KR102011927B1 - Catalyst composition and method for preparing polyolefin using the same - Google Patents
Catalyst composition and method for preparing polyolefin using the same Download PDFInfo
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- KR102011927B1 KR102011927B1 KR1020150018103A KR20150018103A KR102011927B1 KR 102011927 B1 KR102011927 B1 KR 102011927B1 KR 1020150018103 A KR1020150018103 A KR 1020150018103A KR 20150018103 A KR20150018103 A KR 20150018103A KR 102011927 B1 KR102011927 B1 KR 102011927B1
- Authority
- KR
- South Korea
- Prior art keywords
- carbon atoms
- group
- formula
- metallocene compound
- catalyst composition
- Prior art date
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- 239000003054 catalyst Substances 0.000 title claims abstract description 49
- 239000000203 mixture Substances 0.000 title claims abstract description 47
- 229920000098 polyolefin Polymers 0.000 title claims abstract description 47
- 238000000034 method Methods 0.000 title claims description 24
- 150000001875 compounds Chemical class 0.000 claims abstract description 114
- 238000009826 distribution Methods 0.000 claims abstract description 16
- 230000000379 polymerizing effect Effects 0.000 claims abstract description 6
- 125000004432 carbon atom Chemical group C* 0.000 claims description 101
- 239000000126 substance Substances 0.000 claims description 34
- 238000006116 polymerization reaction Methods 0.000 claims description 26
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 claims description 24
- -1 cationic Lewis base Chemical class 0.000 claims description 18
- 125000000217 alkyl group Chemical group 0.000 claims description 17
- 229910052739 hydrogen Inorganic materials 0.000 claims description 17
- 239000001257 hydrogen Substances 0.000 claims description 17
- 125000003118 aryl group Chemical group 0.000 claims description 16
- 125000003342 alkenyl group Chemical group 0.000 claims description 10
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 9
- 229910052782 aluminium Inorganic materials 0.000 claims description 9
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 9
- 229910052796 boron Inorganic materials 0.000 claims description 9
- 239000000178 monomer Substances 0.000 claims description 9
- 150000001336 alkenes Chemical class 0.000 claims description 8
- 125000003545 alkoxy group Chemical group 0.000 claims description 8
- 125000002877 alkyl aryl group Chemical group 0.000 claims description 8
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 8
- 229910052736 halogen Inorganic materials 0.000 claims description 8
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 8
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 8
- 125000001931 aliphatic group Chemical group 0.000 claims description 6
- 125000003277 amino group Chemical group 0.000 claims description 6
- 150000002367 halogens Chemical group 0.000 claims description 6
- 125000005842 heteroatom Chemical group 0.000 claims description 6
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 claims description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 5
- CRSBERNSMYQZNG-UHFFFAOYSA-N 1-dodecene Chemical compound CCCCCCCCCCC=C CRSBERNSMYQZNG-UHFFFAOYSA-N 0.000 claims description 4
- GQEZCXVZFLOKMC-UHFFFAOYSA-N 1-hexadecene Chemical compound CCCCCCCCCCCCCCC=C GQEZCXVZFLOKMC-UHFFFAOYSA-N 0.000 claims description 4
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 claims description 4
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 claims description 4
- 125000002947 alkylene group Chemical group 0.000 claims description 4
- 125000000732 arylene group Chemical group 0.000 claims description 4
- 125000004104 aryloxy group Chemical group 0.000 claims description 4
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 4
- 125000002993 cycloalkylene group Chemical group 0.000 claims description 4
- PXBRQCKWGAHEHS-UHFFFAOYSA-N dichlorodifluoromethane Chemical compound FC(F)(Cl)Cl PXBRQCKWGAHEHS-UHFFFAOYSA-N 0.000 claims description 4
- 125000005843 halogen group Chemical group 0.000 claims description 4
- 125000001183 hydrocarbyl group Chemical group 0.000 claims description 4
- VAMFXQBUQXONLZ-UHFFFAOYSA-N n-alpha-eicosene Natural products CCCCCCCCCCCCCCCCCCC=C VAMFXQBUQXONLZ-UHFFFAOYSA-N 0.000 claims description 4
- CCCMONHAUSKTEQ-UHFFFAOYSA-N octadec-1-ene Chemical compound CCCCCCCCCCCCCCCCC=C CCCMONHAUSKTEQ-UHFFFAOYSA-N 0.000 claims description 4
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 claims description 4
- 239000004215 Carbon black (E152) Substances 0.000 claims description 3
- 229930195733 hydrocarbon Natural products 0.000 claims description 3
- 150000002430 hydrocarbons Chemical class 0.000 claims description 3
- 230000008569 process Effects 0.000 claims description 3
- 229940106006 1-eicosene Drugs 0.000 claims description 2
- FIKTURVKRGQNQD-UHFFFAOYSA-N 1-eicosene Natural products CCCCCCCCCCCCCCCCCC=CC(O)=O FIKTURVKRGQNQD-UHFFFAOYSA-N 0.000 claims description 2
- 239000002879 Lewis base Substances 0.000 claims description 2
- 229910052795 boron group element Inorganic materials 0.000 claims description 2
- 229940069096 dodecene Drugs 0.000 claims description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 2
- 230000007935 neutral effect Effects 0.000 claims description 2
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 9
- 238000002360 preparation method Methods 0.000 description 33
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 30
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 28
- 239000002002 slurry Substances 0.000 description 27
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 24
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 22
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 21
- 230000000052 comparative effect Effects 0.000 description 20
- 239000012968 metallocene catalyst Substances 0.000 description 18
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 16
- UHOVQNZJYSORNB-MZWXYZOWSA-N benzene-d6 Chemical compound [2H]C1=C([2H])C([2H])=C([2H])C([2H])=C1[2H] UHOVQNZJYSORNB-MZWXYZOWSA-N 0.000 description 12
- 239000000243 solution Substances 0.000 description 12
- 229910052751 metal Inorganic materials 0.000 description 11
- 239000002184 metal Substances 0.000 description 11
- 230000000694 effects Effects 0.000 description 10
- 239000003446 ligand Substances 0.000 description 10
- 229920000642 polymer Polymers 0.000 description 10
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 8
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 8
- 235000011089 carbon dioxide Nutrition 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 8
- 150000002431 hydrogen Chemical class 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- 239000012190 activator Substances 0.000 description 6
- 150000002736 metal compounds Chemical class 0.000 description 6
- 150000002739 metals Chemical class 0.000 description 6
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 5
- 239000005977 Ethylene Substances 0.000 description 5
- 230000004913 activation Effects 0.000 description 5
- HMUNWXXNJPVALC-UHFFFAOYSA-N 1-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)C(CN1CC2=C(CC1)NN=N2)=O HMUNWXXNJPVALC-UHFFFAOYSA-N 0.000 description 4
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Chemical compound C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 description 4
- LDXJRKWFNNFDSA-UHFFFAOYSA-N 2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound C1CN(CC2=NNN=C21)CC(=O)N3CCN(CC3)C4=CN=C(N=C4)NCC5=CC(=CC=C5)OC(F)(F)F LDXJRKWFNNFDSA-UHFFFAOYSA-N 0.000 description 4
- JQMFQLVAJGZSQS-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-N-(2-oxo-3H-1,3-benzoxazol-6-yl)acetamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)CC(=O)NC1=CC2=C(NC(O2)=O)C=C1 JQMFQLVAJGZSQS-UHFFFAOYSA-N 0.000 description 4
- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 4
- CONKBQPVFMXDOV-QHCPKHFHSA-N 6-[(5S)-5-[[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]methyl]-2-oxo-1,3-oxazolidin-3-yl]-3H-1,3-benzoxazol-2-one Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)C[C@H]1CN(C(O1)=O)C1=CC2=C(NC(O2)=O)C=C1 CONKBQPVFMXDOV-QHCPKHFHSA-N 0.000 description 4
- 229910007926 ZrCl Inorganic materials 0.000 description 4
- 229910052786 argon Inorganic materials 0.000 description 4
- GGSUCNLOZRCGPQ-UHFFFAOYSA-O diethyl(phenyl)azanium Chemical compound CC[NH+](CC)C1=CC=CC=C1 GGSUCNLOZRCGPQ-UHFFFAOYSA-O 0.000 description 4
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 4
- MZRVEZGGRBJDDB-UHFFFAOYSA-N n-Butyllithium Substances [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 4
- 239000012044 organic layer Substances 0.000 description 4
- IMFACGCPASFAPR-UHFFFAOYSA-O tributylazanium Chemical compound CCCC[NH+](CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-O 0.000 description 4
- ZMANZCXQSJIPKH-UHFFFAOYSA-O triethylammonium ion Chemical compound CC[NH+](CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-O 0.000 description 4
- YFTHZRPMJXBUME-UHFFFAOYSA-N tripropylamine Chemical compound CCCN(CCC)CCC YFTHZRPMJXBUME-UHFFFAOYSA-N 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- DXQXWMYUGOTNGJ-UHFFFAOYSA-N [4-(trifluoromethyl)phenyl]boron Chemical compound [B]C1=CC=C(C(F)(F)F)C=C1 DXQXWMYUGOTNGJ-UHFFFAOYSA-N 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 239000012043 crude product Substances 0.000 description 3
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical group C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 3
- 239000000706 filtrate Substances 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- DLEDOFVPSDKWEF-UHFFFAOYSA-N lithium butane Chemical compound [Li+].CCC[CH2-] DLEDOFVPSDKWEF-UHFFFAOYSA-N 0.000 description 3
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical compound C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 description 3
- 239000004711 α-olefin Substances 0.000 description 3
- GWUXLTRGPPIDJA-UHFFFAOYSA-N (4-methylphenyl)alumane Chemical compound CC1=CC=C([AlH2])C=C1 GWUXLTRGPPIDJA-UHFFFAOYSA-N 0.000 description 2
- VKMQKNJWQNCEQV-UHFFFAOYSA-N (4-methylphenyl)boron Chemical compound [B]C1=CC=C(C)C=C1 VKMQKNJWQNCEQV-UHFFFAOYSA-N 0.000 description 2
- OHVLMTFVQDZYHP-UHFFFAOYSA-N 1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-2-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound N1N=NC=2CN(CCC=21)C(CN1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)=O OHVLMTFVQDZYHP-UHFFFAOYSA-N 0.000 description 2
- HFDVRLIODXPAHB-UHFFFAOYSA-N 1-tetradecene Chemical compound CCCCCCCCCCCCC=C HFDVRLIODXPAHB-UHFFFAOYSA-N 0.000 description 2
- WZFUQSJFWNHZHM-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)CC(=O)N1CC2=C(CC1)NN=N2 WZFUQSJFWNHZHM-UHFFFAOYSA-N 0.000 description 2
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-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
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 2
- 239000011954 Ziegler–Natta catalyst Substances 0.000 description 2
- 229940100198 alkylating agent Drugs 0.000 description 2
- 239000002168 alkylating agent Substances 0.000 description 2
- 230000029936 alkylation Effects 0.000 description 2
- 238000005804 alkylation reaction Methods 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- SHGOGDWTZKFNSC-UHFFFAOYSA-N ethyl(dimethyl)alumane Chemical compound CC[Al](C)C SHGOGDWTZKFNSC-UHFFFAOYSA-N 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-O triphenylphosphanium Chemical compound C1=CC=CC=C1[PH+](C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-O 0.000 description 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
- VFWCMGCRMGJXDK-UHFFFAOYSA-N 1-chlorobutane Chemical compound CCCCCl VFWCMGCRMGJXDK-UHFFFAOYSA-N 0.000 description 1
- HSFRODBENVJLHS-UHFFFAOYSA-N 2,3-bis(bromomethyl)naphthalene Chemical compound C1=CC=C2C=C(CBr)C(CBr)=CC2=C1 HSFRODBENVJLHS-UHFFFAOYSA-N 0.000 description 1
- YVSMQHYREUQGRX-UHFFFAOYSA-N 2-ethyloxaluminane Chemical compound CC[Al]1CCCCO1 YVSMQHYREUQGRX-UHFFFAOYSA-N 0.000 description 1
- PLGVIJOQDDMWAO-UHFFFAOYSA-N CCCCN(CCCC)CCCC.FC(C(F)=C(C([Al+2])=C1F)F)=C1F.FC(C(F)=C(C([Al+2])=C1F)F)=C1F.FC(C(F)=C(C([Al+2])=C1F)F)=C1F.FC(C(F)=C(C([Al+2])=C1F)F)=C1F Chemical compound CCCCN(CCCC)CCCC.FC(C(F)=C(C([Al+2])=C1F)F)=C1F.FC(C(F)=C(C([Al+2])=C1F)F)=C1F.FC(C(F)=C(C([Al+2])=C1F)F)=C1F.FC(C(F)=C(C([Al+2])=C1F)F)=C1F PLGVIJOQDDMWAO-UHFFFAOYSA-N 0.000 description 1
- JEVCOCKVSCRHMR-UHFFFAOYSA-N CCN(CC)C1=CC=CC=C1.FC(C(F)=C(C([Al+2])=C1F)F)=C1F.FC(C(F)=C(C([Al+2])=C1F)F)=C1F.FC(C(F)=C(C([Al+2])=C1F)F)=C1F.FC(C(F)=C(C([Al+2])=C1F)F)=C1F Chemical compound CCN(CC)C1=CC=CC=C1.FC(C(F)=C(C([Al+2])=C1F)F)=C1F.FC(C(F)=C(C([Al+2])=C1F)F)=C1F.FC(C(F)=C(C([Al+2])=C1F)F)=C1F.FC(C(F)=C(C([Al+2])=C1F)F)=C1F JEVCOCKVSCRHMR-UHFFFAOYSA-N 0.000 description 1
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- 239000009566 Mao-to Substances 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- SHPVKUQHCZKKRP-UHFFFAOYSA-N [B+2]C(C(F)=C(C(F)=C1F)F)=C1F.[B+2]C(C(F)=C(C(F)=C1F)F)=C1F.[B+2]C(C(F)=C(C(F)=C1F)F)=C1F.[B+2]C(C(F)=C(C(F)=C1F)F)=C1F.CCCCN(CCCC)CCCC Chemical compound [B+2]C(C(F)=C(C(F)=C1F)F)=C1F.[B+2]C(C(F)=C(C(F)=C1F)F)=C1F.[B+2]C(C(F)=C(C(F)=C1F)F)=C1F.[B+2]C(C(F)=C(C(F)=C1F)F)=C1F.CCCCN(CCCC)CCCC SHPVKUQHCZKKRP-UHFFFAOYSA-N 0.000 description 1
- XIBZTAIPROXEDH-UHFFFAOYSA-N [B+2]C(C(F)=C(C(F)=C1F)F)=C1F.[B+2]C(C(F)=C(C(F)=C1F)F)=C1F.[B+2]C(C(F)=C(C(F)=C1F)F)=C1F.[B+2]C(C(F)=C(C(F)=C1F)F)=C1F.CCN(CC)C1=CC=CC=C1 Chemical compound [B+2]C(C(F)=C(C(F)=C1F)F)=C1F.[B+2]C(C(F)=C(C(F)=C1F)F)=C1F.[B+2]C(C(F)=C(C(F)=C1F)F)=C1F.[B+2]C(C(F)=C(C(F)=C1F)F)=C1F.CCN(CC)C1=CC=CC=C1 XIBZTAIPROXEDH-UHFFFAOYSA-N 0.000 description 1
- RPXNIXOOFOQCKJ-UHFFFAOYSA-N [B+2]C(C(F)=C(C(F)=C1F)F)=C1F.[B+2]C(C(F)=C(C(F)=C1F)F)=C1F.[B+2]C(C(F)=C(C(F)=C1F)F)=C1F.[B+2]C(C(F)=C(C(F)=C1F)F)=C1F.CCNCC Chemical compound [B+2]C(C(F)=C(C(F)=C1F)F)=C1F.[B+2]C(C(F)=C(C(F)=C1F)F)=C1F.[B+2]C(C(F)=C(C(F)=C1F)F)=C1F.[B+2]C(C(F)=C(C(F)=C1F)F)=C1F.CCNCC RPXNIXOOFOQCKJ-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000003849 aromatic solvent Substances 0.000 description 1
- 230000002902 bimodal effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229960004424 carbon dioxide Drugs 0.000 description 1
- IZMHKHHRLNWLMK-UHFFFAOYSA-M chloridoaluminium Chemical compound Cl[Al] IZMHKHHRLNWLMK-UHFFFAOYSA-M 0.000 description 1
- 238000010960 commercial process Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 description 1
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- MYBJXSAXGLILJD-UHFFFAOYSA-N diethyl(methyl)alumane Chemical compound CC[Al](C)CC MYBJXSAXGLILJD-UHFFFAOYSA-N 0.000 description 1
- ISEJRLXHKSHKPM-UHFFFAOYSA-N dimethyl(2-methylpropyl)alumane Chemical compound CC(C)C[Al](C)C ISEJRLXHKSHKPM-UHFFFAOYSA-N 0.000 description 1
- JGHYBJVUQGTEEB-UHFFFAOYSA-M dimethylalumanylium;chloride Chemical compound C[Al](C)Cl JGHYBJVUQGTEEB-UHFFFAOYSA-M 0.000 description 1
- MWNKMBHGMZHEMM-UHFFFAOYSA-N dimethylalumanylium;ethanolate Chemical compound CCO[Al](C)C MWNKMBHGMZHEMM-UHFFFAOYSA-N 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229910021482 group 13 metal Inorganic materials 0.000 description 1
- JQOAQUXIUNVRQW-UHFFFAOYSA-N hexane Chemical compound CCCCCC.CCCCCC JQOAQUXIUNVRQW-UHFFFAOYSA-N 0.000 description 1
- 239000002815 homogeneous catalyst Substances 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 125000005647 linker group Chemical group 0.000 description 1
- 238000006138 lithiation reaction Methods 0.000 description 1
- BQBCXNQILNPAPX-UHFFFAOYSA-N methoxy(dimethyl)alumane Chemical compound [O-]C.C[Al+]C BQBCXNQILNPAPX-UHFFFAOYSA-N 0.000 description 1
- 150000002902 organometallic compounds Chemical group 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- WNFSFUSCVXIYGN-UHFFFAOYSA-N phenylaluminum Chemical compound [Al]C1=CC=CC=C1 WNFSFUSCVXIYGN-UHFFFAOYSA-N 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- VSZWPYCFIRKVQL-UHFFFAOYSA-N selanylidenegallium;selenium Chemical compound [Se].[Se]=[Ga].[Se]=[Ga] VSZWPYCFIRKVQL-UHFFFAOYSA-N 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- NDUUEFPGQBSFPV-UHFFFAOYSA-N tri(butan-2-yl)alumane Chemical compound CCC(C)[Al](C(C)CC)C(C)CC NDUUEFPGQBSFPV-UHFFFAOYSA-N 0.000 description 1
- SQBBHCOIQXKPHL-UHFFFAOYSA-N tributylalumane Chemical compound CCCC[Al](CCCC)CCCC SQBBHCOIQXKPHL-UHFFFAOYSA-N 0.000 description 1
- CMHHITPYCHHOGT-UHFFFAOYSA-N tributylborane Chemical compound CCCCB(CCCC)CCCC CMHHITPYCHHOGT-UHFFFAOYSA-N 0.000 description 1
- PYLGJXLKFZZEBJ-UHFFFAOYSA-N tricyclopentylalumane Chemical compound C1CCCC1[Al](C1CCCC1)C1CCCC1 PYLGJXLKFZZEBJ-UHFFFAOYSA-N 0.000 description 1
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 1
- LALRXNPLTWZJIJ-UHFFFAOYSA-N triethylborane Chemical compound CCB(CC)CC LALRXNPLTWZJIJ-UHFFFAOYSA-N 0.000 description 1
- ORYGRKHDLWYTKX-UHFFFAOYSA-N trihexylalumane Chemical compound CCCCCC[Al](CCCCCC)CCCCCC ORYGRKHDLWYTKX-UHFFFAOYSA-N 0.000 description 1
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 description 1
- WXRGABKACDFXMG-UHFFFAOYSA-N trimethylborane Chemical compound CB(C)C WXRGABKACDFXMG-UHFFFAOYSA-N 0.000 description 1
- YWWDBCBWQNCYNR-UHFFFAOYSA-O trimethylphosphanium Chemical compound C[PH+](C)C YWWDBCBWQNCYNR-UHFFFAOYSA-O 0.000 description 1
- JOJQVUCWSDRWJE-UHFFFAOYSA-N tripentylalumane Chemical compound CCCCC[Al](CCCCC)CCCCC JOJQVUCWSDRWJE-UHFFFAOYSA-N 0.000 description 1
- JQPMDTQDAXRDGS-UHFFFAOYSA-N triphenylalumane Chemical compound C1=CC=CC=C1[Al](C=1C=CC=CC=1)C1=CC=CC=C1 JQPMDTQDAXRDGS-UHFFFAOYSA-N 0.000 description 1
- CNWZYDSEVLFSMS-UHFFFAOYSA-N tripropylalumane Chemical compound CCC[Al](CCC)CCC CNWZYDSEVLFSMS-UHFFFAOYSA-N 0.000 description 1
- ZMPKTELQGVLZTD-UHFFFAOYSA-N tripropylborane Chemical compound CCCB(CCC)CCC ZMPKTELQGVLZTD-UHFFFAOYSA-N 0.000 description 1
- XDSSGQHOYWGIKC-UHFFFAOYSA-N tris(2-methylpropyl)borane Chemical compound CC(C)CB(CC(C)C)CC(C)C XDSSGQHOYWGIKC-UHFFFAOYSA-N 0.000 description 1
- WSITXTIRYQMZHM-UHFFFAOYSA-N tris(4-methylphenyl)alumane Chemical compound C1=CC(C)=CC=C1[Al](C=1C=CC(C)=CC=1)C1=CC=C(C)C=C1 WSITXTIRYQMZHM-UHFFFAOYSA-N 0.000 description 1
- 238000013022 venting Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/62—Refractory metals or compounds thereof
- C08F4/64—Titanium, zirconium, hafnium or compounds thereof
- C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
- C08F4/6592—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- 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
-
- 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
- C08F2410/00—Features related to the catalyst preparation, the catalyst use or to the deactivation of the catalyst
- C08F2410/03—Multinuclear procatalyst, i.e. containing two or more metals, being different or not
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Abstract
본 발명은 높은 분자량 및 넓은 분자량 분포를 갖고 생산성이 뛰어난 고품질의 폴리올레핀을 중합할 수 있는 새로운 구조의 이핵 메탈로센 화합물을 포함하는 촉매 조성물 및 이를 이용한 폴리올레핀의 제조방법에 관한 것이다.The present invention relates to a catalyst composition comprising a binuclear metallocene compound having a high molecular weight and a wide molecular weight distribution and capable of polymerizing a high quality polyolefin having excellent productivity, and a method for producing a polyolefin using the same.
Description
본 발명은 촉매 조성물 및 이를 이용한 폴리올레핀의 제조방법에 관한 것이다. 보다 상세하게는, 높은 분자량 및 넓은 분자량 분포를 갖는 폴리올레핀을 제조할 수 있는 신규한 구조의 이핵 메탈로센 화합물을 포함하는 촉매 조성물 및 이를 이용한 폴리올레핀의 제조방법에 관한 것이다.The present invention relates to a catalyst composition and a method for producing a polyolefin using the same. More specifically, the present invention relates to a catalyst composition comprising a dinuclear metallocene compound having a novel structure capable of producing a polyolefin having a high molecular weight and a wide molecular weight distribution, and a method for producing a polyolefin using the same.
기존의 상업 프로세스에 널리 적용되는 지글러-나타 촉매는 다활성점 촉매이기 때문에 생성 고분자의 분자량 분포가 넓은 것이 특징이며 공단량체의 조성 분포가 균일하지 않아 원하는 물성 확보에 한계가 있다.The Ziegler-Natta catalyst widely applied to the existing commercial processes is characterized by a wide molecular weight distribution of the produced polymer because it is a multi-site catalyst, and the composition of the comonomer is not uniform, thereby limiting the desired physical properties.
반면, 메탈로센 촉매는 하나의 종류의 활성점을 가진 단일 활성점 촉매로 생성 중합체의 분자량 분포가 좁고 촉매와 리간드의 구조에 따라 분자량, 입체 규칙도, 결정화도, 특히 공단량체의 반응성을 대폭 조절할 수 있는 장점이 있다. 그러나, 메탈로센 촉매로 중합한 폴리올레핀은 분자량 분포가 좁아 일부 제품에 응용할 경우, 압출부하 등의 영향으로 생산성이 현저히 떨어지는 등 현장적용이 어려운 문제가 있어 이와 관련된 폴리올레핀의 분자량 분포를 조절하려는 노력을 많이 해왔다.Metallocene catalysts, on the other hand, are single-site catalysts with one type of active site, which have a narrow molecular weight distribution of polymers and greatly control the molecular weight, stereoregularity, crystallinity, and especially the reactivity of comonomers, depending on the structure of the catalyst and ligand. There are advantages to it. However, the polyolefin polymerized with a metallocene catalyst has a narrow molecular weight distribution, so when applied to some products, there is a problem that it is difficult to apply in the field, such as productivity is significantly reduced due to the extruded load, etc. I've done a lot.
이를 위해, 단핵 메탈로센 화합물과 이핵 메탈로센 화합물을 이용한 방법이 알려져 있다.To this end, methods using mononuclear metallocene compounds and dinuclear metallocene compounds are known.
단핵 메탈로센 화합물에 대한 예를 들면, 미국 특허 제5,032,562호에는 두 개의 상이한 전이금속 촉매를 한 개의 담지 촉매 상에 지지시켜 중합 촉매를 제조하는 방법이 기재되어 있다. 이는 고분자량을 생성하는 티타늄(Ti) 계열의 지글러-나타 촉매와 저분자량을 생성하는 지르코늄(Zr) 계열의 메탈로센 촉매를 하나의 지지체에 담지시켜 이정 분산(bimodal distribution) 고분자를 생성하는 방법으로써, 담지 과정이 복잡하고, 조촉매로 인해 중합체의 형상(morphology)이 나빠지는 단점이 있다.For example, for mononuclear metallocene compounds, US Pat. No. 5,032,562 describes a process for preparing a polymerization catalyst by supporting two different transition metal catalysts on one supported catalyst. It is a method of producing a bimodal distribution polymer by supporting a titanium (Ti) -based Ziegler-Natta catalyst that generates a high molecular weight and a zirconium (Zr) -based metallocene catalyst that produces a low molecular weight on one support As a result, the supporting process is complicated, and the morphology of the polymer is degraded due to the promoter.
또한, 이핵 메탈로센 화합물을 이용하여 공중합시 촉매의 공중합체 선택성, 활성 등을 변화시키고자 하는 연구가 보고되어 있으며, 일부 메탈로센 촉매의 경우 공중합체 병합(incorporation) 및 활성이 높아지는 경우가 보고되어 있다.In addition, studies have been made to change the copolymer selectivity, activity, etc. of the catalyst when copolymerizing using a heteronuclear metallocene compound. Some metallocene catalysts have increased copolymer incorporation and activity. Reported.
예들 들어, 대한민국 특허출원 제2003-12308호에는 담체에 이중핵 메탈로센 촉매와 단일핵 메탈로센 촉매를 활성화제와 함께 담지하여 반응기 내 촉매의 조합을 변화시키며 중합함으로써 분자량 분포를 제어하는 방안을 개시하고 있다. 그러나, 이러한 방법은 각각의 촉매의 특성을 동시에 구현하기에 한계가 있으며, 또한 완성된 촉매의 담체 성분에서 메탈로센 촉매 부분이 유리되어 반응기에 파울링(fouling)을 유발하는 단점이 있다.For example, Korean Patent Application No. 2003-12308 discloses a method of controlling molecular weight distribution by supporting a dual nucleus metallocene catalyst and a mononuclear metallocene catalyst on a carrier together with an activator to polymerize by changing the combination of catalysts in the reactor. Is starting. However, this method is limited in realizing the characteristics of each catalyst at the same time, and also has the disadvantage of freeing the metallocene catalyst portion in the carrier component of the finished catalyst, causing fouling in the reactor.
또한, 바이페닐렌 브릿지를 가지는 4족 금속 메탈로센 촉매의 합성법과 이 촉매를 이용한 에틸렌과 스타이렌의 중합에 대해 보고되고 있다(Organometallics, 2005, 24, 3618). 상기 방법에 따르면, 단핵 메탈로센 촉매에 비해 촉매의 활성이 높고 얻어진 고분자의 분자량이 크다고 기재하고 있다. 또 다른 방법은 4족 이핵 메탈로센 촉매의 브릿지 구조를 변환하여 촉매의 반응성에 변화를 줄 수 있다는 보고가 된 바 있다(Eur. Polym, J. 2007, 43, 1436).In addition, a synthesis method of a Group 4 metal metallocene catalyst having a biphenylene bridge and polymerization of ethylene and styrene using the catalyst have been reported (Organometallics, 2005, 24, 3618). According to the method, the activity of the catalyst is higher than that of the mononuclear metallocene catalyst and the molecular weight of the obtained polymer is described. Another method has been reported that the bridge structure of the Group 4 heteronuclear metallocene catalyst can be changed to change the reactivity of the catalyst (Eur. Polym, J. 2007, 43, 1436).
하지만, 상기 방법들을 이용하게 되면, 이전에 보고된 바이페닐렌 브릿지를 가지는 4족 금속 메탈로센 촉매의 경우 치환기의 첨가 및 구조의 변경에 문제가 있으므로, 올레핀 제조에 유용한 새로운 메탈로센 촉매의 개발이 필요한 실정이다.However, using the above methods, in the case of the Group 4 metal metallocene catalyst having a biphenylene bridge previously reported, there is a problem in the addition of substituents and the change of the structure. Development is needed.
상기와 같은 과제를 해결하고자, 본 발명은 새로운 구조의 이핵 메탈로센 화합물을 포함하는 촉매 조성물을 제공하는 것을 목적으로 한다.In order to solve the above problems, an object of the present invention is to provide a catalyst composition comprising a dinuclear metallocene compound of a novel structure.
또한 본 발명은 상기 촉매 조성물을 이용한 폴리올레핀의 제조방법을 제공하고자 한다.In another aspect, the present invention is to provide a method for producing a polyolefin using the catalyst composition.
상기와 같은 과제를 해결하기 위하여, 본 발명의 일 측면은 하기 화학식 1로 표시되는 이핵 메탈로센 화합물을 포함하는 촉매 조성물을 제공한다.In order to solve the above problems, an aspect of the present invention provides a catalyst composition comprising a binuclear metallocene compound represented by the following formula (1).
[화학식 1][Formula 1]
상기 화학식 1에서,In Chemical Formula 1,
R1 내지 R8은 서로 같거나 다를 수 있으며, 각각 독립적으로 수소, 탄소수 1 내지 20의 알킬기, 탄소수 2 내지 20의 알케닐기, 탄소수 6 내지 20의 아릴기, 탄소수 7 내지 20의 알킬아릴기, 탄소수 7 내지 20의 아릴알킬기, 또는 탄소수 1 내지 20의 아민기이고, 상기 R1 내지 R8 중 인접하는 2개가 서로 연결되어 1개 이상의 지방족 고리, 방향족 고리, 또는 헤테로 고리를 형성할 수 있고, 단 R1 내지 R8가 모두 수소인 경우는 제외하며; R1 to R8 may be the same or different from each other, and each independently hydrogen, an alkyl group of 1 to 20 carbon atoms, an alkenyl group of 2 to 20 carbon atoms, an aryl group of 6 to 20 carbon atoms, an alkylaryl group of 7 to 20 carbon atoms, 7 carbon atoms An arylalkyl group of 20 to 20, or an amine group having 1 to 20 carbon atoms, and two adjacent groups of R1 to R8 may be connected to each other to form one or more aliphatic rings, aromatic rings, or hetero rings, provided that R1 to R8 Except when are all hydrogen;
R9 및 R10은 서로 동일하거나 상이하고, 각각 독립적으로 수소, 탄소수 1 내지 20의 알킬기, 탄소수 3 내지 20의 시클로알킬기, 탄소수 1 내지 20의 알콕시기, 탄소수 6 내지 20의 아릴기, 탄소수 6 내지 10의 아릴옥시기, 탄소수 2 내지 20의 알케닐기, 탄소수 7 내지 40의 알킬아릴기, 또는 탄소수 7 내지 40의 아릴알킬기이고;R9 and R10 are the same as or different from each other, and each independently hydrogen, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and 6 to 10 carbon atoms An aryloxy group, an alkenyl group having 2 to 20 carbon atoms, an alkylaryl group having 7 to 40 carbon atoms, or an arylalkyl group having 7 to 40 carbon atoms;
Q는 탄소수 1 내지 20의 알킬렌기, 탄소수 3 내지 20의 시클로알킬렌기, 탄소수 6 내지 20의 아릴렌기, 탄소수 7 내지 40의 알킬아릴렌기, 또는 탄소수 7 내지 40의 아릴알킬렌기이고; Q is an alkylene group having 1 to 20 carbon atoms, a cycloalkylene group having 3 to 20 carbon atoms, an arylene group having 6 to 20 carbon atoms, an alkylarylene group having 7 to 40 carbon atoms, or an arylalkylene group having 7 to 40 carbon atoms;
X는 할로겐 원자이고;X is a halogen atom;
n은 1 내지 10의 정수이며;n is an integer from 1 to 10;
m은 0 또는 1의 정수이다.m is an integer of 0 or 1.
또한, 본 발명은 상기 촉매 조성물의 존재 하에, 적어도 1종 이상의 올레핀 단량체를 중합시키는 단계를 포함하는 폴리올레핀의 제조방법을 제공한다.The present invention also provides a method for producing a polyolefin comprising the step of polymerizing at least one or more olefin monomers in the presence of the catalyst composition.
본 발명에 따른 이핵 메탈로센 촉매를 포함하는 촉매 조성물을 이용하여 폴리올레핀 제조시 다른 균일계 촉매의 장점을 그대로 가지면서 높은 활성을 나타낼 수 있다. By using the catalyst composition comprising a binuclear metallocene catalyst according to the present invention, it is possible to exhibit high activity while maintaining the advantages of other homogeneous catalysts when producing polyolefins.
또한 본 발명의 촉매는 분자량 및 분자량 분포를 자유롭게 조절하여, 높은 분자량 및 넓은 분자량 분포를 갖고 생산성이 뛰어난 고품질의 폴리올레핀을 생산할 수 있다.In addition, the catalyst of the present invention can freely adjust the molecular weight and molecular weight distribution, thereby producing a high quality polyolefin having high molecular weight and wide molecular weight distribution and excellent productivity.
본 발명의 이핵 메탈로센 화합물은 신규한 구조의 이핵 메탈로센 화합물이며, 이러한 이핵 메탈로센 화합물을 포함하는 촉매 조성물은 원하는 물성과 분자량 분포를 가지는 폴리올레핀을 생산할 수 있다. The dinuclear metallocene compound of the present invention is a dinuclear metallocene compound having a novel structure, and the catalyst composition including the dinuclear metallocene compound can produce a polyolefin having a desired physical property and a molecular weight distribution.
또한 본 발명의 폴리올레핀 제조방법에 따르면, 상기 이핵 메탈로센 화합물을 포함하는 촉매 조성물을 이용하여 높은 분자량 및 넓은 분자량 분포를 갖는 폴리올레핀을 중합할 수 있다.In addition, according to the polyolefin production method of the present invention, it is possible to polymerize a polyolefin having a high molecular weight and a wide molecular weight distribution by using the catalyst composition comprising the heteronuclear metallocene compound.
이하에서 본 발명을 상세하게 설명한다.
Hereinafter, the present invention will be described in detail.
본 발명의 일 측면에 따르면, 하기 화학식 1의 이핵 메탈로센 화합물을 포함하는 촉매 조성물이 제공된다. According to one aspect of the invention, there is provided a catalyst composition comprising a binuclear metallocene compound of formula (1).
본 발명의 일 구현예에 따른 촉매 조성물은, 하기 화학식 1의 이핵 메탈로센 화합물과 조촉매를 포함하는 조성물일 수 있다. The catalyst composition according to one embodiment of the present invention may be a composition including a dinuclear metallocene compound represented by Chemical Formula 1 and a promoter.
또는 본 발명의 다른 구현예에 따른 촉매 조성물은, 하기 화학식 2의 일핵 메탈로센 화합물 및 상기 화학식 3으로 표시되는 링커 화합물과 조촉매를 포함하는 조성물일 수 있다.Alternatively, the catalyst composition according to another embodiment of the present invention may be a composition including a mononuclear metallocene compound of Formula 2 and a linker compound represented by Formula 3 and a promoter.
[화학식 1][Formula 1]
상기 화학식 1에서,In Chemical Formula 1,
R1 내지 R8은 서로 같거나 다를 수 있으며, 각각 독립적으로 수소, 탄소수 1 내지 20의 알킬기, 탄소수 2 내지 20의 알케닐기, 탄소수 6 내지 20의 아릴기, 탄소수 7 내지 20의 알킬아릴기, 탄소수 7 내지 20의 아릴알킬기, 또는 탄소수 1 내지 20의 아민기이고, 상기 R1 내지 R8 중 인접하는 2개가 서로 연결되어 1개 이상의 지방족 고리, 방향족 고리, 또는 헤테로 고리를 형성할 수 있고, 단 R1 내지 R8가 모두 수소인 경우는 제외하며;R1 to R8 may be the same or different from each other, and each independently hydrogen, an alkyl group of 1 to 20 carbon atoms, an alkenyl group of 2 to 20 carbon atoms, an aryl group of 6 to 20 carbon atoms, an alkylaryl group of 7 to 20 carbon atoms, 7 carbon atoms An arylalkyl group of 20 to 20, or an amine group having 1 to 20 carbon atoms, and two adjacent groups of R1 to R8 may be connected to each other to form one or more aliphatic rings, aromatic rings, or hetero rings, provided that R1 to R8 Except when are all hydrogen;
R9 및 R10은 서로 동일하거나 상이하고, 각각 독립적으로 수소, 탄소수 1 내지 20의 알킬기, 탄소수 3 내지 20의 시클로알킬기, 탄소수 1 내지 20의 알콕시기, 탄소수 6 내지 20의 아릴기, 탄소수 6 내지 10의 아릴옥시기, 탄소수 2 내지 20의 알케닐기, 탄소수 7 내지 40의 알킬아릴기, 또는 탄소수 7 내지 40의 아릴알킬기이고;R9 and R10 are the same as or different from each other, and each independently hydrogen, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and 6 to 10 carbon atoms An aryloxy group, an alkenyl group having 2 to 20 carbon atoms, an alkylaryl group having 7 to 40 carbon atoms, or an arylalkyl group having 7 to 40 carbon atoms;
Q는 탄소수 1 내지 20의 알킬렌기, 탄소수 3 내지 20의 시클로알킬렌기, 탄소수 6 내지 20의 아릴렌기, 탄소수 7 내지 40의 알킬아릴렌기, 또는 탄소수 7 내지 40의 아릴알킬렌기이고;Q is an alkylene group having 1 to 20 carbon atoms, a cycloalkylene group having 3 to 20 carbon atoms, an arylene group having 6 to 20 carbon atoms, an alkylarylene group having 7 to 40 carbon atoms, or an arylalkylene group having 7 to 40 carbon atoms;
X는 할로겐 원자이고;X is a halogen atom;
n은 1 내지 10의 정수이며;n is an integer from 1 to 10;
m은 0 또는 1의 정수이다.m is an integer of 0 or 1.
[화학식 2][Formula 2]
[화학식 3][Formula 3]
상기 화학식 2에서, In Chemical Formula 2,
R1 내지 R10, Q, X 및 m은 상기 화학식 1에서 정의한 바와 같고, R1 to R10, Q, X and m are as defined in Formula 1,
상기 화학식 3에서, Z는 Cl 또는 Br이며, n은 1 내지 10이다.In Formula 3, Z is Cl or Br, n is 1 to 10.
본 발명에서 "촉매 조성물" 이라 함은 상기 화학식 2의 일핵 메탈로센 화합물, 링커 화합물 및 조촉매의 3 성분이 또는 대안적으로, 상기 화학식 1의 이핵 메탈로센 화합물 및 조촉매의 2 성분이 동시에 또는 임의의 순서로 순차적으로, 임의의 적합한 용매의 존재 또는 부존재 하에서, 단량체의 존재 또는 부재 하에 함께 첨가되어 활성이 있는 조성물로 수득될 수 있는 상태의 것을 의미한다. In the present invention, "catalyst composition" means three components of the mononuclear metallocene compound of Formula 2, a linker compound and a promoter or alternatively, two components of the dinuclear metallocene compound of Formula 1 and the promoter of By the same time or in any order, in the presence or absence of any suitable solvent, in the presence or absence of monomers is meant a state which can be obtained as an active composition.
즉, 본 발명에 따른 촉매 조성물은 상기 화학식 2의 일핵 메탈로센 화합물, 상기 화학식 3의 링커 화합물, 및 조촉매를 포함하거나 또는 상기 화학식 1의 이핵 메탈로센 및 조촉매를 포함하는 것일 수 있다. 상기 촉매 조성물이 상기 일핵 메탈로센 화합물, 링커 화합물 및 조촉매를 포함하는 경우에도, 실질적인 올레핀 중합 반응은 상기 일핵 메탈로센 화합물과 링커 화합물이 반응하여 생성된 이핵 메탈로센 화합물에 의해 수행될 수 있다.That is, the catalyst composition according to the present invention may include a mononuclear metallocene compound of Formula 2, a linker compound of Formula 3, and a cocatalyst, or may include a binuclear metallocene and a promoter of Formula 1 . Even when the catalyst composition comprises the mononuclear metallocene compound, the linker compound and the cocatalyst, the substantial olefin polymerization reaction may be performed by the binuclear metallocene compound produced by the reaction of the mononuclear metallocene compound with the linker compound. Can be.
상기 촉매 조성물의 3 성분 또는 2 성분들은 담체에 담지하지 않고 사용될 수 있으며, 또는 필요에 따라 담체에 담지되어 사용될 수도 있다. The three components or two components of the catalyst composition may be used without being supported on a carrier, or may be supported and used on a carrier as necessary.
본 발명의 일 구현예에 따르면, 본 발명의 이핵 메탈로센 화합물은 하기 화학식 1로 표시될 수 있다.According to one embodiment of the present invention, the dinuclear metallocene compound of the present invention may be represented by the following Chemical Formula 1.
[화학식 1][Formula 1]
상기 화학식 1에서,In Chemical Formula 1,
R1 내지 R8은 서로 같거나 다를 수 있으며, 각각 독립적으로 수소, 탄소수 1 내지 20의 알킬기, 탄소수 2 내지 20의 알케닐기, 탄소수 6 내지 20의 아릴기, 탄소수 7 내지 20의 알킬아릴기, 탄소수 7 내지 20의 아릴알킬기, 또는 탄소수 1 내지 20의 아민기이고, 상기 R1 내지 R8 중 인접하는 2개가 서로 연결되어 1개 이상의 지방족 고리, 방향족 고리, 또는 헤테로 고리를 형성할 수 있고, 단 R1 내지 R8가 모두 수소인 경우는 제외하며;R1 to R8 may be the same or different from each other, and each independently hydrogen, an alkyl group of 1 to 20 carbon atoms, an alkenyl group of 2 to 20 carbon atoms, an aryl group of 6 to 20 carbon atoms, an alkylaryl group of 7 to 20 carbon atoms, 7 carbon atoms An arylalkyl group of 20 to 20, or an amine group having 1 to 20 carbon atoms, and two adjacent groups of R1 to R8 may be connected to each other to form one or more aliphatic rings, aromatic rings, or hetero rings, provided that R1 to R8 Except when are all hydrogen;
R9 및 R10은 서로 동일하거나 상이하고, 각각 독립적으로 수소, 탄소수 1 내지 20의 알킬기, 탄소수 3 내지 20의 시클로알킬기, 탄소수 1 내지 20의 알콕시기, 탄소수 6 내지 20의 아릴기, 탄소수 6 내지 10의 아릴옥시기, 탄소수 2 내지 20의 알케닐기, 탄소수 7 내지 40의 알킬아릴기, 또는 탄소수 7 내지 40의 아릴알킬기이고;R9 and R10 are the same as or different from each other, and each independently hydrogen, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and 6 to 10 carbon atoms An aryloxy group, an alkenyl group having 2 to 20 carbon atoms, an alkylaryl group having 7 to 40 carbon atoms, or an arylalkyl group having 7 to 40 carbon atoms;
Q는 탄소수 1 내지 20의 알킬렌기, 탄소수 3 내지 20의 시클로알킬렌기, 탄소수 6 내지 20의 아릴렌기, 탄소수 7 내지 40의 알킬아릴렌기, 또는 탄소수 7 내지 40의 아릴알킬렌기이고;Q is an alkylene group having 1 to 20 carbon atoms, a cycloalkylene group having 3 to 20 carbon atoms, an arylene group having 6 to 20 carbon atoms, an alkylarylene group having 7 to 40 carbon atoms, or an arylalkylene group having 7 to 40 carbon atoms;
X는 할로겐 원자이고;X is a halogen atom;
n은 1 내지 10의 정수이며;n is an integer from 1 to 10;
m은 0 또는 1의 정수이다.m is an integer of 0 or 1.
상기 화학식 1의 이핵 메탈로센 화합물은 구조 중에 2개의 중심 금속으로 Zr를 포함하고, 각각의 중심 금속에 연결된 리간드는 2개의 사이클로펜타디엔기 골격이 브릿지(bridge)로 결합되어 있거나, 또는 결합되어 있지 않은 구조의 화합물이다. 또한 본 발명의 화학식 1의 이핵 메탈로센 화합물은 2개의 중심 금속의 상호 작용을 줄이기 위해 중심 금속 사이에 알킬 체인으로 간격을 부여함으로써 안정적인 촉매 활성을 나타낼 수 있다. The dinuclear metallocene compound of Formula 1 includes Zr as two center metals in a structure, and a ligand linked to each center metal has two cyclopentadiene group skeletons bonded or bridged thereto It is a compound having no structure. In addition, the dinuclear metallocene compound of Chemical Formula 1 of the present invention may exhibit stable catalytic activity by providing a spacing with an alkyl chain between the center metals in order to reduce the interaction of the two center metals.
본 발명의 일 실시예에 따르면, 상기 화학식 1의 이핵 메탈로센 화합물에서, 상기 R1 내지 R8은 각각 독립적으로 수소, 탄소수 1 내지 20의 알킬기, 탄소수 2 내지 20의 알케닐기 또는 탄소수 1 내지 20의 아민기이거나, 상기 R1 내지 R8 중 인접하는 2개가 서로 연결되어 1개 이상의 지방족 고리, 방향족 고리 또는 헤테로 고리를 형성할 수 있다. 또한, R9 및 R10은 각각 독립적으로 수소, 탄소수 1 내지 20의 알킬 또는 탄소수 1 내지 20의 알콕시일 수 있고, X는 Cl이며, n 은 2 내지 6의 정수일 수 있다. According to an embodiment of the present invention, in the dinuclear metallocene compound of Chemical Formula 1, R 1 to R 8 are each independently hydrogen, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, or a carbon atom having 1 to 20 carbon atoms. It may be an amine group, or two adjacent groups of R1 to R8 may be connected to each other to form one or more aliphatic rings, aromatic rings, or hetero rings. In addition, R9 and R10 may be each independently hydrogen, alkyl having 1 to 20 carbon atoms or alkoxy having 1 to 20 carbon atoms, X is Cl, n may be an integer of 2 to 6.
또한, m은 0 또는 1의 정수일 수 있으며, m이 0인 경우 2개의 사이클로펜타디엔기 골격이 연결되어 있지 않은 것을 의미하고, m이 1인 경우 -Q(R9R10)- 브릿지에 의해 연결된 구조를 나타낸다. Also, m may be an integer of 0 or 1, and when m is 0, it means that two cyclopentadiene group skeletons are not connected, and when m is 1, a structure connected by a -Q (R9R10)-bridge is represented. Indicates.
보다 바람직하게, 상기 화학식 1의 이핵 메탈로센 화합물은 하기 화학식 1a 내지 1e의 구조식들 중 하나로 표시될 수 있으나, 이에 제한되는 것은 아니다.More preferably, the dinuclear metallocene compound of Formula 1 may be represented by one of the structural formulas of Formulas 1a to 1e, but is not limited thereto.
[화학식 1a][Formula 1a]
[화학식 1b][Formula 1b]
[화학식 1c][Formula 1c]
[화학식 1d][Formula 1d]
[화학식 1e][Formula 1e]
본 발명의 일 실시예에 따르면, 상기 화학식 1의 이핵 메탈로센 화합물은 하기 화학식 2의 화합물과, 하기 화학식 3의 링커(linker) 화합물을 2:1의 몰 비율로 반응시켜 화학식 2의 화합물의 중심 금속(Zr)을 알킬 체인으로 연결시키는 방법으로 제조될 수 있다.According to an embodiment of the present invention, the dinuclear metallocene compound of Chemical Formula 1 is a compound of Chemical Formula 2 by reacting a compound of Chemical Formula 2 with a linker compound of Chemical Formula 3 at a molar ratio of 2: 1. It can be prepared by the method of connecting the central metal (Zr) with an alkyl chain.
[화학식 2][Formula 2]
[화학식 3][Formula 3]
상기 화학식 2에서, R1 내지 R10, Q, X 및 m은 상기 화학식 1에서 정의한 바와 같고, 상기 화학식 3에서 Z는 Cl 또는 Br이며, n은 1 내지 10이다.In Formula 2, R1 to R10, Q, X and m are as defined in Formula 1, Z in Formula 3 is Cl or Br, n is 1 to 10.
상기 화학식 1의 이핵 메탈로센 화합물의 제조를 위한 반응은 이 기술 분야에 잘 알려진 통상의 유기 합성 방법을 사용할 수 있으므로, 그 조건이 특별히 한정되지 않으며, 후술하는 실시예에서 보다 구체화하여 설명한다. Since the reaction for the preparation of the binuclear metallocene compound of Chemical Formula 1 may use a conventional organic synthesis method well known in the art, the conditions are not particularly limited, and will be described in more detail in the following Examples.
또한, 상기 화학식 2의 일핵 메탈로센 화합물의 제조를 위한 반응은 이 기술 분야에 잘 알려진 통상의 유기 합성 방법을 사용할 수 있으므로, 그 조건이 특별히 한정되지 않으며, 후술하는 실시예에서 보다 구체화하여 설명한다.In addition, since the reaction for the preparation of the mononuclear metallocene compound of Chemical Formula 2 may use a conventional organic synthesis method well known in the art, the conditions are not particularly limited, and the embodiment will be described in detail below. do.
이러한 방법으로 제조된 화학식 1로 표시되는 이핵 메탈로센 화합물은 신규한 구조를 가지며, 이에 포함된 리간드 구조는 사이클로펜타디에닐 또는 그 유도체 골격을 포함한다. The dinuclear metallocene compound represented by Chemical Formula 1 prepared in this manner has a novel structure, and the ligand structure included therein includes cyclopentadienyl or a derivative skeleton thereof.
또한 2개의 메탈로센 화합물의 중심 금속 사이에 결합된 알킬 체인이 각각의 메탈로센 화합물의 금속 중심을 연결하는 링커(linker)의 역할을 하여 금속 사이의 불필요한 상호 작용을 줄일 수 있어 안정적인 이핵 메탈로센의 특성을 가지며 리간드 구조의 변형이 용이한 특성을 가지게 된다.In addition, an alkyl chain bonded between the center metals of the two metallocene compounds acts as a linker that connects the metal centers of the respective metallocene compounds, thereby reducing unnecessary interactions between the metals, thereby providing stable binuclear metals. It has the properties of rosene and easy to modify the ligand structure.
본 발명의 촉매 조성물에 포함될 수 있는 조촉매는 13족 금속을 포함하는 유기 금속 화합물로서, 일반적인 메탈로센 촉매 하에 올레핀을 중합할 때 사용될 수 있는 것이라면 특별히 한정되는 것은 아니다.The cocatalyst which may be included in the catalyst composition of the present invention is not particularly limited as long as it is an organometallic compound including a Group 13 metal, and can be used when polymerizing an olefin under a general metallocene catalyst.
바람직하게, 상기 조촉매는 하기 화학식 4 내지 6으로 표시되는 화합물들로 이루어진 군에서 선택된 1종 이상을 사용할 수 있다.Preferably, the promoter may be used one or more selected from the group consisting of compounds represented by the formula (4) to (6).
[화학식 4][Formula 4]
-[Al(R11)-O]c--[Al (R 11 ) -O] c-
상기 화학식 4에서, R11은 서로 동일하거나 상이하고, 각각 독립적으로 할로겐 라디칼, 탄소수 1 내지 20의 하이드로카빌 라디칼, 또는 할로겐으로 치환된 탄소수 1 내지 20의 하이드로카빌 라디칼이고, c는 2 이상의 정수이며,In Formula 4, R 11 is the same as or different from each other, and each independently a halogen radical, a hydrocarbyl radical having 1 to 20 carbon atoms, or a hydrocarbyl radical having 1 to 20 carbon atoms substituted with halogen, and c is an integer of 2 or more. ,
[화학식 5][Formula 5]
D(R12)3 D (R 12 ) 3
상기 화학식 5에서,In Chemical Formula 5,
D는 알루미늄 또는 보론이고, R12는 탄소수 1 내지 20의 하이드로카빌 또는 할로겐으로 치환된 탄소수 1 내지 20의 하이드로카빌이고,D is aluminum or boron, R 12 is hydrocarbyl having 1 to 20 carbon atoms or hydrocarbyl having 1 to 20 carbon atoms substituted with halogen,
[화학식 6][Formula 6]
[L-H]+[ZA4]- 또는 [L]+[ZA4]- [LH] + [ZA 4] - or [L] + [ZA 4] -
상기 화학식 6에서,In Chemical Formula 6,
L은 중성 또는 양이온성 루이스 염기이고, H는 수소 원자이며, Z는 13족 원소이고, A는 서로 동일하거나 다를 수 있으며, 각각 독립적으로 1 이상의 수소 원자가 할로겐, 탄소수 1 내지 20의 탄화수소, 알콕시 또는 페녹시로 치환 또는 비치환된 탄소수 6 내지 20의 아릴기 또는 탄소수 1 내지 20의 알킬기이다.L is a neutral or cationic Lewis base, H is a hydrogen atom, Z is a Group 13 element, A may be the same or different from each other, and each independently one or more hydrogen atoms is halogen, hydrocarbon having 1 to 20 carbon atoms, alkoxy or Or an aryl group having 6 to 20 carbon atoms or an alkyl group having 1 to 20 carbon atoms unsubstituted or substituted with phenoxy.
상기 화학식 4로 표시되는 화합물로는, 예를 들어 메틸알루미녹산(MAO), 에틸알루미녹산, 이소부틸알루미녹산, 부틸알루미녹산 등이 될 수 있다.Examples of the compound represented by Formula 4 include methyl aluminoxane (MAO), ethyl aluminoxane, isobutyl aluminoxane, butyl aluminoxane, and the like.
상기 화학식 5로 표시되는 알킬 금속 화합물로는, 예를 들어 트리메틸알루미늄, 트리에틸알루미늄, 트리이소부틸알루미늄, 트리프로필알루미늄, 트리부틸알루미늄, 디메틸클로로알루미늄, 디메틸이소부틸알루미늄, 디메틸에틸알루미늄, 디에틸클로로알루미늄, 트리이소프로필알루미늄, 트리-s-부틸알루미늄, 트리씨클로펜틸알루미늄, 트리펜틸알루미늄, 트리이소펜틸알루미늄, 트리헥실알루미늄, 에틸디메틸알루미늄, 메틸디에틸알루미늄, 트리페닐알루미늄, 트리-p-톨릴알루미늄, 디메틸알루미늄메톡시드, 디메틸알루미늄에톡시드, 트리메틸보론, 트리에틸보론, 트리이소부틸보론, 트리프로필보론, 트리부틸보론 등일 수 있다.Examples of the alkyl metal compound represented by Formula 5 include trimethylaluminum, triethylaluminum, triisobutylaluminum, tripropylaluminum, tributylaluminum, dimethylchloroaluminum, dimethylisobutylaluminum, dimethylethylaluminum and diethyl. Chloro aluminum, triisopropyl aluminum, tri-s-butyl aluminum, tricyclopentyl aluminum, tripentyl aluminum, triisopentyl aluminum, trihexyl aluminum, ethyl dimethyl aluminum, methyl diethyl aluminum, triphenyl aluminum, tri-p- Tolyl aluminum, dimethyl aluminum methoxide, dimethyl aluminum ethoxide, trimethyl boron, triethyl boron, triisobutyl boron, tripropyl boron, tributyl boron and the like.
상기 화학식 6으로 표시되는 화합물로는, 예를 들어 트리에틸암모니움테트라페닐보론, 트리부틸암모니움테트라페닐보론, 트리메틸암모니움테트라페닐보론, 트리프로필암모니움테트라페닐보론, 트리메틸암모니움테트라(p-톨릴)보론, 트리프로필암모니움테트라(p-톨릴)보론, 트리에틸암모니움테트라(o,p-디메틸페닐)보론, 트리메틸암모니움테트라(o,p-디메틸페닐)보론, 트리부틸암모니움테트라(p-트리플루오로메틸페닐)보론, 트리메틸암모니움테트라(p-트리플로로메틸페닐)보론, 트리부틸암모니움테트라펜타플루오로페닐보론, N,N-디에틸아닐리니움테트라페닐보론, N,N-디에틸아닐리니움테트라페닐보론, N,N-디에틸아닐리니움테트라펜타플루오로페닐보론, 디에틸암모니움테트라펜타플루오로페닐보론, 트리페닐포스포늄테트라페닐보론, 트리메틸포스포늄테트라페닐보론, 트리에틸암모니움테트라페닐알루미늄, 트리부틸암모니움테트라페닐알루미늄, 트리메틸암모니움테트라페닐알루미늄, 트리프로필암모니움테트라페닐알루미늄, 트리메틸암모니움테트라(p-톨릴)알루미늄, 트리프로필암모니움테트라(p-톨릴)알루미늄, 트리에틸암모니움테트라(o,p-디메틸페닐)알루미늄, 트리부틸암모니움테트라(p-트리플루오로메틸페닐)알루미늄, 트리메틸암모니움테트라(p-트리플루오로메틸페닐)알루미늄,트리부틸암모니움테트라펜타플루오로페닐알루미늄, N,N-디에틸아닐리니움테트라페닐알루미늄, N,N-디에틸아닐리니움테트라페닐알루미늄, N,N-디에틸아닐리니움테트라펜타플로로페닐알루미늄, 디에틸암모니움테트라펜타플루오로페닐알루미늄, 트리페닐포스포늄테트라페닐알루미늄, 트리메틸포스포늄테트라페닐알루미늄, 트리페닐카보니움테트라페닐보론, 트리페닐카보니움테트라페닐알루미늄, 트리페닐카보니움테트라(p-트리플로로메틸페닐)보론, 트리페닐카보니움테트라펜타플루오로페닐보론 등일 수 있다.As the compound represented by the formula (6), for example, triethyl ammonium tetraphenyl boron, tributyl ammonium tetraphenyl boron, trimethyl ammonium tetraphenyl boron, tripropyl ammonium tetraphenyl boron, trimethyl ammonium tetra (p -Tolyl) boron, tripropylammonium tetra (p-tolyl) boron, triethylammonium tetra (o, p-dimethylphenyl) boron, trimethylammonium tetra (o, p-dimethylphenyl) boron, tributylammonium Tetra (p-trifluoromethylphenyl) boron, trimethylammonium tetra (p-trifluoromethylphenyl) boron, tributylammonium tetrapentafluorophenylboron, N, N-diethylanilinium tetraphenylboron, N , N-diethylanilinium tetraphenylboron, N, N-diethylanilinium tetrapentafluorophenylboron, diethylammonium tetrapentafluorophenylboron, triphenylphosphonium tetraphenylboron, trimethyl phosph Nium tetraphenyl boron, triethyl ammonium tetraphenyl aluminum, tributyl ammonium tetraphenyl aluminum, trimethyl ammonium tetraphenyl aluminum, tripropyl ammonium tetraphenyl aluminum, trimethyl ammonium tetra (p-tolyl) aluminum, tripropyl ammonium Umtetra (p-tolyl) aluminum, triethylammonium tetra (o, p-dimethylphenyl) aluminum, tributylammonium tetra (p-trifluoromethylphenyl) aluminum, trimethylammonium tetra (p-trifluoromethylphenyl Aluminum, tributylammonium tetrapentafluorophenylaluminum, N, N-diethylanilinium tetraphenylaluminum, N, N-diethylanilinium tetraphenylaluminum, N, N-diethylanilinium tetra Pentafluorophenylaluminum, diethylammonium tetrapentafluorophenylaluminum, triphenylphosphonium tetraphenylaluminum, trimethylphosphonium tetra Phenylaluminum, triphenylcarbonium tetraphenylboron, triphenylcarbonium tetraphenylaluminum, triphenylcarbonium tetra (p-trifluoromethylphenyl) boron, triphenylcarbonium tetrapentafluorophenylboron, etc. have.
본 발명에 따른 촉매 조성물은, 첫 번째 방법으로서 1) 상기 화학식 1로 표시되는 메탈로센 화합물과 상기 화학식 4 또는 화학식 5로 표시되는 화합물을 접촉시켜 혼합물을 얻는 단계; 및 2) 상기 혼합물에 상기 화학식 6으로 표시되는 화합물을 첨가하는 단계를 포함하는 방법으로 제조될 수 있다.The catalyst composition according to the present invention comprises the steps of 1) contacting a metallocene compound represented by Formula 1 with a compound represented by Formula 4 or Formula 5 to obtain a mixture; And 2) it may be prepared by a method comprising the step of adding a compound represented by the formula (6) to the mixture.
또한, 본 발명에 따른 촉매 조성물은, 두 번째 방법으로서 상기 화학식 1로 표시되는 메탈로센 화합물과 상기 화학식 4로 표시되는 화합물을 접촉시키는 방법으로 제조될 수 있다.In addition, the catalyst composition according to the present invention may be prepared by contacting the metallocene compound represented by Chemical Formula 1 with the compound represented by Chemical Formula 4 as a second method.
상기 촉매 조성물의 제조방법 중에서 첫 번째 방법의 경우에, 상기 화학식 1로 표시되는 메탈로센 화합물/상기 화학식 4 또는 화학식 5로 표시되는 화합물의 몰 비율은 1/5,000 ~ 1/2이 바람직하고, 더욱 바람직하게는 1/1,000 ~ 1/10이고, 가장 바람직하게는 1/500 ~ 1/20이다. 상기 화학식 1로 표시되는 메탈로센 화합물/상기 화학식 4 또는 화학식 5로 표시되는 화합물의 몰 비율이 1/2을 초과하는 경우에는 알킬화제의 양이 매우 작아 금속 화합물의 알킬화가 완전히 진행되지 못하는 문제가 있고, 몰 비율이 1/5,000 미만인 경우에는 금속 화합물의 알킬화는 이루어지지만, 남아있는 과량의 알킬화제와 상기 화학식 6의 활성화제 간의 부반응으로 인하여 알킬화된 금속 화합물의 활성화가 완전히 이루어지지 못하는 문제가 있다.In the first method of preparing the catalyst composition, the molar ratio of the metallocene compound represented by Chemical Formula 1 / the compound represented by Chemical Formula 4 or Chemical Formula 5 is preferably 1 / 5,000 to 1/2, More preferably, it is 1 / 1,000-1/10, Most preferably, it is 1/500-1/20. When the molar ratio of the metallocene compound represented by Chemical Formula 1 / the compound represented by Chemical Formula 4 or Chemical Formula 5 is more than 1/2, the amount of alkylating agent is so small that the alkylation of the metal compound does not proceed completely. In the case where the molar ratio is less than 1 / 5,000, alkylation of the metal compound is performed, but there is a problem that activation of the alkylated metal compound is not completely performed due to a side reaction between the remaining excess alkylating agent and the activator of Chemical Formula 6.
또한, 상기 화학식 1로 표시되는 메탈로센 화합물/상기 화학식 6으로 표시되는 화합물의 몰 비율은 1/25 ~ 1이 바람직하고, 더욱 바람직하게는 1/10 ~ 1이고, 가장 바람직하게는 1/5 ~ 1이다. 상기 화학식 1로 표시되는 메탈로센 화합물/상기 화학식 6으로 표시되는 화합물의 몰 비율이 1을 초과하는 경우에는 활성화제의 양이 상대적으로 적어 금속 화합물의 활성화가 완전히 이루어지지 못해 생성되는 촉매 조성물의 활성도가 떨어지는 문제가 있고, 몰 비율이 1/25 미만인 경우에는 금속 화합물의 활성화가 완전히 이루어지지만, 남아 있는 과량의 활성화제로 촉매 조성물의 단가가 경제적이지 못하거나 생성되는 고분자의 순도가 떨어지는 문제가 있다.In addition, the molar ratio of the metallocene compound represented by Chemical Formula 1 / the compound represented by Chemical Formula 6 is preferably 1/25 to 1, more preferably 1/10 to 1, and most preferably 1 /. 5 to 1. When the molar ratio of the metallocene compound represented by Chemical Formula 1 / compound represented by Chemical Formula 6 is greater than 1, the amount of the activator is relatively small, so that the activation of the metal compound may not be completed. If the activity is inferior, and if the molar ratio is less than 1/25, the activation of the metal compound is completely made, but the excess of the activator, the cost of the catalyst composition is not economical or the purity of the resulting polymer is inferior .
상기 촉매 조성물의 제조방법 중에서 두 번째 방법의 경우에, 상기 화학식 1로 표시되는 메탈로센 화합물/화학식 4로 표시되는 화합물의 몰 비율은 1/10,000 ~ 1/10이 바람직하며, 더욱 바람직하게는 1/5,000 ~ 1/100이고, 가장 바람직하게는 1/3,000 ~ 1/500이다. 상기 몰 비율이 1/10을 초과하는 경우에는 활성화제의 양이 상대적으로 적어 금속 화합물의 활성화가 완전히 이루어지지 못해 생성되는 촉매 조성물의 활성도가 떨어지는 문제가 있고, 1/10,000 미만인 경우에는 금속 화합물의 활성화가 완전히 이루어지지만, 남아 있는 과량의 활성화제로 촉매 조성물의 단가가 경제적이지 못하거나 생성되는 고분자의 순도가 떨어지는 문제가 있다.In the second method of the method for preparing the catalyst composition, the molar ratio of the metallocene compound represented by Chemical Formula 1 / Compound 4 is preferably 1 / 10,000 to 1/10, more preferably 1 / 5,000-1/100, most preferably 1 / 3,000-1/500. If the molar ratio is greater than 1/10, the amount of the activator is relatively small, so that the activation of the metal compound is not fully performed, resulting in a decrease in the activity of the resulting catalyst composition. Although the activation is complete, there is a problem that the unit cost of the catalyst composition is not economical or the purity of the resulting polymer is inferior with the excess activator remaining.
상기 촉매 조성물의 제조시에 반응 용매로서 펜탄, 헥산, 헵탄 등과 같은 탄화수소계 용매, 또는 벤젠, 톨루엔 등과 같은 방향족계 용매가 사용될 수 있다. 또한, 메탈로센 화합물과 조촉매 화합물은 실리카나 알루미나에 담지된 형태로도 이용할 수 있다.In preparing the catalyst composition, a hydrocarbon solvent such as pentane, hexane, heptane, or the like, or an aromatic solvent such as benzene, toluene, or the like may be used. The metallocene compound and the cocatalyst compound can also be used in the form of silica or alumina.
또한, 본 발명은 상기 촉매 조성물의 존재 하에서, 올레핀계 단량체를 중합시키는 단계를 포함하는 폴리올레핀을 중합하는 방법을 제공한다.The present invention also provides a method of polymerizing a polyolefin comprising the step of polymerizing an olefinic monomer in the presence of the catalyst composition.
본 발명에 따른 폴리올레핀의 제조방법에 있어서, 상기 올레핀계 단량체의 구체적인 예로는 에틸렌, 프로필렌, 1-부텐, 1-펜텐, 1-헥센, 4-메틸-1-펜텐, 1-옥텐, 1-데센, 1-도데센, 1-테트라데센, 1-헥사데센, 1-옥타데센, 1-에이코센 등이 있으며, 이들을 2종 이상 혼합하여 공중합할 수도 있다.In the method for producing a polyolefin according to the present invention, specific examples of the olefin monomers include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene and 1-decene , 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene, and the like, and these may be mixed and copolymerized.
상기 폴리올레핀은 에틸렌/알파올레핀 공중합체인 것이 보다 바람직하나, 이에만 한정되는 것은 아니다.The polyolefin is more preferably an ethylene / alpha olefin copolymer, but is not limited thereto.
상기 폴리올레핀이 에틸렌/알파올레핀 공중합체인 경우에 있어서, 상기 공단량체인 알파올레핀의 함량은 특별히 제한되는 것은 아니며, 폴리올레핀의 용도, 목적 등에 따라 적절하게 선택할 수 있다. 보다 구체적으로는 약 1 내지 약 99 몰% 일 수 있다.In the case where the polyolefin is an ethylene / alpha olefin copolymer, the content of the alpha olefin which is the comonomer is not particularly limited and may be appropriately selected according to the use, purpose, and the like of the polyolefin. More specifically, it may be about 1 to about 99 mol%.
상기 중합 반응은 하나의 연속식 슬러리 중합 반응기, 루프 슬러리 반응기, 기상 반응기 또는 용액 반응기를 이용하여, 하나의 올레핀 단량체로 호모중합하거나 또는 2종 이상의 단량체로 공중합하여 진행할 수 있다.The polymerization reaction may be performed by homopolymerizing one olefin monomer or copolymerizing two or more monomers using one continuous slurry polymerization reactor, a loop slurry reactor, a gas phase reactor, or a solution reactor.
본 발명의 일 실시예에 따르면, 상기 폴리올레핀의 중합은 약 20 내지 약 110℃의 온도 및 약 20 내지 약 100 bar의 압력에서 약 10 분 내지 약 2 시간 동안 반응시켜 수행할 수 있다. 바람직하게는 약 80 내지 약 100℃의 온도 및 약 30 내지 약 60 bar의 압력에서 반응을 수행할 수 있다.According to one embodiment of the invention, the polymerization of the polyolefin may be carried out by reacting for about 10 minutes to about 2 hours at a temperature of about 20 to about 110 ℃ and a pressure of about 20 to about 100 bar. Preferably the reaction can be carried out at a temperature of about 80 to about 100 ° C and a pressure of about 30 to about 60 bar.
이러한 본 발명의 제조 방법으로 제조된 상기 폴리올레핀은 중량 평균 분자량이 약 5,000 내지 약 500,000 이고, 바람직하게 약 10,000 내지 약 300,000 일 수 있다. 또한 상기 폴리올레핀의 분자량 분포(Mw/Mn)가 약 2 내지 약 15, 또는 약 3 내지 약 13, 또는 약 5 내지 약 12일 수 있다. The polyolefin prepared by the production method of the present invention has a weight average molecular weight of about 5,000 to about 500,000, preferably about 10,000 to about 300,000. In addition, the molecular weight distribution (Mw / Mn) of the polyolefin may be about 2 to about 15, or about 3 to about 13, or about 5 to about 12.
이하, 발명의 구체적인 실시예를 통해, 발명의 작용 및 효과를 보다 상세히 상술하기로 한다. 다만, 이러한 실시예는 발명의 예시로 제시된 것에 불과하며, 이에 의해 발명의 권리범위가 정해지는 것은 아니다.
Hereinafter, the operation and effects of the invention will be described in more detail with reference to specific embodiments of the invention. However, these embodiments are only presented as an example of the invention, whereby the scope of the invention is not determined.
<< 실시예Example >>
이핵Nucleus 메탈로센Metallocene 화합물의 합성 Synthesis of Compound
제조 Produce 실시예Example 1 One
1-1) 리간드 화합물의 제조1-1) Preparation of Ligand Compound
인덴(indene) (6.7g, 40mmol) 의 THF 용액에 2.5M n-BuLi (in hexane) 16mL를 -20℃에서 투입하고 상온(RT)에서 밤새 교반하였다. 이 용액을 자일렌 디브로마이드(xylene dibromide) (5.279g, 20mmol) THF 용액 50mL에 dry ice/acetone bath 하에서 옮겼다. 상온(RT)에서 밤새 교반한 후, 물을 투입하고 유기층을 에테르(ether)로 추출하였다. 유기층을 분리한 후, MgSO4로 잔류하는 수분을 제거하고 용매를 진공 건조하여 light yellow 색상의 조 생성물(crude product)을 얻었다. 이를 에테르(ether)/헥산(hexane)으로 재결정하여 높은 순도의 리간드 화합물을 얻었다(수율 67%).16 mL of 2.5 M n-BuLi (in hexane) was added to a THF solution of indene (6.7 g, 40 mmol) at −20 ° C. and stirred overnight at room temperature (RT). This solution was transferred to a 50 mL xylene dibromide (5.279 g, 20 mmol) THF solution under dry ice / acetone bath. After stirring overnight at room temperature (RT), water was added and the organic layer was extracted with ether. After separating the organic layer, water remaining in MgSO 4 was removed and the solvent was dried in vacuo to give a crude product of light yellow color. This was recrystallized with ether (hexane) / hexane (hexane) to obtain a high purity ligand compound (yield 67%).
1H NMR (500 MHz, CDCl3): 3.24 (4H, s), 3.89 (4H, s), 5.92 (2H, d), 7.18~7.44 (12H, m) 1 H NMR (500 MHz, CDCl 3 ): 3.24 (4H, s), 3.89 (4H, s), 5.92 (2H, d), 7.18-7.44 (12H, m)
1-2) 메탈로센 화합물의 제조 1-2) Preparation of Metallocene Compound
상기 1-1)에서 제조한 리간드 화합물 5mmol의 톨루엔 용액 50mL에 MTBE 11mmol (2.2eq.)을 투입하고, 2.5M n-BuLi 10mmol, 4mL를 -20℃에서 투입하여 상온에서 밤새 교반하였다. ZrCl4(THF)2 5.3mmol의 톨루엔 슬러리에 상기 용액을 dry ice/acetone bath 하에서 옮긴 후, 상온에서 밤새 교반하였다. 이를 여과하여 LiCl이 포함된 표제의 노란색(yellow)의 메탈로센 화합물 얻었다. (수율 60%)MTBE 11 mmol (2.2eq.) Was added to 50 mL of the toluene solution of 5 mmol of the ligand compound prepared in 1-1), 10 mmol of 2.5M n-BuLi, 4 mL were added at -20 ° C, and the mixture was stirred at room temperature overnight. The solution was transferred to a slurry of ZrCl 4 (THF) 2 5.3 mmol toluene under a dry ice / acetone bath, followed by stirring at room temperature overnight. This was filtered to give the titled yellow metallocene compound containing LiCl. (Yield 60%)
1H NMR (500 MHz, CDCl3): 4.24 (2H, d), 4.37 (2H, d), 5.72 (2H, s), 6.26 (2H, s), 7.15~7.61(12H, m)
1 H NMR (500 MHz, CDCl 3 ): 4.24 (2H, d), 4.37 (2H, d), 5.72 (2H, s), 6.26 (2H, s), 7.15-7.61 (12H, m)
1-3) 이핵 메탈로센 화합물의 제조1-3) Preparation of Dinuclear Metallocene Compound
건조된 플라스크에 BrMg-(CH2)4-MgBr 1.68g (6mmol, 순도 95wt%)를 넣고 에테르를 주입하여 슬러리 상태로 만들었다. 다른 건조된 플라스크에 상기 1-2)에서 합성한 메탈로센 화합물 10mmol을 넣고 에테르를 주입하여 슬러리 형태로 만든 후, dry ice/acetone bath 하에서 BrMg-(CH2)4-MgBr 슬러리를 메탈로센 화합물이 녹아있는 슬러리 쪽으로 옮겼다. 하룻동안 교반한 후 필터하고, 여과물(filtrate)의 용매를 모두 제거하였다. 그 후 헥산(hexane)으로 재결정을 한 다음 한번 더 필터하여 이핵 메탈로센 화합물을 수득하였다. BrMg- (CH 2 ) 4 -MgBr 1.68g (6mmol, purity 95wt%) was added to the dried flask, and ether was injected to make a slurry. 10mmol of the metallocene compound synthesized in the above 1-2) was added to another dried flask to form a slurry by injecting ether, and then, the BrMg- (CH 2 ) 4 -MgBr slurry was dried under a dry ice / acetone bath. The compound was transferred to the dissolved slurry. After stirring for one day, the filter was filtered off and all the solvent in the filtrate was removed. After recrystallization with hexane and then filtered once more to obtain a dinuclear metallocene compound.
1H NMR (500MHz, CDCl3): 1.82 (4H, m), 2.03 (4H, m), 3.41 (4H, dd), 3.72(4H, dd), 5.4(4H, m), 6.4 (4H, m), 7.0 ~ 7.9 (24H, m)
1 H NMR (500 MHz, CDCl3): 1.82 (4H, m), 2.03 (4H, m), 3.41 (4H, dd), 3.72 (4H, dd), 5.4 (4H, m), 6.4 (4H, m) , 7.0 to 7.9 (24H, m)
제조 Produce 실시예Example 2 2
2-1) 메탈로센 화합물의 제조2-1) Preparation of Metallocene Compound
J. AM. CHEM. SOC. VOL. 126, No. 46, 2004 pp. 15231~15244에 개시된 바에 따라 메탈로센 화합물(1, 2-ethylene bis(indenyl)ZrCl2)을 합성하였다. J. AM. CHEM. SOC. VOL. 126, No. 46, 2004 pp. Metallocene compounds (1, 2-ethylene bis (indenyl) ZrCl 2 ) were synthesized as disclosed in 15231-15244.
1H NMR (500MHz, C6D6): 2.96 (4H, m), 5.75 (2H, d), 6.45 (2H, q), 6.90 ~ 7.28 (8H, m)
1 H NMR (500MHz, C6D6): 2.96 (4H, m), 5.75 (2H, d), 6.45 (2H, q), 6.90-7.28 (8H, m)
2-2) 이핵 메탈로센 화합물의 제조2-2) Preparation of Dinuclear Metallocene Compound
건조된 플라스크에 BrMg-(CH2)4-MgBr 1.68g (6mmol, 순도 95wt%)를 넣고 에테르를 주입하여 슬러리 상태로 만들었다. 다른 건조된 플라스크에 2-1)의 메탈로센 화합물 4.18g (10mmol)을 넣고 에테르를 주입하여 슬러리 형태로 만든 후, dry ice/acetone bath 하에서 BrMg-(CH2)4-MgBr 슬러리를 메탈로센 화합물 슬러리 쪽으로 옮겼다. 하룻동안 교반한 후 여과하고, 헥산(hexane)으로 재결정한 후 한번 더 여과하여 이핵 메탈로센 화합물을 수득하였다. (수율 34%)BrMg- (CH 2 ) 4 -MgBr 1.68g (6mmol, purity 95wt%) was added to the dried flask, and ether was injected to make a slurry. In another dried flask, 4.18 g (10 mmol) of the metallocene compound of 2-1) was added to form a slurry by injecting ether, and then a BrMg- (CH 2 ) 4 -MgBr slurry was metallized under a dry ice / acetone bath. Transferred to the thick compound slurry. After stirring for one day, the mixture was filtered, recrystallized with hexane, and then filtered once more to obtain a dinuclear metallocene compound. (Yield 34%)
1H NMR (500MHz, C6D6) : 1.52 (4H, m), 1.85 (4H, m), 2.56 (4H, d), 2.74 (4H, d), 5.54 (4H, d), 6.75 (4H, d), 6.84 (4H, t), 6.91 (4H, d), 7.09 (4H, t), 7.56 (4H,d)
1 H NMR (500MHz, C6D6): 1.52 (4H, m), 1.85 (4H, m), 2.56 (4H, d), 2.74 (4H, d), 5.54 (4H, d), 6.75 (4H, d) , 6.84 (4H, t), 6.91 (4H, d), 7.09 (4H, t), 7.56 (4H, d)
제조 Produce 실시예Example 3 3
3-1) 메탈로센 화합물의 제조3-1) Preparation of Metallocene Compound
건조된 플라스크를 준비하여 상기 제조 실시예 2-1)의 메탈로센 촉매 8g (20 mmol)을 준비하였다. 플라스크 내부를 아르곤으로 치환한 후 건조한 디클로로메탄(dichloromethane) 800 mL를 주입하여 슬러리 상태로 만들었다. 글러브 박스(glove box) 안에서 플라스크에 PtO2 580 mg을 무게 재어 나온 뒤 이 역시 디클로로메탄 300 mL를 주입한 후 슬러리 상태로 만들어 메탈로센 촉매 슬러리 쪽으로 옮긴 후 약 5분 정도 교반하였다. The dried flask was prepared to prepare 8 g (20 mmol) of the metallocene catalyst of Preparation Example 2-1). After replacing the inside of the flask with argon, 800 mL of dry dichloromethane was injected to make a slurry. In a glove box, 580 mg of PtO 2 was weighed into a flask, and then 300 mL of dichloromethane was added to make a slurry, which was transferred to a metallocene catalyst slurry and stirred for about 5 minutes.
하루 전에 오토클레이브(autoclave) 압력 용기를 미리 세척하여 오븐에서 건조하여 준비한 후 압력용기 안을 아르곤으로 치환한 다음 위에서 메탈로센 촉매와 PtO2가 혼합된 슬러리를 압력용기 안으로 캐뉼라(cannula)를 이용하여 옮겼다. 압력용기 안의 아르곤을 모두 벤트(vent)한 후 30 atm의 H2를 치환하고 300 rpm으로 stirring하면서 20시간 동안 반응시켰다. 외부 공기와 닿지 않는 필터 시스템(filter system)에서 이 혼합물을 필터한 후 여과물(filtrate)의 용매를 제거함으로써 표제의 메탈로센 화합물을 얻었다.After one day, the autoclave pressure vessel was pre-washed, dried in an oven, prepared, and then replaced with argon in the pressure vessel, and then a slurry of the metallocene catalyst and PtO 2 was mixed into the pressure vessel using a cannula. Moved. After venting all the argon in the pressure vessel, 30 atm of H 2 was substituted and reacted for 20 hours while stirring at 300 rpm. The title metallocene compound was obtained by filtering this mixture in a filter system that was not in contact with outside air and then removing the solvent in the filtrate.
1H NMR (500MHz, C6D6): 1.34 (4H, m), 1.83 (2H, m), 1.85 (2H, m), 2.16 (4H, m), 2.42 (6H, m), 3.14 (2H, m), 5.25 (2H, d), 6.34 (2H, d)
1 H NMR (500MHz, C6D6): 1.34 (4H, m), 1.83 (2H, m), 1.85 (2H, m), 2.16 (4H, m), 2.42 (6H, m), 3.14 (2H, m) , 5.25 (2H, d), 6.34 (2H, d)
3-2) 이핵 메탈로센 화합물의 제조3-2) Preparation of Dinuclear Metallocene Compound
건조된 플라스크에 BrMg-(CH2)4-MgBr 0.4g (1.4mmol, 순도 95wt%)를 넣고 에테르를 주입하여 슬러리 상태로 만들었다. 다른 건조된 플라스크에 3-1)의 메탈로센 화합물 1g (2.3mmol)을 넣고 에테르를 주입하여 슬러리 형태로 만든 후, dry ice/acetone bath 하에서 BrMg-(CH2)4-MgBr 슬러리를 메탈로센 화합물 슬러리 쪽으로 옮겼다. 하룻동안 교반한 후 여과하여 이핵 메탈로센 화합물을 수득하였다. (수율 45%)0.4 g (1.4 mmol, purity 95 wt%) of BrMg- (CH 2 ) 4 -MgBr was added to the dried flask, and ether was injected to make a slurry. 1-1 (2.3 mmol) of the metallocene compound of 3-1) was added to another dried flask, and ether was injected to make a slurry, and then a BrMg- (CH 2 ) 4 -MgBr slurry was metallized under a dry ice / acetone bath. Transferred to the thick compound slurry. The mixture was stirred for one day and then filtered to obtain a dinuclear metallocene compound. (Yield 45%)
1H NMR (500MHz, C6D6): 1.32 (8H, m), 1.84 (8H, m), 1.94 (8H, m), 2.4 (16H, m), 3.32 (8H, m), 5.24 (4H, d), 6.56 (4H, d)
1 H NMR (500MHz, C6D6): 1.32 (8H, m), 1.84 (8H, m), 1.94 (8H, m), 2.4 (16H, m), 3.32 (8H, m), 5.24 (4H, d) , 6.56 (4H, d)
제조 Produce 실시예Example 4 4
4-1) 메탈로센 화합물의 제조4-1) Preparation of Metallocene Compound
알려진 방법에 따라 n-부틸클로라이드(n-butylchloride)와 NaCp로 n-BuCp를 제조하고, 여기에 ZrCl4(THF)2를 반응시켜 메탈로센 화합물을 제조하였다. N-BuCp was prepared from n-butylchloride and NaCp according to a known method, and ZrCl 4 ( THF) 2 was reacted thereto to prepare a metallocene compound.
1H NMR (500MHz, C6D6): 0.82 (6H, t), 1.20 (4H, m), 1.42 (4H, m), 2.63 (4H, t), 5.72 (3H, t), 5.90 (3H, t)
1 H NMR (500MHz, C6D6): 0.82 (6H, t), 1.20 (4H, m), 1.42 (4H, m), 2.63 (4H, t), 5.72 (3H, t), 5.90 (3H, t)
4-2) 이핵 메탈로센 화합물의 제조4-2) Preparation of Dinuclear Metallocene Compound
건조된 플라스크에 BrMg-(CH2)4-MgBr 2.75g (5mmol, 순도 95wt%)를 넣고 에테르를 주입하여 슬러리 상태로 만들었다. 다른 건조된 플라스크에 상기 4-1)의 메탈로센 화합물 4.04g (10mmol)을 넣고 에테르를 주입하여 슬러리 형태로 만든 후, dry ice/acetone bath 하에서 BrMg-(CH2)4-MgBr 슬러리를 메탈로센 화합물 슬러리 쪽으로 옮겼다. 하룻동안 교반한 후 여과하여 이핵 메탈로센 화합물을 수득하였다. (수율 85%)BrMg- (CH 2 ) 4 -MgBr 2.75g (5mmol, purity 95wt%) was added to the dried flask, and ether was injected to make a slurry. In another dried flask, 4.04 g (10 mmol) of the metallocene compound of 4-1) was added to form a slurry by injecting ether, and then a BrMg- (CH 2 ) 4 -MgBr slurry was metallized under a dry ice / acetone bath. Transferred to the Rosene compound slurry. The mixture was stirred for one day and then filtered to obtain a dinuclear metallocene compound. (Yield 85%)
1H NMR (500MHz, C6D6): 0.89 (12H, m), 1.23 (4H, m), 1.28 (8H, m), 1.42 (4H, m), 1.48 (8H, m), 2.62 (8H, m), 5.37~6.20 (12H, m)
1 H NMR (500MHz, C6D6): 0.89 (12H, m), 1.23 (4H, m), 1.28 (8H, m), 1.42 (4H, m), 1.48 (8H, m), 2.62 (8H, m) , 5.37 ~ 6.20 (12H, m)
제조 Produce 실시예Example 5 5
5-1) 메탈로센 화합물의 제조5-1) Preparation of Metallocene Compound
인덴(indene) 1.16g (10mmol)을 THF soltion에 녹인 후 -78℃하에서 2.5M n-BuLi in hexane 4.8ml (12mmol)를 투입하고 상온에서 하룻밤 동안(overnight) 교반하였다. 이 용액을 2,3-bis(bromomethyl)naphthalene 1.57g (5mmol)의 THF solution 50ml에 dryice/acetone bath 하에서 옮겼다. 상온에서 하룻밤 동안(overnight) 교반한 후 물을 투입하고 유기층을 에테르로 추출하였다. 유기층을 분리한 후 MgSO4로 잔류수분을 제거한 후 용매를 진공 건조하여 light yellow의 조 생성물을 얻었다. 조 생성물을 에테르/헥산(ether/hexane)으로 재결정하여 높은 순도의 리간드 화합물을 얻었다(yield 100%).After dissolving 1.16 g (10 mmol) of indene in THF soltion, 4.8 ml (12 mmol) of 2.5M n-BuLi in hexane was added at -78 ° C, and the mixture was stirred overnight at room temperature. The solution was transferred to 50 ml of THF solution of 1.57 g (5 mmol) of 2,3-bis (bromomethyl) naphthalene under a dryice / acetone bath. After stirring at room temperature overnight (overnight), water was added and the organic layer was extracted with ether. The organic layer was separated, residual water was removed with MgSO 4, and the solvent was dried in vacuo to obtain a crude product of light yellow. The crude product was recrystallized from ether / hexane to give a high purity ligand compound (yield 100%).
건조한 250 mL schlenk flask에 상기에서 합성한 리간드 화합물 3.8 g(10 mmol)을 넣고 톨루엔 100 mL 에 녹인 다음, 여기에 MTBE 2 mL (10 mmol)을 추가로 넣은 후 8 mL (20 mmol)의 2.5 M nBuLi hexane solution 을 가해 lithiation을 시켰다. 하루가 지난 후 글러브 박스(glove box) 내에서 3.7 g(10 mmol)의 ZrCl4(THF)2를 취해 250 mL schlenk flask에 담고 톨루엔을 넣은 서스펜션(suspension)을 준비하였다. 위의 두 개의 플라스크 모두 -78℃까지 냉각시킨 후 lithiation된 리간드 화합물을 천천히 Zr suspension에 가하였다. 주입이 끝난 후, 반응 혼합물은 천천히 상온까지 올렸다. 하루 동안 반응을 진행시킨 후 외부 공기와 닿지 않는 필터 시스템(filter system)에서 이 혼합물을 필터하여 LiCl을 제거하고 용매를 모두 날린 후 헥산(hexane)을 부어 재결정하여 다시 필터함으로써, 필터 케이크(filter cake)에서 메탈로센 화합물을 얻었다(yield 100%). 3.8 g (10 mmol) of the ligand compound synthesized above was dissolved in a dry 250 mL schlenk flask, and dissolved in 100 mL of toluene. Then, 2 mL (10 mmol) of MTBE was added thereto, followed by 8 mL (20 mmol) of 2.5 M. nBuLi hexane solution was added and lithiation was performed. After one day, 3.7 g (10 mmol) of ZrCl 4 (THF) 2 was taken in a glove box and placed in a 250 mL schlenk flask to prepare a suspension with toluene. After cooling the above two flasks to -78 ℃, lithiated ligand compound was slowly added to the Zr suspension. After the injection was over, the reaction mixture was slowly raised to room temperature. After the reaction was carried out for one day, the mixture was filtered in a filter system that did not come into contact with outside air to remove LiCl, blow out all the solvent, and then re-crystallized by pouring hexane to filter the filter cake. ) To obtain a metallocene compound (yield 100%).
1H NMR (500MHz, CDCl3): 4.4(2H, d), 4.54 (2H, d), 5.71 (4H, br s), 7.15 ~ 7.99 (14H, m)
1 H NMR (500 MHz, CDCl 3): 4.4 (2H, d), 4.54 (2H, d), 5.71 (4H, br s), 7.15-7.99 (14H, m)
5-2) 이핵 메탈로센 화합물의 제조5-2) Preparation of Binary Metallocene Compounds
건조된 플라스크에 BrMg-(CH2)4-MgBr 1.68g (6mmol, 순도 95wt%)를 넣고 에테르를 주입하여 슬러리 상태로 만들었다. 다른 건조된 플라스크에 상기 5-1)에서 합성한 메탈로센 화합물 5.4g (10mmol)을 넣고 에테르를 주입하여 슬러리 형태로 만든 후, dry ice/acetone bath 하에서 BrMg-(CH2)4-MgBr 슬러리를 메탈로센 화합물이 녹아있는 슬러리 쪽으로 옮겼다. 하룻동안 교반한 후 필터하고, 여과물(filtrate)의 용매를 모두 제거하였다. 그 후 헥산(hexane)으로 재결정을 한 다음 한번 더 필터하여 이핵 메탈로센 화합물을 수득하였다. BrMg- (CH 2 ) 4 -MgBr 1.68g (6mmol, purity 95wt%) was added to the dried flask, and ether was injected to make a slurry. In another dried flask, 5.4 g (10 mmol) of the metallocene compound synthesized in the above 5-1) was added to form a slurry by injecting ether, followed by BrMg- (CH 2 ) 4 -MgBr slurry under a dry ice / acetone bath. Was transferred to the slurry in which the metallocene compound was dissolved. After stirring for one day, the filter was filtered off and all the solvent in the filtrate was removed. After recrystallization with hexane and then filtered once more to obtain a dinuclear metallocene compound.
1H NMR (500MHz, CDCl3): 1.25 (4H, m), 1.31(4H, m), 4.2(2H, d), 4.28(2H, d), 4.4(2H, d), 4.45 (2H, d), 6.1 (8H, m), 6.8 ~ 8.0 (28H, m)
1 H NMR (500 MHz, CDCl 3): 1.25 (4H, m), 1.31 (4H, m), 4.2 (2H, d), 4.28 (2H, d), 4.4 (2H, d), 4.45 (2H, d), 6.1 (8H, m), 6.8-8.0 (28H, m)
폴리올레핀Polyolefin 중합 polymerization 실시예Example
실시예Example 1-1 1-1
300mL 용량의 Andrew bottle을 준비하여, impeller part와 조립한 후, 글러브 박스(glove box) 내에서 내부를 아르곤으로 치환하였다. 글러브 박스의 처리가 끝난 Andrew bottle 내부에 소량의 트리메틸알루미늄(TMA)이 처방되어 있는 180mL의 톨루엔(toluene)을 넣고 5mL의 MAO(10wt% 톨루엔) 용액을 가하였다. 별도로 준비한 100mL 플라스크에 제조 실시예 1의 이핵 메탈로센 화합물 10 μmol을 넣고 20mL의 MAO에 용해시켜 촉매 용액을 만들었다. 5mL의 촉매 용액을 취해 Andrew bottle에 주입하고, 90℃로 가열된 oil bath에 담근 채 mechanical stirrer에 bottle의 상부를 고정시켰다. Bottle의 내부를 에틸렌 가스로 3회 퍼지한 후, 에틸렌 밸브를 열고 mechanical stirrer를 가동시켜 500rpm에서 30분간 반응을 진행하였다. A 300 mL Andrew bottle was prepared, assembled with an impeller part, and then replaced with argon in a glove box. 180 mL of toluene prescribed with a small amount of trimethylaluminum (TMA) was added to the finished Andrew bottle in a glove box, and 5 mL of MAO (10 wt% toluene) solution was added thereto. In a 100 mL flask prepared separately, 10 μmol of the heteronuclear metallocene compound of Preparation Example 1 was dissolved in 20 mL of MAO to prepare a catalyst solution. 5 mL of catalyst solution was taken and injected into the Andrew bottle, and the top of the bottle was fixed to the mechanical stirrer while soaking in an oil bath heated to 90 ° C. After purging the inside of the bottle three times with ethylene gas, the ethylene valve was opened and a mechanical stirrer was operated to proceed the reaction at 500 rpm for 30 minutes.
반응이 완료된 후 상온까지 온도를 내린 다음 용기 내부의 가스를 벤트시켰다. 약 500mL의 에탄올을 부어 넣고 1시간 정도 교반한 후, 필터(filtraion)를 거쳐 얻어진 고분자를 60℃ 오븐에서 20시간 동안 건조시켰다. 얻어진 고분자의 질량을 계산하여 이로부터 촉매의 활성을 산출하고 고분자 샘플을 취해 GPC분석을 하여 분자량 및 분자량 분포(PDI)를 확인하였다.
After the reaction was completed, the temperature was lowered to room temperature, and the gas in the vessel was vented. After pouring about 500 mL of ethanol and stirring for about 1 hour, the obtained polymer through a filter (dry) was dried for 20 hours in a 60 ℃ oven. The mass of the obtained polymer was calculated to calculate the activity of the catalyst therefrom, and a polymer sample was taken to perform GPC analysis to confirm molecular weight and molecular weight distribution (PDI).
실시예Example 1-2 1-2
실시예 1-1에서, 공단량체로 1-헥센(1-hexene) 5ml를 더 투입하여 반응을 진행한 것을 제외하고는 상기 실시예 1-1과 동일한 방법으로 폴리올레핀 중합을 실시하였다.
In Example 1-1, polyolefin polymerization was carried out in the same manner as in Example 1-1, except that 5 ml of 1-hexene was added to the comonomer to proceed with the reaction.
실시예Example 2-1 2-1
실시예 1-1에서, 제조 실시예 2의 이핵 메탈로센 화합물 10 μmol을 사용한 것을 제외하고는 상기 실시예 1-1과 동일한 방법으로 폴리올레핀 중합을 실시하였다.
In Example 1-1, polyolefin polymerization was carried out in the same manner as in Example 1-1, except that 10 μmol of the heteronuclear metallocene compound of Preparation Example 2 was used.
실시예Example 2-2 2-2
실시예 1-2에서, 제조 실시예 2의 이핵 메탈로센 화합물 10 μmol을 사용한 것을 제외하고는 상기 실시예 1-2와 동일한 방법으로 폴리올레핀 중합을 실시하였다.
In Example 1-2, polyolefin polymerization was carried out in the same manner as in Example 1-2, except that 10 μmol of the heteronuclear metallocene compound of Preparation Example 2 was used.
실시예Example 3-1 3-1
실시예 1-1에서, 제조 실시예 3의 이핵 메탈로센 화합물 10 μmol을 사용한 것을 제외하고는 상기 실시예 1-1과 동일한 방법으로 폴리올레핀 중합을 실시하였다.
In Example 1-1, polyolefin polymerization was carried out in the same manner as in Example 1-1, except that 10 μmol of the heteronuclear metallocene compound of Preparation Example 3 was used.
실시예Example 3-2 3-2
실시예 1-2에서, 제조 실시예 3의 이핵 메탈로센 화합물 10 μmol을 사용한 것을 제외하고는 상기 실시예 1-2와 동일한 방법으로 폴리올레핀 중합을 실시하였다.
In Example 1-2, polyolefin polymerization was carried out in the same manner as in Example 1-2, except that 10 μmol of the heteronuclear metallocene compound of Preparation Example 3 was used.
실시예Example 4-1 4-1
실시예 1-1에서, 제조 실시예 4의 이핵 메탈로센 화합물 10 μmol을 사용한 것을 제외하고는 상기 실시예 1-1과 동일한 방법으로 폴리올레핀 중합을 실시하였다.
In Example 1-1, polyolefin polymerization was carried out in the same manner as in Example 1-1, except that 10 μmol of the heteronuclear metallocene compound of Preparation Example 4 was used.
실시예Example 4-2 4-2
실시예 1-2에서, 제조 실시예 4의 이핵 메탈로센 화합물 10 μmol을 사용한 것을 제외하고는 상기 실시예 1-2와 동일한 방법으로 폴리올레핀 중합을 실시하였다.
In Example 1-2, polyolefin polymerization was carried out in the same manner as in Example 1-2, except that 10 μmol of the heteronuclear metallocene compound of Preparation Example 4 was used.
실시예Example 5-1 5-1
실시예 1-1에서, 제조 실시예 5의 이핵 메탈로센 화합물 10 μmol을 사용한 것을 제외하고는 상기 실시예 1-1과 동일한 방법으로 폴리올레핀 중합을 실시하였다.
In Example 1-1, polyolefin polymerization was carried out in the same manner as in Example 1-1, except that 10 μmol of the heteronuclear metallocene compound of Preparation Example 5 was used.
실시예Example 5-2 5-2
실시예 1-2에서, 제조 실시예 5의 이핵 메탈로센 화합물 10 μmol을 사용한 것을 제외하고는 상기 실시예 1-2와 동일한 방법으로 폴리올레핀 중합을 실시하였다.
In Example 1-2, polyolefin polymerization was carried out in the same manner as in Example 1-2, except that 10 μmol of the heteronuclear metallocene compound of Preparation Example 5 was used.
비교예Comparative example 1-1 1-1
실시예 1-1에서, 제조 실시예 1 중 1-2)에서 수득된 일핵 메탈로센 화합물 20 μmol을 사용한 것을 제외하고는 상기 실시예 1-1과 동일한 방법으로 폴리올레핀 중합을 실시하였다.
In Example 1-1, polyolefin polymerization was carried out in the same manner as in Example 1-1, except that 20 μmol of the mononuclear metallocene compound obtained in 1-2) of Preparation Example 1 was used.
비교예Comparative example 1-2 1-2
실시예 1-2에서, 제조 실시예 1 중 1-2)에서 수득된 일핵 메탈로센 화합물 20 μmol을 사용한 것을 제외하고는 상기 실시예 1-2와 동일한 방법으로 폴리올레핀 중합을 실시하였다.
In Example 1-2, polyolefin polymerization was carried out in the same manner as in Example 1-2, except that 20 μmol of the mononuclear metallocene compound obtained in 1-2) of Preparation Example 1 was used.
비교예Comparative example 2-1 2-1
실시예 1-1에서, 제조 실시예 2 중 2-1)에서 수득된 일핵 메탈로센 화합물 20 μmol을 사용한 것을 제외하고는 상기 실시예 1-1과 동일한 방법으로 폴리올레핀 중합을 실시하였다.
In Example 1-1, polyolefin polymerization was carried out in the same manner as in Example 1-1, except that 20 μmol of the mononuclear metallocene compound obtained in 2-1) of Preparation Example 2 was used.
비교예Comparative example 2-2 2-2
실시예 1-2에서, 제조 실시예 2 중 2-1)에서 수득된 일핵 메탈로센 화합물 20 μmol을 사용한 것을 제외하고는 상기 실시예 1-2와 동일한 방법으로 폴리올레핀 중합을 실시하였다.
In Example 1-2, polyolefin polymerization was carried out in the same manner as in Example 1-2, except that 20 μmol of the mononuclear metallocene compound obtained in 2-1) of Preparation Example 2 was used.
비교예Comparative example 3-1 3-1
실시예 1-1에서, 제조 실시예 3 중 3-1)에서 수득된 일핵 메탈로센 화합물 20 μmol을 사용한 것을 제외하고는 상기 실시예 1-1과 동일한 방법으로 폴리올레핀 중합을 실시하였다.
In Example 1-1, polyolefin polymerization was carried out in the same manner as in Example 1-1, except that 20 μmol of the mononuclear metallocene compound obtained in 3-1) of Preparation Example 3 was used.
비교예Comparative example 3-2 3-2
실시예 1-2에서, 제조 실시예 3 중 3-1)에서 수득된 일핵 메탈로센 화합물 20 μmol을 사용한 것을 제외하고는 상기 실시예 1-2와 동일한 방법으로 폴리올레핀 중합을 실시하였다.
In Example 1-2, polyolefin polymerization was carried out in the same manner as in Example 1-2, except that 20 μmol of the mononuclear metallocene compound obtained in 3-1) of Preparation Example 3 was used.
비교예Comparative example 4-1 4-1
실시예 1-1에서, 제조 실시예 4 중 4-1)에서 수득된 일핵 메탈로센 화합물 20 μmol을 사용한 것을 제외하고는 상기 실시예 1-1과 동일한 방법으로 폴리올레핀 중합을 실시하였다.
In Example 1-1, polyolefin polymerization was carried out in the same manner as in Example 1-1, except that 20 μmol of the mononuclear metallocene compound obtained in 4-1) of Preparation Example 4 was used.
비교예Comparative example 4-2 4-2
실시예 1-2에서, 제조 실시예 4 중 4-1)에서 수득된 일핵 메탈로센 화합물 20 μmol을 사용한 것을 제외하고는 상기 실시예 1-2와 동일한 방법으로 폴리올레핀 중합을 실시하였다.
In Example 1-2, polyolefin polymerization was carried out in the same manner as in Example 1-2, except that 20 μmol of the mononuclear metallocene compound obtained in 4-1) of Preparation Example 4 was used.
비교예Comparative example 5-1 5-1
실시예 1-1에서, 제조 실시예 5 중 5-1)에서 수득된 일핵 메탈로센 화합물 20 μmol을 사용한 것을 제외하고는 상기 실시예 1-1과 동일한 방법으로 폴리올레핀 중합을 실시하였다.
In Example 1-1, polyolefin polymerization was carried out in the same manner as in Example 1-1, except that 20 μmol of the mononuclear metallocene compound obtained in 5-1) of Preparation Example 5 was used.
비교예Comparative example 5-2 5-2
실시예 1-2에서, 제조 실시예 5 중 5-1)에서 수득된 일핵 메탈로센 화합물 20 μmol을 사용한 것을 제외하고는 상기 실시예 1-2와 동일한 방법으로 폴리올레핀 중합을 실시하였다.
In Example 1-2, polyolefin polymerization was carried out in the same manner as in Example 1-2, except that 20 μmol of the mononuclear metallocene compound obtained in 5-1) of Preparation Example 5 was used.
상기 실시예들 및 비교예들에서 촉매활성 및 올레핀계 중합체의 물성을 하기 표 1에 나타내었다.The catalytic activity and physical properties of the olefin polymer in the above Examples and Comparative Examples are shown in Table 1 below.
(단위: ton/mol hr)Activity
(Unit: ton / mol hr)
분자량(Mw)
(단위: g/mol)Weight average
Molecular Weight (Mw)
(Unit: g / mol)
상기 표 1을 참조하면, 실시예들과 비교예들을 각각 비교할 때, 단일핵 구조의 메탈로센 촉매보다 본 발명의 이핵성 메탈로센 촉매를 사용하였을 때 고분자량 및 분자량 분포가 넓은 올레핀계 중합체를 얻을 수 있음을 알 수 있다. 이러한 효과는 공단량체로 1-hexene을 사용하였을 때에도 동일하게 나타났다. Referring to Table 1, when comparing the Examples and Comparative Examples, the olefin polymer having a high molecular weight and a broad molecular weight distribution when using the heteronuclear metallocene catalyst of the present invention rather than a mononuclear metallocene catalyst It can be seen that can be obtained. This effect was also the same when 1-hexene was used as comonomer.
Claims (9)
조촉매를 포함하는 촉매 조성물:
[화학식 1]
상기 화학식 1에서,
R1 내지 R8은 서로 같거나 다를 수 있으며, 각각 독립적으로 수소, 탄소수 1 내지 20의 알킬기, 탄소수 2 내지 20의 알케닐기, 탄소수 6 내지 20의 아릴기, 탄소수 7 내지 20의 알킬아릴기, 탄소수 7 내지 20의 아릴알킬기, 또는 탄소수 1 내지 20의 아민기이고, 상기 R1 내지 R8 중 인접하는 2개가 서로 연결되어 1개 이상의 지방족 고리, 방향족 고리, 또는 헤테로 고리를 형성할 수 있고, 단 R1 내지 R8가 모두 수소인 경우는 제외하며;
R9 및 R10은 서로 동일하거나 상이하고, 각각 독립적으로 수소, 탄소수 1 내지 20의 알킬기, 탄소수 3 내지 20의 시클로알킬기, 탄소수 1 내지 20의 알콕시기, 탄소수 6 내지 20의 아릴기, 탄소수 6 내지 10의 아릴옥시기, 탄소수 2 내지 20의 알케닐기, 탄소수 7 내지 40의 알킬아릴기, 또는 탄소수 7 내지 40의 아릴알킬기이고;
Q는 탄소수 1 내지 20의 알킬렌기, 탄소수 3 내지 20의 시클로알킬렌기, 탄소수 6 내지 20의 아릴렌기, 탄소수 7 내지 40의 알킬아릴렌기, 또는 탄소수 7 내지 40의 아릴알킬렌기이고;
X는 할로겐 원자이고;
n은 1 내지 10의 정수이고;
m은 1의 정수이다.
A dinuclear metallocene compound represented by Formula 1 below; And
Catalyst composition comprising a promoter:
[Formula 1]
In Chemical Formula 1,
R1 to R8 may be the same or different from each other, and each independently hydrogen, an alkyl group of 1 to 20 carbon atoms, an alkenyl group of 2 to 20 carbon atoms, an aryl group of 6 to 20 carbon atoms, an alkylaryl group of 7 to 20 carbon atoms, 7 carbon atoms An arylalkyl group of 20 to 20, or an amine group having 1 to 20 carbon atoms, and two adjacent groups of R1 to R8 may be connected to each other to form one or more aliphatic rings, aromatic rings, or hetero rings, provided that R1 to R8 Except when are all hydrogen;
R9 and R10 are the same as or different from each other, and each independently hydrogen, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and 6 to 10 carbon atoms An aryloxy group, an alkenyl group having 2 to 20 carbon atoms, an alkylaryl group having 7 to 40 carbon atoms, or an arylalkyl group having 7 to 40 carbon atoms;
Q is an alkylene group having 1 to 20 carbon atoms, a cycloalkylene group having 3 to 20 carbon atoms, an arylene group having 6 to 20 carbon atoms, an alkylarylene group having 7 to 40 carbon atoms, or an arylalkylene group having 7 to 40 carbon atoms;
X is a halogen atom;
n is an integer from 1 to 10;
m is an integer of 1.
According to claim 1, wherein R1 to R8 are each independently hydrogen, an alkyl group of 1 to 20 carbon atoms, an alkenyl group of 2 to 20 carbon atoms or an amine group of 1 to 20 carbon atoms, or two adjacent to each other of the R1 to R8 are Connected to form one or more aliphatic rings, aromatic rings, or hetero rings, except where R 1 to R 8 are all hydrogen.
The catalyst composition of claim 1, wherein in Formula 1, R9 and R10 are each independently hydrogen, alkyl having 1 to 20 carbon atoms or alkoxy having 1 to 20 carbon atoms, X is Cl, and n is an integer of 2 to 6.
[화학식 1a]
[화학식 1b]
[화학식 1c]
[화학식 1d]
The catalyst composition of claim 1, wherein the dinuclear metallocene compound is represented by one of the structural formulas of Formulas 1a to 1d.
[Formula 1a]
[Formula 1b]
[Formula 1c]
[Formula 1d]
[화학식 4]
-[Al(R11)-O]c-
상기 화학식 4에서, R11은 서로 동일하거나 상이하고, 각각 독립적으로 할로겐 라디칼, 탄소수 1 내지 20의 하이드로카빌 라디칼, 또는 할로겐으로 치환된 탄소수 1 내지 20의 하이드로카빌 라디칼이고, c는 2 이상의 정수이며,
[화학식 5]
D(R12)3
상기 화학식 5에서,
D는 알루미늄 또는 보론이고, R12는 탄소수 1 내지 20의 하이드로카빌 또는 할로겐으로 치환된 탄소수 1 내지 20의 하이드로카빌이고,
[화학식 6]
[L-H]+[ZA4]- 또는 [L]+[ZA4]-
상기 화학식 6에서,
L은 중성 또는 양이온성 루이스 염기이고, H는 수소 원자이며, Z는 13족 원소이고, A는 서로 동일하거나 다를 수 있으며, 각각 독립적으로 1 이상의 수소 원자가 할로겐, 탄소수 1 내지 20의 탄화수소, 알콕시 또는 페녹시로 치환 또는 비치환된 탄소수 6 내지 20의 아릴기 또는 탄소수 1 내지 20의 알킬기이다.
The catalyst composition of claim 1, wherein the promoter is at least one selected from the group consisting of compounds represented by Formulas 4 to 6 below:
[Formula 4]
-[Al (R 11 ) -O] c-
In Formula 4, R 11 is the same as or different from each other, and each independently a halogen radical, a hydrocarbyl radical having 1 to 20 carbon atoms, or a hydrocarbyl radical having 1 to 20 carbon atoms substituted with halogen, and c is an integer of 2 or more. ,
[Formula 5]
D (R 12 ) 3
In Chemical Formula 5,
D is aluminum or boron, R 12 is hydrocarbyl having 1 to 20 carbon atoms or hydrocarbyl having 1 to 20 carbon atoms substituted with halogen,
[Formula 6]
[LH] + [ZA 4] - or [L] + [ZA 4] -
In Chemical Formula 6,
L is a neutral or cationic Lewis base, H is a hydrogen atom, Z is a Group 13 element, A may be the same or different from each other, and each independently one or more hydrogen atoms is halogen, hydrocarbon having 1 to 20 carbon atoms, alkoxy or Or an aryl group having 6 to 20 carbon atoms or an alkyl group having 1 to 20 carbon atoms unsubstituted or substituted with phenoxy.
A process for producing a polyolefin comprising polymerizing at least one or more olefin monomers in the presence of a catalyst composition according to claim 1.
The method of claim 6, wherein the polymerization of the olefin monomer is performed at a temperature of 20 to 110 ° C. and a pressure of 20 to 100 bar.
The method of claim 6 wherein the olefin monomer is ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetra A process for producing at least one polyolefin selected from the group consisting of decene, 1-hexadecene, 1-octadecene, 1-eicosene, and mixtures thereof.
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