가지는 올레핀 중합체를 중합체를 제공할 수 있음이 확인된다. 이에 반해, 비교예 1 및 2는 리간드를 변경하더라도 분자량이 쉽게 조절되지 않으며, 제조된 올레핀 중합체의 모폴로지가 좋지 않아 낮은 bulk density를 가지는 것이 확인된다. In addition, referring to Examples 1 to 4, using the transition metal compound according to one embodiment of the present invention, the molecular weight of the olefin polymer can be easily controlled by varying the C 1 ligand of Formula 1, It is confirmed that olefin polymers having a high bulk density can provide polymers. On the other hand, in Comparative Examples 1 and 2, even if the ligand was changed, the molecular weight was not easily controlled, and the morphology of the prepared olefin polymer was poor and it was confirmed that the bulk density was low.
한편, 실시예 1 및 3을 실시예 2 및 4와 비교하면 화학식 1의 C1 리간드를 달리하여 공중합성도 용이하게 조절할 수 있음이 확인된다. On the other hand, when Examples 1 and 3 are compared with Examples 2 and 4, it is confirmed that the copolymerization can be easily controlled by varying the C 1 ligand of Formula 1.
Claims (13)
[화학식 1]
상기 화학식 1에서,
M1은 3족 전이 금속, 4족 전이 금속, 5족 전이 금속, 란타나이드 계열의 전이 금속 및 악타나이드 계열의 전이 금속 중 어느 하나이고,
X1 및 X2는 서로 동일하거나 상이하며 각각 독립적으로 할로겐 및 탄소수 1 내지 20의 알킬 중 어느 하나이고,
A는 14족의 원소 중 어느 하나이며, n은 1 내지 20 사이의 정수이고,
R1은 탄소수 1 내지 20의 알킬, 탄소수 2 내지 20의 알케닐, 탄소수 7 내지 30의 알킬아릴, 탄소수 7 내지 30의 아릴알킬 및 탄소수 6 내지 30의 아릴 중 어느 하나이며,
R2는 수소, 탄소수 1 내지 20의 알킬, 탄소수 2 내지 20의 알케닐, 탄소수 7 내지 30의 알킬아릴, 탄소수 7 내지 30의 아릴알킬 및 탄소수 6 내지 30의 아릴 중 어느 하나이고,
R3 및 R4는 각각 독립적으로 수소, 헤테로 원자로 치환되거나 치환되지 않은 탄소수 1 내지 20의 알킬 중 어느 하나이고,
C1은 -NR5-,
상기 R5는 탄소수 1 내지 20의 알킬 중 어느 하나이고,
상기 R6 내지 R21은 각각 독립적으로 수소 및 탄소수 1 내지 20의 알킬 중 어느 하나이다.
A transition metal compound represented by the following general formula (1)
[Chemical Formula 1]
In Formula 1,
M 1 is any one of a Group 3 transition metal, a Group 4 transition metal, a Group 5 transition metal, a lanthanide series transition metal, and an ethanide series transition metal,
X 1 and X 2 are the same or different from each other and are each independently any one of halogen and alkyl of 1 to 20 carbon atoms,
A is any one of the elements of Group 14, n is an integer of 1 to 20,
R 1 is any one of alkyl having 1 to 20 carbon atoms, alkenyl having 2 to 20 carbon atoms, alkylaryl having 7 to 30 carbon atoms, arylalkyl having 7 to 30 carbon atoms, and aryl having 6 to 30 carbon atoms,
R 2 is any one of hydrogen, alkyl having 1 to 20 carbon atoms, alkenyl having 2 to 20 carbon atoms, alkylaryl having 7 to 30 carbon atoms, arylalkyl having 7 to 30 carbon atoms, and aryl having 6 to 30 carbon atoms,
R 3 and R 4 are each independently hydrogen or alkyl having 1 to 20 carbon atoms which is optionally substituted with a heteroatom,
C 1 is -NR 5 -,
R 5 is any of alkyl having 1 to 20 carbon atoms,
Each of R 6 to R 21 is independently hydrogen or alkyl having 1 to 20 carbon atoms.
The transition metal compound according to claim 1, wherein R 3 and R 4 are each independently any one of hydrogen and straight chain alkyl of 1 to 5 carbon atoms.
The transition metal compound according to claim 1, wherein C 1 is -NR 5 - and R 5 is any of branched alkyl having 4 to 8 carbon atoms.
The compound according to claim 1, wherein C 1 is
The transition metal compound according to claim 1, wherein R 1 is any one of branched alkyl having 4 to 6 carbon atoms and n is 4 to 8.
The transition metal compound according to claim 1, wherein R 2 is any one of straight chain alkyl having 1 to 6 carbon atoms.
The transition metal compound according to claim 1, wherein M 1 is any one of Group 4 transition metals.
A catalyst composition comprising a transition metal compound represented by the general formula (1) of claim 1.
[화학식 2]
R23-[Al(R22)-O]m-R24
상기 화학식 2에서,
R22, R23 및 R24는 각각 독립적으로 수소, 할로겐, 탄소수 1 내지 20의 하이드로카빌기 및 할로겐으로 치환된 탄소수 1 내지 20의 하이드로카빌기 중 어느 하나이고,
m은 2 이상의 정수이며,
[화학식 3]
D(R25)3
상기 화학식 3에서,
D는 알루미늄 또는 보론이고,
R25는 각각 독립적으로 할로겐, 탄소수 1 내지 20의 하이드로카빌기, 탄소수 1 내지 20의 하이드로카빌옥시기 및 할로겐으로 치환된 탄소수 1 내지 20의 하이드로카빌기 중 어느 하나이며,
[화학식 4]
[L-H]+[W(J)4]- 또는 [L]+[W(J)4]-
상기 화학식 4에서,
L은 중성 또는 양이온성 루이스 염기이고,
W는 13족 원소이며, J는 각각 독립적으로 탄소수 1 내지 20의 하이드로카빌기; 탄소수 1 내지 20의 하이드로카빌옥시기; 및 이들 치환기의 1 이상의 수소 원자가 할로겐, 탄소수 1 내지 20의 하이드로카빌옥시기 및 탄소수 1 내지 20의 하이드로카빌(옥시)실릴기 중 1 이상의 치환기로 치환된 치환기들 중 어느 하나이다.
The catalyst composition according to claim 8, comprising at least one cocatalyst selected from the group consisting of compounds represented by the following formulas (2) to (4):
(2)
R 23 - [Al (R 22 ) -O] m -R 24
In Formula 2,
R 22 , R 23 and R 24 are each independently any one of hydrogen, halogen, hydrocarbyl group having 1 to 20 carbon atoms and hydrocarbyl group having 1 to 20 carbon atoms substituted with halogen,
m is an integer of 2 or more,
(3)
D (R 25) 3
In Formula 3,
D is aluminum or boron,
R 25 is each independently any one of halogen, a hydrocarbyl group having 1 to 20 carbon atoms, a hydrocarbyloxy group having 1 to 20 carbon atoms, and a hydrocarbyl group having 1 to 20 carbon atoms substituted with halogen,
[Chemical Formula 4]
[LH] + [W (J ) 4] - or [L] + [W (J ) 4] -
In Formula 4,
L is a neutral or cationic Lewis base,
W is a Group 13 element, J is independently a hydrocarbyl group having 1 to 20 carbon atoms; A hydrocarbyloxy group having 1 to 20 carbon atoms; And substituents in which at least one hydrogen atom of these substituents is substituted with at least one substituent selected from halogen, a hydrocarbyloxy group having 1 to 20 carbon atoms and a hydrocarbyl (oxy) silyl group having 1 to 20 carbon atoms.
The catalyst composition according to claim 8, further comprising a carrier carrying the transition metal compound.
11. The catalyst composition according to claim 10, wherein the carrier is silica, alumina, magnesia or a mixture thereof.
A process for producing an olefin polymer comprising the step of polymerizing an olefin monomer in the presence of the catalyst composition of claim 8.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020150185300A KR102089057B1 (en) | 2015-12-23 | 2015-12-23 | Transition metal compound, catalyst composition comprising the same, and method for preparing olefin polymer using the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020150185300A KR102089057B1 (en) | 2015-12-23 | 2015-12-23 | Transition metal compound, catalyst composition comprising the same, and method for preparing olefin polymer using the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| KR20170075529A true KR20170075529A (en) | 2017-07-03 |
| KR102089057B1 KR102089057B1 (en) | 2020-03-13 |
Family
ID=59357946
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| KR1020150185300A KR102089057B1 (en) | 2015-12-23 | 2015-12-23 | Transition metal compound, catalyst composition comprising the same, and method for preparing olefin polymer using the same |
Country Status (1)
| Country | Link |
|---|---|
| KR (1) | KR102089057B1 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI676633B (en) * | 2017-08-21 | 2019-11-11 | 新加坡商沙特基礎工業愛思開奈克斯林恩私人有限公司 | Novel transition metal compound, catalyst composition including the same, and method for preparing ethylene homopolymer or copolymer of ethylene and α-olefin using the same |
| CN111875486A (en) * | 2020-07-13 | 2020-11-03 | 京博农化科技有限公司 | Synthesis method of 2, 6-dimethyl-1-indanone |
| WO2021118103A1 (en) * | 2019-12-12 | 2021-06-17 | 주식회사 엘지화학 | Polyolefin |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20150037652A (en) * | 2013-09-30 | 2015-04-08 | 주식회사 엘지화학 | Method for preparing polypropylene and polypropylene prepared therefrom |
-
2015
- 2015-12-23 KR KR1020150185300A patent/KR102089057B1/en active IP Right Grant
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20150037652A (en) * | 2013-09-30 | 2015-04-08 | 주식회사 엘지화학 | Method for preparing polypropylene and polypropylene prepared therefrom |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI676633B (en) * | 2017-08-21 | 2019-11-11 | 新加坡商沙特基礎工業愛思開奈克斯林恩私人有限公司 | Novel transition metal compound, catalyst composition including the same, and method for preparing ethylene homopolymer or copolymer of ethylene and α-olefin using the same |
| WO2021118103A1 (en) * | 2019-12-12 | 2021-06-17 | 주식회사 엘지화학 | Polyolefin |
| CN114746455A (en) * | 2019-12-12 | 2022-07-12 | 株式会社Lg化学 | Polyolefins |
| CN114746455B (en) * | 2019-12-12 | 2024-02-13 | 株式会社Lg化学 | Polyolefin |
| CN111875486A (en) * | 2020-07-13 | 2020-11-03 | 京博农化科技有限公司 | Synthesis method of 2, 6-dimethyl-1-indanone |
| CN111875486B (en) * | 2020-07-13 | 2022-08-26 | 京博农化科技有限公司 | Synthesis method of 2, 6-dimethyl-1-indanone |
Also Published As
| Publication number | Publication date |
|---|---|
| KR102089057B1 (en) | 2020-03-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR101650092B1 (en) | Metallocene compound, catalyst composition comprising the same, and method for preparation of olefin-based polymer using the same | |
| KR101637026B1 (en) | Metallocene supported catalyst and method for preparing polyolefin using the same | |
| JP6681462B2 (en) | Hybrid supported catalyst system for ethylene slurry polymerization and method for producing ethylene polymer using the same | |
| KR20160084181A (en) | Supported hybrid catalyst and method for preparing olefin polymer using the same | |
| KR102028063B1 (en) | Transition metal compound, catalyst composition comprising the same, and method for preparing olefin polymer using the same | |
| JP6440832B2 (en) | Metallocene compound, metallocene supported catalyst, and method for producing polyolefin using the same | |
| KR101927460B1 (en) | Supported hybrid catalyst and method for preparing olefin polymer using the same | |
| KR20170076550A (en) | Method for preparing of supported hybrid metallocene catalyst, the supported hybrid metallocene catalyst prepared by the same method, and method for preparing polyolefin using the same | |
| CN106795229B (en) | Metallocene-supported catalyst and method for preparing polyolefin using the same | |
| KR20140049452A (en) | Novel metallocene compound, catalyst composition comprising the same, and method for preparing olefin-based polymers using the same | |
| KR20150057964A (en) | Metallocene compound, catalyst composition comprising the same, and method for preparation of olefin-based polymer using the same | |
| CN107406475B (en) | Transition metal compound, catalyst composition comprising the same, and method for preparing olefin polymer using the catalyst composition | |
| KR101725350B1 (en) | Supported catalyst and method for preparing olefin polymer using the same | |
| KR101725349B1 (en) | Supported hybrid catalyst and method for preparing olefin polymer using the same | |
| KR102089057B1 (en) | Transition metal compound, catalyst composition comprising the same, and method for preparing olefin polymer using the same | |
| KR20170106801A (en) | Olefin polymer and preparation method thereof | |
| KR102074510B1 (en) | Supported hybrid catalyst and method for preparing olefin polymer using the same | |
| KR20190076136A (en) | Method For Preparing Supported Hybrid Metallocene Catalyst, Supported Hybrid Metallocene Catalyst Prepared By The Same Method, And Method For Preparing Polyolefin Using The Same | |
| JP2018509508A (en) | Metallocene supported catalyst and method for producing polyolefin using the same | |
| KR101792170B1 (en) | Method for preparing supported catalyst and method for preparing olefin polymer using the supported catalyst prepared by the same method | |
| KR102029447B1 (en) | Transition metal compound, catalyst composition comprising the same, and method for preparing olefin polymer using the same | |
| KR101828930B1 (en) | Transition metal compound, catalyst composition comprising the same, and method for preparing olefin polymer using the same | |
| WO2015056974A1 (en) | Method for producing hybrid-supported metallocene catalyst | |
| KR20180055155A (en) | Method for preparing supported metallocene catalyst | |
| KR20180074389A (en) | Transition metal compound, catalyst composition comprising the same, and method for preparing olefin polymer using the same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A201 | Request for examination | ||
| E902 | Notification of reason for refusal | ||
| E701 | Decision to grant or registration of patent right | ||
| GRNT | Written decision to grant |